REVIEW
Pseudocapacitive Materials
Definitions of Pseudocapacitive Materials: A Brief Review
Yuqi Jiang, and Jinping Liu*
Pseudocapacitive materials generally offer both high capacitance and high
rate capability, which has stimulated great efforts in developing the materials
system and related energy storage devices. In recent years, however, with the
extensive use of nanomaterials in batteries, fast redox kinetics comparable to
pseudocapacitive have been achieved in many kinds of battery materials due
to the much shortened ion diffusion lengths and highly exposed surface/
interface as a result of nanosize effect. Consequently, the terms
“pseudocapacitive materials” and “battery materials” are becoming more and
more confusing. In this review, different opinions on the definition of
pseudocapacitive materials and the evolution of the definitions as well as the
resulting confusion will be firstly reviewed. Then, to accurately distinguish
pseudocapacitive and battery materials, method with the consideration of
both the electrochemical signatures (CVs and GCD) and quantitative kinetics
analysis as a supplement is proposed. Finally, we end this review by
discussing the possible device configurations of asymmetric supercapacitors
and hybrid supercapacitors. The present review will help understanding the
differences between pseudocapacitive materials and battery materials, and
thus avoiding the definition confusion.
1. Introduction
Gradual exhaustion of fossil fuel as well as the increase of CO2 emis-
sions has been arousing the search and development of renewable
energy sources, such as solar, wind, ocean and biomass. To use such
energy sources efficiently, high energy/power and long-lifetime energy
storage devices are generally required. Meanwhile, future extensive
popularization of electric vehicles, smart grids, and various portable and
wearable electronics also stimulates the demand for high-performance
power sources.[1] It is exactly clear that electrochemical energy storage
devices such as batteries and supercapacitors will play a critical role in
these fields (Figure 1a). For advanced batteries such as lithium-ion bat-
teries, because of the ability to store large amount of energy
(>100 Wh kg
1) via bulk redox reactions in electrodes, it has already
been widely used in portable electronics such as laptop computers and
is anticipated to power large-scale electric vehicles in the near future.
Y. Jiang, Prof. J. Liu
State Key Laboratory of Advanced Technology for Materials Synthesis and
Processing, Wuhan University of Technology, Wuhan, Hubei 430070, China
E-mail: liujp@whut.edu.cn
Prof. J. Liu
School of Chemistry, Chemical Engineering and Life Science, Wuhan
University of Technology, Wuhan, Hubei 430070, China
E-mail: liujp@whut.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12028.
DOI: 10.1002/eem2.12028
Energy Environ. Mater. 2019, 2, 30–37 30
Nevertheless, low power density of lithium-ion
batteries cannot simply meet the requirements
for acceleration, braking, and climbing of elec-
tric vehicles. For other applications that need
the power sources being rapidly charged, bat-
teries are also not qualified.
Different from batteries, supercapacitors gen-
erally possess high power density; they are able
to harvest energy in very short periods and to
subsequently provide burst of energy when
needed. Traditional supercapacitors are called as
electric double layer capacitors (EDLCs), the
electrochemical signature of which mainly
arises from the potential independence of the
surface density of charges stored electrostatically
at the interface of electrodes (a non-faradaic
process). Based on the state-of-the-art carbon
electrode materials, the device typically delivers
high power densities (~15 kW kg
1) with a
lower energy density (5–10 Wh kg
1). How-
ever, the limited energy density has restricted
their application in energy storage.[2,3] In real-
ity, many new devices such as cranes and emer-
gency systems are in great demand for high
energy besides the high-rate power supply. Based on the simultaneous
pursuit of high energy and high power, pseudocapacitive materials
were put forward.[4–10] Electrochemical features of pseudocapacitive
materials are neither purely capacitive nor bulk Faradaic process (Fig-
ure 1b). Energy storage devices involving pseudocapacitive materials
occupy a middle ground between EDLCs and batteries, which, in the
classical definition, rely predominantly on the surface Faradaic electron
transfer to metal centers that is made possible by the intercalation or
adsorption of charge-compensating ions.[11] Pseudocapacitor can be
considered as a complementary form of EDLC as it is not electrostatic
in origin but exhibits similar cyclic voltammetry (CV) and galvanos-
tatic charge–discharge (GCD) shapes with EDLC. Hence, the “pseudo”
prefix is used to differentiate it from EDLC. The surface or near-sur-
face charge transfer leads to surface Faradaic reaction of pseudocapaci-
tor that is different from batteries and ultrafast reaction kinetics
similar to EDLC.[12–14] As a consequence, pseudocapacitive electrodes
basically exhibit near-rectangular CV profiles and almost linear GCD
curves.
However, with the rapid development of nanoscience and nanotech-
nology, electrodes based on nanomaterials are playing important roles
in electrochemical energy storage in recent years. Nanomaterials have
small sizes and large surface areas, and in this case, “surface” and
“bulk” cannot be clearly distinguished. Accordingly, some faradaic elec-
trode materials that typically show strong redox reactions in bulk exhi-
bit behaviors like pseudocapacitive materials with the size reduced to
nanoscale, characteristic of the disappearance of the redox peaks in CVs
and plateaus in GCD curves.[15] For some other battery electrode
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materials, although the size reduction cannot significantly change the
CV and GCD profiles, their redox kinetics are entirely different from Yuqi Jiang obtained her bache-
that in bulk. This is reflected by quite rapid charging rates and much lor’s degree at the School of
reduced voltage polarizations, even approaching to pseudocapacitive Chemistry, Chemical Engineer-
kinetics.[16,17] Such phenomenon has been demonstrated in a wide ing and Life Science at Wuhan
range of electrode materials for lithium-ion batteries and even for next- University of Technology
generation secondary batteries such as sodium-ion batteries and potas- (WHUT). She is currently pur-
sium ion batteries. The involved materials and charge storage mecha- suing her doctorate under the
nisms include TiO2, Nb2O5, MoOx, MXene (intercalation/de- supervision of Prof. Jinping Liu
intercalation type), metals like Sn (alloying–dealloying), and metal oxi- in School of Materials Science
des/sulfides (conversion type).[9,18-21] Exactly due to the extensive uti- and Engineering, WHUT. Her
lization of thin electrode films in literatures, the above mentioned current research interest is
pseudocapacitive kinetics are more obvious in battery electrodes of mainly focused on aqueous zinc-ion storage materials and
nanomaterials due to the significantly decreased ion diffusion length related devices.
from electrolyte to the inside electrode. In particular, when designed
into mesoporous/iso-oriented bulk nanostructured architecture with Jinping Liu received his Ph.D.
direct ionic transport pathways and little structural variation upon inter- degree from Central China
calation, some specific intercalation-type materials such as a-MoO3 and Normal University (CCNU) in
orthorhombic Nb2O5 demonstrate capacities that are mostly indepen- June 2009. During the period
dent of rate and redox peaks that exhibit small voltage offsets even at of 2008–2011, he did visiting
ultrahigh rates, and these interesting results can even be observed in and post-doctoral research at
quite thick electrode film.[9,20] More and more works have further Nanyang Technological
demonstrated that the crystal phase, surface, or interfacial effects may University (NTU) in Singapore.
introduce pseudocapacitive contribution in the charge storage process He is currently Chair Professor
of battery electrodes. As a direct consequence, the boundary between at Wuhan University of Tech-
battery material and pseudocapacitive material has been becoming nology. The research interests
blurred in recent years. Terms such as “intercalation pseudocapaci- in Dr. Liu’s group include the
tance” and “extrinsic pseudocapacitance” as well as kinetic analysis nanostructures synthesis and their electrochemical applica-
toward CVs have been proposed to better understand the charge storage tions (batteries, supercapacitors, & electrocatalysis).
mechanisms of emerging electrode materials. Indeed, these definitions
or methods are helpful to distinguish battery and pseudocapacitive
materials; unfortunately, nowadays many researchers unintentionally
misunderstand or misuse them and make the two concepts much
unclear in the current electrochemistry community. end this review by putting forward our opinion on how to accurately
In this review, we aimed to summarize the different opinions on the distinguish pseudocapacitive and battery materials, and how to correctly
definition of pseudocapacitive materials. The overall content is orga- use quantitative kinetics analysis to elucidate the charge storage mecha-
nized as follows: First, we specifically introduce the traditional defini- nism of electrodes. Finally, on the basis of the criterion, we will briefly
tion and key characteristics of traditional pseudocapacitive materials; provide the device configurations of asymmetric supercapacitors and
then, we will review the evolution of the definitions and the resulting hybrid supercapacitors, which are two kinds of important capacitive
confusion with the rise of nanostructured electrodes; after that, we will devices extensively studied currently.

Figure 1. a) Ragone plot of different energy storage devices. b) Schematic diagram comparing the fundamental charge storage mechanisms of electrode
materials in batteries and supercapacitors.

Energy Environ. Mater. 2019, 2, 30–37 31 © 2019 Zhengzhou University

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Figure 2. Pseudocapacitive signatures of some typical materials: a) CV curve of amorphous MnO2 electrode in KCl electrolyte. Reproduced with
permission.[8] Copyright 1999, Elsevier. b) Cyclic performance of amorphous MnO2 electrode in KCl electrolyte. Reproduced with permission.[22] Copyright
2008, Elsevier. c) CV of MnO2 electrode in sulfate solutions. Reproduced with permission.[23] Copyright 2009, American Chemical Society. d) CV and e) GCD
curves of RuO2 electrode in H2SO4 electrolyte. Reproduced with permission.[24] Copyright 2002, Elsevier. f) CVs of Fe2O3 electrode in Na2SO4 aqueous
electrolyte. Reproduced with permission.[25] Copyright 2018, American Chemical Society.

2. Traditional Definition
The first definition of pseudocapacitance can be found in B. E. Conway’s
influential book entitled “Electrochemical Supercapacitors: Scientific
Fundamentals and Technological Applications”, in which pseudocapaci-
tance is proposed to arise at the electrode surfaces where materials
undergo fast and reversible redox reaction; it is faradaic in origin as
compared to EDLC. The capacitance arises in account of the special rela-
tion between the extent of charge acceptance (DQ) and the change of
potential (DV), so that the derivative dQ/dV is equal to a capacitance.[12]
Based on this definition, pseudocapacitance reflects a Faradaic process
that takes place on the surface or near-surface of the electrode materials,
and the related materials are considered as “pseudocapacitive materials”.
The fact that charge storage is based on a redox process implies that the
electrode material acts a bit like battery in the reaction behavior; never-
theless, the electrochemical signatures are reflected with the presence of
(quasi)-rectangular CVs and the almost linear GCD curves similar to
EDLC, indicative of rapid faradaic reactions that are not limited by solid-
state diffusion. EDLC represents a non-Faradaic process based on charge
separation, although it is also stored on the surface of the electrode.
Therefore, whether having the Faradaic reaction or not gives the capaci-
tance and the pseudocapacitance a clear borderline, which also explains
the prefix of the term “pseudocapacitance”.
Despite that appreciable or large values of pseudocapacitance may
exist in several types of systems as pointed out by Conway,[13] typical
examples of pseudocapacitive materials are transition metal oxides of
manganese dioxide (MnO2), ruthenium oxide (RuO2), and iron oxides
(narrow potential window in aqueous electrolytes).[8,22–25] As shown
in Figure 2, quasi-rectangular CVs and quasi-linear GCD curves are
always found for these materials in different electrolytes and under dif-
ferent charging rates, which are completely different from the electro-
chemical signatures of rechargeable batteries. In addition, the reaction
kinetics (rate capability) of pseudocapacitive materials is generally better
than battery materials. For instance, in Figure 2e, with the current den-
sity increased 4 times to 400 mA cm
2, RuO2 can still keep specific
capacitance of 277 F g
1, ~80.5% of the value at 100 mA cm
2.[24]
When comparing with EDLC materials, pseudocapacitive materials usu-
ally have larger capacitance. As in Figure 2d, the specific capacitances of
RuO2 are in the range of 270–350 F g
1, much higher than that of
the commercial capacitive activated carbon (~150 F g
1). Nevertheless,
the cycling stability of pseudocapacitive materials cannot always reach
the level of EDLC. If not optimized, they may still have obvious capaci-
tance decay during long-term cycling, as for amorphous MnO2 in
Figure 2b.[22]
3. Evolution of the Definition and Confusion
In the past decades, electrodes based on nanomaterials have been exten-
sively investigated in batteries. Compared to traditional bulk battery
materials, these nanomaterials have much larger specific surface area. In
this regard, the so-called “bulk redox reaction” is basically changed to
“surface redox reaction” and the ion diffusion length has been signifi-
cantly shortened. Consequently, some battery materials exhibit either
pseudocapacitive signatures in CVs and GCD profiles or dramatically
enhanced redox kinetics (fast charging rate with good capacity

Energy Environ. Mater. 2019, 2, 30–37 32 © 2019 Zhengzhou University

 25750356, 2019, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/eem2.12028 by Koc University, Wiley Online Library on [28/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Figure 3. a) Crystallite size effect of LiCoO2 electrode. Reproduced with permission.[15] Copyright 2007, American Chemical Society. b) CV and c) GCD
curves of Ni(OH)2 nanospheres in alkaline solution. Reproduced with permission.[28] Copyright 2013, Springer Nature. d) CV curves of TiO2 electrode for Li+
storage; inset displays the normalized peak current versus scan rate. Reproduced with permission.[16] Copyright 2005, American Chemical Society. e) CVs of
MoO3 electrode for Li+ storage. Shaded region shows the capacitive contribution. Reproduced with permission.[20] Copyright 2010, Springer Nature. f) CVs of
Nb2O5 electrode for Li+ storage. g) Relationship of the Nb2O5 anodic and cathodic peak against the scan rate. Reproduced with permission.[9] Copyright
2013, Springer Nature. h) CVs of MXene in H2SO4 electrolyte. i) Plot of the anodic peak current against the scan rate. Reproduced with permission.[26]
Copyright 2018, Springer Nature.

retention) after nanosizing.[9,15,20,26] Under such circumstances, the
traditional definition of “pseudocapacitive materials” cannot well differ-
entiate it from “battery materials”, which stimulated some new under-
standings about pseudocapacitance and pseudocapacitive materials.
The most notable representative of such battery materials is LiCoO2.
LiCoO2 is well-known as a lithium intercalation positive electrode
material in traditional lithium-ion batteries. Obvious redox CV peaks
and GCD voltage plateaus are typically observed upon the intercalation/
de-intercalation of lithium ion in the host structure. However, it is
interesting to find that there are situations where the common battery
characteristics of LiCoO2 disappear when the material size reaches a crit-
ical value. As illustrated in Figure 3a, in contrast to the case that a flat
discharging plateau around 3.9 V versus Li is dominant for bulk
LiCoO2, the voltage plateau generally slopes in a continuous voltage
window over the entire intercalation process when the LiCoO2 dimen-
sion is reduced from 17 to 6 nm, and in particular, 6 nm LiCoO2 exhi-
bits an almost linear discharging curve as “pseudocapacitive” behavior
with faradaic process.[15] This electrochemical feature is unlike that of
traditional RuO2 and MnO2, which are intrinsically pseudocapacitive
regardless of the particle size of the materials. To distinguish such elec-
trode materials with traditional pseudocapacitive ones, Dunn et al.[27]
provided their ideas that those like LiCoO2 can be categorized as materi-
als with “extrinsic pseudocapacitance”; and for extrinsic pseudocapaci-
tive materials, in the bulk phase, they behave as battery materials, but
after the size reduced, pseudocapacitive behavior emerges. It is believed
that the increased surface area via nanostructuring suppresses phase
transformation of LiCoO2 to a large extent and promotes the high-rate
capability due to decrease in the diffusion length and increase in the

Energy Environ. Mater. 2019, 2, 30–37 33 © 2019 Zhengzhou University


surface lithium-ion storage sites.[10] The example of LiCoO2 clearly
demonstrates how extrinsic pseudocapacitance emerges when an elec-
trode material is engineered so that a large percentage of ion storage
sites are dominant on the surface. Similar to LiCoO2, nanosized layered
Ni(OH)2 has also been considered by some researchers as the material
with so-called “extrinsic pseudocapacitance”.[28] In this case, despite
there are still obvious redox peaks and peak offset in CV profiles at dif-
ferent sweep rates, the redox kinetics (charging rate) is found to be
quite rapid and the charge storage mechanism is believed to be surface-
controlled (Figure 3b and c).
Besides layered Ni(OH)2 and its analogues, some intercalation-type
nano-metal oxides such as TiO2, Nb2O5, and MoO3 were reported to
exhibit fast charge storage rates approaching or even surpassing the tradi-
tional pseudocapacitive materials.[9,16,20] These materials cannot be
directly classified into the traditional pseudocapacitive definition while
the reaction kinetics is much superior to the conventional battery materi-
als. Conway previously mentioned that such an intercalation process is a
transitional behavior between supercapacitors and batteries, similar to
two-dimensional chemisorption: Li+ ions are actually accommodated in
quasi-two-dimensional planes in the van der Waals gap of the host lattice
material.[13] To explain the charge storage mechanism, Dunn and Simon
et al. further defined a term “intercalation pseudocapacitance”, which is
common in non-aqueous electrolyte system, occurs when ions intercalate
into the tunnels or layers of the electrode material accompanied by a fara-
daic charge transfer with no crystallographic phase change.[27,29] They
further combined Conway’s traditional opinions and classified the pseu-
docapacitive mechanisms into three types as follows: 1) underpotential
deposition, 2) redox pseudocapacitance, and 3) intercalation pseudoca-
pacitance.[12,27] Underpotential deposition is infrequent, it mainly occurs
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when metal ions form an absorption monolayer on a different metal sur-
face above their redox potential.[30] Redox pseudocapacitance is the most
common pseudocapacitive reaction occurs when ions are electrochemi-
cally absorbed onto near-surface of materials with a faradaic charge trans-
fer, mostly occurs in aqueous electrolytes, including the state-of-the-art
MnO2 and RuO2. Based on the above Faradaic mechanisms, Dunn et al.
summarized the electrochemical characteristics of pseudocapacitive mate-
rials as follows: 1) rectangular CV shape or broad peaks with small peak-
to-peak voltage separation; 2) sloping GCD curve; 3) Nyquist representa-
tion containing a vertical line with a phase angle of 90° or less.[27] The
appearance of the term “intercalation pseudocapacitance” has greatly
broaden the family members of pseudocapacitive materials in recent
years. However, in most cases, electrode materials with intercalation
pseudocapacitance still demonstrate non-negligible CV peaks and it is
well-known that intercalation process in batteries, basically, is kinetically
limited by the ion diffusion into the bulk phase of host materials. The
question then arises: How to confirm that the intrinsic kinetics of interca-
lation pseudocapacitance is not controlled by ion diffusion?
To understand the newly developed “pseudocapacitance” definition
and related materials, quantification of the kinetics is one of the most
important methods. As is well known, electrochemically, redox electrode
materials deliver specific features on the basis of their response to (i) a
voltage sweep, as in CVs; (ii) constant current, as in GCD curves, and
(iii) alternating current, as in electrochemical impedance spec-
troscopy.[9,12]. Especially, in the CV experiments, the current response to
the sweep rate is varied depending on whether the redox reaction is con-
trolled by ion diffusion or not. Actually, there have been many methods
reported for deconvoluting diffusion-controlled process and non-
diffusion limitation process for electrode materials.[31–37] In 2007, Dunn

Figure 4. a) Li+ storage of Li4Ti5O12 with capacitive currents (k1m) being plotted at certain potentials around redox peaks. Reproduced with permission.[38]
Copyright 2014, American Chemical Society. b) CV and capacitive contribution and diffusion contribution (gray) of SnS2 electrode for Na+ storage. c)
Relationship between logarithm cathodic peak current and logarithm scan rates. d) Capacitive capacities contribution ratio at different scan rates.
Reproduced with permission.[39] Copyright 2016, American Chemical Society. e) K+ storage of VSe2 with the pseudocapacitive contribution. f) The
pseudocapacitive contributions at different sweep rates. Reproduced with permission.[40] Copyright 2018, John Wiley and Sons.

Energy Environ. Mater. 2019, 2, 30–37 34 © 2019 Zhengzhou University


Figure 5. Criterion for distinguishing EDLC, pseudocapacitive, and battery materials. Please refer to the reaction electrodes of typical lithium-ion batter-
main text for more details.
Figure 6. CV features for different device configurations of asymmetric supercapacitors and hybrid realized via “pseudocapacitance”. The terms
supercapacitors (A and B are different materials).
et al.[34] put forward a normalization formula for CV kinetics analysis:
1=2
iðV Þ ¼ k1 v þ k2 v
As reported, in this formula, V is the potential, v is the sweep rate
(mV s
1), and the values of k1 and k2 are used to distinguish diffusion
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and capacitive currents. This formula is typi-
cally simplified to i(V) = avb. It was proposed
that by calculating the value of b, the diffusion-
controlled contribution and capacitive contribu-
tion can be quantitatively determined.[34] For
example, the peak current of MnO2 scales lin-
early with sweep rate over a broad range of
sweep rates (b = 1), which obviously proves
that MnO2 is pseudocapacitive, while LiFePO4
displays battery signatures due to the value of b
is 0.5. This analysis method has been exten-
sively utilized to evaluate the kinetics perfor-
mance of various nano-electrode materials since
it was reported. With it, the above mentioned
TiO2, MoO3, and Nb2O5 were considered to
have intercalation pseudocapacitance with the b
value approaching to 1, and some emerging
pseudocapacitive materials such as MXene.
were also successfully discovered (Figure 3d-
i).[9,16,20,26]
In recent years, this quantitative kinetics anal-
ysis method was also applied to strong Faradaic
ies. As shown in Figure 4a, using Dunn’s equa-
tion, the lithium storage process in Li4Ti5O12
was calculated with a large ratio that is without
ion diffusion limitation at low sweep rate of
2 mV s
1 (the “pseudocapacitive” contribution
was denoted with red curves).[38] It is surpris-
ing that the so-called “pseudocapacitive” cur-
rent even emerges in the redox Faradaic peaks at
~1.55 V versus Li. Similar phenomenon was
even observed in sodium-ion and potassium-
ion batteries and even for electrodes based on
conversion reactions and alloying mecha-
nism.[39,40] For instance, in Figure 4b–d, when
B-SnS2 was employed as anode for sodium-ion
batteries, the capacity contribution resulting
from non-diffusion-controlled electrochemical
process was estimated as high as 58–77% at the
scan rates of 0.2–5.0 mA s
1.[39] In another
example of using VSe2 as a conversion anode
for potassium ion batteries, the capacity percent-
age of non-diffusion-controlled process even
reached 90.7% at 1.1 mV s
1.[40] Such large
non-diffusion current contribution has been
reported in a wide range of battery electrode
materials in recent years. By calling such part of
contribution as “capacitive” as in these litera-
tures, it is therefore awkward that the capacity
of these battery electrode materials is mainly
“battery materials” and “pseudocapacitive mate-
rials” have been becoming confusing.
It is noted that all the reported battery elec-
trodes with significant “pseudocapacitive” contributions are nanomate-
rials or nano-thin films. Basically, if we consider the capacity
contribution with b value  1 in Dunn’s method as “surface process”
which was pointed out by Conway ~30 years ago,[32] it is not difficult
35 © 2019 Zhengzhou University

to understand why the charge storage process of these nanomaterial
electrodes are not diffusion-controlled. It is probably better to explain
that b value1 means the process is either a capacitive process or a fast
redox reaction process that has no diffusion limitation benefiting from
small size and much exposed surface of electrode materials (nanosize
effect). On the other hand, there is no doubt that kinetics analysis is
much helpful to understand the Faradic mechanism, but it cannot be
solely used to determine whether an electrode material is a pseudoca-
pacitive one or not since the basic electrochemical signatures should be
firstly considered.
Brousse and Long et al. strongly recommended to determine pseudo-
capacitive materials by considering the physical meaning of the tradi-
tional definition and checking the basic electrochemical signatures. As C
is defined as DQ/DV, within a fixed voltage or potential window, this
value should be almost constant and the unit is Farad (F).[11,41] How-
ever, when the material has battery behavior, such as the appearance of
significant plateaus in GCD curves, or there are obvious redox peaks in
CV profiles, then the ratio of DQ to DV is not a constant. For these cases,
“capacity” should be used to reflect the charge storage ability with the
physical unit of Coulomb (C) or mAh. On this basis, Brousse et al.
believed that the “extrinsic pseudocapacitance” should be expressed by
“capacity”, and some electrode materials with so-called “extrinsic pseu-
docapacitance” such as nickel hydroxides are actually battery materials.
4. Concluding Remarks
Different from EDLC and battery materials, pseudocapacitive materials
generally offer both high rate and high capacitance. This merit has
stimulated numerous research efforts to pseudocapacitive materials and
related energy storage devices. In recent years, with the rapid progress
achieved in nanoscience and nanotechnologies, more and more nano-
material-based electrodes have been developed for batteries and super-
capacitors. On one hand, the nanoscale size leads to short diffusion
lengths for ions in batteries (even negligible ion diffusion, approaching
a surface process), and together with surface/interfacial effects acceler-
ates the redox kinetics; thus, simple kinetics analysis cannot be sufficient
to distinguish battery- and pseudocapacitive materials. On the other
hand, with more composite electrodes employed in next-generation
electrochemical energy storage devices, the electrode components and
electrochemical reactions have become more complex, to well under-
stand the reaction mechanisms, it is still quite necessary to analyze the
electrochemical kinetics in addition to firstly estimate the basic electro-
chemical features based on Conway’s definition. The kinetics analysis
will also aids to understand the relationship between “structure and
rate” of some electrode materials.
To help accurately distinguish pseudocapacitive and battery materials,
herein, we propose a method that considering both the electrochemical
signatures (CVs and GCD) and quantitative kinetics analysis as a supple-
ment (calculation of b in formula i(V) = avb), as schematically illustrated
in Figure 5. EDLC electrode is also included for comparison. For EDLC
materials, there is no doubt that the CV curve is rectangular, the potential
of GCD is linear with respect to time, and the value of b is always equal to
1. For pseudocapacitive materials, in general, it should show approxi-
mately rectangular CV, and accordingly, the GCD curve exhibits almost
linear relationship between potential and time, and compared with EDLC,
there are some inflection points, but no obvious plateaus. When calculat-
ing the b value, it is close to 1, and F is used as the unit for the charge stor-
age capability. By contrast, for battery-type materials, the typical CV has
Energy Environ. Mater. 2019, 2, 30–37
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obvious redox peaks and GCD shows detectable plateaus (no matter
whether the peaks/plateaus may disappear at high rates or not). Regard-
ing the b value, b equals to 0.5 is generally obtained in traditional bulk
battery electrode materials, however, nanomaterial battery electrodes or
those with specific electrode engineering and structural design, the b
value may also be >0.5 provided that the redox process is no longer lim-
ited by ion diffusion. To rightly use the above criterion, it is emphasized
that all the electrochemical signatures should be presented in a wide
ranges of sweep rate and current density, and for a true pseudocapacitive
material, its signatures should not be varied with material size or film
thickness. For using Dunn’s method to estimate b value, we recommend
1) to analyze CVs at relatively low sweep rates as Dunn et al. did. It has
been realized that this quantitative analysis may not be suitable for high-
rate CVs where ohmic drop cannot be neglected.[37] 2) correctly under-
stand the meaning of b  1. b  1 is indicative of a capacitive process
(either EDLC or pseudocapacitive) or a process that is not limited by ion
diffusion due to small material size/electrode thickness (nanosize effect;
surface process) or specific material structure engineering. Please do not
simply consider b  1 as the indication of a capacitive process; when a
battery material is estimated with b  1, it exactly means that the redox
kinetics is as fast as a pseudocapacitive material, which is just an effect. Of
course, other electrochemical methods such as electrochemical impe-
dance spectroscopy (EIS) may also be much helpful when determining
the charge storage mechanism of electrode materials.[42]
On the basis of the above discussion, the definitions of two typical
supercapacitor devices (asymmetric supercapacitor and hybrid superca-
pacitor) can also be clarified. As illustrated in Figure 6a, four possible
kinds of device configurations can be considered as asymmetric super-
capacitors: EDLC positive electrode and pseudocapacitive negative elec-
trode, pseudocapacitive positive electrode and EDLC negative electrode,
EDLC positive electrode A and EDLC negative electrode B (A6¼B), pseu-
docapacitive positive electrode A and pseudocapacitive negative elec-
trode B (A6¼B). Hybrid supercapacitors have one battery electrode and
one capacitive electrode.[5,6] Similarly, there are still four situations for
hybrid device: EDLC positive electrode and battery-type negative elec-
trode, battery-type positive electrode and EDLC negative electrode, bat-
tery-type positive electrode and pseudocapacitive negative electrode,
pseudocapacitive positive electrode and battery-type negative electrode.
In all the configurations, electrolyte can be aqueous, organic, ionic liq-
uid, or even (quasi)-solid state, depending on which electrode materi-
als are used. With the charge balance and optimization between
positive and negative materials, the typical CVs and GCD curves of these
devices will show negligible redox peaks and plateaus, respectively.[5,6]
We hope that our review will help understanding the differences
between pseudocapacitive materials and battery materials, and thus
avoiding the definition confusion.
Acknowledgements
This work was supported by grants from the National Natural Science Foundation
of China (Grant Nos. 51672205, 51872104 and 21673169), the National Key R&D
Program of China (Grant No. 2016YFA0202602), the Research Start-Up Fund
from Wuhan University of Technology, and the Fundamental Research Funds for
the Central Universities (WUT: 2016IVA083, 2017IB005, 185220011).
Conflict Interest
The authors declare no conflict of interest.
36 © 2019 Zhengzhou University
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