Chemical Engineering Journal 444 (2022) 136533

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

Recent advance in physical description and material development for single

component SOFC: A mini-review
Taimoor Raza a, 1, Jingjing Yang a, 1, Ruoming Wang a, Chen Xia b, Rizwan Raza c, Bin Zhu d,
Sining Yun a, e, *
a
Functional Materials Laboratory (FML), School of Materials Science and Engineering, Xi’an University of Architecture and Technology, Xi’an, Shaanxi 710055, China
b
Faculty of Physics and Electronic Science, Hubei University, Wuhan 430062, China
c
Clean Energy Research Lab, Department of Physics, COMSATS University Islamabad, Lahore Campus, 54000, Pakistan
d
Jiangsu Provincial Key Laboratory of Solar Energy Science and Technology/Energy Storage Joint Research Center, School of Energy and Environment, Southeast
University, Nanjing 210096, China
e
Qinghai Building and Materials Research Academy Co., Ltd, The Key Lab of Plateau Building and Eco-community in Qinghai, Xining 810000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Despite the high capabilities to replace combustion systems and produce sustainable energy, solid oxide fuel cells
SOFC (SOFCs) still have not yet been successfully commercialized. In this context, single component SOFC has been
Single component developed as a new oriented fuel cell R&D strategy in the past decades, providing great promise to commer­
Semiconductor-ionic hetero-structure
cialization. This paper presents a mini review on recent studies with respect to the development of the state-of-
Schottky-junction
the-art single component SOFC to overcome the constraints of high operating temperatures. Different from
P-n junction, built-in electric field, dual ions
conduction conventional three-component SOFC, the single component SOFC is featured of containing a homogeneous layer
with hybrid dual ions (O2–/H+) conduction based on semiconductor-ion hetero-structure materials. The Schottky
or p-n junction built-in electric field evidence the cell operation even at low-temperature up to (300–600 ◦ C),
which brings a new overwhelming framework for research and development of fuel cell. The functionality of the
single component is principally determined by the interface kinetics, which has dimensions of super-fast (hybrid)
ionic transport. Therefore, innovative design of semiconducting-ionic materials is systematically reviewed in
terms of inter-facial properties/mechanisms, and transition from non-functional to functional materials with
potential of dual ions conduction. Further, it is followed by weighted the potential of this new device as
compared with conventional SOFCs. Finally, the future framework, advancement, and bright perspectives of this
innovative device have been discussed.

emission, quietness, and fuels flexibility [18–25]. These advantages of

1. Introduction
In the past two decades, energy crisis and environmental pollution
increase the global warming through the emission of greenhouse gas,
leading to consequential climate change [1–5]. Fossil fuels are currently
the major part of energy demand, but the release of CO, CO2, SO2, and
many other toxic substances from fossil fuel seriously contaminate the
environment [6–11]. In addition, the fuel utilization of these fossil fuels
is depleting fast. Therefore, world is moving towards renewable energy
sources as a substitute to fossil fuels [12–17]. Fuel cells are one of the
most attractive renewable energy technologies that can directly convert
chemical energy from fuel into electricity with high efficiency, low
fuel cells make them one of the most effective devices to alleviate the
environmental pollution [26–30]. Fuel cells are categorized into five
kinds, but our motivation is towards the solid oxide fuel cell (SOFC). The
solid state of materials, high current and power density, higher effi­
ciency involving combined heat and power application, the SOFC is
widely regarded as the most capable in both stationary and trans­
portation applications [31–34].
However, currently the high operating temperatures of SOFCs (up to
700–750 ◦ C) brings technological complexities and creates hurdle for
the full use of such technology [35–37]. This is due to the fact that the
common SOFC electrolyte, yttria-stabilized zirconia (YSZ) always re­
quires high temperatures to motivate its ionic transport to a sufficiently

* Corresponding author.
E-mail addresses: alexsyun1974@aliyun.com, yunsining@xauat.edu.cn (S. Yun).
1
These authors contributed equally.

https://doi.org/10.1016/j.cej.2022.136533
Received 14 January 2022; Received in revised form 6 April 2022; Accepted 19 April 2022
Available online 22 April 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

Nomenclature LNSDC Sm0.2Ce0.8O2-(Li/Na)2CO3

MZSDC Mg0.4Zn0.6O/Ce0.8Sm0.2O2− δ
Acronyms & Abbreviation NCAL Ni0.8Co0.15Al0.05LiO2− δ
BSCF Ba0.5Sr0.5Co0.8Fe0.2O3-δ NSDC SDC Composited with Na2CO3
BHJ Bulk heterojunction ORR Oxygen reduction reaction
BSFSb Ba0.5Sr0.5Fe0.8Sb0.2O3-δ PECs Photo electrochemical Cells
BZSY BaZr0.7Sm0.1Y0.2O3− δ PSCFN Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3− δ
EFFCs Electrolyte-layer free fuel cells PEMFC proton exchange membrane fuel cell
GDC Gadolinium doped Ceria PFC Photocatalytic fuel cell
HOR Hydrogen Oxidation reaction SDC Samarium doped Ceria
LNCA LiNi0.8Co0.15Al0.05O2 SDC-NC Sm0.2Ce0.8O1.9-Na2CO3
LSCF La0.6Sr0.4Co0.2Fe0.8O3-δ SFM Sr2Fe4/3Mo2/3O6
LCN Co/Li co-doped NiO SOFCs Solid Oxide fuel cells
LCP Lanthanum and praseodymium doped ceria SCDC Sm/Ca Co-doped Ceria
LNCS Li0.3Ni0.6Cu0.07Sr0.03O2-δ YSZ Yttria-Stabilized Zirconia

high ionic conductivity [38–40]. The high temperature operations of
SOFC is a barrier to its commercialization as efficient energy-conversion
devices. Large internal-strain gradients caused by a mismatch in thermal
expansion behavior between different fuel cell components are the pri­
mary cause of this instability, which can result in cell degradation,
delamination, or fracture [41,42]. In this regard, a lot of researches have
focused on the development of ultra-thin film electrolytes based on YSZ
to reduce ohmic loss of the devices, which can ensure high power output
at lower temperatures. Another approach to address this challenge is to
develop new advanced electrolyte medium with high ionic conductiv­
ities at 300–600 ◦ C, for examples, Sm-doped ceria (SDC) and Gd-doped
ceria (GDC) can lower the operating temperatures of SOFCs [43–46].
However, a drop in temperature always results in significant power
output losses. It can create large interfacial resistance and reaction ki­
netics losses between the electrolyte and electrodes of the fuel cell
[47–49]. Until now, the commercialization of YSZ electrolytes in SOFCs
has been hampered by the high costs associated with use of advanced
and ultra-high thin films technology to reduce resistance, while doped-
ceria has a disadvantage in that it is easily reduced in H2 atmosphere,
this poses a short circuit risk to the entire cell [50–52].
Nonstoichiometric oxide catalyst for oxygen reduction reaction
(ORR) and oxygen evolution reaction (OER) in Low Temperature Fuel
cells (LTFCs) includes simple oxide, perovskite, layered perovskite, and
pyrochlore. The development of even more active and stable oxygen
catalysts is critical for large-scale commercialization [53,54]. In addi­
tion, single and double phase semiconductor can develop hetero-
junctions. This present modern trend towards development of electro­
chemical devices [55–61]. The emerging challenge for manufacturers of
energy conversion devices, such as batteries, photo electrochemical cells
(PECs), and fuel cells, is to ensure stable hetero-interfaces [62–66].
Moreover, a revitalization interests towards multi-cation oxide hetero-
structure are found to display an emergent electronic and super ionic
conducting behavior, i.e., La/SrTiO3 epitaxial hetero-structure inclines
to display strongly enhanced ionic conductivity that make them highly
promising electrolyte materials in fuel cells [67].
In order to have high power output at low operating temperature of
SOFC, Zhu et al., [68] proposed an improved version type of SOFC,
single component fuel cell, which is composed of a homogenous layer
made of electrolyte and electrode materials. It was highlighted by Na­
ture Nanotechnology as “three in one” fuel cells. The invented feature of
single component integrates the functionalities of anode, electrolyte,
and cathode simultaneously into one component. A single component
SOFC can realize the same electrochemical reactions (hydrogen oxida­
tion–oxygen reduction) [69,70]. In a conventional membrane electrode
assembly, the electrolyte layer is sandwiched between the anode and the
cathode, as shown in Fig. 1a, the electrolyte plays a key role in con­
ducting ions and preventing electrons from crossing over the cell
[52,71]. However, single component SOFC as shown in Fig. 1b is
significantly different as compared with the conventional three-layer
structure of SOFC [72].
The materials used in single component SOFC are primarily semi­
conductors and electronic/ionic conducting materials, which include
not only the existing SOFC electrolyte and electrode, but also more
semiconductors and hetero-structured composites than traditional
SOFCs [69,73,74]. The key understanding on the single component
SOFCs is that a homogenous layer of a semiconductor hetero-structure
can realize the charge separation (electrons and ions) to avoid internal
short circuiting. To explain the underlying mechanisms, some physical
models are introduced on the basis of semiconductor properties in terms
of multi junction effects at particle level. The development of these

Fig. 1. (a) Three layer conventional fuel cell consists of cathode, anode, and electrolyte for ionic transportation [75], (b) Novel structure of single component SOFC
consisting of single layer and Schottky-junction to separate charge distribution [72].

2
T. Raza et al.
junctions in single component SOFC will be reviewed in later section in
details.
2. Physical description for single component SOFC
In 2011, Zhu et al., [70] invented the first single component SOFC,
which was built by using an individual layer consisting of semiconductor
and ionic conductor with mixed conductivity, rather than using three
layers. It is worth noting that the overall reaction of single component
SOFC is the same as traditional SOFC, i.e. H2 is being oxidized and
electrons are discharged at fuel side (anode) and oxygen is reduced to
O2− at the air side (cathode). When ions passing through the electrolyte
layer, the anode-produced electrons transport in external circuit to
produce electricity. The fuel cell reactions in single component SOFC
can be explained as reaction at hydrogen-fueling side: [76].
H2 →2H+ + 2e− (1)
Reaction at air side:
1/2O2 + 2e− →O2− (2)
Generally, a single layer can conduct hybrid protons and oxide ions,
resulting in the generation of water on both the anode and cathode sides.
Thus, the total electrochemical reaction is:
H2 + 1/2O2 →H2 O + electricity + heat (3)
Note that H2 is catalyzed to lose electrons to form H and O2 is
+ different properties involved in hetero-junctions [37,86]. It is quite
catalyzed to gain electrons to form O2– at their respective contacting
sides in a single component SOFC. To further improve the catalytic
performance of single component SOFC, Ni0.8Co0.15Al0.05LiO2− δ (NCAL)
catalyst has been used on both single component sides. It can still be
called a single component SOFC, which is due to the bi-catalyst function
and hybrid H+/O2– conduction of the single component that always
made by electrode and electrolyte materials. In conventional SOFC, the
only one process of H+ or O2– is formed at the anode or cathode side,
which is defined by either a proton or oxygen ion conducting electrolyte
that conducts individual H+ or O2–, respectively [12,77]. A critical
fundamental issue of single component SOFC is the electronic short-
circuiting problem and current pathway. To interpret the working
principle of the single component SOFC, different mechanisms have
been proposed. Firstly, it was explained based on the similarities with
solar cells, that a p-n bulk-hetero-junction effect and nano redox process
play the major roles in the charge separation and phase separations
(conductions/phases) for the electrons and ions. Later, Schottky-
junction and energy band alignment were employed to further
describe the underlying mechanisms, which are discussed in details in
next sections.
2.1. Charge separation in single component SOFC
In single component SOFC, the single component layer with multi-
function of electrodes and electrolyte always consists of semi­
conductor materials in a hetero-structure composite form. When the
single component layer is placed in fuel cell operating atmosphere, the
anodic part closer to reducing atmosphere tends to be n type and the
cathodic part tends to be p type or maintain its original conduction type
[78]. In this way, the diffusion and drift of electrons and holes at p-n
interfaces will establish a space charge region until the condition of
thermal equilibrium is reached [79,80]. The energy bands at the in­
terfaces can bend upward or downward to form p-n junction, commonly
known as band bending, which can be the local change in energy band
offset [81]. In fact, the high performance of single-component SOFC is
majorly based on the high ionic conductivity and dual Hydrogen
Oxidation reaction (HOR) and ORR catalytic function of the single
component layer made of composite materials, by virtue of the hetero-
interface superionic conduction and catalytic effect of these composite
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Chemical Engineering Journal 444 (2022) 136533
materials. In the meanwhile, the Schottky-junction and p-n junction
effects play a supporting role to block or suppress the electronic con­
duction to avoid short circuiting by the Schottky barrier heights and p-n
interface space charge region, in which the ionic transport is very likely
promoted. The space charge region can be established by the imbalance
in charge neutrality of the two semiconductors materials. Practically,
the charge imbalance can be caused by different reasons, i.e., at p-n
junction the bands fluctuate continuously as the dopants are distributed,
which perturb the system, resulting in sharp shifts in band energies at
the interface, and thus force the band offsets to bend. If the junction is
between the semiconductor–metal, the bands of the semiconductor can
be pinned within the Fermi level of metal. The amount of space charge
region/built-in field/junction barrier is determined by the carrier con­
centration and Fermi levels of the semiconductors. Usually, it is viewed
that in p-n junction, the built-in field direction points from n-type ma­
terials to p-type materials, showing higher barrier at p-type side
[82–85].
On the other hand, energy band alignments are also considered. The
transport behavior of charge separation of such device is strictly con­
nected to the energy band arrangement of materials, which has to follow
the principle of solid state physics. In multi-junction semiconductor
devices such as solar cells, PECs, and lithium ion batteries (LIBs), the
energy band diagram is widely considered to investigate the charge
transport of electrons and holes. Mostly, there are discontinuities in the
conduction and valence bands. Such discontinuities are the origin to
usual to estimate energy band alignment using work functions ϕ and
electron affinities χ . The vacuum level is then used to determine the
barrier heights at the interfaces. At a semiconductor/metal interface, the
Schottky barrier heights for electrons ΦB,n and holes ΦB,p are given by:
[87].
ΦB,n = ϕm − χ sc = Δχ (4)
ΦB,p = IP,sc − ϕm = ΔIP (5)
Where IP denotes the semiconductor’s ionization potential and m and
sc denote the metal and semiconductor, respectively. At semiconductor/
semiconductor interface, the valence band and conduction band dis­
continuities are given by:
ΔECB = χ 2 − χ 1 = Δχ (6)
ΔEVB = IP,2 − IP,1 = ΔIP (7)
Noted that the band alignment is determined by the electron affinity
and the ionization potential. In both circumstances, any change in
semiconductor doping affects the built-in potential or band bending
(qVd), but not the barrier heights.
The electronegativity X and the work function ϕ are inextricably
linked. Considerable agreement can be established using Pauling’s or
Miedema’s electronegativity,
ϕm ≈ 1.79⋅Xm, + 1.11eV (8)
Pauling
ϕm ≈ 0.86⋅Xm, + 0.59eV (9)
Miedema
The semiconductor hetero-structures play a key role to identify
intrinsically aligning of the energy bands. Chemical reactivity at in­
terfaces and defect formation, as discussed in sections 2.2, 2.3, and 2.4,
can cause significant variations in barrier height.
2.2. Schottky-junction
The Schottky-junction is the simplest fuel cell technology, with low-
cost components and a simple fabrication that only requires one type of
composite building (p or n) semiconducting–ionic material. The
Schottky-junction fuel cell is also a novel advanced technology that
effectively combines physical and electrochemical processes to create
T. Raza et al.
great performance of fuel cells [88]. Schottky-junction effect was
introduced to separate the charge transportation in the cell. The
Schottky-junction is developed by the configuration of metal with n-type
semiconductor materials or p-type semiconductor materials. The
Schottky-junction generates a potential, called Schottky barrier at the
interface, which is used as a separator between electrons and ions.
Generally, p-type Schottky-junction is preferred because the field
generated in such junction is directed in the same plane, which provides
driving force for the ionic conduction. By creating metal–semiconductor
interface (Schottky-type) junction, a Schottky barrier can be formed
between the reduced metal and p-type semiconductor regime [12],
where electrons become localized and Schottky barrier can resist these
electrons to flow internally, different types of Schottky-junction devices,
such as solar cells and sensors, have been developed using this idea and
the depletion layer is generated between the metal and the semi­
conductor. Schottky-junction has a well-known function of separating
electron/hole pairs by increasing internal device voltage. In the
Schottky-junction fuel cell, a driving force is provided by a chemical
potential difference created across the device when H2 and air are given
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Chemical Engineering Journal 444 (2022) 136533
to opposite sides, allowing ions (H+ and O2–) to be transported. The
latter procedure is critical in preventing electrons from travelling
through the device internally, typical example can be seen in Fig. 2a, in
which Schottky-junction device was successfully developed by making a
composite of hybrid O2–/H+ conducting material Ce0.8Sm0.2O1.9-
Na2CO3 (NSDC) and a p-type semiconductor Co/Li co-doped NiO. The
cell showed excellent power output up to 1000 mW/cm2 at 550 ◦ C [89].
Deng et al., [90] synthesized a single component SOFC by a composite
layer of perovskite Sr2Fe1.5Mo0.5O6-δ (SFM) and Ce0.8Sm0.2O2-δ (SDC).
The cell achieved the power output about 841 mW/cm2 at 550 ◦ C.
2.3. p-n hetero-structure junctions
Singh et al., [78] proposed a new way of thinking about SOFCs in
which the anode, electrolyte, and cathode are interpreted as n-type,
ionic, and p-type zones, respectively. When the middle electrolyte layer
of a conventional SOFC (ionic zone) is removed, the device is trans­
formed into a two-component (layer) device with n-(anode) and p-
(cathode)-type conduction, also known as a p-n junction device. Due to
Fig. 2. (a) Schottky-junction in fuel cell mode [89],
(b) Principle of p–n hetero-junction for single
component SOFC [93], (c) Built-in electric field using
semiconductor-ionic hetero-structure materials and
mechanism of energy band alignment involved in
charge separation and ionic transportation [96], (d)
Hetero-junction structure used to separate electron/
hole transportation in solar cells, (e) Prevention of
short circuiting in fuel cell mechanism by forming
Bulk heterojunction followed by p–n junction at de­
vice level [97].
T. Raza et al.
the charge separation function of the p-n junction, which is the same as
the principle of a p-n solar cell, the risk of electronic short-circuiting can
be avoided. This shows that a physically separated electrolyte layer may
not be required for a SOFC to function. A single-component device based
on p-n junction semiconductors was reported by Zhu et al., [68], in
which NiOx and ZnO created a homogenous nanocomposite to provide
the essential electrochemical reaction sites and charge transport routes
for a fuel cell. In another work, a hetero-structure composite of
LiNiCuZn-oxide and (Na/K)2CO3-SDC was fabricated. The fuel cell
achieved a high power density of greater than 600 mW/cm2 at 550 ◦ C,
along with open-circuit voltage (OCV) over 1.0 V. It was explained that
the p-n hetero-junction formed between p-type NiO and n-type ZnO,
leading to the depletion of electrons and holes, creating a space charge
region for blocking the electron to across from n-type semiconductor
materials side to p-type semiconductor materials side [76]. In this way,
the cell potential is guaranteed and electrical energy can be taken out of
the device. Afterwards, a series of analogous semiconductor-ion hetero-
structure materials were developed for single component SOFC, which
promoted the cell power density to below 600 ◦ C [91,92]. To describe
the cell’s working mechanism, energy band theory was used to infer that
during cell operation, internally p-n junctions were formed in the
hetero-structure composite, which can influence charge carrier trans­
port. Schematic diagram of this junction structure is shown in Fig. 2b.
The nanoscale redox process of the material is that NCAL catalyzes
hydrogen to protons and electrons at the anode side, and reduces oxygen
to oxygen ions at the cathode side. Considering that fuel cell electrolyte
is a three-in-one system, protons and oxygen ions can be transmitted in
the electrolyte at the same time. This leads to the depletion region and
internally built-in field, which plays a key role in charge separation. As
much as the difference is in the barrier height of the field, there are less
chances for the electrons to transfer through internal path which can
cause short circuiting [93–95]. To further improve the performance of
single component SOFC at low temperature, the NCAL electrode has
been used. Another example is reported by Xia et al., [96] where they
shaped a triple charge conducting BaCo0.4Fe0.4Zr0.1Y0.1O3-δ-ZnO into the
electrolyte layer of SOFC by constructing a spatial p-n hetero-structure.
The energy band alignment at particle/grain level based on a p-n bulk-
hetero-junction was used to explain the suppression of electronic con­
ductivity and advancement of ionic conductivity in the hetero-structure.
This junction effect is illustrated in Fig. 2c, showing the charge sepa­
ration process and promotion of ionic conductivity by built-in electric
field. Besides, based on perovskite solar cell principle shown in Fig. 2d,
p-n junction formation is used to separate charges. A single component
fuel cell shown in Fig. 2e was also successfully developed using a com­
posite layer of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) and Sm/Ca Co-doped
Ceria (SCDC) [97]. The p-n conducting layers were involved in the
conversion process while preventing the short circuiting and allowing
the transportation of ions, reaching a high fuel cell power density of
1080 mW/cm2 operating at 550 ◦ C.
Studies show that single component SOFC p-n hetero-structure
should satisfy the following requirements. (1) Phase with a well-
balanced ion and electron conductivity; (2) Electron and hole contin­
uous clusters (n- and p-type semiconductors); (3) The formulated p–n
junctions are directed uniformly, restricting electrons from flowing
throughout the device.
2.4. Nano-redox and wide band gap oxides
By integrating the anode, electrolyte, and cathode components into a
nano-scale composite layer, i.e. through nano-particles consisting of n-
type, ionic and p-type materials, the nano-redox could be constructed in
single-component SOFC. In this way, fuel cell redox reactions can be
realized at nano-particle scale, and the single-component SOFC is
regarded as an up-scale device of the nano-redox units [69]. In fuel cell
operating condition, the single-component unit forms a bulk p-n heter­
ostructure junction where nano-particles of p and n types generate micro
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Chemical Engineering Journal 444 (2022) 136533
p-n junction to form a band alignment, the generated electrons from
anode side are limited to pass though the cell. By using this mechanism,
the electronic short-circuit could be suppressed. Zhu et al., [68] reported
such single-component device built on n-p junction semiconductors,
ZnO and NiOx forming a homogenous nanocomposite to provide the
necessary electrochemical reaction sites and charge transport paths for
the cell. These can be accomplished via tailoring ionic and electronic (n,
p) conductivities and catalyst activities which enable redox reactions
occurring on nano-particles and ultimately accomplish an SOFC func­
tion. The electronic conduction in the ZnO and NiOx homogenous layer
can be avoided via the energy band alignment, as when the junction
between the two semiconductors is formed, the charge carriers (elec­
trons in n-ZnO and holes in p-NiO) diffuse through the p-n interface
causing the potential to increase until the flow flux caused by the po­
tential and diffusion cancels out. This cause Fermi levels to align and the
band edges of the semiconductor to adjust accordingly to reach thermal
equilibrium. Such bulk-heterojunction is associated with the ionic
conductor (e.g. SDC) that act like an electrolyte layer to facilitate the
charge transfer processes for protons and oxygen ions, and with the
electron-hole, implementing the fuel cell reactions among the particles
of n-ZnO/p-NiO and SDC, to realize the nano-redox reaction.
Recently, an approach to enable durable single-layer fuel cells was
reported by Shao et al., [98], which promotes electro-activity and charge
separation in single layer via redox exsolution. The research group
prepared a single layer fuel cell by using mixed electronic and ionic
conductors (MEICs) Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3-δ (PSCFN) and ionic
conductors Sm0.2Ce0.8O2-(Li/Na)2CO3 (LNSDC), as shown in Fig. 3a. The
cell exhibited high performance and resistance at low temperatures as
shown in Fig. 3b–c. In addition, the operational stability has been
addressed for fundamental interests. Thereby, redox stable perovskite
oxide was explored to determine a possible solution that can improve
the feasible working principle and durability of the single layer fuel cell
(SLFC). Additionally, a smart material design and cell structure pro­
cessing extended nonstop testing period of up to two days, which
confirmed the feasibility of durable operation of the SLFCs as shown in
Fig. 3d. The precipitated metal/alloy nanoparticle of PSCFN can not
only improve the electrode reaction kinetics but also facilitate the
charge separation and ionic conduction in SLFCs, consequently
enhancing the fuel cell performance and electrical efficiency. The results
confirmed that potential of stable operation of SLFCs for future practical
deployment via appropriate selection of material and cell structure
design.
Furthermore, Asghar et al., [99] purposed to utilize wide band gap
oxides as the single-layered composite for low-temperature fuel cell, a
composite made of lithium-nickel-zinc-oxide (LNZ) and GDC have been
systematically analyzed in single component fuel cell, as shown in
Fig. 3e–f. In the operating voltage regime of the fuel cell, the mixture of
oxides with almost electronically insulating properties has prevented
short-circuiting. Since high charge transport resistance and leakage
currents are dominant in limiting the single-component fuel cell per­
formance, and the catalytic properties of the oxide mixture can drive the
HOR and oxygen reduction reaction (ORR) faster. The fuel cell device
was fabricated by using homogeneous mixture of LNZ-GDC layer and
exhibited a power density of 357 mW/cm2 at 550 ◦ C with Au as current
collector, and finally reached 801 mW/cm2 by using NCAL coated Ni
foam as current collector.
3. Intrinsic and extrinsic natures of materials
The properties of materials in solid state ionic (SSI) is normally
investigated in intrinsic systems, normally by the structure, ions doping,
defects, and mobility. However, for extrinsic conducting properties of
the materials systems, i.e. coupling to an external environment, like
extrinsic ions promotion, are largely unexplored, which is of great
challenge for basics of SSI to develop functional materials. However, it is
difficult to consider the intrinsic properties of the material in fuel cell
T. Raza et al.
Fig. 3. (a) Structure and working principle of fabricated fuel cell, (b) I-V and I-P curve of fuel cell, (c) Electrochemical impedance analysis of fuel cell, and (d)
durability test [98], (e) XRD patterns of the composite layer SLFC consisting of electrolyte and electrode, and (f) Working I-V and I-P curves of SLFC [99].
operating condition [100]. Here, we will provide some examples, in
which, extrinsic nature (operating conditions) changed the property of
the materials. This is necessary to develop a basic understanding of
extrinsic nature, i.e., ions concentration and mobility. It may be chal­
lenging task for developing the innovative materials and working prin­
ciple for charge separation in single component SOFC. Like SmNiO3, a
pure semiconductor in extrinsic conduction, can turn to be electron-
insulating after experiencing a Mott transition in H2 when used in fuel
cell as shown in Fig. 4a, and its energy band changes with insertion of H+
into the lattice, presenting high protonic conductivity (0.1 S/cm) with
extrinsic ionic transportation properties [16]. Such transitions are also
reported on remarkable conductivity at fuel cell operation [101,102].
Another well-known example is proton incorporated layer-structured
LiCo0.5Al0.5O2 with high electronic (hole) conduction, which has been
widely applied as the positive electrode in LIBs. Fig. 4b is the illustration
of such remarkable property holder which has mixed electronic (hole)
conducting property by incorporating H+ into the inter-layer spaces
during fuel cell operation. The high proton conductivity of roughly 0.1
S/cm in these two systems has been reported [103]. In other approach,
decorating the ceria-based electrolyte with carbonates is also introduced
to enhance the ionic conductivity. Such ceria-carbonate composite
structure can influence the material interfaces and create new interfacial
paths. Considering the positive effect, Wang et al., [104] developed SDC-
Na2CO3 composite and detected hybrid H+/O2– conduction in the ma­
terial during fuel cell operation. It was found that the O2– showed the
similar conduction and activation energy as in bulk ceria while H+
conduction showed a low Ea of 0.27 eV and 0.1 S/cm conductivity at
300 ◦ C. The interfacial ionic transport model of such composite is shown
6
Chemical Engineering Journal 444 (2022) 136533
in Fig. 4c, in which O2– are following the conventional route while the
H+ are travelling along ceria and carbonate interface region. Such
extrinsic H+ conduction way in ceria composite is projected to design
the single component SOFC. In another study, Dong et al., [105] has
observed that the intercalation of Li into TiO2 can increase oxygen va­
cancies in the TiO2 semiconductor. The process of proton diffusion has
been schematized in Fig. 4d, showing that the proton incorporation is
occurring into TiO2 by developing OH bond with O at the edges of Ti4+
and Ti3+, involving rotational diffusion, transfer of proton to the
neighboring vacancy, bending and elongation of the Ti-O bonds. In these
works, the proton conducting properties exposed from SmNiO3 and
LiCo0.5Al0.5O2, TiO2 and ceria-based composite point out a new vision
for the development of single component SOFC.
3.1. Models for material selection
The material selection for single component SOFC is usually based on
semiconductor materials, which can be single semiconductor or doped-
semiconductor. Different kind of materials have been investigated
recently, reflecting that both metal oxides semiconductors can be used in
fuel cells as electrolyte. Furthermore, some researches also focus on
tuning the band gap on semiconductor to wider one through doping,
enhancing the performance and durability. For example, metal oxide
semiconductor, such as CeO2, TiO2, ZnO, LaNiO3, CuFe2O4, GDC, SCDC
can be used as electrolyte with special structure or doping method.
Besides, common perovskite semiconductors, such as SmTiO3 and
SmNiO3, which are electronic semiconductors but they change their
phase from electronic to ionic conduction in operating condition of
T. Raza et al.
single component SOFC [106,107]. Xing et al., [19] studied a confined
proton transportation in the CeO2/CeO2− δ core–shell structure to build
up proton shuttles, leading to a super proton conductivity of 0.16 S/cm
for the electrolyte and fuel cell performance of 697 mW/cm2 at 520 ◦ C.
Wang et al., [104] introduced a logical design of non-stoichiometric
CeO2-δ based on non-doped ceria with a focus on the surface proper­
ties of the particles. The CeO2-δ reached an ionic conductivity of 0.1 S/
cm and was used as the electrolyte in a fuel cell, resulting in a remark­
able power output of 660 mW/cm2 at 550 ◦ C. Tu et al., [108] investi­
gated the phase structure, morphology and UV–vis absorption
perspectives. Utilized Li-doped ZnO as electrolyte layer and founded the
corresponding fuel cell that exhibited a remarkable maximum power
density of 443 mW/cm2 along with OCV of 1.07 V at 550 ◦ C. The cell
represented a lower-temperature operation feasibility with power out­
puts of 138–165 mW/cm2 at 450 ◦ C. Liu et al., [33] doped ceria with
Sm3+, Pr3+ and Nd3+ cations via two-step doping method. Firstly,
samarium doped ceria (SDC) is synthesized by co-precipitation method.
The Sm3+ ions were doped into ceria lattice to synthesize Ce0.8Sm0.2O2
oxides. In the second step, Pr3+/Nd3+ solution is also introduced as
dopant in SDC solution to synthesize triple-doped ceria. The doping
method resulted in a balanced ionic and electronic conductivity in the
material and realized high fuel cell performance.
3.2. Modified semiconductor-ionic materials
The novel semiconductor approach appears to be similar to prepar­
ing the SOFC electrode component: all three layers materials can operate
together in a single component. Hetero-structures, which can easily
generate ionic conductivities by integrating ionic conductors, are the
most typical demonstrations. Bulk p–n heterostructure materials have
been proposed as a way to tune semiconductors to superionic conduc­
tion because the p and n materials can balance free electrons, decreasing
electron leakage and leaving no net electrons. By establishing an ionic
conducting motorway at/along the interface based on band bending and
induced built-in field conditions, semiconductors and heterostructures
offer considerably superior ionic transport capabilities than existing
ionic materials, which can assist ionic transport/transfer. The
7
Chemical Engineering Journal 444 (2022) 136533
Fig. 4. (a) Semiconductor SmNiO3 Mott transition in
fuel cell operation, proton incorporation can be done
by rotational diffusion, transferring to neighboring
oxygen ion facilitated by hydrogen bond and the
bending or stretching of the bonds [16], (b) Illustra­
tion of proton insertion in LixAl0.5Co0.5O2 during fuel
cell operation. Red spheres Li+, blue spheres are H+
ions [103], (c) Schematic Model of the ionic conduc­
tion involved in SDC-Na2CO3 during fuel cell opera­
tion [104], (d) Incorporation and proton conduction
in TiO2, green arrow representing the bottom points
to c-axis [105].
semiconductor electrochemistry plays a key role in fuel cell design by
incorporating band structure and alignment fundamentals. Further­
more, by lowering the required Ea, band alignment can significantly
contribute to the acceleration of electrode reaction of HOR and ORR
[17,91,109].
In single component SOFCs, a wide range of modified
semiconductor-ionic composite materials have been developed. In the
latest study, Zhu et al., [110] developed semiconductor-ionic hetero-
structure consisting of LSCF with SCDC. The most essential feature at the
device level is that electrons are generated in an anode reaction by H2
oxidation and interacted with SCDC, but they cannot cross through the
LSCF (p) - SCDC (ion)/NCAL (p) layers, and the energy band alignment
drives the electrons to the anode side. The cell shows both ionic and
electronic conductivities beyond 0.1 S/cm at 550 ◦ C. The cell displayed
promising performance by maintaining the OCV above 1.0 V without
short circuit and power density output of 1000 mW/cm2. Afzal et al.,
[88] synthesized Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF) via chemical co-
precipitation technique and composited it with SDC in mass ratio of
40:60 to assemble single component fuel cell. The cell obtained OCV of
1.0 V and a peak power density of 655 mW/cm2 at 550 ◦ C. High per­
formance of the single component device can be attributed to a well-
balanced combination of ionic and electronic (sholes) conduction
characteristics. The Schottky barrier protects the Electrolyte-layer free
fuel cells (EFFC) from electronic short circuiting, resulting in increased
power production. In another approach, Wang et al., [111] developed a
single component SOFC using a composite of LSCF semiconductor with
SCDC. An enrichment of oxygen in the LSCF–SCDC interface region were
dramatically mitigated, resulting in an increase in ionic conductivity of
semiconductor–ionic LSCF–SCDC composites. The cell obtained OCV up
to 1.06 V and power density of 814 mW/cm2 at 550 ◦ C. At the same
temperature, Meng et al., [112] developed a redox stable semiconductor
La0.7Sr0.3Cr0.5Fe0.5O3-δ (LSCrF) that shows two phase ionic and elec­
tronic conductivities. The composite of perovskite oxide LSCrF with
ionic conductor SDC offered OCV of 1.0 V and high peak power density
of 1059 mW/cm2. The same group used co-precipitation technique to
prepare LCN, and the composite NSDC–LCN ionic–semiconducting sin­
gle component SOFC reaches OCV of 0.8 V and peak power density of
 T. Raza et al.
500 mW/cm2 at 550 ◦ C. Zhang et al., [113] have used the combination of
p-type semiconductor Ni0.8Co0.15Al0.05LiO2-δ with doped ceria NSDC to
develop single component SOFC. The NSDC–NCAL composite has
significantly better grain boundary conduction and reduced electrode
polarizations. The cell obtained the OCV of ~ 1 V and excellent power
density of 1072 mW/cm2 operating at 550 ◦ C. Recently Mushtaq et al.,
[114] tuned the energy band structure of a redox stable semiconductor
SrFe0.75Ti0.25O3-δ (SFT) with an ionic conductor Sm0.25Ce0.75O2. The
SFT–SDC heterostructure materials have both electronic and ionic con­
duction, with electron states modulating the local electrical field to
facilitate ion transport. In this study, the semiconductor-ionic hetero­
structure obtained a high ionic conductivity over 0.1 S/cm at 520 ◦ C.
Raza et al., [115] investigated the physical-electrochemical mechanism
of SLFC by synthesizing BaZr0.7Sm0.1Y0.2O3-δ (BZSY)-La0.8Sr0.2Co0.2
Fe0.8O3-δ (LSCF) nanocomposites for SLFC. The SLFC’s high power
output was facilitated by the synergistic impact of the junction and
energy band gap in charge separation, as well as the promotion of ions
transport by the junction built-in field. The prepared nanocomposite
8
­
Chemical Engineering Journal 444 (2022) 136533
material has mixed conductivity of 2.3 S/cm. Zhu et al., [116] developed
a cell using semiconductor LiNiZn-oxide and ceria-carbonate nano­
composites. Fe is also introduced as a redox catalyst element. The cell
achieved the maximum power density of 700 mW/cm2 at 550 ◦ C. Zhu et
al., [117] also developed a layer of electronic and ionic conductors
composed of SDC-LiNiCuZn-oxides. The physics of the device show a
critical principle comparable to that of solar cells, which is the effective
separation of electronic and ionic conductions and phases inside a
single-component device. The cell achieved maximum power density of
450 mW/cm2 at 550 ◦ C. Dong et al., [118] successfully fabricated a
single component SOFC by developing a composite of Sr2Fe1.5Mo0.5O6-δ
(SFM) and SDC-Na2CO3 materials. The SDC-Na2CO3 is used to modify
the ratio of ionic and electronic conductivities. SFM provides more re­
action areas than a simple mixture of ionic and electronic conductors,
which provides a triple phase boundary. The cell has the highest OCV of
1.05 V and output of 360 mW/cm2 at 750 ◦ C. Fan et al., [119] developed
a composite layer of electronic conductor LNCZO and ion conductor
SDC-Na2CO3, the study improves our understanding of the electron
Fig. 5. (a) LNCA-SDC hetero-junction mechanism
[120], (b) A schematic diagram of a typical p-n
hetero-junction formed at the hetero-phase interface
of the LiZnO-SnO2 electrolyte layer and the proposed
energy band alignment mechanism for interpreting
the charge separation and ionic transportation process
[122], (c) Band hetero-structure of CeO2-NiO com­
posite [123], (d) Interfacial band mechanism of
SrCo0.3Sn0.7O3-δ and CeO2 [74], (e) Diagram of a
typical p-n-n hetero-junction generated at the hetero-
phasic interface of the NCAL-ZnO-SnO2 electrolyte
layer, as well as the hypothesised energy band align­
ment mechanism for understanding charge separation
and ionic transit [125], (f) UV–vis and Ultraviolet
photoelectron spectroscopy were used to determine
the energy band structure at the interface of BSFSb
and SDC particles, as well as the schematic effect of
built-in electric field in the direction of ionic transport
[46], (g) In LTO-LSCF composite, the mechanism of n-
p junction hetero-structure and the related energy
band alignment [126].
T. Raza et al.
transfer and ion conductive phases, as well as the balance of p and n-type
conductions. The cell having thickness of 1.10 mm obtained the highest
power density of 350 mW/cm2 at 550 ◦ C.
Besides, a significant number of works on this topic have been
published in recent year, reporting super-ionic conduction, resulting in
several other breakthrough achievements. Tayyab et al., [120] devel­
oped hetero-structured composite of mixed ionic-electronic semi­
conductors Sm0.2Ce0.8O2-δ (SDC) and LiNi0.8Co0.15Al0.05O2 (LNCA). The
configuration of the heterostructure and the reconstruction of energy
bands at the interface play critical roles in improving electrochemical
performance by enhancing ionic conduction. The configuration of en­
ergy bands shown in Fig. 5a at the interface are critical in improving
ionic conduction and designed composite of LNCA-SDC cell, which de­
livers power output of 735 mW/cm2 at 520 ◦ C. Zagorski et al., [121]
synthesized a MEIC composite layer of BaCe0.6Zr0.2Y0.2O3-δ and Li2O,
NiO, and ZnO. On the nanoscale, an irregular distribution of p-type
(NiO) and n-type (ZnO) heterojunctions generated by nearby grains of
NiO and ZnO could result in a non-uniform dispersion of semiconducting
oxides. This single layer fuel cell obtained the OCV up to 0.83 V and
power density of 3.86 mW/cm2 at 600 ◦ C. In another work, Li et al.,
[122] developed a p-n heterostructure (LiZnO-SnO2) displayed in
Fig. 5b, energy band alignment strategies based on p-n heterojunction
and n-n heterostructure are used to demonstrate the ionic enhancement
and electronic suppression processes. The cell performance shows high
ionic conductivities and achieved peak power outputs of 376 mW/cm2
at 530 ◦ C. Li et al., [123] also developed a heterostructure of a p-type
semiconductor (NiO) and an n-type semiconductor (CeO2). In­
vestigations revealed that the higher ionic conductivity and cell power
output were due to the reconstruction of the energy band at the in­
terfaces, which was caused by a proton and oxygen ionic co-conducting
mechanism. The CeO2-NiO heterostructure shown in Fig. 5c has high
ionic conductivity of 0.2 S/cm, which was improved to 0.29 S/cm by the
addition of Na+ ions. The cell produced an excellent power density of
571 mW/cm2 at 530 ◦ C. Hu et al., [124] developed a single component
SOFC by a composite of Mg0.4Zn0.6O/Ce0.8Sm0.2O2-δ (MZSDC) and
Li0.3Ni0.6Cu0.07Sr0.03O2-δ (LNCS). Li+ doped NiO is a p-type semi­
conductor, whereas CuO is an n-type semiconductor, when exposed to
H2 and O2 environment, a p-n junction may form within LNCS to
maintain an effective charge separation and impede internal electrical
conduction in EFFC. The complex MZSDC-LNCS cell achieved the power
output of 600 mW/cm2 at 650 ◦ C. Shah et al., [74] synthesized a bi-layer
of SrCo0.3Sn0.7O3-δ and CeO2-δ semiconductors. This bi-layer established
a hetero-junction shown in Fig. 5d significantly improved the ionic
conductivity up to 0.2 S/cm. The cell achieved a OCV of 1.001 V and
peak power density of 672 mW/cm2 at 520 ◦ C. Recently, Lu et al., [125]
developed a p-n-n hetero-structure using p-type NCAL, n-type ZnO, and
n-type SnO2. The interfacial junction formation is shown in Fig. 5e.
Investigation indicates the possible existence of p-n-n heterojunction in
the NCAL-ZnO-SnO2 fuel cell with rectifying behavior for charge carrier
modulation. Electrochemical studies show that the cell achieved ionic
conductivity up to 0.389 S/cm and power density of 1267 mW/cm2 at
530 ◦ C. Mushtaq et al., [46] has reported a semiconductor-ionic hetero-
structure of Ba0.5Sr0.5Fe0.8Sb0.2O3-δ (BSFSb) and Sm0.2Ce0.8O2-δ (SDC).
The BSFSb-SDC cell is forming the interfacial energy-band reconstruc­
tion shown in Fig. 5f. The charge transfer at particle level is due to built-
in electric field and creating the electronic confinement. The cell ex­
hibits a high ionic conductivity of greater than 0.1 S/m and power
density of 1000 mW/cm2 at 550 ◦ C. Wang et al., [126] also reported a p-
n heterojunction composite of a p-type La0.8Sr0.2Co0.8Fe0.2O3-δ (LSCF)
and n-type Li2TiO3 (LTO) shown in Fig. 5g. Electronic conduction in the
membrane electrolyte is effectively reduced by altering the apriority
composition of the n-type and p-type components. Meanwhile, such
components have achieved high ionic conductivity, high current, and
power outputs for low temperature fuel cells by developing a p-n het­
erostructure with a built-in field. The cell achieved power density of 350
mW/cm2 at 550 ◦ C. Xia et al., [127] developed a composite layer of
9
Chemical Engineering Journal 444 (2022) 136533
perovskite LSCF and LaCePr-oxide (LCP). This single component SOFC
achieved OCV up to 1.01 V and a power density of 745 mW/cm2 at
575 ◦ C. The modification and doping in oxide ions would be preferred in
the enhancement of single layer SOFC. The ionic vacancies for cerium
oxide can be modulated by doping. This leads us to the new direction of
semiconductor ionic engineering. For instance, Fan et al., [119] used a
doping method to realize high ionic conduction in LNSDC. This incli­
nation increases the ionic vacancies in the co-doped ceria. Zhao et al.,
[128] have provided an input as La0.6Sr0.4CoO3− δ (LSC)-impregnated
porous SDC and GDC that has sustained encouraging and steady per­
formance upon thermal cycling at temperature ranges from 500 to
800 ◦ C for 30 days, the conventional GDC electrode delivered very high
initial resistance of 2.42 Ω cm2, the impregnated LSC-GDC electrode has
just showed the resistance of 0.3 Ω cm2. The collective effect of energy
band gap and ion transport gives high output power in SLFCs. This type
of perovskite hetero-structure has great potential to develop new gen­
eration SOFCs.
Single and double phase semiconductor based hetero-junctions
would enhance the single component SOFC performance. Their
hetero-structure, phase changes, band gap variations, ionic and elec­
tronic transfer routes should be greatly emphasized. All of these fun­
damentals focus on doping, composition, and fabrication that would
improve the electro kinetics of cell operation at the nano-redox level,
including ionic conduction and electrode reaction. The multiple func­
tionality of the developed materials should have following characteris­
tics. 1) In hetero-structure with p–n junction or Schottky-junction. 2)
Establishment of built-in electric field (for blocking the electrons and
favors the ionic conduction). 3) Interfacial super ionic conduction. 4)
High dual ions (H+/O2–) conduction at low temperatures.
4. Charge transfer dynamics
Due to the ionic charge distribution, the hetero-structure semi­
conductors form dipoles on their surface, which also affects the Fermi
energy level of the semiconductors. The applied voltage reveals the
Fermi energy difference. In single component SOFC, the OCV is deter­
mined by the Nernst equation [129,130].
( )
RT PH2 PO2 1/2
Vo = V o + ln (10)
zF P H2 O
Here, Vo is the open circuit voltage, PH2 , PO2 and PH2 O represents the
partial pressures of hydrogen, oxygen and water, respectively, and z
represents the electrical charge transfer at interfaces. R and F are ideal
gas constants, and V o represents ideal voltage.
During single component SOFC operation, the output voltage is
affected by different types of losses (polarization losses), such as acti­
vation polarization, ohmic polarization and mass transfer losses.
Therefore, these polarization losses should be deducted from open cir­
cuit voltage.
V = Vo − ηact − ηohm − ηcon (11)
Here ηact represents the the activation polarization loss while ηohm and
ηcon represents the ohmic and concentration polarization loss on voltage,
respectively, which are determined by the following equations:
{ ( ) [ ]}
j = jo exp β
zF ηact
− exp − (1 − β)
zF ηact
(12)
RT RT
ηohm = ir (13)
RT j
ηcon = ln(1 − ) (14)
zF jlim
Here, β is the charge transfer co-efficient. It is usually in the range of
0–1. During cell operation, internally resistance is measured using
electrical impedance spectroscopy (EIS) apparatus. The exchange cur­
rent density jo is calculated using the following equation:
T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

RT 5.1. Conventional SOFC vs. single component SOFC

jo = (15)
zFRct
Schematic diagram of the chemical reactions at boundaries of three
Where, Rct represents the charge transfer resistivity of the electrodes.
component SOFC and single component SOFC is shown in Fig. 6a [16].
The limiting current density jlim can be calculated by equation:
In conventional 3-layer structure, electrodes are externally connected to
CRo delivery output across the circuit. A relative dense layer of electrolyte is
jlim = zFDε (16)
δ sandwiched between anode and cathode that allows the ion conduction
Where, Dε is the reactant diffusivity, δ is the diffusion layer and CoR but resists electronic conduction. The physical compatibility and power
represents concentration of bulk reactant. losses are difficult to handle in such dynamic three-layer component
When fuel and air are introduced, the diffusion of H2 and O2 is structure. By contrast, in the case of single component SOFC, they are
calculated by using Fick law. easy to assemble and handle. Studies show that the single component
SOFC generally composed of two-phase materials and it has promising
Jα = − Dεi
∂Ci
(17) results over conventional SOFC structure operating at different oper­
∂α ating temperatures. In a study, our group has successfully developed
three-layer SOFC and single component SOFC for better comparison,
∂Ci ∂2 Ci using perovskite of BSCF in composite with samarium doped ceria
= Dεi 2 (18)
∂t ∂α (SDC). Three-layer cell is composed of NCAL: SDC (anode), SDC (elec­
Where α represents the measurement of depth from electrodes sur­ trolyte), and BSCF: SDC (cathode). Single layer SOFC is composed of
face, while the diffusion in the porous single component SOFC is SDC: BSCF single membrane [88]. Fig. 6b–c is the electrochemical re­
established by molecular and Knudsen diffusion, kinetic theory of ideal sults of both the cells. The polarization curves show that the mass
gas is used to study the behaviour of the gas transportation, it is given as: transfer resistance of three-layer cell is 0.2023 Ω/cm2 and single layer
[131]. cell has mass transportation resistance of 0.135 Ω/cm2, respectively.
√̅̅̅̅̅̅̅̅̅ Comparing the values of polarization curves, we concluded that the
4 ′ 8RT
Di,k = r (19) interfacial charge transfer for single component is 0.053 Ω/cm2, while it
3 πMi is 0.215 Ω/cm2 for three components SOFC. It indicates that the major
Here r′ represents the electrode porosity radius and Mi represents the ohmic losses are due to the electrolyte layer and the migration of oxygen
molar weight of gas specie i. Bird et al., also used the Chapman-Enskog ions that was high in single component SOFC. Fig. 6d shows that the
theory of ideal gas to calculate the molecular diffusion coefficient Dij single component SOFC reveals a power density of 655 mW/cm2 at
550 ◦ C while the three component SOFC obtains a lower power density
Dij =
0.00143T 1.75
( ) (20) of 425 mW/cm2. The single component configuration has edge over
1/2
ptM ij
1/3
Vi + Vj
1/3
conventional SOFC configuration because it dominates the two in­
terfaces of anode/electrolyte and electrolyte/cathode. Due to this
Using Bosanquet formula, combining equation (13) and (14), the interface elimination, it reduced the polarization losses, and results in
effective diffusion coefficient Dεi is determined as: [132]. the enhancement of cell output.
( ) In Table 1, the performances of some typical single component
1 τ 1 1
= + (21) SOFCs are summarized for comparison with the traditional 3-layer
Dεi ε Dij Di,k
structure. Due to its simple and single layer structure, it has edge of
in which ετ corresponds to the ratio of tortuosity vs porosity. operational management. and its thermal expansions can also be easily
Thereby, according to above description, it is known that overall controlled.
efficiency of an SOFC can be optimized by reducing the operational
temperature, obtaining a high OCV and lowering losses related to fuel 5.2. Single component SOFC vs. other energy conversion devices
reforming process. To realize normal operation of SOFC at reduced
temperatures, it is crucial to minimize the polarization losses induced by The performance of the energy conversion devices can be understood
temperature decrease. This can be achieved by using new advanced through their efficiency and power density. These two parameters are
electrolytes with high ionic conductivities at 300–500 ◦ C (decreasing the key for industrial applications. The merit of high efficiency (greater
ohmic polarization), increasing the three-phase boundary (TPB) density than 65%) with continuous enhancement and modification enable this
and specific reactivity of electrodes (decreasing activation polarization), technology to produce heat, water, and high-power outputs. The
as well as ensuring sufficient porosity of electrodes (reducing concen­ transportation of modern world, such as electric vehicles (EV), hybrid-
tration polarization). In this regard, single-component SOFCs inte­ electric vehicles (HEV) and plug-in-hybrid vehicles (PHEV), relies on
grating ionic conductors and catalytic semiconductors have great the volumetric and gravimetric power densities. This hybridization
advantages in high ionic conduction and electrode activity, indicating a consists of two energy conversion mechanisms. Energy conversion de­
great potential of single-component SOFCs to enable high efficiency of vices, like lead acid batteries, LIBs and supercapacitors, are being used in
SOFC at reduced operational temperatures. such transport hybridization. The plug-in batteries support the vehicle
working up to their maximum power density. After exceeding to their
5. A general comparison maximum power density, vehicles use traditional Carnot engine to
produce additional power density. But the combustion of fossil fuel in
The renewable energy markets have been growing rapidly over the such engine produces carbon dioxide, carbon monoxide, sulphur dioxide
last decade. Renewable energy sources are supposed to get grow three and other particulate that is harming our surroundings [139,140].
times from year 2010 to 2035. During this era the consumption of the Therefore, the replacement of such engine is required with energy
conventional fuel will reach about 4.5 billion barrels per day. It is esti­ conversion devices which have high volumetric power density.
mated that the energy production from renewable sources play a crucial In a previous study, it is pointed out that a single component SOFC
demand in future. Generally, the fuel cell has been well-known is the button cell with thickness of 1 mm have produced the power density ≥ 1
best energy device for the utilization of renewable energy resources. W/cm2 at 550 ◦ C [141,142]. The large surface area building and
stacking of such single component SOFC would produce power densities
up to 5 kW/kg. This indicates that the single component SOFC can
replace the traditional engine and hybridization of vehicles. Fig. 7a-7b

10
T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

Fig. 6. (a) Schematic diagram of the chemical reactions at boundaries of three component SOFC and Single component SOFC [16], EIS measurements of (b) 3 layer
SOFC and (c) single component SOFC, (d) Cell performance of three layer and single component SOFC at 550 ◦ C [88].

shows the graph of specific power among different energy conversion

Table 1
technologies [143]. The generation of heat, electricity, and high-power
SOFC structural Comparison.
density of the single component SOFC motivates the innovators because
Single Component SOFC it has full potential to achieve the desired production of heat, electricity,
Catalytic ionic Operating temperature Maximum Ref. and power generation for the modern time transport. Investigations took
material vacancy power place at different scales indicate that the SOFC have significant superi­
(phase 1) holder density
orities among other energy conversion devices as shown in Fig. 7c.
(phase 2)

CuFe2O4 Gd- 550 ◦ C 344 mW/ [133]

6. Single component SOFC evaluation
SmCeO2 cm2
LSCrF SDC 550 ◦ C 1059 [112]
mW/cm2 6.1. Advantages of single component SOFC
LSCF SCDC 500 ◦ C 814 mW/ [113]
cm2 The single component SOFC still belongs to the fuel cell family, its
BSCF SmCeO2 550 ◦ C 655 mW/ [88]
fabrication process is simple and cost-effective, as the cell converts from
cm2
LNZ GDC 550 ◦ C 801 mW/ [99] three layers into single layer structure. It has multiple merits over the
cm2 conventional SOFC structural design, which are summarized below.
NCAL SmCeO2- 550 ◦ C 1072 [113] i) This structure can ensure the long-term stability of the cell,
NaCO3 mW/cm2
because it is composed of single layer and the thermal expansions of
LSCF SmCaCeO2 550 ◦ C 1000 [112]
mW/cm2
such structure can be controlled easily, while in conventional SOFC,
thermal expansion mismatch of anode/electrolyte/cathode causes se­
vere challenges.
Conventional 3-layer component SOFC
ii) The single component SOFC is fabricated by mixing nano-
Anode Electrolyte Cathode Operating Maximum Ref. composites of semiconductor-ionic materials. The hetero-structure ef­
Temperature power
density
fect such as interfacial conduction and built-in field can enhance the
ionic conductivities to promote the device performance at low opera­
Ni-YSZ YSZ LSZ-YSZ 650 ◦ C 270 mW/ [134]
tional temperature.
cm2
TiOC-GDC GDC LSCF-GDC 700 ◦ C 130 mW/ [135] iii) The anode/electrolyte and electrolyte/cathode interfaces are
cm2 removed. This interfacial elimination would result in reduction of the
LiNiCoZnO- SGeDC LiNiCoZnO 600 ◦ C 600 mW/ [49] polarization losses.
SDC cm2
BCFZ- NKCDC BCFZ- 550 C
◦
741 mW/ [136]
NKCDC NKCDC cm2 6.2. Key for optimization of performance
NiO/SDC- NSDC LiNiO2/ 550 ◦ C 421 mW/ [137]
NC NSDC cm2 The single component SOFC performs the same function as conven­
NiO-YSZ YSZ LSM-YSZ 800 ◦ C 292 mW/ [43]
cm2
tional SOFC by using a homogenous layer made of electrolyte and
BCNZ NSDC LNCZ 600 ◦ C 350 mW/ [138] electrode materials. The single layer replaces the traditional anode/
cm2 electrolyte/cathode configuration of SOFC. In such devices, fuel and air
are introduced to the slight porous surface of electrodes to attend HOR
and ORR reaction, while the crossover of fuel and air should be avoided.
Therefore, the balanced porosity and density of the single component

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T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

reveal the porosity of the layer more reliable due to the presence of very
close pores in the layer. While adsorption techniques, like Barrett-
Joyner-Halenda (BJH) method, only estimate electrode porosity
ranging from 1 nm to 300 nm.
Furthermore, incorporating other energy conversion device with
single component SOFC can be also a promising way for performance
optimization. For instance, recent studies have indicated the trends of
integrating silicon solar cells, dye-sensitized solar cells and electrolysis
cells into one-unit device [2,145,146].
The Photocatalytic fuel cell (PFC) model is a typical device
combining working principle as well as configuration of solar cells and
fuel cells, as shown in Fig. 8b–f. The fuel cell generates electricity from
H2 and O2 while the PFC configured devices produces H2 and O2 from
the water with the help of solar radiations. In Fig. 8b, Wang et al., [147]
used an CdS quantum dot-sensitized TiO2 nano-arrays as the photo
anode, which is deposited on Fluorine doped tin oxide glass substrate to
produces protons from waste water and generates current power at
cathode. Similar approach is used in another study, in which, Xie et al.,
[148] used ZnFe2O4/TiO2-NTs heterostructure with air breathing cath­
ode for power generation as shown in Fig. 8c. Following the similar
approach, Zhang et al., [149] developed coupling of solar cell with
proton exchange membrane fuel cell (PEMFC) as shown in Fig. 8d, The
result indicated that the OCV of such coupled device increased from 0.64
to 1.18 V and the output current was also doubled. In addition, Zhu et al.,
[97] proposed a novel fuel cell with nanocomposite functional layer
designed by perovskite solar cell configuration, indicative of the possi­
bility to apply the charge separation working principle of perovskite
solar cell to avoid short circuit risk of fuel cell as shown in Fig. 8e. Zhang
et al., [149] also reported accelerated ORR step in H2-O2 fuel cells by
making use of photocatalysis, which is a novel tandem structure
combining polymer solar cell and fuel cell to enable the simultaneous
utilization of photo and electrochemical energy as shown in Fig. 8f.
These coupled configurations can be used in single component SOFC to
drive ionic conduction and catalytic activity, suggesting promising po­
tential of combining other energy conversion techniques with single
component SOFC for performance optimization.

7. Future framework and summary

Fig. 7. (a) Comparison of various energy devices [143], (b) Comparison of
obtained efficiency against power output of different energy conversion devices
[144], (c) Illustration of fuel resources devices to obtain electrical efficiency.
In recent years, Bloom Energy built a conventional SOFC stack with
40 cells that individually produce 25 W of electricity, which are powered
by natural gas or biogas. Mitsubishi Hitachi Power Systems, Ltd. (MHPS)
cell significantly affects its OCVs and power outputs, which is quite
started testing a pressurized hybrid power-generation system that
crucial to achieve optimal fuel cell performance. Recently, Asghar et al.,
included a SOFC stack and a micro gas turbine in 2016. The demon­
[133] developed a single component SOFC by using a composite of
stration system had a power output of 250 kW and a generation effi­
CuFe2O4 with Gd-Sm co-doped ceria. They sintered the cell pellets at
ciency of 55%, and it could run on a variety of fuels, including natural
various temperature ranging from 600 to 1000 ◦ C to form different
gas, biogas, and hydrogen. Elcogen also signed a commercialization
porosity and density of the single component, and found the cell per­
agreement with Magnex CO, a Japanese SOFC system designer, in April
formance was sensitive to the sintering temperature. Fig. 8a presents the
2020, to bring SOFC products to mass manufacturing and commercial­
comparison of electrochemical performances of these cells. The cell
ization. Magnex CO is developing a 1 kW SOFC cell stack, a 250 W SOFC
sintered at 700 ◦ C showed the best performance with power density of
portable system, and a 1–5 kW SOFC CHP production system fed by
344 mW/cm2 at 550 ◦ C.
biogas/ethanol [36]. However, if we look into the price of these SOFC
It was found that sintering temperature has direct impact on the
stack, it will be found their products are very expensive. Most of these
porosity, as normally the crystalline size of the material expanded with
stacks are based on YSZ electrolytes which requires high operating
the increase of temperature [144]. Sintering is beneficial to the densi­
temperatures above 800 ◦ C to operate, and are constructed in multi-
fication and calcination of the nanomaterials. If the temperature is very
layer, resulting in high cost and technical complexity. This limits the
high, the density of the single component layer will increase, and affect
widespread application of SOFC stack in fuel cell vehicle. Instead of a
the electrochemical process. If the sintering temperature is low, the
traditional 3-layer SOFC structure, the single-component SOFC in­
resulting layer could be too porous and cause gas crossover without
tegrates the cathode, electrolyte, and anode into one simple homoge­
taking part in electrochemical process. Therefore, the sintering tem­
neous structure, and requires much lower operating temperatures
peratures of the nanoparticle layers should be emphasized to optimize
(400–550 ◦ C) to achieve comparable or even higher fuel cell power
the cell performance. In this regard, the porosity of the single component
outputs as compared with YSZ based SOFCs (greater than 800 ◦ C). These
layer should be carefully maintained and examined with Archimedes
features will simplify the manufacturing process of single-component
method or scattering mechanism to have more realistic values. The
SOFC single cell and stack, reduce the polarization loss and in­
Archimedes principle and scattering mechanism, like index-matching
compatibility issues between different components, and lower down the
light scattering and contract-match small angle neutron scattering, can
thermal, materials and sealing costs of such technology to increase its

12
T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

Fig. 8. (a) Electrochemical performances at various temperature ranging from 600 to 1000 ◦ C [133], (b) Produces protons from waste water and generates current
power at cathode [147], (c) Heterostructure with air breathing cathode for power generation [148], (d) Coupling of solar cell with PEMFC [149], (e) Novel fuel cell
with nanocomposite functional layer designed by perovskite solar cell configuration [97], (f) Tandem structure combining polymer solar cell and fuel cell to enable
the simultaneous utilization of photo- and electrochemical energy [149].

market competitiveness. Currently, the commercialism progress of sin­
gle component SOFC is still in lab scale, for instance, 6 × 6 cm2 planar
designs [150,151], which demands more considerations to develop it
into stacking of the cells. It has been reviewed that all the studies and
characterization achievement noticed is for the button cells of few di­
ameters. Shifting towards the application process, the characterization
and interface kinetics should be noted for the large surface area single
component SOFCs. Tape casting technique can be used in the develop­
ment of planar design large surface area single component SOFCs.
Furthermore, in conventional SOFC several attempts to the fuel feeding
and tolerability to trace compounds have been witnessed [152,153].
Geis et al., [154] studied the impact of phenol as a biogenic model
pollutant on the performance of single SOFC. For this reason, simulated
bio-syngas were used to operate Ni/YSZ anode supported cells. Phenol
was introduced to the fuel gas at regular intervals over a period of
hundreds of hours. The experiments revealed that the cell potential and
electrical impedance measures were affected. The most prominent
mechanism of degradation was shown to be metal dusting of the anode.
Din et al., [155] has reviewed a comparison to state-of-the-art Ni/YSZ
and Ni/GDC anodes, extensive literatures shows that Ni/GDC anodes are
more tolerant of production gas pollutants. The trace chemicals found in
biofuels can interact with SOFC components, causing noticeable per­
formance decreases and drastically lowering the system’s lifetime. The
primary effects of the existence of trace chemicals impact are anode
deactivation and porous blocking electrodes. Therefore, the impact of
trace compounds on single component SOFC performance should be
examined in genuine cases and practical applications. It also requires
electrochemical characterization and stability test of the cell at large
scale. As for now, the best stability test applied on button cells is several
hundred hours. A summary of stability performance of full cell between
2011 and 2020 is shown in Table 2 [1,17,80,90,97,150,151,156–163]. It
is found some works reported good durability of the cell, for example,
two 6 × 6 cm2 planar cells in reference can be stably operated for 120
and 70 h, due to the elaborate fabrication process by hot/cold cycles,
tape casting and hot pressing [150,151]. Some works only reported
9–10 h for the sake of flaws of fuel cell fixtures, material incompatibility,
and lab condition. This means the stability of single-component SOFC
are sensitive to fabrication process and testing environment. Therefore,
more engineering efforts in terms of material design, device assembly,
and facility optimization are required to improve the stability and test at

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T. Raza et al. Chemical Engineering Journal 444 (2022) 136533

Table 2 least 100 h even more than 500 h in future work, to further improve the
A summary of stability performance studies of full cell between 2011 and 2020. development of such new technology. The researchers working in the
Configuration Temp. Stability Refs. development of the single component SOFC should focus at the band
(℃) variation and tuning of the band structure, ionic phase and double phase
Li0.4Mg0.3Zn0.3O2- 400–600 120 h@peak power, 15 hot/ [150] semiconductors by doping them with suitable materials. This type of
δ/Ce0.9Sm0.1O2-δ cold cycles, 6 cm × 6 cm × 0.1 semiconductor materials is the fundamentals for the configuration of
cm large cell low temperature single component SOFC. The illustration of the future
Ni/NCAL + CeO2/ 500–600 16 h@312.5 mA cm− 2, 530 ◦ C [156] dynamics for single components SOFC is shown in Fig. 9. On the other
Sr2Fe0.5Mo0.5Ox + Ni/
NCAL
hand, modeling and simulation methods can provide additional tools
Ni/NCAL + LSCF/SCDC + 550 32 h@300 mA cm− 2, 530 ◦ C [97] and other solutions to recognize critical features included in the per­
Ni/NCAL formance and enhancement of the materials at the atomic, molecular,
− 2
Ni/NCAL + LiNiFeO2/SDC 550 10 h@680 mA cm [17] and nano-scale levels, even though this subject is beyond the scope of
+ Ni/NCAL
2 this article but we will encourage the integration of such techniques with
Ni/NCAL + 6LaCePrOx/ 550 14 h@0.7 V, 251 mA cm− [1]
4LSCF + Ni/NCAL investigation and demonstrations mechanisms. Since the simulation
La/Pr doped CeO2/NCAL 550 70 h@380 mA cm− 2, cold [151] may be helpful for expecting new guidelines in the sensible design and
pressing hot pressing, 6 cm × production of novel materials with progressive properties. In addition to
6 cm large cell this, innovative materials, and structure characterization techniques in
NCAL + 5LSCF/5SCDC + 550 60 h@180 mA cm− 2 [80]
NCAL
particular to describe the in-situ and quantitative dimensions, such as
4Sr2Fe1.5Mo0.5O2- 550 24 h@156 mA cm− 2
[90] XRD, NMR, 3D X-ray, and the tomography microscopy which is usually
δ/6Ce0.8Sm0.2O2-δ focused on ion beam-scanning electron microscopy. The isotopic effect
LixZnO-Sm0.2Ce0.8O2- 550 42 h@80 mA cm− 2, 550 ◦ C [157] studies, impedance microscopy and electrostatic force microscopy might
δ/CuFeO2
− 2 be used to analyze the grain boundaries, surfaces interaction, confined
NiO-YSZ-LSCF 600 100 h@115 mA cm [158]
Ni/NCAL + BZCFY/ZnO + 400–500 30 h@470 mA cm− 2 [96] oxygen vacancies/imperfections/disorders, material microstructure
Ni/NCAL changes with time and material kinetics [164–167].
Ni/NCAL + 3LSCeCrF/ 550 18 h@0.9 V, 234 mA cm− 2
[159] The hard efforts result in lowering the operational temperature from
7SDC + Ni/LSCeCrF 1000 ◦ C to 600 ◦ C. The fully commercialism of the cell demands more
2
Ni/NCAL + 5% SCNT/SDC 550 20 h@0.8 V, 100 mA cm− [160]
lowering in the operational temperature. The role of semiconductor-
+ Ni/NCAL
Ni/NCAL + 7SDC/3LSCu 550 75 h@100 mA cm − 2
[161] ionic materials is critical for designing the single component SOFC.
+ Ni/NCAL This single layer cell is also weighted in comparison with conventional
− 2
Ni/NCAL + 3NSDC/ 550 9 h@210 mW cm , 469 mA [162] SOFC structure and other energy conversion devices. The significant
LiCoCuN + Ni/NCAL cm− 2
result states that the semiconductor-ionic hetero-structure materials
Ni/NCAL + 7 BSCFZY/ 370–520 38 h@0.82 V, 120 mA cm− 2 [163]
3SCDC + Ni/NCAL have potential to develop new generation SOFCs. The fuel choice and
high efficiency of the SOFC specify it as the future technology in energy
conversion devices. However, the high operating temperature and

Fig. 9. Illustration in the development and scaling of single component SOFC.

14
T. Raza et al.
complicated structure of conventional SOFCs is main problem for
commercialization. This review article presents innovative ideas to
resolve such complication by introducing single component SOFC that is
composed of semiconductor-ionic materials. On the basis of band gap
theory, the single layer SOFC is easy to assemble. During operation, two
different phases based on hetero-structure semiconductor materials are
developed based on n-p junction. The single component SOFC exhibits
high power output at reduced temperatures, which indicates the
promising potential for the application of such structural SOFC in
coming future. It can be anticipated that this single component device
using innovative semi-ionic materials is revolutionary fuel cell tech­
nologies, but also allowing for considerably simpler and more cost-
effective constructions and system designs to full fill the electricity de­
mand capacity in future. Finally, this effort is dedicated to the devel­
opment of single component SOFC family. However, the rule of principle
of this structure is nearly related to other energy conversion devices. In
future, the coupling of other energy conversion devices with single
component SOFC will integrate the targets of the high efficiency and
power production that eventually will be a sustainable and environment
friendly development.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
Authors thank Naveed Mushtaq for useful suggestion and local
modification in the process of this manuscript. Financial support from
Key Program for International S&T Cooperation Projects of Shaanxi
Province (2019KWZ-03), Key Program for Nature Science Foundation of
Shaanxi Province (2019JZ-20), Key Science and Technology Innovation
Team of Shaanxi Province (2022TD-34), and Open foundation Project of
Key Laboratory of Plateau Green Building and Ecological Community of
Qinghai Province (KLKF-2019-002) is greatly acknowledged.
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