Bubble Evolution and Transport in PEM Water Electrolysis Mechanism

Progress in Energy and Combustion Science 96 (2023) 101075
Contents lists available at ScienceDirect
Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs
Bubble evolution and transport in PEM water electrolysis: Mechanism,

impact, and management
Shu Yuan a, Congfan Zhao a, Xiyang Cai a, Lu An a, Shuiyun Shen a, Xiaohui Yan a, **,
Junliang Zhang a, b, *
a
Institute of Fuel Cells, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, PR China
b
MOE Key Laboratory of Power Machinery and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, PR China
A R T I C L E I N F O A B S T R A C T
Keywords: Proton exchange membrane water electrolysis (PEMWE), as a promising technology for hydrogen production
Proton exchange membrane water electrolysis from renewable energy sources, has great potential for industrial application. Gas bubbles are known to influence
Hydrogen production the PEMWE cell performance significantly, but a full picture of bubble behaviors and their impacts on cell
Bubbles
performance has been lacking. In this review, we first discuss the most recent advances toward understanding the
Gas evolution reactions
bubble evolution and transport processes as well as the mechanisms of how bubbles impact the PEMWE. Then the
Oxygen evolution reactions
state-of-the-art bubble management methods to mitigate bubble-induced performance losses are summarized.
Due to the similarity between PEMWE and anion exchange membrane water electrolysis (AEMWE), we also
extend related discussions for AEMWE. Lastly, we present principles of bubble management, followed by an
outlook of scientific questions and suggestions for future research priorities.
1. Introduction chance for massive hydrogen production from water electrolysis, which
makes the locally shackled renewable energy storable and transportable
The increasing demand for energy consumption and the need for [10].
carbon-emission reduction worldwide are the main momentums for The main water electrolysis techniques include alkaline water elec
developing renewable energies. In the past decades, the booming trolysis (AWE), proton exchange membrane water electrolysis
development of hydro, wind, solar, and tide energy has shown their (PEMWE), and solid oxide electrolysis (SOEC) [11]. Some excellent re
great potential to replace the fossil energy. However, most of these en views have detailedly introduced differences between these water
ergy sources are known to be locally shackled because of geographical electrolysis techniques [11–15]. Among these techniques, PEMWE
dislocations between energy-producing and energy-consuming regions shows unique advantages over other electrolytic water technologies.
and are difficult to integrate into the grid because of intermittent elec First, PEMWE can operate at a higher current density compared to AWE
tricity production [1,2]. Therefore, an efficient energy carrier for stor and SOEC [16]. During the operation, its excellent dynamic performance
age and transport is highly needed. Hydrogen has been regarded as an allows PEMWE to have high load flexibility (down to 0% and also sup
ideal energy carrier in future energy society for its advantages of port overload operation) [11]. Compared to PEMWE, the limited dy
zero-emission and high energy density. The International Renewable namic performance of AWE and SOEC are less suitable for transient
Energy Agency forecasts that hydrogen and its derivatives will operation. Second, PEMWE has a much faster cold start (seconds to
contribute to 12% of final energy consumption by 2050 [3]. Thanks to minutes) than AWE (minutes to hours) and SOEC [14]. In addition, the
the development of various fuel cells and hydrogen internal combustion cross-permeability in the PEM electrolysis cell is very low, and it pro
engine techniques, we can see a promising future of hydrogen as a daily duces hydrogen with a purity higher than the AEW, which is usually
fuel for powering vast applications [4–9]. For the source of hydrogen, greater than 99.99% after drying [17]. The compact module design of
the decreasing price of renewable electricity provides an excellent PEMWE also supports high pressure operation and can even work under
* Corresponding author. Institute of Fuel Cells, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, PR
China.
** Corresponding author.
E-mail addresses: yanxiaohui@sjtu.edu.cn (X. Yan), junliang.zhang@sjtu.edu.cn (J. Zhang).
https://doi.org/10.1016/j.pecs.2023.101075
Received 17 August 2022; Received in revised form 27 December 2022; Accepted 9 January 2023
Available online 18 January 2023
0360-1285/© 2023 Elsevier Ltd. All rights reserved.
S. Yuan et al. Progress in Energy and Combustion Science 96 (2023) 101075
differential pressure conditions of 350 bar [18]. Taken together, these rational bubble management is highly desired. Almost all main PEMWE
advantages make PEMWE more suitable for working with renewable cell components affect the trip of bubbles from generation to removal
energy sources, which are usually dynamic and intermittent. which is somewhat similar to the water management in PEM fuel cells
Although promising, the high cost due to the use of precious metal and the entire process in turn greatly influences the cell performance
catalysts and poor practical performance at high current densities hinder [38,39]. The modification of the relevant components can lead to dra
the commercialization of PEMWE [19–21]. As shown in Fig. 1, a typical matic performance improvements. For example, a new electrode design
PEMWE cell consists of several main components as follows. A aiming to achieve rational bubble management improves the anode
catalyst-coated membrane (CCM) where hydrogen evolution reaction catalyst utilization, which is 24 times that of conventional design and
(HER) and oxygen evolution reaction (OER) take place, locates in the achieve an ultra-low catalyst loading [40]; a porous transport layer
middle of the cell and is composed of a cathode catalyst layer (CL), an (PTL) design that resolves the gas accumulation issue can reduce the
anode CL and a PEM. Right next to the CCM, liquid and gas transport mass transport overpotential by up to 76.7% [41]. These reports
through two pieces of porous transport layers (PTL) [22–24]. Because demonstrate the importance of bubble management, which warrants a
most of the water-gas transport occurs in the anode in a typical complete understanding of bubble behaviors in the PEMWE cell. Many
anode-circulation operation, some literature also denotes the anode similar bubble management designs can also be found in the recent
porous transport layer as the liquid-gas diffusion layer (LGDL) and the anion exchange membrane water electrolysis (AEMWE) reports and
cathode porous transport layer as the gas diffusion layer (GDL) [25–27]. significantly improve the electrolyzer performance. Since AEMWE has
The CCM and PTL are tightly clamped by flow fields and end-plates, almost the same MEA and cell structure as PEMWE, except that each
where flow fields are responsible for water distribution and gas component uses a different material and a different liquid feed mode,
drainage, and end-plates ensure that the components are tightly some discussion on bubbles in PEMWE can be extended to AEMWE.
assembled to prevent leakage. Alternatively, some PEMWE cells may This article focuses on the evolution, transport, impact, and man
employ catalyst-coated PTLs (PTE) instead of CCM, which is similar to agement of bubbles in PEMWE cells. For the entire process from bubble
gas diffusion electrodes in fuel cells (GDE) [28–31]. The self-supported generation to removal, we start with a comprehensive review of the
electrode where the catalyst is grown directly on the surface of PTL can bubble evolution process, i.e., nucleation, growth, detachment; and the
also be considered as a type of PTE [32]. bubble transport process, i.e., all the processes bubble experienced after
Current research has been focusing on reducing the cost of PEMWE detaching from the catalyst surface that occurs in different parts of
through developing new catalysts and electrode materials but often ig PEMWE cell and at their interfaces. We then discuss the influence of
nores the impacts of electrolysis products, and gas bubbles, on cell both bubble evolution and transport on PEMWE, followed by reviewing
performance during practical operations. Although bubbles can facili the most recent advances in bubble management strategies, including
tate local convection to some extent, they have an overall negative effect components design (catalyst layer, porous transport layer, flow field,
on the reaction [28,33–37]. The situation becomes more complex within and new cell architecture design) and active management approaches.
a PEMWE cell, where both bubble evolution and bubble transport pro Additionally, the related discussion has also been extended to AEMWE
cesses take place. While the former occurs on the catalytic surface, the to be a more general guide to MEA-type water electrolyzers. Finally, the
latter involves multistep through various components. remaining challenges are presented and discussed and the directions for
The bubble evolution and transport processes occurring inside the future research work toward designing and developing high-
practical PEMWE cell and their impacts on cell performance are performance PEMWE are proposed.
currently understudied. In recent reports, it has been found that the high
bubble coverage, slow bubble detachment, insufficient bubble genera
tion sites, as well as gas accumulation issues in PEMWE cells lead to a
series of negative impacts, including high mass transport loss, low
catalyst utilization and unstable cell performance (Fig. 1). Therefore,
Fig. 1. The structure of a typical proton exchange water electrolysis cell and the bubble issues within it.
2
2. Bubble evolution (~130) is much lower than in the homogeneous case [45]. In PEM water
electrolysis, which is a heterogeneous nucleation scenario, △Gcrit de
2.1. Overview pends not only on the interaction of the liquid phase and gas phase but
also on the interaction between the solid phase and gas phase. The CL
In PEMWE, hydrogen is evolved from the proton in the cathode and surface provides favored nucleation sites and has a reduction effect on
oxygen is evolved from the water molecules in the anode. According to the △Gcrit. The CL’s morphology and surface contact angle in this het
this electrolysis mechanism, water as the reactant is usually supplied on erogeneous nucleation system greatly influence this reduction effect
the anode side. Therefore, the bubbles evolution process is mainly [42].
happened on the OER side, while most hydrogen gas can directly flow The sites of bubble evolution and gas evolution reaction can be
out from the cell without forming bubbles. Therefore, in the case of decoupled. Although bubbles usually nucleate where the OER is most
PEMWE, the relevant discussion is focused on oxygen bubbles. active, it is clear from the nucleation conditions that bubbles do not
Three main stages are involved in the bubble evolution process necessarily nucleate precisely at the site where OER occurs. For
during water electrolysis. With the continuous generation of oxygen example, Peñas et al. designed a ring microelectrode and they found that
from the catalytic surface, bubbles experience nucleation, growth, and the bubbles form at the center of the ring microelectrode where no
detachment processes and then leave the CL (Fig. 2). This section revisits catalysts exist (Fig. 3a) [46]. The dissolved gas molecules gather in the
the bubble dynamic and discusses the factors that affect the evolution hydrophobic microcavity and form the first bubble nuclei just a few
processes. seconds after the reaction begins. The bubble is kept out of reach of the
ring electrode during the subsequent bubble growth. This separation of
the bubble evolution site and the gas evolution reaction site eliminates
2.2. Nucleation the direct coverage of the catalytic surface by bubbles and significantly
reduces the overpotential fluctuations of the gas evolution reaction
The nucleation of bubbles in water electrolysis is driven by the during the bubble evolution process [47,48]. Similar separation phe
continuous increase of the dissolved gas concentration near the catalytic nomenon of the bubble evolution site and the gas evolution reaction site,
surface Cgas. During the operation of the water electrolyzer, the OER as well as chronopotentiometric fluctuation reduction has also been
release gas molecules in the liquid phase and cause Cgas to be higher than observed in the electrolyzer with superaerophobic array electrodes [49].
its saturation concentration Csat. According to Henry’s law, the gas In PEMWE cells, the bubble nucleation sites are influenced by the
saturation concentration Csat is proportional to its partial pressure P: three-phase interface properties. In the case where the reaction surface
is submerged in water, the activity of the catalytic site is mainly influ
Csat = PKH (T) (1)
enced by the proton-electron transport properties, and bubbles appear
In this equation, KH is Henry’s solubility which is temperature- around where OER is most active. For the effect of electron transfer, it
dependent and gas-liquid pair dependent. When Cgas > Csat, the gas in has been confirmed that bubbles are preferentially generated near the
the liquid phase is supersaturated. The gas supersaturation ζ is defined surface with better conductivity on the same CL (Fig. 3b1–2) [50]. The
as: effect of proton conductivity on bubble formation has not been reported
in the literature. However, it can be speculated that its effect on bubble
Cgas − Csat
ζ= (2) generation sites is similar to that of electron conduction. It is also
Csat
noteworthy that in PEMWE, perfluorosulfonic acid (PFSA) ionomer has
With the increasing of ζ, nucleation of bubbles occurs at certain sites the ability to transport water in addition to proton conduction. There
at some point (Fig. 2a). A higher supersaturation level implies a higher fore, the locations covered by ionomer are theoretically still active for
tendency for bubble nucleation. OER, but the separation of the OER site and the bubble evolution site
The nucleation of bubbles is usually described by classical nucleation may occur. To date, there are few reports in the literature discussing
theory (CNT) [42,43]. The free energy for bubble formation is defined as how the ionomer-covered surface specifically affects the bubble dy
the sum of surface energy for forming a gas− liquid interface and the namics and electrochemical response. Since the percentage of such
volume energy for forming a bulk gas phase. The peak energy barrier ionomer-covered surfaces in CL is non-negligible, it is necessary to un
△Gcrit for bubble nucleation implies the nucleation of bubbles takes derstand the role of ionomer in bubble evolution.
place when a critical size rcrit of the gas bubble is reached. Supersatu
ration drives the bubbles to cross the critical point. For homogeneous
nucleation, the critical supersaturation predicted by CNT for bubble 2.3. Growth
nucleation is ~1400 (based on γ = 0.071 N m− 1) [44]. For heteroge
neous nucleation, which is more common in real-world scenarios, the The bubbles grow when the dissolved gas concentration immediately
critical supersaturation observed for the nucleation of O2 bubbles near a bubble’s interface (Cb) is lower than the dissolved gas
Fig. 2. Bubble evolution process at the CL of PEMWE (taking the anode as an example): (a) nucleation; (b) growth; (c) detachment.
3
Fig. 3. (a) A hydrogen bubble nucleate and grow

from the mid of a ring electrode. The red line in
dicates the position of the Pt ring electrode. Repro
duced with permission from Peñas et al. [46].
Copyright 2019, IOP Publishing. (b1) Bubble evolu
tion observed through perforated PTL. (b2) Effect of
conductive (tungsten) and non-conductive (polymer)
fibers between PTL and CL on bubble evolution.
Reproduced with permission from Mo et al. [50].
Copyright 2017, Royal Society of Chemistry.
concentration near the catalytic surface Cgas [51]. Cb can be calculated ( )1

by the Laplace-Young equation and Henry’s law [33]. rd =
3γrc 3
(4)
( ) 2 ρg
2γ
Cb = KH Pi = KH + P0 (3)
r where rc is the radius of contact area between a bubble and solid surface,
In this equation, the gas pressure within the bubble with radius r is γ is the surface tension, g is the gravitational constant and ρ is the liquid
denoted by Pi, while the surface tension is denoted by γ. Although the density. The case of water electrolysis is much more complicated. The
nucleation process of bubbles can partially reduce Cgas (almost impos electrostatic interactions between charged bubble and electrode surface
sible to reduce to equilibrium level), when HER and OER continually and the Marangoni force also influence the bubble detachment behavior
increase Cgas, Cgas is higher than Cb [42]. This concentration difference [42,56]. The detailed discussion and modeling of this case are reviewed
drives the flux of dissolved gas from the liquid phase to bubbles (Fig. 2b) in Taqieddin’s work [57]. According to the models, in addition to the
[51]. The growing rate of the bubbles is mainly dependent on the su current density of electrolysis, the surface morphology and contact angle
persaturation level ζ [42]. At the same time, the ζ at the same current of the electrodes also affect the bubble detachment radius and rate.
density is affected by many factors, such as geometry and the wettability Many aerophobic electrode designs have demonstrated that increasing
of the catalyst layer [25,33]. The porous transport layer and flow field the bubble contact angle can substantially reduce the bubble detach
may also influence ζ by affecting the bubble removal rate from CL. ment size and increase the detachment rate [58].
Three bubble growth stages are involved in water electrolysis [33,34, The bubble detachment is not a complete unpinning process from the
42,51,52]. In the first stage, the internal and surface tension forces catalytic surface (Fig. 2c). The detachment of a bubble starts with
dominate the bubble growth. The growth rate of the bubble can be creating a neck between the bubble and the substrate. With more un
described by a time-dependent bubble radius r(t) = A⋅t, where A is the balanced forces, the neck keeps narrowing until it disappears. After
growth coefficient and t is the time. In the second stage, the growth rate ward, the bubble detaches from the catalytic surface and sinks into the
of the bubble is controlled by the flux rate of dissolved gas from the liquid phase [55,59]. The remaining small gas pocket on the substrate
liquid phase to the bubble, and r(t) = A⋅t1/2. The last stage is governed facilitates another bubble growth and detachment cycle in the same
by the electrochemical reaction rate or so-called direct injection of gas place [33].
into the bubble and r(t) = A⋅t1/3. For water electrolysis, the growth of
bubble radius usually negatively impacts the overall hydrogen and ox 2.5. Multiple bubbles evolution during the practical electrolysis process
ygen production performance due to the coverage effect on the active
area and slower bubble detachment [53]. The above parts focus on individual bubble behavior to show the
mechanism of bubble evolution. While during the practical electrolysis
2.4. Detachment process, multiple bubbles evolution processes occur simultaneously.
Understanding the multiple bubbles evolution process during practical
Detachment takes place when upward forces overcome the down electrolysis is very important for bubble management. It may be more
ward forces (Fig. 2c). In a most simple model given by Fritz’s formula meaningful to compare parameters such as bubble density, bubble size
[54], where buoyant force is considered as the only upward force to distribution, average bubble detachment period and bubble coverage of
balance the adhesion force, the detachment radius of bubbles can be the sample at the same current density than those investigated in the
obtained by [55]. evolution of individual bubbles to perform optimization of bubble
management.
4
In an open electrolysis system (like the three-electrode cell), char of supplying electrolyte to both cathode and anode and the mode of
acterizing the behavior of bubbles is relatively simple. Using a high- supplying electrolyte to anode alone are commonly used [84–88].
speed camera, it is possible to qualitatively investigate the multiple Therefore, both hydrogen bubble evolution and oxygen bubble evolu
bubbles evolution behavior during the electrolysis (Fig. 4a). Combined tion are involved in AEMWE. The relevant discussion of oxygen bubbles
with the electrochemical data, the electrochemical response of different can be drawn from the PEMWE. The subsequent discussion will focus on
bubble evolution characteristics (such as growth behavior, and detach the cathode, which is associated with hydrogen bubbles. For the
ment behavior) can be compared and confirmed [60]. As Fig. 4a shows, nucleation, the reported supersaturation for H2 bubbles nucleation is
it is clear that electrodes with denser and smaller bubbles show lower about 310, which is higher than the oxygen bubble (~130) [45,89]. For
overpotential and overpotential fluctuation. Methods to analyze the the growth and detachment, the produced hydrogen molecules are twice
changes in overpotential and cell performance by characterizing the as oxygen at the same electrolysis current density (Fig. 5b). This may
changes in bubble behavior have been used in many reports [50,61–64]. bring a higher growth rate and higher detachment frequency. Corre
Further, with the help of techniques like particle image velocimetry, spondingly, the evolution period is significantly reduced compared to
particle tracking velocimetry and simulation, the bubble size, 2D/3D the OER, and more bubbles are generated, which can be clearly observed
velocity and bubble-electrolyte two-phase flow behavior can be inves in the electrolyzed water in the open system (Fig. 5c) [61].
tigated and compared quantitatively (Fig. 4b and c) [65–67]. Another major difference in bubble evolution between AEMWE and
In PEMWE, as a closed system, the characterization of bubble evo PEMWE is the catalyst materials. In PEMWE, the most common catalyst
lution is much more difficult. The bubbles originate from the CL, and in the cathode is PGMs and the catalyst in the anode is Ir, IrOx and RuOx.
their outflow pathway from the cell is influenced by the structure and In contrast, the choice of catalysts is much broader in AEMWE. Usually,
physical characteristics of both PTL and flow field [68]. It is commonly transition metal-based materials are used in AEMWE for both anode and
believed that bubbles mainly evolved at the three-phase interface in the cathode [88]. There are also studies that will use the same catalyst
CL [28,50,69]. However, due to the limitation of visualization tech configuration as PEMWE for the AEMWE experiments [90]. For
niques, the detailed bubble evolution behavior at CL and CL-PTL inter CCM-type CL, the use of different catalysts on the one hand leads to
face is still unclear [50,70–72]. In order to investigate the characteristics different CL surface properties, which may lead to different bubble
of bubble evolution, it is desirable to observe the behavior of bubbles at evolution features at the same current density [91]. On the other hand,
the CL-PTL interface and even inside the CL, but the direct observation the flexibility of the catalyst in AEMWE makes it easier to control the
of bubbles is substantially limited due to compact cell structure. A bubble evolution by changing the catalyst as well as the CL structure
common approach to observing the bubbles inside the cell is to use a [92,93]. In addition, self-supported PTE design is widely employed in
transparent flow field plate [71,73,74]. But the bubbles observed in this many AEMWE studies [32,94,95]. The evolution of bubbles and their
method are the bubbles that flow from the PTL rather than those bubbles transport behavior in the self-supported PTEs are more complicated than
directly generated from the CL. Although it is possible to demonstrate in the CCM type CL. Since AEMWE is usually fed with liquid alkaline
some characteristics of bubbles employing a perforated PTL and a electrolytes instead of pure water to both provide reactant and enhance
transparent flow field, it is difficult to decouple the effect of the CL the conductivity of the OH− , most of the self-supported PTE surface is
characteristics and the characteristics of PTL [50,75]. Techniques such active during electrolysis [88,96]. Therefore, the bubble is able to grow
as X-ray computed tomography and in operando in-plane neutron im anywhere in the self-supported PTE, and its growth and detachment
aging are able to penetrate the cell to obtain the gas distribution as well process is constrained by the porous structure. Meanwhile, while the
as the changes in gas distribution to observe the gas transport processes, bubble in the upper position of the PTE is still growing, the bubble
but their resolution is not sufficient to investigate the evolution behavior transported from the below region may have also reached this position
of the bubbles [76–80]. To understand the behavior of bubble evolution, and influenced the growing bubble. This leads to a hybrid of bubble
some indirect electrochemical methods have been developed. Based on evolution and transport processes. Iwata et al. observed and summarized
the fact that the current fluctuation during constant voltage operation of three modes of bubble evolution in PTE by changing the wettability of
the electrolyzer mainly originated from bubble evolution at a specific porous nickel foams (Fig. 5d): internal growth and departure mode,
frequency range, frequency analysis can be a method to understand the wicking mode, and gas-filled mode [60]. For the internal growth and
multiple bubbles evolution behaviors in practical electrolyzers departure mode, both bubble nucleation and detachment occur on the
(Fig. 4d1) [81,82]. The different frequency ranges represent the surface and inside the porous foam, and the diameter of the bubble
different bubble states at the CL-PTL interface [83]. The frequency leaving is smaller than the pore diameter. When the bubble detachment
characteristics in the current fluctuations can be extracted by the Fourier diameter increases and becomes comparable to the pore size, frequent
transform. By integrating the Fourier transform results of current data bubble coalescence occurs within the porous structure. It makes the
for three frequency ranges, bubbles can be divided into three types: 0.03 bubbles removal from the internal pores significantly suppressed, and at
Hz < f<1 Hz, 1 Hz < f<10 Hz, 10 Hz < f<50 Hz. Most bubbles are at this time, it enters the wicking mode. In the gas-filled mode, the bubble
10–50Hz, this type of bubble can be roughly attributed to evolution process is fully coupled with the transport process, and the
nucleation-driven, and its share is usually increasing with current den growth of the large bubbles observed on the surface is affected both by
sity increase, which is similar to the bubble evolution in the open sys diffusion and by the coalescence of the bubbles transported up from
tem. The low-frequency fluctuation is derived from the huge bubbles below.
that are confined by PTL channel which detach from the CL with at a The difference in PTL also affects the bubble evolution in the cell. In
much lower frequency. As shown in Fig. 4d2, by performing a frequency AEMWE, the PTL used in the cathode is usually Ni foam, carbon paper
analysis of the fluctuations in the current, the percentage of bubbles in and carbon cloth, while in PEMWE, the main PTL in the anode is usually
different frequency ranges at different current densities can be roughly Ti-based, such as fibrous Ti or sintered Ti powder [25,97]. This leads to
analyzed. differences in wettability, porosity, corresponding MPL properties, and
mechanical properties among PTLs, and will eventually lead to different
2.6. Bubble evolution in AEMWE CL-PTL interfaces formed when CL and PTL are tightened by pressure.
Eventually, the distribution of bubble nucleation sites, bubble detach
The bubble evolution process in AEMWE is highly similar to that in ment size, and bubble detachment frequency will be affected.
PEMWE. However, in addition to the OER, the bubbles produced by HER
also need to be considered. In AEMWE, water is firstly involved in HER
and produces H2 and OH− . The generated OH- diffuses through the AEM
to the anode side for OER, producing O2 (Fig. 5a). In AEMWE, the mode
5
Fig. 4. (a) Combining optical characterization and electrochemical characterization measurements to investigate the bubble evolution in an open electrolysis system.
Reproduced with permission from Iwata et al. [60]. Copyright 2021, Elsevier B.V. (b) Investigate multiple bubble evolution behavior using CFD simulation approach.
Reproduced with permission from Wosiak et al. [67]. Copyright 2022, Elsevier B.V. (c) Quantifying bubble size and 3D velocity with particle tracking velocimetry
technique. Reproduced with permission from Wu et al. [65]. Copyright 2020, Elsevier B.V. (d1) Current fluctuation during constant voltage electrolyzer operation.
(d2) The percentage of different fluctuation frequency range at each current density after performing FFT on current-time data. Reproduced with permission from
Kwan et al. [81]. Copyright 2022, IOP Publishing.
6
Fig. 5. (a) The difference between the working mechanism of PEMWE (left) and AEMWE (right). AEMWE is usually operated using either a cathode and anode
water/electrolyte supply mode or an anode water/electrolyte supply mode. (b) The hydrogen production is twice as much as the oxygen when the electrolysis cell is
working. Reproduced with permission from Liang et al. [98]. Copyright 2020, Royal Society of Chemistry. (c) Hydrogen gas produces significantly more bubbles than
oxygen during water electrolysis. Reproduced with permission from Matsushima et al. [99]. Copyright 2003, Elsevier B.V. (d) Three bubble evolution modes when
using foam electrode. Reproduced with permission from Iwata et al. [60]. Copyright 2021, Elsevier B.V.
3. Bubble transport that PEMWE is supplied with water at the anode only. In addition, due to
the limitation of analytical tools and methods, the knowledge about
3.1. Overview bubble transport within CL is still insufficient and needs more effort to
be investigated further. The following discussion will start with bubble
The bubble transport process involves the processes in CLs, PTLs and transport in PTL.
flow fields. Water is supplied and distributed to the whole reaction area
through the anode flow field and PTL. After applying voltage, OER and 3.2. In porous transport layer
HER occur and produce gases from the anode and cathode, respectively.
As shown in Fig. 6, because the anode is filled with liquid water, the The bubble transport in PTL is a complex two-phase flow process in
produced oxygen leaves the anode CL in the form of gas bubbles across the cell. Many efforts have recently been devoted to understanding this
the PTL and then reaches flow field, which is further removed from the process through imaging techniques, including optical, neutron, X-ray
cell driven by the water flow. Usually, the PEMWE only needs a water imaging, and computational studies [77,103–106]. With their efforts,
supply at the anode side because water is consumed by anodic OER we can now give a comprehensive illustration of bubble behavior in this
reaction [100,101]. But in some cases, the cathode is also supplied with transport process.
water [102]. In the later discussions, we will focus on the common case Bubble transport routes in PTL are guided by the porous structure.
7
Fig. 6. Overview of the bubble transport process in PEMWE (anode side).
Fig. 7. Bubble transport in PTL. (a) Captured images during constant injection of 10 mL min− 1 gas in PTL-on-Chip. Reproduced with permission from Lee et al.
[108]. Copyright 2017, Elsevier B.V. (b–c) Oxygen content distribution in PTL. In (b) PTL is shown in gray and oxygen content is shown in red. The coordinate axes
and arrows indicate the corresponding position of figures c–e. In (c) the saturation distribution of oxygen along the PTL cross-section is plotted for different current
densities. Reproduced with permission from Angelis et al. [113]. Copyright 2021, Royal Society of Chemistry. (d1-2) Comparison of the oxygen content of different
parts of PTL under the operating conditions of 1.0 A cm− 2 and 4.0 A cm− 2. Reproduced with permission from Satjaritanun et al. [77]. Copyright 2020, Elsevier B.V.
(e) Neutron radiographs of a working PEMWE cell at different current densities. The water thickness (indicate the water saturation) is displayed as a color map and
represents the water distribution across the whole cell. Reproduced with permission from Maier et al. [27]. Copyright 2020, Elsevier B.V.
8
Oxygen generated in the anode tends to transport through large voids bubble transport routes, changes in some operating conditions alter the
and may be stopped by the throat at some locations. This transport water/gas saturation profiles across the anode PTL at the through-plane
behavior consists of two repeating steps: pressurization and penetration direction, and affect the electrochemical reaction. In a PEMWE cell
[107]. A microfluidic platform developed by the Bazylak group, termed operating at a steady state, the water saturation decreases from the PTL-
PTL-on-Chip, explained this bubble transport behavior [107–110]. The flow field interface to the PTL-CL interface [111,113,114]. This trend of
manufactured PTL-on-Chip can simulate felt, sintered powder, and foam decreasing water saturation with decreasing distance from the PTL-CL
PTLs using volumetric pore space information (through-plane porosity interface is the same for different current densities, but the final water
distributions and throat size distributions) collected from saturation near the PTL-CL interface is different. As current density in
micro-computed tomography (micro CT) images. Gas is then injected creases (Fig. 8a), the gas generation rate also increases, and the water
into simulated PTLs through the gas inlet to simulate the produced gas saturation near the PTL-CL interface decreases. Under a current density
bubbles from CL [108]. With the continuous gas injection, it can be of 2.0 A cm− 2, a water saturation of about 0.4 was observed near the
observed that the total saturation of gas in simulated PTL remains the PTL-CL interface. In addition, the time required to reach a stable water
same most of the time while sometimes encountering a sharp increase. saturation distribution after loading current also decreases with
This long-time constant total saturation implies that the gas hardly increasing current. The temperature also has a significant impact on the
moves in the PTL and is under increasing pressurization. As shown in gas saturation distribution [78]. The increasing temperature has a
Fig. 7a, the bubble flow in the pressurization state is hindered by the bubble transport enhancement effect under different current densities
limiting throat in PTL. The following steep increase of the total satura (Fig. 8b). This enhancement effect is most significant for the transport
tion after a long pressurization time indicates a rapid gas penetration in process near the PTL-CL interface at low current densities, causing a
new voids in PTL. During penetration, the limited gas flow suddenly notable gas saturation decrease, which is beneficial for improving OER
breaches the previous limiting throat and grows with the low resistance performance. Near the PTL-flow field interface, the increasing temper
direction. The gas flow in different simulated PTLs followed the same ature causes a gas saturation increase. Unlike what occurs near the
behavior but exhibited different flow pathways. The porosity distribu PTL-CL interface, this saturation elevation effect also increases as the
tions and throat size distributions determine the primary flow pathway current ramps up. Additionally, the increasing temperature reduces the
under different gas injection rates. The primary flow pathway remains oxygen accumulation in the PTL under the rib. These phenomena
the same at all gas injection rates in one simulated PTL. At a higher gas observed at PTL-flow field interface are consistent with the results
injection rate, new flow pathways will be opened up to increase trans observed inside the flow channel, corresponding to an increase in bubble
port flux. Moreover, the gas flow behavior may switch from capillary size and an increase in the number of bubbles in the flow channel at the
fingering to viscous-fingering in some PTL morphology at a higher gas same current [71,75,115].
injection rate, resulting in a decrease in the local saturation near the gas Under the same flow field, the water/gas saturation distribution
inlet. within different PTLs at the cell scale is similar [27]. Since bubbles are
Bubble transport in practical PEMWE operation follows some similar generated everywhere in the CL and their removal from the cell involves
behavior as observed in the simulated PTL experiment. In the same PTL, a long path, the degree of gas accumulation in the PTL increases as it gets
bubbles tend to follow some preferential pathways guided by PTL’s closer to the outlet (Fig. 7e). As the current density increases, the region
structure. These pathways are not significantly influenced by varying of relatively insufficient water saturation within the PTL gradually ex
current density, water feed rate and operating pressure [77,111,112]. pands from the outlet to the inlet. However, there is still some PTL
Satjaritanun et al. have observed a working PEMWE cell through oper volume near the outlet location that maintains a high water saturation.
ando X-ray computed tomography [77]. From the in-plane view of the
cell, the oxygen followed almost the same transport pathways under 1.0
3.3. At the PTL-flow field interface
A cm− 2 and 4.0 A cm− 2 at the same water feed rate. At the same time, a
three times larger water circulation speed did not influence in-plane
Bubbles develop from various sites on the PTL surface when the gas
bubble transport behavior at 1.0 A cm− 2. In the through-plane view
travels to the PTL-flow field interface and remain attached owing to
(Fig. 7d1–2), the oxygen content in each part of PTL also showed a
surface tension forces (Fig. 9a). As time progresses, the bubble gradually
similar pattern at different current densities. Similar transport behavior
grows. When the dynamic pressure of flowing water surpasses the sur
has also been observed in Angelis’ works [113]. As shown in Fig. 7b and
face adhesion force, the gas bubbles detach from the PTL surface and
c, the in-plane oxygen content distribution at different current densities
join the water flow. The bubble growth and detachment process on the
showed a similar pattern, implying that oxygen escapes the cell by
PTL-flow field interface was observed to be a sub-second event (Fig. 9b)
preferential routes. The oxygen distribution region is slightly wider at
[116]. The time of this process, termed bubble residence time, decreases
high currents than at low currents, which could mean the original pri
with increasing current (Fig. 9c). The average detachment diameter of
mary transport pathways have been extended. This result is consistent
bubbles increases with increasing current (Fig. 9d). Leonard et al.
with the transport pathway extension phenomenon in the simulated PTL
modeled the bubble residence time as a function of the detachment
case [107].
diameter of bubbles for different current densities (Fig. 9e) [116].
The visualization of oxygen content distribution illustrates the whole
( 3 )
bubble transport route in PTL (Fig. 7b–e) [77,113]. The flow pathways 4πzF pl rdet 2
+ 2γrdet
of the oxygen bubbles begin when the bubbles detach from the CL into t= (5)
3RTj
the preferred pores. In the first step, when the bubbles occupy the voids
with the low resistance in the part of PTL near the CL, the distribution of Where z is charge number, F is Faraday’s constant, pl is the liquid
oxygen seems not relevant to the ribs and channels but depends more on pressure, r is bubble radius, γ is surface tension, and j indicates the
the PTL’s morphology. Subsequently, some bubbles have a chance to current density. The current density determines the growth rate of
move on and have a tendency to move gradually toward the pathways bubbles on the PTL surface and thus affects the residence time. As dis
underneath the channel. When the bubble reaches the PTL near the cussed in 3.2, the temperature can affect the bubble transport behavior.
channel, it is rapidly discharged and the occupied pores are released. Higher temperature can enhance upward gas transport. On the PTL
During this process, some bubbles are trapped in the PTL under the ribs, surface, more upward gas migration could result in a larger average
leading to a higher oxygen content than that in the PTL under the bubble size leaving the PTL and entering the channel at higher tem
channel. It can be found that the rib and channel features of flow field peratures. This effect was observed by Li et al. in their PTL with straight-
play a critical role in shaping the bubble transport pathway in PTL. through pores [75]. The water feed rate was found to have only a tiny
Although most operating conditions do not significantly affect the effect on the detachment diameter of bubbles, but was able to increase
9
Fig. 8. Gas/water saturation distribution in PTL. (a) Water saturation profiles and water saturation establishment dynamics across the thickness of the PTL.
Reproduced with permission from Zlobinski et al. [111]. Copyright 2020, IOP Publishing. (b) Oxygen gas saturation profiles across the thickness of the anode PTL of
an operating electrolyzer and the effect of temperature on gas distribution. Reproduced with permission from Lee et al. [78]. Copyright 2020, Elsevier B.V.
the frequency of bubble detachment [117,118]. significantly increase the size of the bubbles in the channel and may also
cause a shift in the flow regime similar to that which occurs when the
current density increases (Fig. 9g2).
3.4. In flow field
In terms of spatial distribution, the rise in operating current/voltage
significantly increases the inhomogeneity of water-gas distribution and,
After detaching from the PTL surface, bubbles are dispersed in the
in turn, affects the distribution of current density. As shown in Fig. 10a1,
water flow. At high current density, bubble flow in the flow channel will
when the flow rate is not large enough, the distribution of current
show different flow regimes. At low current density, bubble coalescence
density gradually becomes more and more uneven as the current density
occurs at a lower frequency and the bubble size in the flow channel is
increases [119]. The current density distribution, compared to the
relatively small. This flow state is known as the bubbly flow regime
(Fig. 9f1) [71,73]. With the current increase, bubble coalescence be water-gas distribution in the flow field, is much more consistent with the
water-gas distribution within the PTL. As shown in Fig. 10a2b2, the
comes more frequent and forms slugs that can fill the diameter of the
channel, transforming the flow regime into slug flow (Fig. 9f2). In the region of lower current density in the parallel flow field is not shown to
be significantly correlated with the gas distribution in the transparent
end, the slug flow develops into the annular flow with increasing gas
production. At this stage, the gas phase occupies most spaces of the flow field [71]. By comparing the current density distribution in the
parallel flow field with the water-gas distribution in the PTL (Fig. 7e), it
channel and water distribute along the channel wall (Fig. 9f3). This
development process in flow field can be observed through transparent is found that these two distribution maps are highly similar, with the
higher current density concentrated in the region of higher water
end-plates [71,75]. In a single-serpentine flow field, the part near the
inlet exhibits a bubbly flow regime. As the water flows, slugs start to thickness. The region of lower current density in the serpentine flow
field is in the second half of the flow field and has some similarity to the
appear, and the flow regime changes to annular flow in the latter part.
Higher current density not only increases the percentage of slug flow distribution of the gas distribution observed in the transparent flow field
(Fig. 10a3b1). Although to date there are no reports on the water-gas
regime and annular regime, but also makes flow enter the annular
regime earlier. The change in flow rate did not show a significant effect distribution in the PTL when using a serpentine flow field, it is still
reasonable to speculate that the water-gas distribution in the PTL is
on the flow regime (Fig. 9g1). Higher operating temperatures
10
Fig. 9. (a) Schematic of bubble transport from CL to flow channel. (b–e) Bubble residence time in the channel and bubble departure diameter observed by operando
X-ray tomography. (b) Radiographs of an oxygen bubble appearing and departure on in flow channel. (c–e) The bubble residence time in the channel and bubble
departure diameter as a function of operating current. Reproduced with permission from Leonard et al. [116]. Copyright 2018, Elsevier B.V. (f) Three flow patterns in
the flow channel. Bubbly flow (f1), Slug flow (f2), Annular flow (f3). Reproduced from with permission Wang et al. [73]. Copyright 2021, Elsevier B.V. (g1-2) O2
bubble flow pattern in flow fields at different flow rate and temperatures. Reproduced with permission from Majasan et al. [71]. Copyright 2018, Elsevier B.V.
consistent with the current density distribution based on the results of the water-gas two-phase flow may be a more severe issue in AEMWE at
the parallel one. Further study of the relationship between changes in high current density. Another significant difference is the CL structure.
flow field characteristics and water-gas distribution in PTL is needed to As discussed in 2.6, bubble evolution and bubble transport happen in the
understand how the flow field affects the performance and stability of same space in self-supported PTE. In some self-supported PTEs made
PEMWE. with electrodeposition and electrospinning, the PTE surface is also the
catalytic surface [120,121]. Therefore, the transport process has an even
3.5. Bubble transport in AEMWE more significant influence on the reaction because the confined bubble
will keep masking the catalytic surface. The gas saturation distribution,
Few articles have been published on the investigation of the trans as in Figs. 7–8, may primarily reflect the gas transport path in PEMWE,
port behavior of bubbles in AEMWE. Since the cell structures of AEMWE while in AEMWE using self-supported PTE, it may reflect which loca
and PEMWE are almost the same, the bubble transport processes tions of the catalytic surface are more likely to be covered by bubbles
involved should be very similar. In addition to some differences in and cause performance loss.
transport behavior due to the differences in hydrophobicity, porosity,
corresponding MPL properties, and mechanical properties brought 4. Impacts of bubble
about when using different materials of PTL, there are probably two
main differences in the behavior of bubble transport between PEMWE The efficiency of PEMWE cells can be conveniently compared by
and AEMWE. Firstly, the hydrogen production rate is twice of oxygen their working voltage at a given current density. The difference between
production rate at the same current density. In contrast to PEMWE, the the cell working voltage and the equilibrium voltage E0 of the electro
gas transport routes and gas saturation in the AEMWE cathode should chemical reaction at a given operating current density indicates the ef
increase substantially. Moreover, considering that AEMWE often oper ficiency loss of PEMWE cells. This voltage loss is derived from three
ates with electrolyte supplied on both sides of the cathode and anode, parts: activation loss, Ohmic loss, and mass transport loss:
11
Fig. 10. (a1) Distribution of current density in electrolysis cell with different operating voltages. (a2) Distribution of current density in a parallel flow field. (a3)
Distribution of current density in triple-serpentine flow field. Reproduced with permission from Roenning et al. [119]. Copyright 2022, Elsevier B.V. (b1) Gas-water
distribution in transparent serpentine flow field at different current densities. (b2) Gas-water distribution in transparent parallel flow field at different current
densities. Reproduced with permission from Majasan et al. [71]. Copyright 2018, Elsevier B.V.
ΔV = E0 + ηact + ηohm + ηmass (6) in stagnant and flow electrolytes experiments [129,130]. The bubble
coverage θ increases nonlinearly with the current density and crudely
A typical polarization curve of PEMWE after dividing the three losses
has a relationship form as:
is shown in Fig. 11e [122]. In most gas evolution reactions, the bubble
( )m
evolution process can affect all these three losses [33,34], and in j
Θ= (8)
PEMWE cells, the impacts on activation loss and mass transport loss are jΘ→1
more significant as no liquid electrolyte is used [41,123–126]. In
Where j is the current density and jΘ→1 is a fictitious limiting current
PEMWE cells, the majority of mass transfer-related losses are derived
density. In their case, the curve correlates with the data points well when
from the anode because of the complex two-phase flow behavior, and
m is 0.3 and jΘ→1 is 30 A cm− 2 (Fig. 11a). The effect of bubble coverage
the mass transport loss is observed to be noticeable when the current
on voltage loss was also observed by controlling the size of bubbles.
density is over 1.0 A cm− 2 [127].
Iwata et al. have observed different bubble growth and detachment
modes by adjusting the wettability of the electrode [60]. The bigger
4.1. Activation loss bubble sizes generated during the electrolysis process reflect the higher
bubble coverage and result in more voltage loss (Fig. 11d1). In addition
Activation overpotential ηact reflects the kinetic losses in electro to directly observing the relationship between bubble growth and
chemical reactions and can be derived from the Butler-Volmer equation detachment and voltage losses, some superior CL designs that favor
[16]: increasing the bubble nucleation sites and decreasing the bubble
[ [ ] [ ]] detachment size also demonstrate the negative effect of bubble coverage
αa nF ( ) αc nF ( )
I = Aj0 exp E − Eeq − exp − E − Eeq (7) on voltage loss [134,135]. However, it is worth noting that the regula
RT RT
tion of the bubble evolution process influences not only the activation
In this equation, A denotes the active area, j0 , αa and αc denotes the loss due to bubble coverage but also the other losses [33,34]. It is still
anodic and cathodic apparent charge transfer coefficients, respectively. hard to quantify the effect of bubble coverage level on cell voltage.
During the gas evolution on the catalyst surface, the attached bubbles
mask part of the electrocatalytic surface area A, resulting in an addi 4.2. Ohmic loss
tional activation overpotential [128,129]. The bubble coverage is usu
ally defined as the ratio of the blocked active area to the total active The Ohmic loss in water electrolysis is mainly derived from ion-
area. Numerous efforts have been devoted to investigating the degree of conducting resistance. For electrolysis using liquid electrolyte, both
bubble coverage of the catalytic surface and its influence on activation attached bubbles and flowing bubbles in the electrolyte can block the
loss [60,129–133]. Vogt provides an empirical relationship between the ion transport and therefore increase the Ohmic loss [33,34]. However, in
bubble coverage and current density by observing the bubble evaluation the case of the PEMWE cell, this ion transport blockage effect is
12
Fig. 11. (a) Coverage of the bubble based on the current density. Reproduced with permission from Balzer et al. [130]. Copyright 2003, IOP Publishing. (b)
Concentration profile around bubbles on the electrode surface during growth. Reproduced with permission from Angulo et al. [33]. Copyright 2020, Elsevier B.V. (c)
Microconvection during bubble evolution. Reproduced with permission from Yang et al. [56]. Copyright 2018, Royal Society of Chemistry. (d1) Estimation of bubble
overpotential based on bubble coverage in water electrolysis (1 M KOH). (d2) Transport loss corresponding to Ni foam electrodes with different PTFE coverages. The
lower the PTFE coverages, the smaller and denser the bubble generated by the electrode in the water electrolysis. Reproduced with permission from Iwata et al. [60].
Copyright 2021, Elsevier B.V. (e) Typical polarization curve of PEMWE after dividing the three losses. Reproduced with permission from Alia et al. [122]. Copyright
2020, IOP Publishing.
eliminated because of the use of solid electrolyte, typically PFSA ion transport loss reduction effect and microconvection effect of bubbles
omer. Literature has reported there is no significant effect of bubbles on were directly observed by Gabrielli and Kempler in the three-electrode
Ohmic loss in PEMWE. The influence of bubbles on activation and mass system [49,136]. Although bubble evolution is beneficial to reduce
transport loss is usually the main consideration when modeling the ef mass transport loss, it is easy to incorrectly correlate the increase of
fect of bubbles on PEMWE [83]. However, considering the conductivity bubble number with the increase in mass transport loss [123,125,
of ionomer is related to its water content, and bubble masking may lead 137–139]. Despite bubbles looking like one of the causes of mass
to a certain decrease in PEM water content, resulting in a decrease in the transport loss when analogous to water management issues in fuel cells
proton conductivity of the membrane, which in turn affects Ohmic loss. in these cases [140], the cause of increasing mass transport loss is not too
many bubbles, but rather too few bubbles. If a single bubble is observed,
at high current density, the generation rate of gas molecules is high and
4.3. Mass transport loss
a faster bubble evolution is required to remove the excess supersatura
tion. As a consequence, more bubbles over a period of time (i.e., higher
Mass transport loss is affected by the concentration gradients of re
detachment frequency) will be observed. When the mass transport loss
actants, intermediates, and products during water electrolysis. The
increases, it means that the supersaturation is high, i.e., the supersatu
Nernst equation can describe the voltage loss related to the concentra
ration is not reduced by a sufficiently high bubble detachment fre
tion profile during PEM water electrolysis. In the case of OER in anode
quency. If an electrode is observed, in the electrode with fewer bubble
[16].
nucleation sites, a higher local bubble detachment frequency is required
RTanode CO2 to reduce the local oxygen supersaturation to avoid high mass transport
ηmass = ln (9)
nF CO2 ,0 loss [141]. As Fig. 11d1–2 shows, the intuitive phenomenon is that the
more bubbles are observed at the same time (high bubble detachment
Where CO2 is the concentration of oxygen at the catalyst surface and
frequency), and the smaller the bubble is (small bubble detachment
CO2 ,0 is the reference working condition. The bubble evolution process is
diameter), the less mass transport overpotential can be observed.
driven by the gas supersaturation near the catalytic surface. Therefore,
the generation of bubbles can reduce the CO2 and lead to a decrease in
mass transport loss (Fig. 11b) [33,42]. In addition to the diffusion pro 4.4. Ideal bubble evolution behavior
cess, bubbles also lead to microconvection near the evolution site, which
is beneficial for mass transport. As the dissolved gas changes the surface Considering the bubble effect on both activation and mass transport
tension, the gas concentration gradient may lead to a local change in loss, the desired bubble evolution behavior in CL involves bubble gen
surface tension at the interface of the bubble. Also, surface tension eration site number, bubble detachment diameter and bubble detach
gradients may form when the electrolyte develops a temperature ment frequency. To reduce the bubble coverage, bubbles need to leave
gradient due to Ohmic heating. At this point, the resulting shear stress before growing too large. Therefore, the bubble detachment diameter
can cause microconvection (Marangoni effect, Fig. 11c) [56]. The mass should be reduced at the same current density. To achieve lower mass
13
transport overpotential, more bubbles are desired to reduce the local gas 4.5. Bubble accumulation and water starvation
supersaturation at a given current density and time. Increasing the
bubble nucleation site number and the bubble detachment frequency are In addition to bubble evolution occurring at the catalytic surface,
needed, especially at a high operating current density [134,142–145]. bubble transport behavior in the PEMWE cell also has a significant
impact on overall cell voltage loss. Since the bubble transport process
affects every process of bubble evolution, its effect on voltage is difficult
to distinguish by a certain overpotential alone. The accumulation of
Fig. 12. (a1-3) Evolution of gas distribution from the in PTL during dynamic operation. (a1) Response of gas saturation during load ramp-down operation. (a2-3) The
response of the average gas saturation and voltage within the PTL during dynamic changes in current. Reproduced with permission from Lee et al. [70]. Copyright
2020, IOP Publishing. (b1) 50.4 cm long segmented single-flow electrolysis cell setup. (b2) Comparison of polarization curves for different segment tests at insuf
ficient water supply. (b3) Polarization curves and voltage loss breakdown for the case of sufficient water supply (ref) versus the case of insufficient water supply(dry).
Reproduced with permission from Immerz et al. [149]. Copyright 2018, IOP Publishing. (c) Current density and temperature distribution at 0.5 A cm− 2 vary with
water stoichiometry. Reproduced with permission from Sun et al. [146]. Copyright 2015, Royal Society of Chemistry. (d) Gas distribution radiographs through the
anode PTL during operation. The top border is the PTL-Flow field interface and the bottom border is the CL-PTL interface. Reproduced from with permission Lee et al.
[72]. Copyright 2020, Elsevier B.V.
14
gaseous oxygen in the anode is the main contributor to this voltage loss critical current density or critical water stoichiometry can be extended
[126]. In the scenario of high current density and poor bubble transport, by optimizing the bubble and water transport in the PEMWE cell. Using
the oxygen bubble generated from CL travels a long and tortuous PTLs and flow fields with enhanced bubble removal capability can
pathway in the PTL and cannot be removed quickly, leading to gas therefore make the water electrolysis more stable and safe.
accumulation [77,107]. The low gas removal rate in the PTL then sup Different operating conditions have different effects on bubble
presses gas evolution and induces voltage losses. Additionally, under accumulation and on the performance of PEMWE. The effect of tem
high gas accumulation levels, the gaseous oxygen forms a barrier in the perature is most straightforward. As shown in Fig. 8b, temperature en
PTL and hinders the water from reaching the CL, which also affects the hances bubble transport and reduces bubble accumulation, which in
electrolysis reaction [53,146]. The gas accumulation can be character turn can improve performance. By separating the mass transport over
ized by a high gas saturation in the PTL and can be observed both during potential, it is found that increasing the temperature can decrease the
steady and dynamic cell operation [78,113]. In steady-state operation, mass transport overpotential at all current densities. The effect of water
the phenomenon of in-plane gas transport in PTL and gas traps under the flow rate on bubble transport is not significant. Through the observation
flow field ribs are the main reasons for gas accumulation [61,77,78, of transparent cells as well as simulation, it can be found that the water
107]. As discussed in 3.2, bubbles tend to move out of the PTL following flow has little effect on the transport behavior of the bubble in PTL and
some preferential pathways. However, these pathways do not always the flow regime of the bubble in the flow field [71,151,152]. However, it
have an orientation aligned with the direction of buoyancy. In PTL, the has been found that changes in water flow rate affect the performance of
bubbles prefer to move from the small pores to the large adjacent pores the cell. There are different opinions in the literature on the effect of
[61,147]. Because of the random size and spatial distribution of the water flow rate on the performance of PEMWE. Majasan et al. conducted
pores, the large adjacent pore may appear in the in-plane direction when their experiments in a parallel flow field (3 cm*3 cm) and showed that
bubbles move, which results in an in-plane bubble movement. This increasing the flow rate from 15 ml min− 1 to 60 ml min− 1 at an oper
behavior makes the bubble transport path tortuous and reduces the ating temperature of 80 ◦ C was able to improve the performance of
bubble transport rate (Fig. 7a). Moreover, some bubble transport path PEMWE [71]. In the results of the Roenning et al. tests in parallel and
ways lead gas to the area under the flow field ribs where the serpentine flow fields (5 cm*5 cm), it was also found that an increase in
through-plane transport is blocked (Fig. 7b and c) [77,113]. For these flow rate from 6 ml min− 1 to 50 ml min− 1 was able to improve the
issues, introducing the through-plane bubble transport pathways with performance of PEMWE [119]. Garcia-Navarro et al. performed exper
low resistance and directing gas flow in PTL to the channel area have iments using a parallel flow field with an active area of 25 cm2, but
been proposed as an effective solution for reducing the accumulation found that an increase in water flow rate would lead to a decrease in cell
induced voltage losses [41,61,148]. During dynamic cell operation, a performance [123]. The electrochemical impedance spectroscopy shows
hysteresis effect of gas saturation was observed [70]. This hysteresis that the low-frequency resistance gradually increases as the water sup
effect is manifested by the fact that the change of gas saturation in the ply rate increases, which indicates that the mass transport resistance is
PTL is much slower than the change of current (Fig. 12a1). During the higher at a high water flow rate. Therefore, the influence of flow rate on
intermittent electrolysis operation, this hysteresis effect resulted in an cell performance should be analyzed case by case, which depends on
increase in residual gas accumulation (Fig. 12a2). With repeating load many factors. In Garcia-Navarro’s experiment, a similar negative impact
up and load down cycles, this gas accumulation level gradually increases was observed in the cell operations with increasing pressure. The in
and reduces the electrolysis efficiency (Fig. 12a3). This dynamic crease in pressure also leads to a decrease in cell performance, as well as
response behavior of gas saturation in PEMWE raises a critical issue for an increase in mass transport resistance. This increase in mass transfer
the control strategy and cell design, especially when considering that resistance is more pronounced when the pressure of the cathode water is
PEMWE usually works with renewable energy sources with intermittent changed.
operation, such as solar and wind energy.
In the worst case of bubble transport, bubbles are accumulated near 4.6. Mechanical damage
the CL, leading to inhomogeneous water distribution and local water
starvation. The current and temperature distribution thus become un The bubble evolution in water electrolysis has also been reported to
even and unstable [79,146]. Without sufficient water supply, large influence the stability of the catalyst and catalyst layer [150,153,154].
voltage gaps can occur in different areas of the same cell under the same The generation and detachment of bubbles might introduce mechanical
current density (Fig. 12b2) [149]. The mass transport loss and Ohmic damage, especially at high current density [150,155]. During the
loss in the overall voltage loss of PEMWE correspondingly increase repeating bubble generation and detachment, the strain induced by
substantially (Fig. 12b3). Moreover, the heat generated during water bubble detachment can be devastating for the catalyst [156]. When
electrolysis cannot be effectively dissipated at the local water starvation bubbles are generated and accumulate in the cavity of the catalyst, they
site, resulting in disastrous hot spots [72]. All of these consequences not may introduce stress and damage to the catalyst structure and might
only reduce the efficiency of the PEMWE cell but also deteriorate its even peel off catalysts from their substrate. It has been directly observed
durability [150]. This extreme condition is usually due to insufficient that the generation and collapse of bubbles in OER can lead to the
water supply rate and excessive current density. For this phenomenon, structural oscillation of the catalyst [157]. Similarly, the stress of bub
Lee et al. defined a critical current density as a cell operation current bles generated inside the pores may also change the porous structure of
density limit when mass transport overpotential suddenly dominates cell CL or reduce triple phase sites by affecting the contact between the
performance and the accumulated gas can result in cell failure [72]. In ionomer and catalysts surface. Therefore, providing facilitated bubble
the same PEMWE cell, the critical current density is related to the water transport in CL may be necessary for improving the durability of CL.
flow rate. A higher water supply rate can provide a higher critical cur Unfortunately, it is still a challenge to directly observe the bubble
rent density (Fig. 12d). Similarly, Sun et al. have discussed the critical induced catalyst degradation in CL, and the mechanism of bubble
water stoichiometry for cell operation [146]. The water stoichiometry induced CL performance degradation has not been fully understood.
indicates the ratio of the supplied water amount to the consumed water However, reducing the bubble detachment size has been revealed to be a
amount corresponding to the working current density. For stable cell solution to enhance catalyst stability [134,158]. In order to reduce the
operation, water stoichiometry should be at least higher than the critical cost of hydrogen production, it is necessary to improve the catalyst
water stoichiometry for the given working current density. Below the lifetime and therefore the principle of this enhancement effect should be
critical water stoichiometry, the current density and temperature dis further investigated in the future.
tribution will become extremely uneven, which can cause undesired
degradation (Fig. 12c). The electrolysis operation region limited by
15
4.7. Impacts of bubbles in AEMWE Optimizing porous structure, thickness, and triple-phase site distri
bution can improve the bubble evolution and transport process. The
Since AEMWE is usually fed with liquid alkaline electrolyte instead ionomer content in CL is a critical parameter that influences the porous
of pure water to enhance the conductivity of the OH− , in addition to structure of CL. Hegge et al. have investigated the influence of ionomer
activation loss and mass transport loss, Ohmic loss also needs to be content on CL structure by reconstructing the anode CL using a combi
considered for both hydrogen and oxygen bubbles [96]. Bubbles nation of FIB-SEM tomography and ionomer modeling [161]. As shown
dispersed in the electrolyte reduce the available pathways for ion in Fig. 14a, in an IrRuOx anode CL, the increasing ionomer content in CL
migration, thus reducing the effective conductivity of the electrolyte. In will fill the void volume and reduce the porosity and increase the pore
addition to preventing ions from reaching the reaction surface, tortuosity in CL. A similar tendency can also be observed in IrO2/TiO2
surface-attached bubbles also lead to a non-uniform current density and Ir black CL [100,162]. At high ionomer content, it is observed that
distribution on the reaction surface adjacent to the bubbles, affecting the the cell performance is reduced and the mass transport loss is increased,
charge transfer process in these regions [33,34]. For mass transport loss which indicates the low porosity and high pore tortuosity in CL result in
in AEMWE, it is more severely affected by bubbles than PEMWE due to higher O2 bubble transport resistance [122,163]. However, as shown in
the simultaneous supply of electrolyte at both cathode and anode in Fig. 14b, although lowering the ionomer content can improve perfor
many studies and the more gas generated on the HER side. The effect is mance by reducing mass transport loss, too low ionomer content would
neglectable at low current density, but after the current density exceeds lead to additional performance loss [122]. Performance losses at lower
1 A cm− 2, mass transport loss can start to be noticed and starts to grow ionomer contents are mainly derived from a higher ionic resistance and
rapidly (Fig. 13a1). Rational bubble management can significantly its associated overpotential [100]. In addition to the ionomer content,
reduce the overall mass transport loss (Fig. 13a2) [94]. In addition to the catalyst loading will also affect the mass transport in CL. The catalyst
mass transport loss, the effect of bubbles on activation loss is amplified loading significantly affects the CL thickness and influences the CL-PTL
when using PTEs, especially self-supported electrodes [32,159]. As interface [164]. From 1 mg cm− 2 to 5 mg cm− 2 Ir loading, the thickness
shown in Figs. 7–8, the bubble accumulation that occurs during bubble of CL increases from 5 μm to greater than 20 μm (Fig. 15a1). The low
transport not only affects the gas saturation distribution on the catalytic thickness due to low loadings results in a more inhomogeneous PTL-CL
surface, but also directly causes bubble coverage, drastically reduces interface and a higher voltage at the same current density. The high Ir
ESCA, and directly causes activation loss [60]. In this case, bubble loading does not always improve CL performance, and as the load in
transport optimization is much more critical than in the PEMWE. creases to a certain level, CL performance at high currents decreases
dramatically (Fig. 15a2). At high current densities, the rise in IR-free
5. Bubble management voltage for high Ir loading CL is mainly due to the difficulty in
water-gas transport caused by the increased thickness and the corre
To reduce the hydrogen production cost, increasing the performance sponding mass transport loss (Fig. 15a3). Therefore, the CL has an
of the PEMWE cell and reducing its catalyst loading are essential. Ac optimal thickness that allows for both an optimal CL-PTL interface and
cording to the previous discussion, rational bubble management can does not cause difficulties in water transport within the CL due to the CL
greatly improve cell performance, improve operation stability and in thickness. Kulkarni et al. have investigated the effects of catalyst load
crease catalyst utilization. In this section, we will introduce the most ings and porous transport layer morphologies on cell performance
recent advances in bubble management strategies. [163]. The interface for different samples is characterized via X-ray
computed tomography along with electrochemical and modeling tech
5.1. Bubble management via catalyst layer design and innovation niques. As shown in Fig. 14d, in CCM type electrodes, lower IrOx loading
can lead to a less even catalyst cluster distribution and fewer areas that
5.1.1. Optimization of conventional catalyst layer PTL contacts well with CL. Collectively, these result in less triple phase
The conventional CCM/PTL design is most widely employed in contact area (TPCA) and uneven oxygen generation, reducing bubble
commercial PEMWE cells [16,25,160]. Minimizing the negative influ generation sites and deteriorating bubble evolution and transport. In the
ence of low bubbles evolution rate and sluggish gas transport in sinter Ti PTL/CCM sample, this effect is most evident. At 1.5 A cm− 2, the
CCM/PTL is of importance to increase the performance of commercial portion of mass transport loss in high catalyst loading sample (2.2 mg
PEMWE cells. In some recent studies, several methods have been re cm− 2) is 23%, while this value increases to 69.9% when catalyst loading
ported to improve gas evolution and transport by optimizing the struc decreases to 0.45 mg cm− 2 (Fig. 14c). In the samples using Ti fiber as
ture of conventional CL. PTL, although the performance decrease due to catalyst loading
Fig. 13. (a1) Polarization curves using Pt/C powder catalyst and carbon paper as cathode. (a2) Polarization curves using Ru2P nanofibers as cathode. Reproduced
from with permission Kim et al. [94]. Copyright 2021, Elsevier B.V.
16
Fig. 14. (a) 3D-representation of the reconstructed IrRuOx catalyst layer with different ionomer content in pore space vol%. Reproduced with permission from Hegge
et al. [161]. Copyright 2018, Elsevier B.V. (b) HFR-corrected Tafel plots of CL with different ratios of ionomer to Ir. Reproduced with permission from Alia et al.
[122]. Copyright 2020, IOP Publishing. (c–d) Effect of catalyst loading on anode CL. (c) Overpotential breakdown of polarization curves for the cell with
CCM-Sintered Ti anode with 0.45 mg cm− 2 IrOx loading. (yellow indicates mass transport, blue indicates Ohmic loss, orange indicates activation loss) (d) 2D
reconstruction and 3D rendering images of catalyst (yellow) and PTLs for the cell with CCM-Sinter Ti PTL from x-ray tomography. Reproduced with permission from
Kulkarni et al. [163]. Copyright 2022, Elsevier B.V. (e) Modify the CL-PTL interface by adding an IrOx interlayer. (e1) SEM image on nanofiber interlayer of the IrOx
hybrid anode with nanoparticle catalyst layer with 2 μm scale bar. (e2) Schematic of the function of nanofiber interlayer in the hybrid IrOx anode. Reproduced with
permission from Hegge et al. [166]. Copyright 2020, American Chemical Society. (f) BF- and HAADF-STEM images with EDS spectrum images (Ir, F) of
cross-sectioned anode catalyst layers for (top to bottom) optimal ink, high ionomer content ink, high solid concentration ink, and high solvent ratio ink. Reproduced
with permission from Alia et al. [122]. Copyright 2020, IOP Publishing.
reduction was not as much, it also showed a trend that mass transport bubble management is to design CL with superaerophobic surfaces.
loss increased with the decrease in catalyst loading. Reducing the clus Superaerophobic CL is a type of superwetting electrodes. Superwetting
tering of catalysts and optimizing the PTL-CL interface can also increase electrode design is attracting elevating attention recently for it can
the TPCA and thus increase performance [163,165]. The clustering of conveniently achieve desired gas management in many gas-involving
catalysts and catalyst homogeneity in CL can be tuned by the catalyst electrochemical reactions [93,172–175]. By modifying the surface
concentration, solvent ratio ionomer content in ink, ink drying process, micro/nanostructure, the bubble wettability on the electrode surface
and the variables in the coating process [122,141]. The PTL-CL interface can be manipulated reliably. The bubble wettability can be character
can be modified by controlling the CL surface texture and optimizing ized by two parameters: bubble contact angle and bubble contact angle
catalyst distribution (Fig. 14f), as well as adding an interlayer between hysteresis. Analogous to superhydrophilic and superhydrophobic sur
CL and PTL (Fig. 14e1–2) [122,141,166,167]. faces, the surface with a high bubble contact angle (usually >150◦ ) and
Another method to improve bubble management is to control crack negligible hysteresis is defined as a superaerophobic surface, and the
patterns in conventional CL. Introducing and utilizing the cracks in CL surface with a small bubble contact angle (usually <10◦ ) and appre
may enhance performance to some extent by creating favored bubble ciable hysteresis is defined as superaerophilic surface [58,176,177].
nucleation sites and limiting bubble growth and coalescence [168–170]. Generally, superwetting surfaces behave exactly opposite in the gas and
The crack size and pattern can be controlled by the tensile stress during liquid phases. The superhydrophobic surface exhibits super
synthesis. Zeradjanin et al. have investigated the roles of cracks based on aerophilicity, while the superhydrophilic surface is superaerophobic in
RuOx-based CLs [171]. Compared to a “crack-free” sample, a “cracked” aqueous media (Fig. 16a) [176,177]. The Wenzel model and Cassie
sample exhibited a higher and more stable bubble release rate at various model can be employed to correlate the surface architectures and sur
voltage levels. As a result, for OER performance, the “cracked” sample face superwettability [178]. In the Wenzel model, the liquids fully
yielded two times higher current density than the “crack-free” sample at occupy the valleys of the microstructure of the surface they touch. The
1.45 V. apparent contact angle θW then can be described by [179]:
cos θW = rcosθY (10)
5.1.2. Superaerophobic catalyst layer
Another effective way to enhance water electrolysis efficiency by Where the actual surface contact angle θY is amplified by a factor r.
17
Fig. 15. (a1) Anode CL thickness for CCM as a function of anode iridium loading. (a2) iR-free cell voltage at different current densities as a function of anode iridium
loading. (a3) Qualitative diagram of the water content profiles inside the anode CL for different thicknesses. Reproduced with permission from Bernt et al. [164].
Copyright 2018, IOP Publishing.
According to this equation, the roughness caused by surface micro extremely small level. As a result, the size of bubbles detached from
structure shows an amplification effect on the wettability. For the nanoplatelets array electrode surface is only 1/10 of that on the flat film
intrinsic smooth aerophobic surface, the surface microstructure can one (Fig. 16b). With the smaller bubble size, the bubble release is also
enlarge its bubble contact angle into a superaerophobic region. enhanced. In corresponding to this bubble management, the HER per
The Wenzel model is valid when the surface roughness is relatively formance of the MoS2 nanoplatelets array CL is significantly improved
small, and the Cassie model explains the high roughness or porous case compared to the flat film one. Specifically, in the range of − 0.2 V to
[178]. In the Cassie case, the high roughness of the surface enables the − 0.5 V, the current increase of MoS2 nanoplatelets array CL was as high
liquids to only contact with the surface of the microstructure and the as 56 mA cm− 2 per 100 mV, while the flat MoS2 film only achieved 33
surface under the droplet is under a non-wetting state. The apparent mA cm− 2 per 100 mV. At higher current density, the performance of
contact angle θC is given by [180]: MoS2 nanoplatelets array CL can even compete with Pt/C film. There are
also many efforts have been devoted to developing superaerophobic CLs
cos θC = − 1 + fs (rcosθY + 1) (11)
with Pt-based, Ru-based, and Ir-based catalysts [134,142,184,191,192].
Where fs denotes the area fractions of the solid. According to previous Li et al. have fabricated a pine-shaped Pt nanoarray superaerophobic CL
analyses of bubble-induced voltage losses, low bubble adhesion that can on inert Ti foil via electrodeposition [134]. The pine-shaped Pt nano
repel bubbles and low bubble coverage are highly desired for bubble array amplifies the contact angle of bubbles of flat Pt from 136.7◦ to
management in water electrolysis. Therefore, designing the electrode 161.3◦ . The gas bubble adhesive force is reduced from 145.6 ± 2.1 μN to
with a surface microstructure that can achieve the Cassie state to realize 11.5 ± 1.2 μN (Fig. 16c1–2). At a current density of 60 mA cm− 2, the size
superaerophobic is a promising way for bubble management in PEMWE. of bubble detached from nanoarray Pt is < 50 μm, while the bubbles on
A wide variety of surface morphologies have been reported to have flat Pt are around 500 μm. The HER performance of nanoarray Pt is
superaerophobic nature in water electrolysis applications. Most of these around 3.85 mA mV− 1, which is 13.75 times higher than Pt flat one
superaerophobic CLs are designed based on an array-like surface struc (Fig. 16c3). Except for modifying the flat CL, growing array-like surface
ture [58,181], including nanosheets array [182–185], nanoplatelets structures on substrates like carbon cloths, carbon fiber papers, and
array [62,186], nanodendrites array [187,188], nanopillars array [182], metal foams can also enable catalyst-coated PTL (PTE) to own super
nanotubes array [189], and nanocones array [190]. These array-like aerophobicity [143,189,193–195]. Han et al. have fabricated a super
structures divide the surface into discontinuous parts and exhibit a aerophobic nitrogen-doped tungsten carbide (N-WC) nanoarray PTE
high surface roughness, which is consistent with the Cassie model based on carbon fiber paper [143]. Using a self-assembled hydrothermal
described. With such surface designs, the detachment bubble size during reaction method, the nanodendrites array is grown on the surface of
electrolysis is significantly reduced and the bubble detachment fre carbon fibers. The resulting N-WC nanoarray PTE enlarges the bubble
quency is greatly improved. Lu et al. have engineered MoS2 CLs into flat contact angle of the flat N-WC CL from 148◦ to 163.5◦ and reduces the
film and nanoplatelets array [62]. The MoS2 flat film exhibits a rela bubble adhesion force from 12 μN to less than 1.2 μN. As a result,
tively low bubble contact angle of 135.2 ± 3.3◦ and large adhesive force compared to the flat N-WC CL, the detached bubble size from the N-WC
(124.8 ± 6.1 μN). With nanoplatelets array, the bubble contact angle is nanoarray PTE decreased from ~15 μm to ~5 μm. Accordingly, the HER
increased to 153.6 ± 2.4◦ , and the adhesive force is decreased to an and OER performance has been substantially improved, even surpassing
some commercial Ir-based catalysts in terms of OER performance.
18
Fig. 16. (a) Diagram illustrating the relationship between wettability of solid substrates in gaseous and aqueous media. Reproduced with permission from Yu et al.
[177]. Copyright 2017, John Wiley and Sons. (b) Images of bubbles generated on the flat electrode and the nanoarray superaerophobic electrode. Reproduced with
permission from Lu et al. [62]. Copyright 2014, John Wiley and Sons. (c1-3) Superaerophobic nano array Pt CL for PEMWE. (c1) SEM image of Flat Pt CL and its
contact angle. (c2) SEM image of Pine-shape nano array Pt CL and its contact angle (c3) Comparison of HER performance of Pt nanoarray electrode, nanosphere
electrode, and flat electrode. Reproduced with permission from Li et al. [134]. Copyright 2015, John Wiley and Sons. (d1-d3) Application of nanoarray electrodes in
PEMWE cells. The adoption of nanoarray morphology substantially enhances the HER performance of the electrode as well as the catalyst mass activity. (d1)
Schematic illustrations of synthesis of Pt nanowires in-situ grown on PTL to fabricate PTE. (d2) HER performance of nanoarray PTE. (d3) Catalyst mass activity in
nanoarray PTE. Reproduced with permission from Xie et al. [209]. Copyright 2021, Elsevier B.V.
Overall, these improvements brought by superaerophobic characteris to directly transfer by decal method on PEM while maintaining the
tics can be observed in many other works, including HER and OER in desired structure. Regarding the PTE, although the superaerophobic
both alkaline and acid environments [134,143,183,196], suggesting nano-structure can be conveniently achieved, the ionomer, on the one
that superaerophobic CL design is reliable and efficient in improving the hand, is challenging to contact well with all catalyst to maximize the
efficiency of water electrolysis. effective triple-phase interface, which may lead to low utilization of
The design principles and synthesis approaches of superaerophobic noble catalyst. Moreover, the addition of ionomer may affect the surface
CLs have been discussed in some review articles comprehensively [58, structure and make the surface lose its original superaerophobic prop
178,181,197–199]. The commonly used synthesis routes for super erties [208]. However, even the compromise preparation method
aerophobic CLs include electrodeposition, template synthesis, demonstrates the enhanced bubble management as well as electrolysis
chemical-vapor-deposition, hydrothermal, and solvent thermal method performance of this structure. For instance, Xie et al. introduced a
on a substrate [200–207]. Although these methods can conveniently compromise approach to integrating a nanoarray electrode (PtNW) into
prepare the desired surface morphology, it is challenging to apply these a PEMWE cell based on their ultra-thin PTL (Fig. 16d1) [209]. Though
methods to the practical CCM and PTE preparation for PEMWE cells. For the tip of the nanoarrays is oriented to the membrane side, this
CCM, these synthesis routes are challenging to directly use PEM as the array-like CL structure still exhibits a detachment size reduction effect.
substrate to grow these superaerophobic structures. Besides, the fabri The bubbles generated from the flat Pt CL are around 150–250 μm, while
cated superaerophobic CLs based on a substrate like Ti foil are difficult on the PtNW CL surface, the bubble size is distributed mainly at < 100
19
μm. The enhanced bubble release brought a significant increase in HER ordered CL structure (3DPNi) to facilitate gas bubble traffic [61]. This
performance and the mass activity of the Pt (Fig. 16d2–3). Although this CL is fabricated by 3D printing with solvent evaporation (Fig. 17a1). The
design is able to take advantage of the bubble enhancement brought by ordered structure and unobstructed channels with orientation aligned
the array structure, it is not yet the ideal method for applying super with buoyancy direction significantly suppressed the bubble in-plane
aerophobic array CLs in practical PEMWE cells. movement and avoided bubble trapping. As shown in Fig. 17a2, when
gas is injected from the bottom of CLs at a rate of 1 mL s− 1, the bubble
5.1.3. 3D ordered catalyst layer release in the disordered nickel foam CL exhibits an interrupted period
Constructing a 3D ordered CL can provide multiple benefits for of 3131 ms, indicating a bubble accumulation within the CL, while the
bubble management compared to the conventional CL. First of all, the 3DPNi CL steadily and periodically releases bubbles by around 124 ms.
3D structure of the CL generally provides a higher effective surface area, By solving the bubble trapping issue, it can be observed that the bubbles
as thus the number of nucleation sites of the bubble is increased. Sec on 3DPNi sample are much smaller than the conventional Ni foam one
ondly, when designing the 3D ordered structure of the CL, the preferred during electrolysis (Fig. 17a3). As a result, the activity (current
nucleation position of the bubbles can be controlled to reduce the normalized the ECSA) of the catalyst loaded on the 3DPNi is noticeably
probability of bubble adhesion. Moreover, a properly designed 3D or higher than the catalyst loaded on normal nickel foam (Fig. 17a4). It is
dered CL can provide facilitated bubble transport paths, reduce the worth noting that the channel size in the ordered 3D structure should be
bubble coalescence within the CL and accelerate the removal of bubbles neither too large nor too small and the thickness also needs to be opti
[61,184,210–214]. Kou et al. have demonstrated an excellent 3D mized. Kim et al. have investigated a 3D ordered structure (WP
Fig. 17. (a1-4) 3DPNi electrode design for solving the bubble trapping. (a1) Schematic illustration fabrication of the 3D printing of 3DPNi electrode. (a2-3) Images of
the bubble release process from a Ni foam electrode and a 3DPNi electrode captured with a high-speed camera. (a2) The bubble trapping phenomenon observed in
gas injection experiment; (a3) Bubble release in water electrolysis. (a4) Polarization curves with current normalized to ECSA for 3DPNi based electrode (red) and Ni
foam based electrode (blue). Reproduced with permission from Kou et al. [61]. Copyright 2020, John Wiley and Sons. (b1-2) 3D Woodpile-structured (WP structure)
Ir electrode. (b1) Schematic illustration of the 3D WP Ir electrode. (b2) Comparison of ECSA and activity normalized to ECSA of different structured 3D WP Ir
electrodes with commercial Ir black. The number after P represents the size of the channel. Reproduced with permission from Kim et al. [210]. Copyright
2020, Nature.
20
structure) with different channel sizes in PEMWE cells [210]. The 3D water electrolysis, both hydrogen and oxygen bubbles are found to be
WP-structured Ir CL is constructed with stacking 1D nanowires arrays mainly generated from the interface between CL and adjacent PTL in
via solvent-assisted nanotransfer printing technology. The formed 3D their works. Introducing conductive and non-conductive bodies to
structure is shown in Fig. 17b1. The vertical channels have large pore create new interfaces with the CL, it can be observed that bubbles are
size (>200 nm), which belongs to the range of macropores, while the only generated around the good electrical conductors [50,69,148]. This
spacing between layers belongs to the range of mesopores (<50 nm). reveals the importance of in-plane electron conduction for the perfor
The facilitated access of water to the catalytic surface and readily mance of CL. Moreover, it also means a significant decrease in catalyst
transport of evolved oxygen bubbles simultaneously improve the mass utilization in the CL region with poor contact with the PTL, which has
activity and ECSA-specific activity of Ir. As shown in Fig. 17b2, the widely been observed in CCM-type CLs [163,165,166,215]. Based on
number after P represents the size of the channel. All WP-structured CLs these findings, CCLGDL was proposed.
present a higher ECSA-specific activity than commercial Ir black nano As shown in Fig. 18a, in contrast to the direct binding of PTL to CCM,
particles (Fig. 17b2). The catalyst mass activity of the P400 sample CL is coated to the surface of thin Ti PTL in advance and then combined
reached up to 4.8 times that of the commercial Ir. The P200 sample has with PEM to form the CCLGDL. The thin Ti PTL provides facilitated
the densest holes, but instead of bringing an increase in ECSA, this bubble removal channels and bubble nucleation sites at the bottom of
caused a significant drop in mass activity and ECSA-specific activity. the vertical channels. The number of bubble generation sites and the
Increasing the pore size from 200 nm to 400 nm brings a significant bubble detachment frequency of the samples prepared by the thin Ti PTL
performance improvement, while continuing to increase the pore size to at the same current density are much higher than those of conventional
1200 nm does not result in any improvement but rather in a perfor Ti-felt samples (Fig. 18c) [73]. The part of the CL zone that is not
mance drop. In the single-cell measurements, it can be found that the accessible to the PTL is removed, thereby reducing the unusable catalyst.
increase in thickness will significantly reduce the performance of the The Ir CCLGDL is fabricated by Ir electroplating and the Pt CCLGDL is
WP-structured CLs. This thickness-related performance reduction may prepared via platinum sputter deposition [40,148]. With much lower
be because the growth of the bubble transport path due to the increase in catalyst loading than the conventional CCM, both Pt CCLGDL and Ir
thickness leads to a decrease in the performance of the catalyst in the CCLGDL exhibit remarkable catalyst mass activity. When using Ir
upper part of the transport path, which ultimately reduces the average CCLGDL as the anode in the PEMWE cell, the performance of the Ir
catalyst activity. CCLGDL cell with only 0.17 mgIr cm− 2 Ir loading can be comparable to a
CCM/Ti felt cell with 3 mgIr cm− 2 Ir loading. The mass activity of Ir in
5.1.4. Zoned catalyst layer: thin catalyst-coated liquid/gas diffusion layer CCLGDL is 16 times that in the CCM/Ti felt (Fig. 18b) [40]. When using
A thin catalyst-coated liquid/gas diffusion layer (CCLGDL) design is Pt CCLGDL as the cathode in the PEMWE cell, the performance of the Pt
a new type of PTE which has a zoned catalyst layer that can significantly CCLGDL cell with only 0.086 mgPt cm− 2 Pt loading can be almost the
increase the catalyst utilization and reduce the thickness of the cell. The same as a CCM/Ti felt cell with 3 mgPt cm− 2 Pt loading. The mass ac
concept of thin CCLGDL is proposed by Zhang group (Fig. 18a) [50,69, tivity of Pt in CCLGDL can reach up to 31 times that in the CCM/Ti felt
73]. The performance enhancements result from the optimization of the (Fig. 18d) [148]. These works provide a new design for water electrol
PTL/CL interface and the facilitated bubble evolution and removal ysis CLs. With a more sophisticated catalyst layer and LGDL morphology
process. The zoned catalyst layer design is based on a thin Ti PTL, where designs, the performance of CCLGDL can be further improved [26,209].
some CL area is beneath the PTL, and some CL area is exposed to the
through-holes of PTL. In the visualization of bubble generation during
Fig. 18. (a–b) Thin catalyst-coated liquid/gas diffusion layer (CCLGDL) design and application in PEMWE anode. (a) Schematic diagram of three different anode
electrode designs and the bubbles in the different electrodes. In CCLGDL, the CL is coated directly on the TT-LGDL, removing the CL that is not in direct contact with
the TT-LGDL to achieve maximum catalyst utilization. (b) Polarization curves and Ir mass-specific current of three designs. Reproduced with permission from Yu et al.
[40]. Copyright 2022, John Wiley and Sons. (c) Comparison of bubble detachment site number, average detachment diameter, and unit detachment frequency
between the Ti felt PTL and TTLGDL at the current density of 200 mA cm− 2. Reproduced with permission from Wang et al. [73]. Copyright 2021, Elsevier B.V. (d) Pt
mass-specific current of Pt CCM with thin Ti PTLs, Pt CCM with Ti felt, and Pt CCLGDL (sample A3). Reproduced with permission from Kang et al. [148]. Copyright
2018, Elsevier B.V. (e) The polarization curve of PEMWE of magnetically modified electrocatalysts was employed. Reproduced with permission from Kaya et al.
[216]. Copyright 2021, Elsevier B.V.
21
5.1.5. Magnetized catalyst layer anode contributes most of the mass transport loss to the performance
Another special method to enhance bubble management in PEMWE loss during water electrolysis [127]. Titanium felt and sintered titanium
is fabricating CLs with magnetized catalysts. Several works reported is the most commonly employed anode PTLs in PEMWE cells. As dis
enhanced bubble management and water electrolysis performance cussed in 3.2 and 3.3, the structure and surface features of PTL signifi
under an external magnetic field due to magnetohydrodynamic and cantly influence the bubble transport process. The blocked upward
magnetoaerodynamic effects [217–219]. The gas product in the anode, pathways and the in-plane transport of bubbles in PTL lead to gas
oxygen, is a paramagnetic molecule and its transport can be influenced accumulation and reduce the performance of PEMWE cells. To address
by the magnetic field [220,221]. Therefore, in addition to applying an these issues, many novel PTL designs toward better bubble management
external magnetic field, it is also possible to enhance the oxygen bubble have been reported recently.
evolution and transport by magnetically modified catalysts [222]. Kaya
et al. have examined the enhancement of magnetically modified elec 5.2.1. With patterned through pores
trocatalysts in PEMWE cell [216]. The anode catalyst IrO2 is modified by Recently, different PTLs with through pores have been reported and
introducing magnetic Fe3O4 via a modified Adam’s fusion method to demonstrated a performance improvement on PEMWE cells. The
enhance bubble detachment (Fig. 18e). A magnetizer magnetizes the through pores PTLs (TPPTL) have a series of holes that penetrate the
samples with adjustable field strength and up to 2 T magnetic flux. Both entire PTL, from the PTL-flow field interface to the CL-PTL interface
on glassy carbon and in the single cell PEMWE, the addition of magnetic [41]. The through pore geometries in PTLs have been proven to have a
Fe3O4 improved the electrolysis efficiency. A CL with 80% IrO2-20% restriction effect on the in-plane transport. The low transport resistance
Fe3O4 exhibits almost three times IrO2 mass activity than the 100% IrO2 in the through pores will guide bubbles transport following them rather
CL. Some studies also investigated magnetized catalysts in alkaline than moving in the high resistance route in the other part of the PTL.
conditions and demonstrated their benefits [223–227]. Bazylak group has investigated the gas transport in the TPPTL in a
working PEMWE cell via in operando X-ray radiography [228]. It has
been observed that although the gas generation site has a wide distri
5.2. Bubble management via porous transport layer design and innovation bution in the CL-PTL interface, the majority of bubbles transfer to the
PTL-flow field interface via the through pores. Followed by a similar
The function of PTL in the PEMWE cell is to provide good thermal design, the Bazylak group added patterned through-pores to a com
and electrical conductivity, support the fragile CCM, and facilitate mercial PTL by machining (Fig. 19a1) [41]. As shown in Fig. 19a2, the
bubble and water transport. The complex two-phase counter flux in the
Fig. 19. (a1-a3) Accelerating bubble transport by patterned through-pores in PTL. (a1) Schematic of the PTL with patterned through-pores. (PTP PTL) (a2) Gas
saturation profiles along the thickness direction (CL-PTL interface: tPTL = 0). In commercial PTL (top). In PTP PTL (bottom). (a3) IR-free cell potential and Tafel slope
of PEMWE cells with PTP PTL and commercial PTL. The green areas indicate the difference between PTP-PTL and commercial PTL in terms of mass transport loss.
Reproduced with permission from Lee et al. [41]. Copyright 2020, American Chemical Society. (b) Gas saturation profiles along the thickness direction (CL-PTL
interface: x/tPTL = 0) in Graded PTL design. In LP → HP PTL (top). In HP → LP PTL (bottom). Reproduced with permission from Lee et al. [232]. Copyright 2020,
Elsevier B.V. (c1-c2) Multilayer PTL design. (c1) Schematic of the PTL with MPL (MPL-PTL) and the function of MPL to improve CL-PTL interface. (c2) IR-free
polarization curves of different PEMWE test cells. MPL 2 represents the cell with MPL-PTL. Reproduced with permission from Schuler et al. [233]. Copyright
2020, John Wiley and Sons.
22
gas accumulation near the CL-PTL interface is significantly decreased. which is a powerful tool of water management [239–241], controlling
Under a current density of 9.0 A cm− 2, the gas saturation near the the wettability of PTL can also influence the mass transport in PEMWE
CL-PTL interface is only around half of that in the cell with sintered ti cells. Li et al. have tested Ti mesh PTL with different wettability in
tanium power-based PTL. In addition, the gas saturation distribution in PEMWE [242]. From hydrophobic to hydrophilic, reducing the contact
the whole TPPTL is very even under every current density in the angle leads to an enhanced performance of the electrolysis cell. In
through-plane direction. This gas saturation profile indicates that the contrast to hydrophobic PTL (120◦ ), hydrophilic PTL (10◦ ) achieves a
TPPTL could greatly enhance the bubble transport. Correspondingly, the voltage drop of about 200 mV at 2 A cm− 2. Further increasing the hy
mass transport loss is reduced by 76.7% at a high current density of 9.0 drophilicity of PTL to superhydrophilicity to improve its aerophobicity
A cm− 2 (Fig. 19a3). Notably, because of less CL-PTL interface, the can improve the bubble management of PTL at high current densities.
activation loss is slightly increased. Future optimization of pore pattern Zhao et al. reported a superhydrophilic PTL in PEMWE cells [243]. The
and pore size may further increase the overall cell performance. surface of titanium surfaces is naturally wetting to water. By boiling Ti
Applying through pores design on a Ti-foil, Zhang group has developed a PTL in a solution consisting of NH4OH (25%), H4O4 (30%), H2O (45%),
series ultra-thin PTLs by lithography [229–231]. Combining the treated PTL exhibits a superhydrophilic feature. The wetting state
catalyst-coated ultra-thin PTLs design, the water electrolyzer perfor changes the water and bubble transport behavior in PTL. The operando
mance is significantly improved by the facilitated bubble transport in neutron visualization reveals that the PEMWE cell equipped with the
through pores. superhydrophilic PTL has lower oxygen gas saturation than the un
treated PTL (Fig. 20a1), indicating a bubble transport rate improvement.
5.2.2. With graded structure With a minor change in activation and Ohmic overpotential, the reduced
In addition to shortening transport pathways, which are beneficial mass transport loss significantly decreases the cell voltage by more than
for bubble management, enlarging CL-PTL interfacial area is also desired 11% for current densities higher than 5.0 A cm− 2, and the enhancement
to improve the electron transfer in PTL design. By analogy with leaves, a becomes more significant as the current increases (Fig. 20a2). Patterned
hierarchic and graded structure may be a good solution that the inter amphiphilic Ti-PTL maybe a more powerful approach to manage the
facial area and bubble management can be taken into account simulta water-bubble counter flow. Lim et al. have proved that by creating hy
neously [28]. An ideal graded PTL design should maximize the contact drophobic and hydrophilic channels (Fig. 20b1–2), the patterned
between CL and PTL using a relatively small pore size near the CL while amphiphilic PTL can significantly improve the performance of polymer
ensuring that bubbles can enter the PTL smoothly from the CL. At the electrolyte membrane unitized regenerative fuel cells under electrolysis
same time, the pore size should increase as it approaches the PTL-flow cell mode [244]. As shown in Fig. 20b3, the channel split by the
field interface. In this way, the discharge of bubbles has a short trans amphiphilic pattern significantly reduce the bubble size on the PTL
mission path because of the minimum resistance in the buoyancy di surface. The growth and separation of oxygen bubbles is faster through
rection. On the other hand, the smaller porosity at the bottom of PTL can hydrophobic channels, while large bubbles appear on the pristine hy
provide facilitated electron conducting routes. Lettenmeier et al. have drophilic surface. This phenomenon represents a separation of gas and
fabricated a graded Ti PTL by vacuum plasma spraying (VPS) and the water transport, allowing the cell using PTL with amphiphilic pattern to
large/medium graded PTL demonstrated a lower mass transport limi reach 3.2 A cm− 2 at 2 V, while only 1.4 A cm− 2 was achieved with
tation [234]. Lee et al. have investigated the liquid water transport pristine PTL.
behavior of graded structures by pore network modeling [235]. When
increasing the porosity of PTL from the CL-PTL interface to the PTL-flow 5.3. Bubble management via flow field designs
field interface (LP→HP), the oxygen saturation is significantly decreased
compared to the conventional structure. At the same time, the liquid The flow field plays an important role in the water management in
water permeability is also enlarged. With an opposite porosity gradient PEM fuel cells, which significantly influences the water removal rate and
(HP→LP), the oxygen is accumulated near the CL-PTL interface. These the reactant distribution. Parallel, serpentine, and interdigitated flow
simulation results are further confirmed in PEMWE cell operation [232]. fields are commonly used in fuel cell [245–249]. Many subsequent new
Lee et al. prepared two PTLs with opposite pore gradients via VPS. The designs have been developed based on them. The optimization of the
experiment result exhibits a good consistency with the simulation result flow field is usually evaluated by water saturation, current density dis
that at different current densities, the gas saturation in LP→HP PTL is tribution, temperature distribution and pressure drop [245,250–254]. In
lower than in HP→LP PTL (Fig. 19b). Correspondingly, the PEMWE cell PEMWE cells, flow field would also affect the water distribution and
with LP→HP PTL achieved better performance than the cell with HP→LP bubble management. In analogy to PEM fuel cell, flow field designs are
one. usually evaluated by gas saturation, current density distribution, tem
Multilayer PTL configuration such as MPL-PTL is also a kind of perature distribution and pressure drop [25,71,255,256]. As discussed
graded PTL [138,233,236–238]. Schuler et al. have co-sintered two by Maier et al., until now, there is conflicting information about the
commercially viable Ti powders to fabricate MPL-PTLs [233]. As shown performance of different flow field designs [25]. Both single serpentine
in Fig. 19c1, a typical MPL-PTL combines an MPL with 35.1% porosity flow field and parallel flow field have been reported to have better
and 11.2 μm mean pore size, and a support layer (SL) with 33.6% performance compared to other designs [71,257,258]. However, it is
porosity and 27.2 μm mean pore size. The addition of MPL drastically noteworthy that an increasing number of works uses bipolar plates with
reduces the surface roughness at the bottom of the PTL and reduces the parallel flow fields recently, which might be because the parallel flow
CCM deformation caused during assembly. The smaller particle size field has shorter channels that enable the bubbles to easily flow out
offers a better bond between MPL and bumpy CL surfaces. The catalyst [122,259–261]. The investigation of the flow field and flow channel
utilization is therefore improved. Compared to PEMWE cells with optimization toward better mass transport beyond the conventional
commercial Ti particle sintered PTL, fiber PTL, the PEMWE cell with designs is still insufficient. Majasan et al. have reported that the anode
MPL-PTL (MPL2) has a significant performance improvement flow channel depth would influence mass transport loss, revealing the
(Fig. 19c2). With the addition of the MPL, the MPL-PTL sample has more potential to improve electrolyzer performance via flow channel opti
than two times higher catalyst utilization compared to the conventional mization [262]. Olesen et al. proposed a circular, interdigitated anode
structure. At a current density of 2.0 A cm− 2, a 45% reduction of mass flow field plate for high-pressure PEMWE [255]. The uniformly
transport loss is observed in MPL-PTL than in the conventional PTL. distributed heat, mass, and current density show the potential of flow
field optimization, especially for the high-pressure PEMWE, where the
5.2.3. Wettability modification flow field plate is usually circular rather than rectangular because of
Similar to the wettability modification of GDL in PEM fuel cells mechanical stability at elevated pressures [263,264]. Wu et al. have
23
Fig. 20. (a1) Spatial distribution of the average gas saturation in anode side of treated PTL and untreated PTL (5 A cm− 2, water flow rate 0.5 mL min− 1). (a2)
Polarization curves of PEMWE using treated PTL and untreated PTL. Reproduced with permission from Zhao et al. [243]. Copyright 2021, Elsevier B.V. (b1-b2) EDS
mapping (top and cross section) results for carbon, and titanium elements. The red area indicating the coated area of P4VP homopolymer after the spraying process.
The red and black regions have hydrophilic and hydrophobic properties, respectively. (b3) Schematic representation of the effect of Amphiphilic pattern on bubble
evolution and transport, and photos of bubbles on the surface of untreated and treated PTL during water electrolysis. Reproduced with permission from Lim et al.
[244]. Copyright 2021, American Association for the Advancement of Science.
proposed a novel structured mesh channel design for PEMWE [265]. bubbles from the PTL surface.
They used the validated 3D full-cell model coupled with a VOF method In addition to the PEMWE cells with conventional flow field, several
and they found that oxygen bubbles are split by the skeleton in the new PEMWE cell architectures have been reported to enhance mass
structured mesh channels, mitigating the formation of slug or annular transport recently. One design removes the flow field plate from the
flow. In addition, the capillary force effect was enhanced by the treat anode and uses the PTL to act as flow fields simultaneously. Stiber et al.
ment schemes of skeleton surface hydrophobicity along the used a combination of a Ti porous sintered layer on a Ti expanded metal
through-plane direction, which facilitated the detachment of oxygen mesh as anode PTL and flow field [24]. As shown in Fig. 21a, the PTL is
Fig. 21. (a–c) Using a Ti mesh PTL to replace the anode flow field. (a) Schematic of the PEMWE cell configuration with double PTL as anode flow field. (b–c) SEM
images of double PTL (Ti porous sintered layer/mesh-PTL). Reproduced with permission from Stiber et al. [24]. Copyright 2021, John Wiley and Sons. (d–f)
All-in-one bipolar electrode design for reducing the interface and bubble transport resistance. (d) Schematic of the difference between conventional cell configuration
and all-in-one bipolar electrode cell configuration. (e–f) Image and 3D model of all-in-one bipolar electrode. Reproduced with permission from Yang et al. [266].
Copyright 2020, Elsevier B.V.
24
directly in contact with a flat plate. The hills and valleys of the Ti mesh The relative orientation of the magnetic field to the PEMWE cell can
serve a function similar to the flow field as a reactant distributor have a different effect on the bubbles. A magnetic field that is perpen
(Fig. 21b and c). The cooperation of sintered Ti with small pores and Ti dicular to the horizontal electrode surface results in the spinning of
mesh with large pores constructs a graded structure that can improve bubbles. Whereas when the vertical electrode is affected by a parallel
oxygen bubbles and water transport. Compared to conventional graded magnetic field, the horizontal Lorentz force can accelerate the bubble
PTL cells [233], this design eliminated the PTL-flow field interface, detachment and reduce the associated performance loss (Fig. 22b).
reduced the related Ohmic loss, and thus increased the PEMWE cell However, if the arrangement of the electrode and magnetic field causes
performance. Compared to the cell with only Ti mesh, the cell with such the Lorentz force to be in the opposite direction of the buoyancy force,
design improved 31% efficiency at a current density of 4.0 A cm− 2. A then the addition of the external magnetic field will in turn become a
similar design idea was reported by Yang et al., who proposed the force that prevents the bubble from breaking away, thus causing addi
all-in-one bipolar electrodes (AIOBE) to minimize the interface resis tional bubble induced loss and reducing the efficiency of water elec
tance [266]. As illustrated in Fig. 21e and f, an AIOBE consists of a pin trolyzer [217]. Several works have reported the performance
flow channel on the substrate, a PTL structure in joint with the pins, and improvement of alkaline water electrolyzers when applying external
a Pt catalyst layer. The AIOBE is fabricated by 3D printing and sputter magnetic fields [274,275]. And Kaya et al. have observed the positive
coating. Compared to the conventional cell, the AIOBE reduced the effect of external magnetic fields on PEMWE cell performance [218].
thickness of the cell and reduced the number of the interface (Fig. 21d). The oxygen bubble removal is enhanced with an appropriate layout of
Benefitting from the compact structure, the AIOBE exhibits an ultra-low an external magnetic field. With a 0.5 T magnetic field, the cell per
Ohmic resistance of ~100 mOhm cm2. The bubble transport is also formance is increased by 33% compared to the conventional cell. This
improved because of the similar design of ultra thin PTL [40]. Conse performance improvement is less pronounced at low water flow rates,
quently, the AIOBE achieved a high hydrogen production performance probably because the bubbles detached from the CL do not leave the cell
of 1000 mA cm− 2 at 1.62 V and a high catalyst mass activity of 4.48 A fast enough at slow water flow rates, thus limiting the effect of bubble
mg−Pt.1 detachment enhancement.
The application of ultrasonic and gravity fields to improve bubble
5.4. Active bubble management methods management has also been investigated in the study of water electrolysis
and other gas evolution reactions [267,268,276]. The ultrasonic field
Bubble evolution and transport in PEMWE can also be improved by can improve the bubble detachment by the influence of cavitation and
active management methods. Applying external physical fields such as thus increase the water electrolysis efficiency. Li et al. have applied an
magnetic field, ultrasonic field and gravity field has been proven to be ultrasonic field to enhance hydrogen production efficiency in an alkaline
capable of enhancing bubble evolution and transport [217,267,268]. water electrolyzer [268]. The ultrasonic generators were directly in
Water electrolysis system control strategies such as pulse voltage and contact with the cell to generate an ultrasonic field at a power of 50 W
pressure swing have also been observed to improve the electrolysis ef and a frequency of 60 Hz. The generated gas bubble quantity is increased
ficiency [269,270]. by the ultrasonic field. At a current density of over 80 mA cm− 2, the
efficiency of water electrolysis is improved by 5–18%. Despite the
5.4.1. External physical fields assisted bubble management additional energy consumption required to introduce the ultrasonic
When applying a magnetic field to the PEMWE cell, the magneto field, the total efficiency still rises. The gravity fields work with a similar
hydrodynamic and magnetoaerodynamic effects will influence the flow mechanism as the magnetic field. By enhancing the force that acceler
regions [216,271–273]. The Lorentz force is expected to be an addi ates bubble transport, the bubble induced loss decreases. Wang et al.
tional force other than buoyancy to push the bubble away from the CL. have carried out water electrolysis under a supergravity field [276]. The
Fig. 22. (a) Illustration of a pressure swing process and the corresponding response of cell voltage and bubbles during water electrolysis. Reproduced with
permission from Bakker et al. [269]. Copyright 2019, Elsevier B.V. (b) Schematic of magnetohydrodynamic and magnetoaerodynamic effect on bubbles and effect of
magnetic field on PEMWE cell performance. Reproduced with permission from Kaya et al. [218]. Copyright 2020, Elsevier B.V. (c) Schematic of pulse voltage
operation in water electrolysis. Reproduced with permission from Demir et al. [270]. Copyright 2018, Elsevier B.V.
25
supergravity field was applied to a cylindrical electrolytic cell by on electrolyzer efficiency. Bakker et al. have demonstrated the possi
centrifuge. The cell was under a horizontal supergravity field and bility of facilitating bubble removal in alkaline water electrolysis via
normal vertical gravity. The cathode and anode are mounted using pressure swing control [269]. Instead of a steady high-pressure
face-to-face and parallel to the direction of supergravity. At 0.5 A cm− 2, operation, sudden pressure drop operations are introduced periodi
a significant overpotential reduction was observed under various gravity cally. As shown in Fig. 22a, a sudden drop in pressure will first cause a
values from 25 G to 256 G. transient voltage rise, followed by a gradual drop in voltage to a new
stable value at the new pressure, and finally the voltage will continue to
5.4.2. Electrolyzer control strategy assisted bubble management drop to a new stable value as the pressure rises back up. At the first
Another method to enhance bubble management is to optimize the moment of pressure drop, there is a rapid bubble growth according to
control strategy of the water electrolysis system. As observed by Lee the ideal gas law and leads to a temporary local gas accumulation,
et al., intermittent unstable current input to the electrolyzer can lead to resulting in the first voltage peak. The bubble that has grown large
an increase in residual gas accumulation, which can negatively affect the enough then detaches, reducing the voltage. In this way, the pressure
performance of the PEM electrolyzer [70]. However, by modifying the swing promotes the bubble evolution process in CL, and the overall ef
operation mode, the fluctuation of current or voltage can also be a tool ficiency of electrolysis is improved through a such periodic operation.
to improve the bubble evolution and transport. Demir et al. have This method may also be effective in PEMWE.
investigated the effect of pulse potential in water electrolysis [270]. As
shown in Fig. 22c, the voltage is applied to the electrolyzer in the form of 5.5. Bubble management in AEMWE
pulses. The energy consumption to produce a unit volume of hydrogen
during electrolysis is decreased under pulses voltages of different duty Many of the bubble management strategies used in PEMWE above
cycles. This reduction may attribute to the pumping effect brought by can be borrowed in AEMWE. Recent AEMWE reports have shown that
the incident pulse voltage. Under such pulse voltage, the bubble on the similar designs can significantly improve the performance of electro
CL surface can be fully detached between two voltage load states, lyzer. Superaerophobic CL has been reported by Wan et al. [87].
reducing the bubble-induced voltage loss. In addition to controlling Combining electrodeposition and direct membrane deposition, they
voltage, pressure swing has also been found to have an enhancing effect create a highly porous CL which has a vertical channel array facing to
Fig. 23. (a) Construct superaerophobic 3D-ordered vertical channels in CL to enhance bubble management. (a1) Schematic of the superaerophobic 3D-ordered MEA
design. (a2) Overpotential breakdown for different MEA at 500 mA cm− 2 and 2000 mA cm− 2. Reproduced with permission from Wan et al. [87]. Copyright 2022,
Royal Society of Chemistry. (b) Catalyst-coated TTLGDL design for AEMWE. (b1) Comparison of catalyst-coated Ti foam and catalyst-coated TTLGDL. (b2) Com
parison of Tafel plots of AEMECs with catalyst-coated Ti foam and catalyst-coated TTLGDL. Reproduced with permission from Li et al. [277]. Copyright 2021,
American Chemical Society. (c) 3D-Printed Electrode for enhancing bubble management. (c1) Schematic of the 3D-Printed Electrode. (c2) HER and OER polarization
curves of the 3D-Printed Ni/Cu electrode and conventional Ni foam. Reproduced with permission from Márquez et al. [278]. Copyright 2022, American Chemical
Society. (d) Self-supported PTE design for enhanced AEMWE performance. (d1) Schematic of the self-supported NiFeOOH PTE (unified electrode). (d2) Comparison
of polarization curves of self-supported NiFeOOH PTE and conventional IrO2 CL. Reproduced with permission from Park et al. [120]. Copyright 2022, American
Chemical Society. (e) Construction of superhydrophilic (superaerophobic) structures on the PTE surface. (e1) Fabrication of superhydrophilic Fe0.2Ni0.8-P-S PTE.
(e2-4) SEM images of porous nanoislands array on superhydrophilic Fe0.2Ni0.8-P-S PTE. (e5) Effect of euperhydrophilic PTE on bubble size. Reproduced with
permission from Wan et al. [121]. Copyright 2022, Elsevier B.V.
26
the PTL (Fig. 23a1). Such a structure takes advantage of the favorable exhibits a bubble contact angle of 142.3◦ , while the bubble contact angle
transport routes brought by the channel structure on the one hand, and of Ni foam is 72.8◦ . This allows the KOH to easily penetrate the entire
the superaerophobic CL surface brought by the array structure on the PTE and the bubbles to detach quickly after formation. At the same
other hand, which significantly reduces the mass transport loss. As operation current density, it can be noticed that the average bubble size
shown in Fig. 23a2, at a current density of 500 mA cm− 2, the mass decreases and the bubble size distribution moves in the direction of
transport loss of superaerophobic 3D-ordered MEA is almost 0, while the decreasing bubble size (Fig. 23e5). This results in a significant reduction
mass transport loss of conventional MEA is noticeable. At a current in mass transport loss for Fe0.2Ni0.8P0.5S0.5 PTE at all current densities
density of 2000 mA cm− 2, the share of mass transport loss in total compared to conventional CL. The percentage of mass transport loss is
voltage loss of conventional CCM type MEA is 32.3%. In contrast, the reduced by about 20% at a current density of 2 A cm− 2. The AEMWE
value of superaerophobic 3D-ordered MEA is only 9.6%. Zoned catalyst using Fe0.2Ni0.8P0.5S0.5 PTE delivers a high current density of 2.5 A cm− 2
layer design has also been reported recently. Zhang group has applied at 2.0 V.
their thin catalyst-coated liquid/gas diffusion layer design in AEMWE In the context of commercialization, AEMWE should aim to run with
[277]. As shown in Fig. 23b, in this design (TTLGDL), the catalyst is pure water as PEMWE in its applications. However, switching AEMWE
coated on perforated titanium thin foil. Compared to conventional from operating with liquid electrolyte to operating with pure water is
Ti-foam, this design reduces the thickness of PTL from about 260 μm to challenging. Many novel electrode designs may suffer from a perfor
about 50 μm. By using the reduced mass transport distance and the mance drop after switching to pure water operation due to the lack of
vertical through-hole, the loss due to bubbles is greatly reduced. As can ion transport paths [85,277]. As shown in Fig. 24a1, the performance of
be seen from Fig. 23b2, the separation of kinetics lines and polarization conventional PTE AEMWE deteriorated quite severely after switching
curves appears later in TTLGDL than in Ti-foam. The separation appears from 1 M KOH to pure water operation. This is mainly due to the loss of
at 0.3 A cm− 2 in Ti-foam, while it appears at 1.6 A cm− 2 in TTLGDL. the additional ion transport pathway provided by KOH when providing
Márquez et al. report on how 3D-printed electrode technology can be pure water and therefore the ECSA is reduced. (Fig. 24a2) [84,86]. After
used for bubble management to improve electrolysis performance [278]. switching to pure water operation, the ion is mainly transferred through
Using 3D print, planar, pyramid, rod, cone and oval array structure can the ionomer network. Therefore, the combination optimization of
be fabricated on a substrate. From planar to oval array, HER perfor electrocatalyst, ionomer, and membrane is critical for better perfor
mance increases with the shape of the array. By increasing the number of mance under pure water operation. Ideally, the ionomer should be able
printed layers, 3D ordered electrodes can be obtained (Fig. 23c1). As to form a continuous network and transport ions to all reaction sites
shown in Fig. 23c2, this 3D ordered structure results in a large perfor without impeding electron transport and mass transport. This optimi
mance improvement per ECSA compared to Ni foam. This improvement zation becomes more necessary and challenging for self-supported PTEs,
comes from lower bubble coverage and good bubble transport, and Kou as well as for some three-dimensional structures, due to the inherent lack
has demonstrated that these 3D ordered electrodes are effective in of reliance on ionomer as a binder and the difficulty of forming a
solving bubble trapping issues compared to the disordered porous continuous ionomer network across the through-plane direction of CL.
structure of Ni foam [61]. Rational optimization of ionomer in combination with PTE can result
Self-supported electrodes have been proven to be highly efficient and in an excellent AEMWE performance under pure water operation. Wan
are widely used as PTE in AEMWE. In contrast to conventional PTE, self- et al. have optimized the distribution of ionomers in Ni foam based self-
supported PTE grows the catalyst directly on the PTL instead of spraying supported PTE [279]. After growing FeNi LDH on the Ni foam surface
CL on the PTL (Fig. 23d1) [32,120]. The surface of the self-supported using the hydrothermal method, the ionomer is coated on the PTE
type PTE has more bubble generating sites than the dense packed con directly using ultrasonic spraying to alter the ionomer content and dis
ventional CL. Therefore, electron transfer and mass transport are both tribution. When the ionomer content is reduced to 0, the ECSA may not
facilitated. For the anode CL, Park et al. have fabricated self-supported be effectively utilized due to poor ion conduction, and the performance
PTE (unified electrode) via the electrodeposition method [120]. The of PTE in pure water operation decreases substantially (Fig. 24b3).
EIS result shows that the unified electrode has lower charge transfer and Compared to bare PTE, even 10% ionomer content can substantially
Ohmic resistance than conventional CL. The AEMWE using Pt/C cathode improve the performance of PTE. However, continuing to raise the
and unified NiFeOOH electrode anode show higher catalytic activity ionomer content does not keep the performance improving. When the
than a conventional CL based on commercial NiFe and IrO2 catalysts. As ionomer content is increased to 20%, the performance of AEMWE de
shown in Fig. 23d2, at 1.9 V and with 1 M KOH supplied to both anode creases instead. From the SEM results (Fig. 24b2), it can be found that
and cathode, the unified electrode performs a current density of 3600 the coverage of the PTE surface by ionomer increases with the increase
mA cm− 2, which is almost twice as the cell with conventional IrO2 CL. of ionomer content. As the ionomer coverage increases, the
For the cathode, the self-supported electrode also shows good perfor high-frequency resistance gradually increases, indicating that the
mance, especially in terms of reducing mass transport loss. Kim et al. excessive ionomer content hinders electron transfer (Fig. 24b1). By
have designed a Ru2P nanofibers PTE through electrospinning [94]. The ionomer optimization for facilitating ion and charge transfer, the FeNi
RuO2 nanofibers constitute a porous network conducive to gas-liquid LDH nanosheet array PTE achieved a high current density of 1900 mA
transport, and the phosphatization process introduces many pores into cm− 2 at 1.90 V with pure water AEMWE operation. This performance is
the nanofiber surface, constituting sites conducive to bubble nucleation. 2.2 folds higher than that of the conventional CCM type CL based on
Compared to the cell using commercial Pt/C and carbon paper as PTL powdered IrO2. In the process of optimizing the ionomer content, it can
(Pt/C/CP), the Ru2P nanofibers/CP cathode exhibit a significant mass also be found that the content of ionomer not only affects the ion and
transport loss reduction of around 0.4 V at 3.5 A cm− 2. In addition to the electron conduction, but also affects the morphology, contact angle,
structural advantages, self-supported PTE has a variable microstructure porosity, and other properties. All these characteristics affect the per
that allows for easy tuning of surface properties to effectively modify formance of bubble management. Moreover, as discussed in 5.1.2, ion
wettability and bubble behavior at the same current density. Wan et al. omer may also deteriorate the surface properties of PTE surfaces that
report a superaerophobic Fe0.2Ni0.8P0.5S0.5 PTE with nanoisland arrays originally exhibited superaerophobic features. Therefore, for pure water
prepared by electrodeposition (Fig. 23e1) [121]. As shown in operation, it is crucial to investigate the influence of ionomer on
Fig. 23e2–4, porous arrays of micron-sized nanoislands are uniformly different CLs to ensure adequate ion and electron transport routes while
formed on nickel foam, where each nanoisland consists of many small utilizing the advantage of CL structure and morphology as much as
nanoparticles of a few nanometers in size. The contact angle of possible.
Fe0.2Ni0.8P0.5S0.5 PTE is 0◦ , while the Ni foam has a contact angle of PTL with a graded structure has been shown to be an effective design
86.1◦ . In the gas bubble contact angle test, the Fe0.2Ni0.8P0.5S0.5 PTE for bubble management and performance enhancement in PEMWE.
27
Fig. 24. (a1) Polarization curves when running AEMWE with DI water and different concentrations of KOH (IrO2 anode and PtRu/C cathode). (a2) Schematic
diagram of the state of the active area in CL when running with KOH and when running with DI water. Reproduced with permission from Liu et al. [84]. Copyright
2021, IOP Publishing. (b1) Schematic of the effect of ionomer content on the construction of three-phase interfaces in self-support PTE. (b2) SEM images of
self-support PTE with and without ionomers on the surface. (b3) Effect of different ionomer contents on the polarization curves of AEMWE using self-support PTE.
Reproduced with permission from Wan et al. [279]. Copyright 2022, John Wiley and Sons.
Likewise, graded structure MPL-PTL has also been reported in AEMWE analysis, the high-frequency resistance and low-frequency resistance
[234,280]. Razmjooei et al. have introduced nickel-based MPL on the results further confirm that this performance improvement comes from a
top of PTL by spraying globular gas-atomized Ni-based powders by significant reduction in electron transfer resistance and mass transport
air-plasma spraying (Fig. 25a1) [280]. The graded PTL with low capil resistance (Fig. 25a3).
lary pressure MPL facilitates the transport of water from the flow
channel to the reaction site, while effectively allowing hydrogen and 6. Challenges and future prospects
oxygen to flow in opposite directions, reducing the masking of the re
action site. Moreover, since MPL has a denser structure, it can also While significant progress has been made in PEMWE technology
improve the contact between PTL and CL, and in turn reduces interfacial development, we believe two important subfields still need particular
contact resistance. As shown in Fig. 25a2, compared with PTL without attention: micro- and nano-scale bubble behavior in PEMWE and bubble
MPL and Ni mesh, the NiMPL-PTL shows a significant performance management techniques in PEMWE engineering practice.
improvement. As seen by the electrochemical impedance spectrum For bubble behavior in PEMWE, some excellent works have revealed
28
Fig. 25. (a1) Schematic of the NiMPL coating prepared on PTL using the APS technique. (a2) Comparison of the polarization curves of AEMWE using stainless steel
PTL, Ni mesh, and stainless steel PTL with NiMPL. (a3) Comparison of Nyquist plots of electrochemical impedance spectroscopy measurements of AEMWE using PTL/
PTL configuration versus AEMWE using NiMPL-PTL/NiMPL-PTL. Reproduced with permission from Razmjooei et al. [280]. Copyright 2021, Elsevier B.V.
the transport processes in PTL and flow fields. However, there is a lack of whole PEMWE cell also need more research. The study of the transient
knowledge about bubble behaviors at nanoscale inside the CL because of gas distribution in PTL reveals the hysteresis of gas transport in response
the challenges associated with analytical techniques and methods. to current changes and the accumulation of gas during repeating load
Although we have been able to describe the bubble generation and changes, which results in performance loss under intermittent load [70].
detachment processes referred to as bubble evolution theory, these Meanwhile, it has also been proved that by applying pulse voltage or
discussions are difficult to directly infer the actual situation within the swinging pressure, bubble detachment can be enhanced and the elec
CL. At the catalyst level, several works presented the enhancement of trolyzer efficiency will also increase accordingly [269,270]. These
OER and HER by using nanostructures and attributed it to the contradictory phenomena indicate the complexity of the dynamic
enhancement of bubble evolution [134,281]. However, how the bubble characteristics and corresponding influence of bubbles under dynamic
evolution process is affected by such nanostructures at the nanoscale operation. Considering the intermittent and fluctuating nature of
and thus enhancing the electrochemical reactions still remains un renewable energy source which powers the PEMWE, more research is
known. At the pore level of the CL, the origin of oxygen and hydrogen needed to understand the dynamic characteristics of bubble transport.
bubbles and their transport behavior within porous structure of CL are
still not acknowledged. More experimental and theoretical work is 7. Conclusions
needed in the understanding of the original production sites of bubbles
and the transport behavior of bubbles inside the CL, which would offer As a promising emerging hydrogen production technology, the
the design principles for catalysts and CL structure. PEMWE has attracted worldwide attention recently due to its charac
Besides, the dynamic characteristics of bubble transport across the teristics of high efficiency, excellent flexibility, and good compatibility
29
with renewable energies. As a result, significant progress has been made (SL2021ZD105).
in increasing current densities at the same precious metal catalyst
loadings. However, as the current density increases, the bubbles References
generated during electrolysis have an increasingly negative impact on
the efficiency of the electrolysis. The bubble evolution process in [1] Hurtubia B, Sauma E. Economic and environmental analysis of hydrogen
production when complementing renewable energy generation with grid
PEMWE includes nucleation, growth, and detachment. On the one hand, electricity. Appl Energy 2021;304:117739. https://doi.org/10.1016/j.
the evolution of bubbles reduces the gas supersaturation near the cata apenergy.2021.117739.
lytic surface to reduce mass transfer losses, while on the other hand, it [2] Hermesmann M, Müller TE. Green, turquoise, blue, or grey? Environmentally
friendly hydrogen production in transforming energy systems. Prog Energy
masks the catalytic surface to cause an increase in activation loss. The Combust Sci 2022;90:100996. https://doi.org/10.1016/j.pecs.2022.100996.
evolution process can be affected by modifying the CL. Designing CL [3] Action on clean hydrogen is needed to deliver net-zero by 2050. Here’s how.
towards increasing the number of bubble nucleation sites, decreasing World Economic Forum n.d, https://www.weforum.org/agenda/2022/05/actio
n-clean-hydrogen-net-zero-2050/. [Accessed 10 June 2022].
the bubble detachment size, and increasing the bubble detachment [4] Jiao K, Xuan J, Du Q, Bao Z, Xie B, Wang B, et al. Designing the next generation of
frequency will significantly improve the water electrolysis performance. proton-exchange membrane fuel cells. Nature 2021;595:361–9. https://doi.org/
After detachment, a bubble transport process happens in the PEMWE 10.1038/s41586-021-03482-7.
[5] Cullen DA, Neyerlin KC, Ahluwalia RK, Mukundan R, More KL, Borup RL, et al.
cell. Bubbles travel from CL to PTL and are then carried away by the
New roads and challenges for fuel cells in heavy-duty transportation. Nat Energy
water flow in the flow field. The transport routes are determined by the 2021;6:462–74. https://doi.org/10.1038/s41560-021-00775-z.
porosity, wettability, and structure of each component in PEMWE. [6] Shelef M, Kukkonen CA. Prospects of hydrogen-fueled vehicles. Prog Energy
Bubble accumulation during the transport process hinders water-gas Combust Sci 1994;20:139–48. https://doi.org/10.1016/0360-1285(94)90008-6.
[7] Yilanci A, Dincer I, Ozturk HK. A review on solar-hydrogen/fuel cell hybrid
transport and reduces cell performance. Especially in the case of dy energy systems for stationary applications. Prog Energy Combust Sci 2009;35:
namic loads, bubble accumulation tends to become severe. Providing 231–44. https://doi.org/10.1016/j.pecs.2008.07.004.
sufficient, straightforward, and low-resistance bubble transport routes [8] Pan ZF, An L, Zhao TS, Tang ZK. Advances and challenges in alkaline anion
exchange membrane fuel cells. Prog Energy Combust Sci 2018;66:141–75.
in CL, PTL, and flow field can reduce bubble accumulation and its https://doi.org/10.1016/j.pecs.2018.01.001.
negative impact on electrolyzer performance. Future PEMWE compo [9] Ozden A, Shahgaldi S, Li X, Hamdullahpur F. A review of gas diffusion layers for
nents design and electrolyzer control strategies should follow these proton exchange membrane fuel cells—with a focus on characteristics,
characterization techniques, materials and designs. Prog Energy Combust Sci
principles towards better bubble evolution and transport behavior to 2019;74:50–102. https://doi.org/10.1016/j.pecs.2019.05.002.
migrate the bubble-induced loss. More effort needs to be devoted to [10] Glenk G, Reichelstein S. Economics of converting renewable power to hydrogen.
developing PEMWE bubble management techniques and engaging in Nat Energy 2019;4:216–22. https://doi.org/10.1038/s41560-019-0326-1.
[11] Buttler A, Spliethoff H. Current status of water electrolysis for energy storage,
engineering practice in the future. In addition, the bubble management grid balancing and sector coupling via power-to-gas and power-to-liquids: a
techniques in PEMWE also provide guidelines and solution for the review. Renew Sustain Energy Rev 2018;82:2440–54. https://doi.org/10.1016/j.
bubble issues in AEMWE and thus facilitate its better development. rser.2017.09.003.
[12] Mohammadi A, Mehrpooya M. A comprehensive review on coupling different
In this article, we have presented a comprehensive review of the
types of electrolyzer to renewable energy sources. Energy 2018;158:632–55.
bubble evolution and transport behaviors in PEMWE cells and their https://doi.org/10.1016/j.energy.2018.06.073.
corresponding impacts on cell performance. In response to the issues [13] Yu Z-Y, Duan Y, Feng X-Y, Yu X, Gao M-R, Yu S-H. Clean and Affordable
induced by bubbles, we have reviewed the most recent advances in Hydrogen Fuel from Alkaline Water Splitting: Past, Recent Progress, and Future
Prospects. Adv Mater n.d.;n/a:2007100.. https://doi.org/10.1002/adma.
bubble management strategies for PEMWE, as well as the remaining 202007100.
challenges and perspectives. Despite the progress made, there is still [14] Götz M, Lefebvre J, Mörs F, McDaniel Koch A, Graf F, Bajohr S, et al. Renewable
much room for improvement of water electrolyzer performance regards Power-to-Gas: a technological and economic review. Renew Energy 2016;85:
1371–90. https://doi.org/10.1016/j.renene.2015.07.066.
bubble management due to a limited understanding of bubble evolution [15] Zeng K, Zhang D. Recent progress in alkaline water electrolysis for hydrogen
and transport in PEMWE. Further development of bubble management production and applications. Prog Energy Combust Sci 2010;36:307–26. https://
in PEMWE can be focused on, but not limited to, the following areas: 1) doi.org/10.1016/j.pecs.2009.11.002.
[16] Carmo M, Fritz DL, Mergel J, Stolten D. A comprehensive review on PEM water
in-situ characterizations of bubble evolution; 2) modeling the complex electrolysis. Int J Hydrogen Energy 2013;38:4901–34. https://doi.org/10.1016/j.
multi-scale bubble transport process and its impact on electrochemical ijhydene.2013.01.151.
performance; 3) optimizing CL and CL-PTL interface for more bubble [17] Shiva Kumar S, Himabindu V. Hydrogen production by PEM water electrolysis – a
review. Mater Sci Energy Technol 2019;2:442–54. https://doi.org/10.1016/j.
nucleation sites, smaller bubble detachment size, and higher bubble mset.2019.03.002.
detachment frequency; 4) designing CL, PTL, flow fields towards suffi [18] Ayers KE, Dalton L, Parker M. Direct electrochemical compression of hydrogen
cient, straightforward and low-resistance bubble transport routes across and oxygen via PEM water electrolysis. Meet Abstr 2017. https://doi.org/
10.1149/MA2017-02/37/1664. MA2017-02:1664.
the whole PEMWE cell; 5) improve electrolyzer operation strategy to
[19] Zhu S, Qin X, Xiao F, Yang S, Xu Y, Tan Z, et al. The role of ruthenium in
prevent bubble accumulation during dynamic load. improving the kinetics of hydrogen oxidation and evolution reactions of
platinum. Nat Catal 2021;4:711–8. https://doi.org/10.1038/s41929-021-00663-
5.
Declaration of competing interest
[20] Gao J, Tao H, Liu B. Progress of nonprecious-metal-based electrocatalysts for
oxygen evolution in acidic media. Adv Mater 2021;33:2003786. https://doi.org/
The authors declare that they have no known competing financial 10.1002/adma.202003786.
interests or personal relationships that could have appeared to influence [21] Sapountzi FM, Gracia JM, Weststrate CJ, Kees-J, Fredriksson HOA,
Niemantsverdriet JW, Hans. Electrocatalysts for the generation of hydrogen,
the work reported in this paper. oxygen and synthesis gas. Prog Energy Combust Sci 2017;58:1–35. https://doi.
org/10.1016/j.pecs.2016.09.001.
Data availability [22] Hackemüller FJ, Borgardt E, Panchenko O, Müller M, Bram M. Manufacturing of
large-scale titanium-based porous transport layers for polymer electrolyte
membrane electrolysis by tape casting. Adv Eng Mater 2019;21:1801201. https://
Data will be made available on request. doi.org/10.1002/adem.201801201.
[23] Lee JK, Bazylak A. Optimizing porous transport layer design parameters via
stochastic pore network modelling: reactant transport and interfacial contact
Acknowledgements considerations. J Electrochem Soc 2020;167:013541. https://doi.org/10.1149/
1945-7111/ab6557.
This paper was supported by National Key Research and Develop [24] Stiber S, Balzer H, Wierhake A, Wirkert FJ, Roth J, Rost U, et al. Porous transport
layers for proton exchange membrane electrolysis under extreme conditions of
ment Program of China (2021YFB4001305), the National Natural Sci current density, temperature, and pressure. Adv Energy Mater 2021;11:2100630.
ence Foundation of China (No. 52276206), and the Science and https://doi.org/10.1002/aenm.202100630.
Technology Commission of Shanghai Municipality (21DZ1208600), the
Oceanic Interdisciplinary Program of Shanghai Jiao Tong University
30
[25] Maier M, Smith K, Dodwell J, Hinds G, Shearing PR, Brett DJL. Mass transport in [52] Yang X, Karnbach F, Uhlemann M, Odenbach S, Eckert K. Dynamics of single
PEM water electrolysers: a review. Int J Hydrogen Energy 2021. https://doi.org/ hydrogen bubbles at a platinum microelectrode. Langmuir 2015;31:8184–93.
10.1016/j.ijhydene.2021.10.013. S0360319921039288. https://doi.org/10.1021/acs.langmuir.5b01825.
[26] Li Y, Kang Z, Deng X, Yang G, Yu S, Mo J, et al. Wettability effects of thin titanium [53] Lee JK, Bazylak A. Bubbles: the good, the bad, and the ugly. Joule 2021;5:19–21.
liquid/gas diffusion layers in proton exchange membrane electrolyzer cells. https://doi.org/10.1016/j.joule.2020.12.024.
Electrochim Acta 2019;298:704–8. https://doi.org/10.1016/j. [54] Kumar R, Kuloor NK. The Formation of bubbles and drops. In: Drew TB,
electacta.2018.12.162. Cokelet GR, Hoopes JW, Vermeulen T, editors. Advances in chemical engineering,
[27] Maier M, Dodwell J, Ziesche R, Tan C, Heenan T, Majasan J, et al. Mass transport 8. Academic Press; 1970. p. 255–368. https://doi.org/10.1016/S0065-2377(08)
in polymer electrolyte membrane water electrolyser liquid-gas diffusion layers: a 60186-6.
combined neutron imaging and X-ray computed tomography study. J Power [55] Oguz HN, Prosperetti A. Dynamics of bubble growth and detachment from a
Sources 2020;455:227968. https://doi.org/10.1016/j.jpowsour.2020.227968. needle. J Fluid Mech 1993;257:111. https://doi.org/10.1017/
[28] Pham CV, Escalera-López D, Mayrhofer K, Cherevko S, Thiele S. Essentials of high S0022112093003015.
performance water electrolyzers – From catalyst layer materials to electrode [56] Yang X. Marangoni convection at electrogenerated hydrogen bubbles, 7; 2018.
engineering. Adv Energy Mater 2021;11:2101998. https://doi.org/10.1002/ [57] Taqieddin A, Allshouse MR, Alshawabkeh AN. Editors’ choice—critical
aenm.202101998. review—mathematical formulations of electrochemically gas-evolving systems.
[29] Yeo K-R, Lee K-S, Kim H, Lee J, Kim S-K. A highly active and stable 3D dandelion J Electrochem Soc 2018;165:E694–711. https://doi.org/10.1149/2.0791813jes.
spore-structured self-supporting Ir-based electrocatalyst for proton exchange [58] Xu W, Lu Z, Sun X, Jiang L, Duan X. Superwetting electrodes for gas-involving
membrane water electrolysis fabricated using structural reconstruction. Energy electrocatalysis. Acc Chem Res 2018;51:1590–8. https://doi.org/10.1021/acs.
Environ Sci 2022. https://doi.org/10.1039/D2EE01042A. 10.1039.D2EE01042A. accounts.8b00070.
[30] Chen Z, Guo L, Pan L, Yan T, He Z, Li Y, et al. Advances in oxygen evolution [59] Schmidt LE, Keim NC, Zhang WW, Nagel SR. Memory-encoding vibrations in a
electrocatalysts for proton exchange membrane water electrolyzers. Adv Energy disconnecting air bubble. Nat Phys 2009;5:343–6. https://doi.org/10.1038/
Mater 2022:2103670. https://doi.org/10.1002/aenm.202103670. nphys1233.
[31] Li L, Wang P, Shao Q, Huang X. Recent progress in advanced electrocatalyst [60] Iwata R, Zhang L, Wilke KL, Gong S, He M, Gallant BM, et al. Bubble growth and
design for acidic oxygen evolution reaction. Adv Mater 2021;33:2004243. departure modes on wettable/non-wettable porous foams in alkaline water
https://doi.org/10.1002/adma.202004243. splitting. Joule 2021;5:887–900. https://doi.org/10.1016/j.joule.2021.02.015.
[32] Wang P, Wang B. Designing self-supported electrocatalysts for electrochemical [61] Kou T, Wang S, Shi R, Zhang T, Chiovoloni S, Lu JQ, et al. Periodic porous 3D
water splitting: surface/interface engineering toward enhanced electrocatalytic electrodes mitigate gas bubble traffic during alkaline water electrolysis at high
performance. ACS Appl Mater Interfaces 2021;13:59593–617. https://doi.org/ current densities. Adv Energy Mater 2020;10:2002955. https://doi.org/10.1002/
10.1021/acsami.1c17448. aenm.202002955.
[33] Angulo A, van der Linde P, Gardeniers H, Modestino M, Fernández Rivas D. [62] Lu Z, Zhu W, Yu X, Zhang H, Li Y, Sun X, et al. Ultrahigh hydrogen evolution
Influence of bubbles on the energy conversion efficiency of electrochemical performance of under-water “superaerophobic” MoS2 nanostructured electrodes.
reactors. Joule 2020;4:555–79. https://doi.org/10.1016/j.joule.2020.01.005. Adv Mater 2014;26:2683–7. https://doi.org/10.1002/adma.201304759.
[34] Zhao X, Ren H, Luo L. Gas bubbles in electrochemical gas evolution reactions. [63] Gross SJ, McDevitt KM, Mumm DR, Mohraz A. Mitigating bubble traffic in gas-
Langmuir 2019;35:5392–408. https://doi.org/10.1021/acs.langmuir.9b00119. evolving electrodes via spinodally derived architectures. ACS Appl Mater
[35] Yang F, Kim MJ, Brown M, Wiley BJ. Alkaline water electrolysis at 25 A cm− 2 Interfaces 2021;13:8528–37. https://doi.org/10.1021/acsami.0c20798.
with a microfibrous flow-through electrode. Adv Energy Mater 2020;10:2001174. [64] Jiang M, Wang H, Li Y, Zhang H, Zhang G, Lu Z, et al. Superaerophobic RuO2-
https://doi.org/10.1002/aenm.202001174. based nanostructured electrode for high-performance chlorine evolution reaction.
[36] Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P, et al. Water Small 2017;13:1602240. https://doi.org/10.1002/smll.201602240.
electrolysis: from textbook knowledge to the latest scientific strategies and [65] Wu Y, Zhang H, Wu X, Cen K. Quantifying bubble size and 3D velocity in a vortex
industrial developments. Chem Soc Rev 2022;51:4583–762. https://doi.org/ with digital holographic particle tracking velocimetry (DHPTV). Flow Meas
10.1039/D0CS01079K. Instrum 2020;76:101826. https://doi.org/10.1016/j.flowmeasinst.2020.101826.
[37] Shih AJ, Monteiro MCO, Dattila F, Pavesi D, Philips M, da Silva AHM, et al. Water [66] Hreiz R, Abdelouahed L, Fünfschilling D, Lapicque F. Electrogenerated bubbles
electrolysis. Nat Rev Methods Primers 2022;2:1–19. https://doi.org/10.1038/ induced convection in narrow vertical cells: PIV measurements and
s43586-022-00164-0. Euler–Lagrange CFD simulation. Chem Eng Sci 2015;134:138–52. https://doi.
[38] Berg P, Promislow K, Pierre JS, Stumper J, Wetton B. Water management in PEM org/10.1016/j.ces.2015.04.041.
fuel cells. J Electrochem Soc 2004;151:A341. https://doi.org/10.1149/ [67] Wosiak G, da Silva J, Sena SS, de Andrade RN, Pereira E. CFD simulation and
1.1641033. experimental comparison of bubble-induced convection during electrochemical
[39] Wang XR, Ma Y, Gao J, Li T, Jiang GZ, Sun ZY. Review on water management water splitting. Chem Eng J 2022;433:133194. https://doi.org/10.1016/j.
methods for proton exchange membrane fuel cells. Int J Hydrogen Energy 2021; cej.2021.133194.
46:12206–29. https://doi.org/10.1016/j.ijhydene.2020.06.211. [68] Lagadec MF, Grimaud A. Water electrolysers with closed and open
[40] Yu S, Li K, Wang W, Xie Z, Ding L, Kang Z, et al. Tuning catalyst activation and electrochemical systems. Nat Mater 2020;19:1140–50. https://doi.org/10.1038/
utilization via controlled electrode patterning for low-loading and high-efficiency s41563-020-0788-3.
water electrolyzers. Small 2022;18:2107745. https://doi.org/10.1002/ [69] Mo J, Kang Z, Retterer ST, Cullen DA, Toops TJ, Green JB, et al. Discovery of true
smll.202107745. electrochemical reactions for ultrahigh catalyst mass activity in water splitting.
[41] Lee JK, Lee C, Fahy KF, Kim PJ, Krause K, LaManna JM, et al. Accelerating bubble Sci Adv 2016;2:e1600690. https://doi.org/10.1126/sciadv.1600690.
detachment in porous transport layers with patterned through-pores. ACS Appl [70] Lee Ch, Lee JK, Zhao B, Fahy KF, Bazylak A. Transient gas distribution in porous
Energy Mater 2020;3:9676–84. https://doi.org/10.1021/acsaem.0c01239. transport layers of polymer electrolyte membrane electrolyzers. J Electrochem
[42] Lubetkin SD. The fundamentals of bubble evolution. Chem Soc Rev 1995;24:243. Soc 2020;167:024508. https://doi.org/10.1149/1945-7111/ab68c8.
https://doi.org/10.1039/cs9952400243. [71] Majasan JO, Cho JIS, Dedigama I, Tsaoulidis D, Shearing P, Brett DJL. Two-phase
[43] Kalikmanov VI. Classical nucleation theory. In: Kalikmanov VI, editor. Nucleation flow behaviour and performance of polymer electrolyte membrane electrolysers:
theory. Dordrecht: Springer Netherlands; 2013. p. 17–41. https://doi.org/ electrochemical and optical characterisation. Int J Hydrogen Energy 2018;43:
10.1007/978-90-481-3643-8_3. 15659–72. https://doi.org/10.1016/j.ijhydene.2018.07.003.
[44] Blander M, Katz JL. Bubble nucleation in liquids. AIChE J 1975;21:833–48. [72] Lee JK, Lee C, Fahy KF, Zhao B, LaManna JM, Baltic E, et al. Critical current
https://doi.org/10.1002/aic.690210502. density as a performance indicator for gas-evolving electrochemical devices. Cell
[45] Ren H, German SR, Edwards MA, Chen Q, White HS. Electrochemical generation Rep Phys Sci 2020;1:100147. https://doi.org/10.1016/j.xcrp.2020.100147.
of individual O2 nanobubbles via H2O2 oxidation. J Phys Chem Lett 2017;8: [73] Wang W, Yu S, Li K, Ding L, Xie Z, Li Y, et al. Insights into the rapid two-phase
2450–4. https://doi.org/10.1021/acs.jpclett.7b00882. transport dynamics in different structured porous transport layers of water
[46] Peñas P, van der Linde P, Vijselaar W, van der Meer D, Lohse D, Huskens J, et al. electrolyzers through high-speed visualization. J Power Sources 2021;516:
Decoupling gas evolution from water-splitting electrodes. J Electrochem Soc 230641. https://doi.org/10.1016/j.jpowsour.2021.230641.
2019;166:H769. https://doi.org/10.1149/2.1381914jes. [74] Wani K, Araki T, Nagasawa K, Mitsushima S. Visualization of bubble behavior on
[47] Raman A, Penas P, Lohse D, Gardeniers H, Rivas DF. Potential response of single hydrophobic coated CL in PEM water electrolysis cell. Meet Abstr 2020;
successive constant-current-driven electrolytic hydrogen bubbles spatially MA2020–02:2459. https://doi.org/10.1149/MA2020-02382459mtgabs.
separated from the electrode n.d.:19. [75] Li Y, Kang Z, Mo J, Yang G, Yu S, Talley DA, et al. In-situ investigation of bubble
[48] Fernández D, Maurer P, Martine M, Coey JMD, Möbius ME. Bubble Formation at a dynamics and two-phase flow in proton exchange membrane electrolyzer cells.
gas-evolving microelectrode. Langmuir 2014;30:13065–74. https://doi.org/ Int J Hydrogen Energy 2018;43:11223–33. https://doi.org/10.1016/j.
10.1021/la500234r. ijhydene.2018.05.006.
[49] Kempler PA, Coridan RH, Lewis NS. Effects of bubbles on the electrochemical [76] Selamet OF, Deevanhxay P, Tsushima S, Hirai S. Investigation of gas generation in
behavior of hydrogen-evolving Si microwire arrays oriented against gravity. regenerative fuel cells by low-energy X-rays. J Power Sources 2015;296:133–41.
Energy Environ Sci 2020;13:1808–17. https://doi.org/10.1039/D0EE00356E. https://doi.org/10.1016/j.jpowsour.2015.07.043.
[50] Mo Jingke, Kang Z, Yang G, Li Y, Retterer ST, Cullen DA, et al. In situ [77] Satjaritanun P, O’Brien M, Kulkarni D, Shimpalee S, Capuano C, Ayers KE, et al.
investigation on ultrafast oxygen evolution reactions of water splitting in proton Observation of preferential pathways for oxygen removal through porous
exchange membrane electrolyzer cells. J Mater Chem 2017;5:18469–75. https:// transport layers of polymer electrolyte water electrolyzers. iScience 2020;23:
doi.org/10.1039/C7TA05681H. 101783. https://doi.org/10.1016/j.isci.2020.101783.
[51] Brandon NP, Kelsall GH. Growth kinetics of bubbles electrogenerated at [78] Lee Ch, Lee JK, Zhao B, Fahy KF, LaManna JM, Baltic E, et al. Temperature-
microelectrodes. J Appl Electrochem 1985;15:475–84. https://doi.org/10.1007/ dependent gas accumulation in polymer electrolyte membrane electrolyzer
BF01059288.
31
porous transport layers. J Power Sources 2020;446:227312. https://doi.org/ Hydrogen Energy 2010;35:9550–60. https://doi.org/10.1016/j.
10.1016/j.jpowsour.2019.227312. ijhydene.2010.06.103.
[79] Panchenko O, Borgardt E, Zwaygardt W, Hackemüller FJ, Bram M, Kardjilov N, [103] Chen L, He A, Zhao J, Kang Q, Li Z-Y, Carmeliet J, et al. Pore-scale modeling of
et al. In-situ two-phase flow investigation of different porous transport layer for a complex transport phenomena in porous media. Prog Energy Combust Sci 2022;
polymer electrolyte membrane (PEM) electrolyzer with neutron spectroscopy. 88:100968. https://doi.org/10.1016/j.pecs.2021.100968.
J Power Sources 2018;390:108–15. https://doi.org/10.1016/j. [104] Ryan EM, Mukherjee PP. Mesoscale modeling in electrochemical devices—a
jpowsour.2018.04.044. critical perspective. Prog Energy Combust Sci 2019;71:118–42. https://doi.org/
[80] Leonard E, Shum AD, Danilovic N, Capuano C, Ayers KE, Pant LM, et al. 10.1016/j.pecs.2018.11.002.
Interfacial analysis of a PEM electrolyzer using X-ray computed tomography. [105] Bhaskaran S, Miličić T, Surasani VK, Tsotsas E, Vidakovic-Koch T, Vorhauer-
Sustain Energy Fuels 2020;4:921–31. https://doi.org/10.1039/C9SE00364A. Huget N. A new design of a microfluidic experimental cell for the study of two-
[81] Kwan JTH, Nouri-Khorasani A, Bonakdarpour A, McClement DG, Afonso G, phase flow inside a PEM water electrolyzer. Meet Abstr 2022;MA2022–02:1641.
Wilkinson DP. Frequency analysis of water electrolysis current fluctuations in a https://doi.org/10.1149/MA2022-02441641mtgabs.
PEM flow cell: insights into bubble nucleation and detachment. J Electrochem Soc [106] Satjaritanun P, Lopata JS, Cho H-S, Kim M-J, Zenyuk IV, Shimpalee S. Applying
2022;169:054531. https://doi.org/10.1149/1945-7111/ac707f. the lattice Boltzmann method to simulate bubble growth in porous media for PEM
[82] Mazloomi K, Sulaiman N, Ahmad SA, Yunus NA. Analysis of the frequency water electrolysis. Meet Abstr 2020;MA2020–02:2472. https://doi.org/10.1149/
response of a water electrolysis cell. Int J Electrochem Sci 2013;8:9. MA2020-02382472mtgabs.
[83] Nouri-Khorasani A, Tabu Ojong E, Smolinka T, Wilkinson DP. Model of oxygen [107] Lee C, Hinebaugh J, Banerjee R, Chevalier S, Abouatallah R, Wang R, et al.
bubbles and performance impact in the porous transport layer of PEM water Influence of limiting throat and flow regime on oxygen bubble saturation of
electrolysis cells. Int J Hydrogen Energy 2017;42:28665–80. https://doi.org/ polymer electrolyte membrane electrolyzer porous transport layers. Int J
10.1016/j.ijhydene.2017.09.167. Hydrogen Energy 2017;42:2724–35. https://doi.org/10.1016/j.
[84] Liu J, Kang Z, Li D, Pak M, Alia SM, Fujimoto C, et al. Elucidating the role of ijhydene.2016.09.114.
hydroxide electrolyte on anion-exchange-membrane water electrolyzer [108] Arbabi F, Kalantarian A, Abouatallah R, Wang R, Wallace JS, Bazylak A.
performance. J Electrochem Soc 2021;168:054522. https://doi.org/10.1149/ Feasibility study of using microfluidic platforms for visualizing bubble flows in
1945-7111/ac0019. electrolyzer gas diffusion layers. J Power Sources 2014;258:142–9. https://doi.
[85] Lindquist GA, Oener SZ, Krivina R, Motz AR, Keane A, Capuano C, et al. org/10.1016/j.jpowsour.2014.02.042.
Performance and durability of pure-water-fed anion exchange membrane [109] Arbabi F, Montazeri H, Abouatallah R, Wang R, Bazylak A. Three-dimensional
electrolyzers using baseline materials and operation. ACS Appl Mater Interfaces computational fluid dynamics modelling of oxygen bubble transport in polymer
2021;13:51917–24. https://doi.org/10.1021/acsami.1c06053. electrolyte membrane electrolyzer porous transport layers. J Electrochem Soc
[86] Hassan NU, Zheng Y, Kohl PA, Mustain WE. KOH vs Deionized water operation in 2016;163:F3062–9. https://doi.org/10.1149/2.0091611jes.
anion exchange membrane electrolyzers. J Electrochem Soc 2022;169:044526. [110] Arbabi F, Kalantarian A, Abouatallah R, Wang R, Wallace J, Bazylak A.
https://doi.org/10.1149/1945-7111/ac5f1d. Visualizing bubble flows in electrolyzer GDLs using microfluidic platforms. ECS
[87] Wan L, Xu Z, Xu Q, Wang P, Wang B. Overall design of novel 3D-ordered MEA Trans 2013;58:907–18. https://doi.org/10.1149/05801.0907ecst.
with drastically enhanced mass transport for alkaline electrolyzers. Energy [111] Zlobinski M, Schuler T, Büchi FN, Schmidt TJ, Boillat P. Transient and steady
Environ Sci 2022;15:1882–92. https://doi.org/10.1039/D2EE00273F. state two-phase flow in anodic porous transport layer of proton exchange
[88] Xu Q, Zhang L, Zhang J, Wang J, Hu Y, Jiang H, et al. Anion exchange membrane membrane water electrolyzer. J Electrochem Soc 2020;167:084509. https://doi.
water electrolyzer: electrode design, lab-scaled testing system and performance org/10.1149/1945-7111/ab8c89.
evaluation. EnergyChem 2022;4:100087. https://doi.org/10.1016/j. [112] Schuler T, De Bruycker R, Schmidt TJ, Büchi FN. Polymer electrolyte water
enchem.2022.100087. electrolysis: correlating porous transport layer structural properties and
[89] Chen Q, Luo L, Faraji H, Feldberg SW, White HS. Electrochemical measurements performance: Part I. Tomographic analysis of morphology and topology.
of single H2 nanobubble nucleation and stability at Pt nanoelectrodes. J Phys J Electrochem Soc 2019;166:F270–81. https://doi.org/10.1149/2.0561904jes.
Chem Lett 2014;5:3539–44. https://doi.org/10.1021/jz501898r. [113] De Angelis S, Schuler T, Charalambous MA, Marone F, Schmidt TJ, Büchi FN.
[90] Chen N, Paek SY, Lee JY, Park JH, Lee SY, Lee YM. High-performance anion Unraveling two-phase transport in porous transport layer materials for polymer
exchange membrane water electrolyzers with a current density of 7.68 A cm− 2 electrolyte water electrolysis. J Mater Chem 2021;9:22102–13. https://doi.org/
and a durability of 1000 hours. Energy Environ Sci 2021;14:6338–48. https://doi. 10.1039/D1TA03379D.
org/10.1039/D1EE02642A. [114] Seweryn J, Biesdorf J, Schmidt TJ, Boillat P. Communication—neutron
[91] Zhuang H, Tkalych AJ, Carter EA. Surface energy as a descriptor of catalytic radiography of the water/gas distribution in the porous layers of an operating
activity. J Phys Chem C 2016;120:23698–706. https://doi.org/10.1021/acs. electrolyser. J Electrochem Soc 2016;163:F3009–11. https://doi.org/10.1149/
jpcc.6b09687. 2.0641607jes.
[92] Gupta G, Selvakumar K, Lakshminarasimhan N, Senthil Kumar SM, Mamlouk M. [115] Hoeh MA, Arlt T, Manke I, Banhart J, Fritz DL, Maier W, et al. In operando
The effects of morphology, microstructure and mixed-valent states of MnO2 on synchrotron X-ray radiography studies of polymer electrolyte membrane water
the oxygen evolution reaction activity in alkaline anion exchange membrane electrolyzers. Electrochem Commun 2015;55:55–9. https://doi.org/10.1016/j.
water electrolysis. J Power Sources 2020;461:228131. https://doi.org/10.1016/j. elecom.2015.03.009.
jpowsour.2020.228131. [116] Leonard E, Shum AD, Normile S, Sabarirajan DC, Yared DG, Xiao X, et al.
[93] Xu Y, Wang C, Huang Y, Fu J. Recent advances in electrocatalysts for neutral and Operando X-ray tomography and sub-second radiography for characterizing
large-current-density water electrolysis. Nano Energy 2021;80:105545. https:// transport in polymer electrolyte membrane electrolyzer. Electrochim Acta 2018;
doi.org/10.1016/j.nanoen.2020.105545. 276:424–33. https://doi.org/10.1016/j.electacta.2018.04.144.
[94] Kim J-C, Kim J, Park JC, Ahn SH, Kim D-W. Ru2P nanofibers for high- [117] Ito K, Maeda Y, Sakaguchi T, Tsukamoto S, Inada A, Tsuchiya Y, et al. Analysis
performance anion exchange membrane water electrolyzer. Chem Eng J 2021; and visualization of water flow impact on hydrogen production efficiency in solid
420:130491. https://doi.org/10.1016/j.cej.2021.130491. polymer water electrolyzer under high-pressure condition. Int J Hydrogen Energy
[95] Jeon SS, Lim J, Kang PW, Lee JW, Kang G, Lee H. Design principles of NiFe- 2015;40:5995–6003. https://doi.org/10.1016/j.ijhydene.2015.03.045.
layered double hydroxide anode catalysts for anion exchange membrane water [118] Li Y, Yang G, Yu S, Mo J, Li K, Xie Z, et al. High-speed characterization of two-
electrolyzers. ACS Appl Mater Interfaces 2021;13:37179–86. https://doi.org/ phase flow and bubble dynamics in titanium felt porous media for hydrogen
10.1021/acsami.1c09606. production. Electrochim Acta 2021;370:137751. https://doi.org/10.1016/j.
[96] Santoro C, Lavacchi A, Mustarelli P, Di Noto V, Elbaz L, Dekel DR, et al. What is electacta.2021.137751.
next in anion-exchange membrane water electrolyzers? Bottlenecks, benefits, and [119] Roenning FH, Roy A, Aaron DS, Mench MM. Mass transport limitations in
future. ChemSusChem 2022;15:e202200027. https://doi.org/10.1002/ polymer electrolyte water electrolyzers using spatially-resolved current
cssc.202200027. measurement. J Power Sources 2022;542:231749. https://doi.org/10.1016/j.
[97] Li C, Baek J-B. The promise of hydrogen production from alkaline anion exchange jpowsour.2022.231749.
membrane electrolyzers. Nano Energy 2021;87:106162. https://doi.org/ [120] Park JE, Park S, Kim M-J, Shin H, Kang SY, Cho Y-H, et al. Three-dimensional
10.1016/j.nanoen.2021.106162. unified electrode design using a NiFeOOH catalyst for superior performance and
[98] Liang C, Zou P, Nairan A, Zhang Y, Liu J, Liu K, et al. Exceptional performance of durable anion-exchange membrane water electrolyzers. ACS Catal 2022;12:
hierarchical Ni–Fe oxyhydroxide@NiFe alloy nanowire array electrocatalysts for 135–45. https://doi.org/10.1021/acscatal.1c04117.
large current density water splitting. Energy Environ Sci 2020;13:86–95. https:// [121] Wan L, Xu Z, Wang P, Liu P-F, Xu Q, Wang B. Dual regulation both intrinsic
doi.org/10.1039/C9EE02388G. activity and mass transport for self-supported electrodes using in anion exchange
[99] Matsushima H, Nishida T, Konishi Y, Fukunaka Y, Ito Y, Kuribayashi K. Water membrane water electrolysis. Chem Eng J 2022;431:133942. https://doi.org/
electrolysis under microgravity: Part 1. Experimental technique. Electrochim Acta 10.1016/j.cej.2021.133942.
2003;48:4119–25. https://doi.org/10.1016/S0013-4686(03)00579-6. [122] Alia SM, Reeves KS, Baxter JS, Cullen DA. The impact of ink and spray variables
[100] Bernt M, Gasteiger HA. Influence of ionomer content in IrO2/TiO2 electrodes on on catalyst layer properties, electrolyzer performance, and electrolyzer durability.
PEM water electrolyzer performance. J Electrochem Soc 2016;163:F3179. J Electrochem Soc 2020;167:144512. https://doi.org/10.1149/1945-7111/
https://doi.org/10.1149/2.0231611jes. abc746.
[101] Bonanno M, Müller K, Bensmann B, Hanke-Rauschenbach R, Peach R, Thiele S. [123] Garcia-Navarro JC, Schulze M, Friedrich KA. Measuring and modeling mass
Evaluation of the efficiency of an elevated temperature proton exchange transport losses in proton exchange membrane water electrolyzers using
membrane water electrolysis system. J Electrochem Soc 2021;168:094504. electrochemical impedance spectroscopy. J Power Sources 2019;431:189–204.
https://doi.org/10.1149/1945-7111/ac2188. https://doi.org/10.1016/j.jpowsour.2019.05.027.
[102] Ito H, Maeda T, Nakano A, Hasegawa Y, Yokoi N, Hwang CM, et al. Effect of flow [124] Fritz DL, Mergel J, Stolten D. PEM electrolysis simulation and validation. ECS
regime of circulating water on a proton exchange membrane electrolyzer. Int J Trans 2014;58:1–9. https://doi.org/10.1149/05819.0001ecst.
32
[125] Suermann M, Schmidt TJ, Büchi FN. Investigation of mass transport losses in [150] Feng Q, Yuan X, Liu G, Wei B, Zhang Z, Li H, et al. A review of proton exchange
polymer electrolyte electrolysis cells. ECS Trans 2015;69:1141–8. https://doi. membrane water electrolysis on degradation mechanisms and mitigation
org/10.1149/06917.1141ecst. strategies. J Power Sources 2017;366:33–55. https://doi.org/10.1016/j.
[126] Lee CH, Banerjee R, Arbabi F, Hinebaugh J, Bazylak A. Porous transport layer jpowsour.2017.09.006.
related mass transport losses in polymer electrolyte membrane electrolysis: a [151] Hoseini Larimi SZ, Ramiar A, Esmaili Q, Shafaghat R. The effect of inlet velocity
review. In: ASME 2016 14th International conference on nanochannels, of water on the two-phase flow regime in the porous transport layer of polymer
microchannels, and minichannels. Washington, DC, USA: American Society of electrolyte membrane electrolyzer. Heat Mass Tran 2019;55:1863–70. https://
Mechanical Engineers; 2016, V001T07A003. https://doi.org/10.1115/ doi.org/10.1007/s00231-018-2436-x.
ICNMM2016-7974. [152] Li G. Lattice Boltzmann simulations of gas bubble transport in proton exchange
[127] Pushkarev AS, Pushkareva IV, Solovyev MA, Prokop M, Bystron T, membrane water electrolysis cells. J Phys: Conf Ser 2022;2280:012048. https://
Rajagopalan SK, et al. On the influence of porous transport layers parameters on doi.org/10.1088/1742-6596/2280/1/012048.
the performances of polymer electrolyte membrane water electrolysis cells. [153] Spöri C, Kwan JTH, Bonakdarpour A, Wilkinson DP, Strasser P. The stability
Electrochim Acta 2021;399:139436. https://doi.org/10.1016/j. challenges of oxygen evolving catalysts: towards a common fundamental
electacta.2021.139436. understanding and mitigation of catalyst degradation. Angew Chem Int Ed 2017;
[128] Gabrielli C, Huet F, Keddam M, Macias A, Sahar A. Potential drops due to an 56:5994–6021. https://doi.org/10.1002/anie.201608601.
attached bubble on a gas-evolving electrode. J Appl Electrochem 1989;19: [154] Li F-B, Robert Hillman A, Lubetkin SD, Roberts DJ. Electrochemical quartz crystal
617–29. https://doi.org/10.1007/BF01320636. microbalance studies of potentiodynamic electrolysis of aqueous chloride
[129] Vogt H, Balzer RJ. The bubble coverage of gas-evolving electrodes in stagnant solution: surface processes and evolution of H2 and Cl2 gas bubbles. J Electroanal
electrolytes. Electrochim Acta 2005;50:2073. https://doi.org/10.1016/j. Chem 1992;335:345–62. https://doi.org/10.1016/0022-0728(92)80253-Z.
electacta.2004.09.025. –9. [155] Chen F-Y, Wu Z-Y, Adler Z, Wang H. Stability challenges of electrocatalytic
[130] Balzer RJ, Vogt H. Effect of electrolyte flow on the bubble coverage of vertical oxygen evolution reaction: from mechanistic understanding to reactor design.
gas-evolving electrodes. J Electrochem Soc 2003;150:E11. https://doi.org/ Joule 2021;5:1704–31. https://doi.org/10.1016/j.joule.2021.05.005.
10.1149/1.1524185. [156] Kou T, Wang S, Li Y. Perspective on high-rate alkaline water splitting. ACS
[131] Vogt H. The quantities affecting the bubble coverage of gas-evolving electrodes. Materials Lett 2021;3:224–34. https://doi.org/10.1021/
Electrochim Acta 2017;235:495–9. https://doi.org/10.1016/j. acsmaterialslett.0c00536.
electacta.2017.03.116. [157] Han B, Stoerzinger KA, Tileli V, Gamalski AD, Stach EA, Shao-Horn Y. Nanoscale
[132] Mandin P, Derhoumi Z, Roustan H, Rolf W. Bubble over-potential during two- structural oscillations in perovskite oxides induced by oxygen evolution. Nat
phase alkaline water electrolysis. Electrochim Acta 2014;128:248–58. https:// Mater 2017;16:121–6. https://doi.org/10.1038/nmat4764.
doi.org/10.1016/j.electacta.2013.11.068. [158] Lee HY, Barber C, Minerick AR. Improving electrokinetic microdevice stability by
[133] Leistra JA, Sides PJ. Voltage components at gas evolving electrodes. controlling electrolysis bubbles. ELECTROPHORESIS 2014;35:1782–9. https://
J Electrochem Soc 1987;134:2442. https://doi.org/10.1149/1.2100218. doi.org/10.1002/elps.201400013.
[134] Li Y, Zhang H, Xu T, Lu Z, Wu X, Wan P, et al. Under-water superaerophobic pine- [159] Wang R, Inoguchi K, Ohashi M, Someya S, Munakata T, Ishida M, et al. Effect of
shaped Pt nanoarray electrode for ultrahigh-performance hydrogen evolution. catalyst distribution and structural properties of anode porous transport
Adv Funct Mater 2015;25:1737–44. https://doi.org/10.1002/adfm.201404250. electrodes on the performance of anion exchange membrane water electrolysis.
[135] Huang H, Kim H, Lee A, Kim S, Lim W-G, Park C-Y, et al. Structure engineering Int J Hydrogen Energy 2021;46:37757–67. https://doi.org/10.1016/j.
defective and mass transfer-enhanced RuO2 nanosheets for proton exchange ijhydene.2021.09.078.
membrane water electrolyzer. Nano Energy 2021;88:106276. https://doi.org/ [160] Grigoriev SA, Fateev VN, Bessarabov DG, Millet P. Current status, research trends,
10.1016/j.nanoen.2021.106276. and challenges in water electrolysis science and technology. Int J Hydrogen
[136] Gabrielli C, Huet F, Nogueira RP. Fluctuations of concentration overpotential Energy 2020;45:26036–58. https://doi.org/10.1016/j.ijhydene.2020.03.109.
generated at gas-evolving electrodes. Electrochim Acta 2005;50:3726–36. [161] Hegge F, Moroni R, Trinke P, Bensmann B, Hanke-Rauschenbach R, Thiele S, et al.
https://doi.org/10.1016/j.electacta.2005.01.019. Three-dimensional microstructure analysis of a polymer electrolyte membrane
[137] Suermann M, Schmidt TJ, Büchi FN. Cell performance determining parameters in water electrolyzer anode. J Power Sources 2018;393:62–6. https://doi.org/
high pressure water electrolysis. Electrochim Acta 2016;211:989–97. https://doi. 10.1016/j.jpowsour.2018.04.089.
org/10.1016/j.electacta.2016.06.120. [162] Trinke P, Keeley GP, Carmo M, Bensmann B, Hanke-Rauschenbach R. Elucidating
[138] Lickert T, Kiermaier ML, Bromberger K, Ghinaiya J, Metz S, Fallisch A, et al. On the effect of mass transport resistances on hydrogen crossover and cell
the influence of the anodic porous transport layer on PEM electrolysis performance in PEM water electrolyzers by varying the cathode ionomer content.
performance at high current densities. Int J Hydrogen Energy 2020;45:6047–58. J Electrochem Soc 2019;166:F465. https://doi.org/10.1149/2.0171908jes.
https://doi.org/10.1016/j.ijhydene.2019.12.204. [163] Kulkarni D, Huynh A, Satjaritanun P, O’Brien M, Shimpalee S, Parkinson D, et al.
[139] Tsushima S, Hirai S. In situ diagnostics for water transport in proton exchange Elucidating effects of catalyst loadings and porous transport layer morphologies
membrane fuel cells. Prog Energy Combust Sci 2011;37:204–20. https://doi.org/ on operation of proton exchange membrane water electrolyzers. Appl Catal B
10.1016/j.pecs.2010.06.001. Environ 2022;308:121213. https://doi.org/10.1016/j.apcatb.2022.121213.
[140] Liu Q, Lan F, Chen J, Zeng C, Wang J. A review of proton exchange membrane [164] Bernt M, Siebel A, Gasteiger HA. Analysis of voltage losses in PEM water
fuel cell water management: membrane electrode assembly. J Power Sources electrolyzers with low platinum group metal loadings. J Electrochem Soc 2018;
2022;517:230723. https://doi.org/10.1016/j.jpowsour.2021.230723. 165:F305–14. https://doi.org/10.1149/2.0641805jes.
[141] Taie Z, Peng X, Kulkarni D, Zenyuk IV, Weber AZ, Hagen C, et al. Pathway to [165] Lopata J, Kang Z, Young J, Bender G, Weidner JW, Shimpalee S. Effects of the
complete energy sector decarbonization with available iridium resources using transport/catalyst layer interface and catalyst loading on mass and charge
ultralow loaded water electrolyzers. ACS Appl Mater Interfaces 2020;12: transport phenomena in polymer electrolyte membrane water electrolysis
52701–12. https://doi.org/10.1021/acsami.0c15687. devices. J Electrochem Soc 2020;167:064507. https://doi.org/10.1149/1945-
[142] Yu S, Xie Z, Li K, Ding L, Wang W, Yang G, et al. Morphology engineering of 7111/ab7f87.
iridium electrodes via modifying titanium substrates with controllable pillar [166] Hegge F, Lombeck F, Cruz Ortiz E, Bohn L, von Holst M, Kroschel M, et al.
structures for highly efficient oxygen evolution reaction. Electrochim Acta 2022; Efficient and stable low iridium loaded anodes for PEM water electrolysis made
405:139797. https://doi.org/10.1016/j.electacta.2021.139797. possible by nanofiber interlayers. ACS Appl Energy Mater 2020;3:8276–84.
[143] Han N, Yang KR, Lu Z, Li Y, Xu W, Gao T, et al. Nitrogen-doped tungsten carbide https://doi.org/10.1021/acsaem.0c00735.
nanoarray as an efficient bifunctional electrocatalyst for water splitting in acid. [167] Yang G, Yu S, Kang Z, Li Y, Bender G, Pivovar BS, et al. Building electron/proton
Nat Commun 2018;9:924. https://doi.org/10.1038/s41467-018-03429-z. nanohighways for full utilization of water splitting catalysts. Adv Energy Mater
[144] Lim J, Park D, Jeon SS, Roh C-W, Choi J, Yoon D, et al. Ultrathin IrO 2 2020;10:1903871. https://doi.org/10.1002/aenm.201903871.
nanoneedles for electrochemical water oxidation. Adv Funct Mater 2018;28: [168] Zeradjanin AR, Narangoda P, Spanos I, Masa J, Schlögl R. How to minimise
1704796. https://doi.org/10.1002/adfm.201704796. destabilising effect of gas bubbles on water splitting electrocatalysts? Current
[145] Li L, Jiang W, Zhang G, Feng D, Zhang C, Yao W, et al. Efficient mesh interface Opinion in Electrochemistry 2021;30:100797. https://doi.org/10.1016/j.
engineering: insights from bubble dynamics in electrocatalysis. ACS Appl Mater coelec.2021.100797.
Interfaces 2021;13:45346–54. https://doi.org/10.1021/acsami.1c07637. [169] Zeradjanin AR, Ventosa E, Masa J, Schuhmann W. Utilization of the catalyst layer
[146] Sun S, Xiao Y, Liang D, Shao Z, Yu H, Hou M, et al. Behaviors of a proton of dimensionally stable anodes. Part 2: impact of spatial current distribution on
exchange membrane electrolyzer under water starvation. RSC Adv 2015;5: electrocatalytic performance. J Electroanal Chem 2018;828:63–70. https://doi.
14506–13. https://doi.org/10.1039/C4RA14104K. org/10.1016/j.jelechem.2018.09.034.
[147] do Nascimento DF, Vimieiro Junior JR, Paciornik S, Carvalho MS. Pore scale [170] Zeradjanin AR, La Mantia F, Masa J, Schuhmann W. Utilization of the catalyst
visualization of drainage in 3D porous media by confocal microscopy. Sci Rep layer of dimensionally stable anodes—interplay of morphology and active surface
2019;9:12333. https://doi.org/10.1038/s41598-019-48803-z. area. Electrochim Acta 2012;82:408–14. https://doi.org/10.1016/j.
[148] Kang Z, Yang G, Mo J, Li Y, Yu S, Cullen DA, et al. Novel thin/tunable gas electacta.2012.04.101.
diffusion electrodes with ultra-low catalyst loading for hydrogen evolution [171] Zeradjanin AR, Topalov AA, Van Overmeere Q, Cherevko S, Chen X, Ventosa E,
reactions in proton exchange membrane electrolyzer cells. Nano Energy 2018;47: et al. Rational design of the electrode morphology for oxygen evolution –
434–41. https://doi.org/10.1016/j.nanoen.2018.03.015. enhancing the performance for catalytic water oxidation. RSC Adv 2014;4:9579.
[149] Immerz C, Bensmann B, Trinke P, Suermann M, Hanke-Rauschenbach R. Local https://doi.org/10.1039/c3ra45998e.
current density and electrochemical impedance measurements within 50 cm [172] Shan X, Liu J, Mu H, Xiao Y, Mei B, Liu W, et al. An engineered superhydrophilic/
single-channel PEM electrolysis cell. J Electrochem Soc 2018;165:F1292–9. superaerophobic electrocatalyst composed of the supported CoMoSx chalcogel for
https://doi.org/10.1149/2.0411816jes. overall water splitting. Angew Chem Int Ed 2020;59:1659–65. https://doi.org/
10.1002/anie.201911617.
33
[173] George JE, Chidangil S, George SD. Recent progress in fabricating [199] Li M, Wei J, Ren L, Zhao Y, Shang Z, Zhou D, et al. Superwetting behaviors at the
superaerophobic and superaerophilic surfaces. Adv Mater Interfac 2017;4: interface between electrode and electrolyte. Cell Rep Phys Sci 2021;2:100374.
1601088. https://doi.org/10.1002/admi.201601088. https://doi.org/10.1016/j.xcrp.2021.100374.
[174] Xu W, Lu Z, Wan P, Kuang Y, Sun X. High-performance water electrolysis system [200] Zhang L, Yang X, Jiang B, Sun Y, Gong Z, Zhang N, et al. Superhydrophilic and
with double nanostructured superaerophobic electrodes. Small 2016;12:2492–8. underwater superoleophobic Ti foam with robust nanoarray structures of TiO2 for
https://doi.org/10.1002/smll.201600189. effective oil-in-water emulsion separation. Separ Purif Technol 2020;252:117437.
[175] Lu Z, Sun M, Xu T, Li Y, Xu W, Chang Z, et al. Superaerophobic electrodes for https://doi.org/10.1016/j.seppur.2020.117437.
direct hydrazine fuel cells. Adv Mater 2015;27:2361–6. https://doi.org/10.1002/ [201] Riyajuddin S, Azmi K, Pahuja M, Kumar S, Maruyama T, Bera C, et al. Super-
adma.201500064. hydrophilic hierarchical Ni-Foam-Graphene-Carbon nanotubes-Ni2P–CuP2 nano-
[176] Huang C, Guo Z. The wettability of gas bubbles: from macro behavior to nano architecture as efficient electrocatalyst for overall water splitting. ACS Nano
structures to applications. Nanoscale 2018;10:19659–72. https://doi.org/ 2021;15:5586–99. https://doi.org/10.1021/acsnano.1c00647.
10.1039/C8NR07315E. [202] Xu Q, Wang P, Wan L, Xu Z, Sultana MZ, Wang B. Superhydrophilic/
[177] Yu C, Zhang P, Wang J, Jiang L. Superwettability of gas bubbles and its superaerophobic hierarchical NiP2@MoO2/Co(Ni)MoO4 core–shell array
application: from bioinspiration to advanced materials. Adv Mater 2017;29: electrocatalysts for efficient hydrogen production at large current densities. ACS
1703053. https://doi.org/10.1002/adma.201703053. Appl Mater Interfaces 2022;14:19448. https://doi.org/10.1021/acsami.2c01808.
[178] Liu K, Yao X, Jiang L. Recent developments in bio-inspired special wettability. –58.
Chem Soc Rev 2010;39:3240–55. https://doi.org/10.1039/B917112F. [203] Barati Darband G, Aliofkhazraei M, Hyun S, Shanmugam S. Pulse
[179] Wenzel RN. Resistance of solid surfaces to wetting by water. Ind Eng Chem 1936; electrodeposition of a superhydrophilic and binder-free Ni–Fe–P nanostructure as
28:988–94. https://doi.org/10.1021/ie50320a024. highly active and durable electrocatalyst for both hydrogen and oxygen evolution
[180] Cassie ABD, Baxter S. Wettability of porous surfaces. Trans Faraday Soc 1944;40: reactions. ACS Appl Mater Interfaces 2020;12:53719–30. https://doi.org/
546–51. https://doi.org/10.1039/TF9444000546. 10.1021/acsami.0c13648.
[181] Lu Z, Li Y, Lei X, Liu J, Sun X. Nanoarray based “superaerophobic” surfaces for gas [204] Shang L, Zhao Y, Kong X-Y, Shi R, Waterhouse GIN, Wen L, et al. Underwater
evolution reaction electrodes. Mater Horiz 2015;2:294–8. https://doi.org/ superaerophobic Ni nanoparticle-decorated nickel–molybdenum nitride nanowire
10.1039/C4MH00208C. arrays for hydrogen evolution in neutral media. Nano Energy 2020;78:105375.
[182] Liu M, Sun Z, Li S, Nie X, Liu Y, Wang E, et al. Hierarchical superhydrophilic/ https://doi.org/10.1016/j.nanoen.2020.105375.
superaerophobic CoMnP/Ni2P nanosheet-based microplate arrays for enhanced [205] Shen J, Li B, Zheng Y, Dai Z, Li J, Bao X, et al. Engineering the composition and
overall water splitting. J Mater Chem 2021;9:22129–39. https://doi.org/ structure of superaerophobic nanosheet array for efficient hydrogen evolution.
10.1039/D1TA04713B. Chem Eng J 2022;433:133517. https://doi.org/10.1016/j.cej.2021.133517.
[183] Shan X, Liu J, Mu H, Xiao Y, Mei B, Liu W, et al. An engineered superhydrophilic/ [206] Hu Q, Wang Z, Huang X, Qin Y, Yang H, Ren X, et al. Integrating well-controlled
superaerophobic electrocatalyst composed of the supported CoMoS x chalcogel for core-shell structures into “superaerophobic” electrodes for water oxidation at
overall water splitting. Angew Chem Int Ed 2020;59:1659–65. https://doi.org/10.1002/ large current densities. Appl Catal B Environ 2021;286:119920. https://doi.org/
anie.201911617. 10.1016/j.apcatb.2021.119920.
[184] Jin J, Xiao T, Luo R, Nie X, Wang Y, Liu Z. Superaerophobic platinum nanosheets [207] Tian Y, Lin Z, Yu J, Zhao S, Liu Q, Liu J, et al. Superaerophobic quaternary
arrays on conductive microgrids: a highly efficient electrocatalytic electrode for Ni–Co–S–P nanoparticles for efficient overall water-splitting. ACS Sustainable
hydrogen evolution reaction. ChemCatChem 2020;12:5062–6. https://doi.org/ Chem Eng 2019;7:14639–46. https://doi.org/10.1021/acssuschemeng.9b02556.
10.1002/cctc.202000979. [208] Tang C, Wang H-F, Zhang Q. Multiscale principles to boost reactivity in gas-
[185] Akbar K, Hussain S, Truong L, Roy SB, Jeon JH, Jerng S-K, et al. Induced involving energy electrocatalysis. Acc Chem Res 2018;51:881–9. https://doi.org/
superaerophobicity onto a non-superaerophobic catalytic surface for enhanced 10.1021/acs.accounts.7b00616.
hydrogen evolution reaction. ACS Appl Mater Interfaces 2017;9:43674–80. [209] Xie Z, Yu S, Yang G, Li K, Ding L, Wang W, et al. Ultrathin platinum nanowire
https://doi.org/10.1021/acsami.7b13918. based electrodes for high-efficiency hydrogen generation in practical electrolyzer
[186] Chen X, Sheng L, Li S, Cui Y, Lin T, Que X, et al. Facile syntheses and in-situ study cells. Chem Eng J 2021;410:128333. https://doi.org/10.1016/j.cej.2020.128333.
on electrocatalytic properties of superaerophobic CoxP-nanoarray in hydrogen [210] Kim YJ, Lim A, Kim JM, Lim D, Chae KH, Cho EN, et al. Highly efficient oxygen
evolution reaction. Chem Eng J 2021;426:131029. https://doi.org/10.1016/j. evolution reaction via facile bubble transport realized by three-dimensionally
cej.2021.131029. stack-printed catalysts. Nat Commun 2020;11:4921. https://doi.org/10.1038/
[187] Zhang L, Huang J, Zheng Q, Li A, Li X, Li J, et al. Superaerophobic” NiCo s41467-020-18686-0.
bimetallic phosphides for highly efficient hydrogen evolution reaction [211] Jensen AW, Sievers GW, Jensen KD, Quinson J, Arminio-Ravelo JA, Brüser V,
electrocatalysts. Chem Commun 2021;57:6173–6. https://doi.org/10.1039/ et al. Self-supported nanostructured iridium-based networks as highly active
D1CC01698A. electrocatalysts for oxygen evolution in acidic media. J Mater Chem 2020;8:
[188] Liu T, Li A, Zhou W, Lyu C. Hierarchical nano/micro/macro-assembled integrated 1066–71. https://doi.org/10.1039/C9TA12796H.
electrode with high-performance water electro-oxidation. Chem Eng J 2021;415: [212] Oh S, Kim H, Kwon Y, Kim M, Cho E, Kwon H. Porous Co–P foam as an efficient
128941. https://doi.org/10.1016/j.cej.2021.128941. bifunctional electrocatalyst for hydrogen and oxygen evolution reactions. J Mater
[189] Li H, Chen S, Zhang Y, Zhang Q, Jia X, Zhang Q, et al. Systematic design of Chem 2016;4:18272–7. https://doi.org/10.1039/C6TA06761A.
superaerophobic nanotube-array electrode comprised of transition-metal sulfides [213] Dutta A, Morstein CE, Rahaman M, Cedeño López A, Broekmann P. Beyond
for overall water splitting. Nat Commun 2018;9:2452. https://doi.org/10.1038/ copper in CO2 electrolysis: effective hydrocarbon production on silver-nanofoam
s41467-018-04888-0. catalysts. ACS Catal 2018;8:8357–68. https://doi.org/10.1021/acscatal.8b01738.
[190] Barati Darband Gh, Aliofkhazraei M, Sabour Rouhaghdam A. Three-dimensional [214] Liu C, Shviro M, Gago AS, Zaccarine SF, Bender G, Gazdzicki P, et al. Exploring
porous Ni-CNT composite nanocones as high performance electrocatalysts for the interface of skin-layered titanium fibers for electrochemical water splitting.
hydrogen evolution reaction. J Electroanal Chem 2018;829:194–207. https://doi. Adv Energy Mater 2021;11:2002926. https://doi.org/10.1002/aenm.202002926.
org/10.1016/j.jelechem.2018.10.012. [215] Kwen J, Doo G, Choi S, Guim H, Yuk S, Lee D-H, et al. Identification of the
[191] Yang Y, Yang P, Zhou L, He R, Hao Y, Wang J, et al. Electrospun IrP2-carbon electrical connection in the catalyst layer of the polymer electrolyte membrane
nanofibers for hydrogen evolution reaction in alkaline medium. Appl Surf Sci water electrolyzer. Int J Hydrogen Energy 2022;47:14017–26. https://doi.org/
2021;565:150461. https://doi.org/10.1016/j.apsusc.2021.150461. 10.1016/j.ijhydene.2022.02.136.
[192] Lu Z-X. Electrochemical fabrication of IrOx nanoarrays with tunable length and [216] Kaya MF, Demir N, Rees NV, El-Kharouf A. Magnetically modified electrocatalysts
morphology for solid polymer electrolyte water electrolysis. Electrochim Acta for oxygen evolution reaction in proton exchange membrane (PEM) water
2020:10. electrolyzers. Int J Hydrogen Energy 2021;46:20825–34. https://doi.org/
[193] Sui C, Chen K, Zhao L, Zhou L, Wang Q-Q. MoS2-modified porous gas diffusion 10.1016/j.ijhydene.2021.03.203.
layer with air–solid–liquid interface for efficient electrocatalytic water splitting. [217] Li Y-H, Chen Y-J. The effect of magnetic field on the dynamics of gas bubbles in
Nanoscale 2018;10:15324–31. https://doi.org/10.1039/C8NR04082F. water electrolysis. Sci Rep 2021;11:9346. https://doi.org/10.1038/s41598-021-
[194] Guo M, Qayum A, Dong S, Jiao X, Chen D, Wang T. In situ conversion of metal 87947-9.
(Ni, Co or Fe) foams into metal sulfide (Ni3S2, Co9S8 or FeS) foams with surface [218] Kaya MF, Demir N, Rees NV, El-Kharouf A. Improving PEM water electrolyser’s
grown N-doped carbon nanotube arrays as efficient superaerophobic performance by magnetic field application. Appl Energy 2020;264:114721.
electrocatalysts for overall water splitting. J Mater Chem 2020;8:9239–47. https://doi.org/10.1016/j.apenergy.2020.114721.
https://doi.org/10.1039/D0TA02337J. [219] Bidin N, Azni SR, Islam S, Abdullah M, Ahmad MFS, Krishnan G, et al. The effect
[195] Cao S, Huang H, Shi K, Wei L, You N, Fan X, et al. Engineering superhydrophilic/ of magnetic and optic field in water electrolysis. Int J Hydrogen Energy 2017;42:
superaerophobic hierarchical structures of Co-CH@NiFe-LDH/NF to boost the 16325–32. https://doi.org/10.1016/j.ijhydene.2017.05.169.
oxygen evolution reaction. Chem Eng J 2021;422:130123. https://doi.org/ [220] Cai J, Wang L, Wu P. Oxygen enrichment from air by using the interception effect
10.1016/j.cej.2021.130123. of gradient magnetic field on oxygen molecules. Phys Lett 2007;362:105–8.
[196] Yu X, Yu Z-Y, Zhang X-L, Zheng Y-R, Duan Y, Gao Q, et al. Superaerophobic” https://doi.org/10.1016/j.physleta.2006.10.004.
nickel phosphide nanoarray catalyst for efficient hydrogen evolution at ultrahigh [221] Ren X, Wu T, Sun Y, Li Y, Xian G, Liu X, et al. Spin-polarized oxygen evolution
current densities. J Am Chem Soc 2019;141:7537–43. https://doi.org/10.1021/ reaction under magnetic field. Nat Commun 2021;12:1–12. https://doi.org/
jacs.9b02527. 10.1038/s41467-021-22865-y.
[197] Feng XJ, Jiang L. Design and creation of superwetting/Antiwetting surfaces. Adv [222] Zhang Y, Liang C, Wu J, Liu H, Zhang B, Jiang Z, et al. Recent advances in
Mater 2006;18:3063–78. https://doi.org/10.1002/adma.200501961. magnetic field-enhanced electrocatalysis. ACS Appl Energy Mater 2020;3:
[198] Liu M, Wang S, Jiang L. Nature-inspired superwettability systems. Nat Rev Mater 10303–16. https://doi.org/10.1021/acsaem.0c02104.
2017;2:1–17. https://doi.org/10.1038/natrevmats.2017.36.
34
[223] Elias L, Chitharanjan Hegde A. Effect of magnetic field on HER of water [247] Wang X-D, Duan Y-Y, Yan W-M, Peng X-F. Local transport phenomena and cell
electrolysis on Ni–W alloy. Electrocatalysis 2017;8:375–82. https://doi.org/ performance of PEM fuel cells with various serpentine flow field designs. J Power
10.1007/s12678-017-0382-x. Sources 2008;175:397–407. https://doi.org/10.1016/j.jpowsour.2007.09.009.
[224] Liu H-B, Zhong D, Han J, Pan L-M, Liu Y. Hydrogen bubble evolution from [248] Yan W-M, Yang C-H, Soong C-Y, Chen F, Mei S-C. Experimental studies on optimal
magnetized nickel wire electrode. Int J Hydrogen Energy 2019;44:31724–30. operating conditions for different flow field designs of PEM fuel cells. J Power
https://doi.org/10.1016/j.ijhydene.2019.10.063. Sources 2006;160:284–92. https://doi.org/10.1016/j.jpowsour.2006.01.031.
[225] Yan J, Wang Y, Zhang Y, Xia S, Yu J, Ding B. Direct magnetic reinforcement of [249] Pan M, Li C, Liao J, Lei H, Pan C, Meng X, et al. Design and modeling of PEM fuel
electrocatalytic ORR/OER with electromagnetic induction of magnetic catalysts. cell based on different flow fields. Energy 2020;207:118331. https://doi.org/
Adv Mater 2021;33:2007525. https://doi.org/10.1002/adma.202007525. 10.1016/j.energy.2020.118331.
[226] Liu Y, Qie Y, Kong F, Yang Z, Yang H. Synthesis and magnetism of single-phase [250] Higier A, Liu H. Optimization of PEM fuel cell flow field via local current density
γ′ -Fe4N by non-ammonia route and applied in oxygen evolution reaction measurement. Int J Hydrogen Energy 2010;35:2144–50. https://doi.org/
electrocatalysis. Mater Today Commun 2022;30:103103. https://doi.org/ 10.1016/j.ijhydene.2009.12.116.
10.1016/j.mtcomm.2021.103103. [251] Roshandel R, Arbabi F, Moghaddam GK. Simulation of an innovative flow-field
[227] Zhou G, Wang P, Li H, Hu B, Sun Y, Huang R, et al. Spin-state reconfiguration design based on a bio inspired pattern for PEM fuel cells. Renew Energy 2012;41:
induced by alternating magnetic field for efficient oxygen evolution reaction. Nat 86–95. https://doi.org/10.1016/j.renene.2011.10.008.
Commun 2021;12:4827. https://doi.org/10.1038/s41467-021-25095-4. [252] Wang Y, Yue L, Wang S. New design of a cathode flow-field with a sub-channel to
[228] Kim PJ, Lee C, Lee JK, Fahy KF, Bazylak A. In-plane transport in water improve the polymer electrolyte membrane fuel cell performance. J Power
electrolyzer porous transport layers with through pores. J Electrochem Soc 2020; Sources 2017;344:32–8. https://doi.org/10.1016/j.jpowsour.2017.01.075.
167:124522. https://doi.org/10.1149/1945-7111/abb173. [253] Chowdhury MZ, Akansu YE. Novel convergent-divergent serpentine flow fields
[229] Mo J, Kang Z, Yang G, Retterer ST, Cullen DA, Toops TJ, et al. Thin liquid/gas effect on PEM fuel cell performance. Int J Hydrogen Energy 2017;42:25686–94.
diffusion layers for high-efficiency hydrogen production from water splitting. https://doi.org/10.1016/j.ijhydene.2017.04.079.
Appl Energy 2016;177:817–22. https://doi.org/10.1016/j. [254] Chisholm G, Kitson PJ, Kirkaldy ND, Bloor LG, Cronin L. 3D printed flow plates
apenergy.2016.05.154. for the electrolysis of water: an economic and adaptable approach to device
[230] Kang Z, Mo J, Yang G, Retterer ST, Cullen DA, Toops TJ, et al. Investigation of manufacture. Energy Environ Sci 2014;7:3026–32. https://doi.org/10.1039/
thin/well-tunable liquid/gas diffusion layers exhibiting superior multifunctional C4EE01426J.
performance in low-temperature electrolytic water splitting. Energy Environ Sci [255] Olesen AC, Frensch SH, Kær SK. Towards uniformly distributed heat, mass and
2017;10:166–75. https://doi.org/10.1039/C6EE02368A. charge: a flow field design study for high pressure and high current density
[231] Steen SM, Mo J, Kang Z, Yang G, Zhang F-Y. Investigation of titanium liquid/gas operation of PEM electrolysis cells. Electrochim Acta 2019;293:476–95. https://
diffusion layers in proton exchange membrane electrolyzer cells. Int J Green doi.org/10.1016/j.electacta.2018.10.008.
Energy 2017;14:162–70. https://doi.org/10.1080/15435075.2016.1253582. [256] Nie J, Chen Y, Cohen S, Carter BD, Boehm RF. Numerical and experimental study
[232] Lee JK, Lee C, Fahy KF, Kim PJ, LaManna JM, Baltic E, et al. Spatially graded of three-dimensional fluid flow in the bipolar plate of a PEM electrolysis cell. Int J
porous transport layers for gas evolving electrochemical energy conversion: high Therm Sci 2009;48:1914–22. https://doi.org/10.1016/j.
performance polymer electrolyte membrane electrolyzers. Energy Convers Manag ijthermalsci.2009.02.017.
2020;226:113545. https://doi.org/10.1016/j.enconman.2020.113545. [257] Li H, Nakajima H, Inada A, Ito K. Effect of flow-field pattern and flow
[233] Schuler T, Ciccone JM, Krentscher B, Marone F, Peter C, Schmidt TJ, et al. configuration on the performance of a polymer-electrolyte-membrane water
Hierarchically structured porous transport layers for polymer electrolyte water electrolyzer at high temperature. Int J Hydrogen Energy 2018;43:8600–10.
electrolysis. Adv Energy Mater 2020;10:1903216. https://doi.org/10.1002/ https://doi.org/10.1016/j.ijhydene.2018.02.171.
aenm.201903216. [258] Lin R, Lu Y, Xu J, Huo J, Cai X. Investigation on performance of proton exchange
[234] Lettenmeier P, Kolb S, Sata N, Fallisch A, Zielke L, Thiele S, et al. Comprehensive membrane electrolyzer with different flow field structures. Appl Energy 2022;
investigation of novel pore-graded gas diffusion layers for high-performance and 326:120011. https://doi.org/10.1016/j.apenergy.2022.120011.
cost-effective proton exchange membrane electrolyzers. Energy Environ Sci 2017; [259] Martin A, Trinke P, Pham CV, Bühler M, Bierling M, Holzapfel PKR, et al. On the
10:2521–33. https://doi.org/10.1039/C7EE01240C. correlation between the oxygen in hydrogen content and the catalytic activity of
[235] Lee JK, Lee Ch, Bazylak A. Pore network modelling to enhance liquid water cathode catalysts in PEM water electrolysis. J Electrochem Soc 2021. https://doi.
transport through porous transport layers for polymer electrolyte membrane org/10.1149/1945-7111/ac38f6.
electrolyzers. J Power Sources 2019;437:226910. https://doi.org/10.1016/j. [260] Holzapfel PKR, Bühler M, Escalera-López D, Bierling M, Speck FD, Mayrhofer KJJ,
jpowsour.2019.226910. et al. Fabrication of a robust PEM water electrolyzer based on non-noble metal
[236] Kang Z, Yu S, Yang G, Li Y, Bender G, Pivovar BS, et al. Performance improvement cathode catalyst: [Mo3S13]2− clusters anchored to N-doped carbon nanotubes.
of proton exchange membrane electrolyzer cells by introducing in-plane transport Small 2020;16:2003161. https://doi.org/10.1002/smll.202003161.
enhancement layers. Electrochim Acta 2019;316:43–51. https://doi.org/ [261] Mo J, Dehoff RR, Peter WH, Toops TJ, Green JB, Zhang F-Y. Additive
10.1016/j.electacta.2019.05.096. manufacturing of liquid/gas diffusion layers for low-cost and high-efficiency
[237] Kim PJ, Lee JK, Lee Ch, Fahy KF, Shrestha P, Krause K, et al. Tailoring catalyst hydrogen production. Int J Hydrogen Energy 2016;41:3128–35. https://doi.org/
layer interface with titanium mesh porous transport layers. Electrochim Acta 10.1016/j.ijhydene.2015.12.111.
2021;373:137879. https://doi.org/10.1016/j.electacta.2021.137879. [262] Majasan JO, Cho JIS, Maier M, Dedigama I, Shearing PR, Brett DJL. Effect of
[238] Lettenmeier P, Kolb S, Burggraf F, Gago AS, Friedrich KA. Towards developing a anode flow channel depth on the performance of polymer electrolyte membrane
backing layer for proton exchange membrane electrolyzers. J Power Sources water electrolyser. ECS Trans 2018;85:1593–603. https://doi.org/10.1149/
2016;311:153–8. https://doi.org/10.1016/j.jpowsour.2016.01.100. 08513.1593ecst.
[239] Wang Y, Liu T, He W, Wang S, Liu S, Yue L, et al. Performance enhancement of [263] Upadhyay M, Lee S, Jung S, Choi Y, Moon S, Lim H. Systematic assessment of the
polymer electrolyte membrane fuel cells with a hybrid wettability gas diffusion anode flow field hydrodynamics in a new circular PEM water electrolyser. Int J
layer. Energy Convers Manag 2020;223:113297. https://doi.org/10.1016/j. Hydrogen Energy 2020;45:20765–75. https://doi.org/10.1016/j.
enconman.2020.113297. ijhydene.2020.05.164.
[240] Niu Z, Bao Z, Wu J, Wang Y, Jiao K. Two-phase flow in the mixed-wettability gas [264] Olesen AC, Rømer C, Kær SK. A numerical study of the gas-liquid, two-phase flow
diffusion layer of proton exchange membrane fuel cells. Appl Energy 2018;232: maldistribution in the anode of a high pressure PEM water electrolysis cell. Int J
443–50. https://doi.org/10.1016/j.apenergy.2018.09.209. Hydrogen Energy 2016;41:52–68. https://doi.org/10.1016/j.
[241] Jiao K, Zhou B. Effects of electrode wettabilities on liquid water behaviours in ijhydene.2015.09.140.
PEM fuel cell cathode. J Power Sources 2008;175:106–19. https://doi.org/ [265] Wu L, An L, Jiao D, Xu Y, Zhang G, Jiao K. Enhanced oxygen discharge with
10.1016/j.jpowsour.2007.09.048. structured mesh channel in proton exchange membrane electrolysis cell. Appl
[242] Li H, Fujigaya T, Nakajima H, Inada A, Ito K. Optimum structural properties for an Energy 2022;323:119651. https://doi.org/10.1016/j.apenergy.2022.119651.
anode current collector used in a polymer electrolyte membrane water [266] Yang G, Xie Z, Yu S, Li K, Li Y, Ding L, et al. All-in-one bipolar electrode: a new
electrolyzer operated at the boiling point of water. J Power Sources 2016;332: concept for compact and efficient water electrolyzers. Nano Energy 2021;90:
16–23. https://doi.org/10.1016/j.jpowsour.2016.09.086. 106551. https://doi.org/10.1016/j.nanoen.2021.106551.
[243] Zhao B, Lee C, Lee JK, Fahy KF, LaManna JM, Baltic E, et al. Superhydrophilic [267] Sakuma G, Fukunaka Y, Matsushima H. Nucleation and growth of electrolytic gas
porous transport layer enhances efficiency of polymer electrolyte membrane bubbles under microgravity. Int J Hydrogen Energy 2014;39:7638–45. https://
electrolyzers. Cell Rep Phys Sci 2021;2:100580. https://doi.org/10.1016/j. doi.org/10.1016/j.ijhydene.2014.03.059.
xcrp.2021.100580. [268] Li S-D, Wang C-C, Chen C-Y. Water electrolysis in the presence of an ultrasonic
[244] Lim A, Jeong H-Y, Lim Y, Kim JY, Park HY, Jang JH, et al. Amphiphilic Ti porous field. Electrochim Acta 2009;54:3877–83. https://doi.org/10.1016/j.
transport layer for highly effective PEM unitized regenerative fuel cells. Sci Adv electacta.2009.01.087.
2021;7:eabf7866. https://doi.org/10.1126/sciadv.abf7866. [269] Bakker MM, Vermaas DA. Gas bubble removal in alkaline water electrolysis with
[245] Azarafza A, Ismail MS, Rezakazemi M, Pourkashanian M. Comparative study of utilization of pressure swings. Electrochim Acta 2019;319:148–57. https://doi.
conventional and unconventional designs of cathode flow fields in PEM fuel cell. org/10.1016/j.electacta.2019.06.049.
Renew Sustain Energy Rev 2019;116:109420. https://doi.org/10.1016/j. [270] Demir N, Kaya MF, Albawabiji MS. Effect of pulse potential on alkaline water
rser.2019.109420. electrolysis performance. Int J Hydrogen Energy 2018;43:17013–20. https://doi.
[246] Li X, Sabir I. Review of bipolar plates in PEM fuel cells: flow-field designs. Int J org/10.1016/j.ijhydene.2018.07.105.
Hydrogen Energy 2005;30:359–71. https://doi.org/10.1016/j. [271] Liu Y, Pan L, Liu H, Chen T, Yin S, Liu M. Effects of magnetic field on water
ijhydene.2004.09.019. electrolysis using foam electrodes. Int J Hydrogen Energy 2019;44:1352–8.
https://doi.org/10.1016/j.ijhydene.2018.11.103.
35
[272] Hunt C, Zhang Z, Ocean K, Jansonius RP, Abbas M, Dvorak DJ, et al. Xiyang Cai earned his Bachelor’s degree in Alternative Energy
Quantification of the effect of an external magnetic field on water oxidation with Science and Engineering from Shanghai Jiao Tong University
cobalt oxide anodes. J Am Chem Soc 2022;144:733–9. https://doi.org/10.1021/ in 2018. Currently, he is pursuing his PhD degree in the Insti
jacs.1c08759. tute of Fuel Cell of the same University under the supervision of
[273] Wang K, Liao C, Wang W, Xiao Y, Liu X, Zuo Y. Removal of gas bubbles on an Professor Junliang Zhang. His research mainly focuses on
electrode using a magnet. ACS Appl Energy Mater 2020;3:6752–7. https://doi. ammonia synthesis by electrochemical nitrogen reduction re
org/10.1021/acsaem.0c00890. action and nitrate reduction reaction.
[274] Kaya MF, Demir N, Albawabiji MS, Taş M. Investigation of alkaline water
electrolysis performance for different cost effective electrodes under magnetic
field. Int J Hydrogen Energy 2017;42:17583–92. https://doi.org/10.1016/j.
ijhydene.2017.02.039.
[275] Garcés-Pineda FA, Blasco-Ahicart M, Nieto-Castro D, López N, Galán-
Mascarós JR. Direct magnetic enhancement of electrocatalytic water oxidation in
alkaline media. Nat Energy 2019;4:519–25. https://doi.org/10.1038/s41560-
019-0404-4.
[276] Wang M, Wang Z, Guo Z. Water electrolysis enhanced by super gravity field for
hydrogen production. Int J Hydrogen Energy 2010;35:3198–205. https://doi.org/ Lu An received her Bachelor’s degree from Central South
10.1016/j.ijhydene.2010.01.128. University, in 2018. She is currently pursuing her PhD degree
[277] Li K, Yu S, Li D, Ding L, Wang W, Xie Z, et al. Engineered thin diffusion layers for under the supervision of Prof. Junliang Zhang at Shanghai Jiao
anion-exchange membrane electrolyzer cells with outstanding performance. ACS Tong University. Her present study focuses on oxygen evolu
Appl Mater Interfaces 2021;13:50957–64. https://doi.org/10.1021/ tion reaction under acidic environment for energy storage and
acsami.1c14693. conversion technology.
[278] Márquez RA, Kawashima K, Son YJ, Rose R, Smith LA, Miller N, et al. Tailoring
3D-printed electrodes for enhanced water splitting. ACS Appl Mater Interfaces
2022;14:42153–70. https://doi.org/10.1021/acsami.2c12579.
[279] Wan L, Liu J, Xu Z, Xu Q, Pang M, Wang P, et al. Construction of integrated
electrodes with transport highways for pure-water-fed anion exchange membrane
water electrolysis. Small 2022;18:2200380. https://doi.org/10.1002/
smll.202200380.
[280] Razmjooei F, Morawietz T, Taghizadeh E, Hadjixenophontos E, Mues L, Gerle M,
et al. Increasing the performance of an anion-exchange membrane electrolyzer
operating in pure water with a nickel-based microporous layer. Joule 2021;5:
1776–99. https://doi.org/10.1016/j.joule.2021.05.006. Shuiyun Shen is an Associate Professor of Institute of Fuel
[281] Faber MS, Dziedzic R, Lukowski MA, Kaiser NS, Ding Q, Jin S. High-performance Cells, School of Mechanical Engineering, Shanghai Jiao Tong
electrocatalysis using metallic cobalt pyrite (CoS2) micro- and nanostructures. University. She received her Bachelor and Master degree both
J Am Chem Soc 2014;136:10053–61. https://doi.org/10.1021/ja504099w. from Harbin Institute of Technology and Ph.D. degree from the
Hong Kong University of Science and Technology. She has ever
worked as a postdoctor in the Hong Kong University of Science
Shu Yuan received his Master’s degree from the University and Technology. Her key expertise is in electrochemistry,
College London, in 2019. He is currently pursuing his PhD electrocatalysis and fuel cells. She has published over 100 peer-
degree under the supervision of Prof. Xiaohui Yan at Shanghai reviewed journal articles on electrochemical energy conversion
Jiao Tong University. His current research focuses on the and storage, which have been cited for more than 1800 times so
mechanism of mass transport and the electrode design in far. She co-authored two books and co-invented 20 plus pat
polymer electrolyte membrane water electrolyzer and anion ents. She won the first prize of Shanghai Technology Invention
exchange membrane water electrolyzer. Award in 2020, ranked second.
Xiaohui Yan is an associate professor at the Department of

Mechanical Engineering, Shanghai Jiao Tong University. He
earned his Bachelor’s degree in Energy and Power Engineering
at Xiꞌan Jiaotong University in 2012 and PhD degree in Me
chanical Engineering at Hong Kong University of Science and
Technology in 2016. His research interests focus on the trans
Congfan Zhao received his Bachelor’s degree from Southeast port phenomena in PEM fuel cells and PEM water electrolysis
University, in 2021. He is currently pursuing his PhD degree cells. He has published over 80 peer-reviewed papers in fuel
under the supervision of Prof. Xiaohui Yan at Shanghai Jiao cells and water electrolysis. He won the first prize of Shanghai
Tong University. His present study focuses on the mechanism Technology Invention Award and Outstanding Teaching Award
of mass transfer and the design of reaction devices for energy of SJTU.
storage and conversion technology.
Junliang Zhang is Chair Professor, Director of Institute of Fuel

Cells, Executive Deputy Dean of Zhiyuan College at Shanghai
Jiao Tong University (SJTU). He received his BS and MS from
SJTU in 1994 and 1997, respectively, and his PhD from State
University of New York at Stony Brook in 2005. He then
worked as a Research Associate till 2007 at Brookhaven Na
tional Laboratory. From 2007 to 2011, Dr. Zhang worked at
General Motors Global Research & Development, Electro
chemical Energy Research Laboratory, as a Research Scientist
and later a Senior Scientist and Team Leader. In 2011, he
joined the Institute of Fuel Cells at SJTU.
36

Bubble Evolution and Transport in PEM Water Electrolysis Mechanism

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Bubble Evolution and Transport in PEM Water Electrolysis Mechanism

Uploaded by

Copyright:

Available Formats

Progress in Energy and Combustion Science 96 (2023) 101075

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

Bubble evolution and transport in PEM water electrolysis: Mechanism,

Fig. 3. (a) A hydrogen bubble nucleate and grow

concentration near the catalytic surface Cgas [51]. Cb can be calculated ( )1

Fig. 6. Overview of the bubble transport process in PEMWE (anode side).

Xiaohui Yan is an associate professor at the Department of

Junliang Zhang is Chair Professor, Director of Institute of Fuel

You might also like