REVIEWS

Achieving high energy density and high

power density with pseudocapacitive
materials
Christopher Choi 1,4, David S. Ashby 1,2,4, Danielle M. Butts 1,4
, Ryan H. DeBlock 1
,
Qiulong Wei 1, Jonathan Lau 1,3 and Bruce Dunn 1*
Abstract | Batteries and supercapacitors serve as the basis for electrochemical energy-​storage
devices. Although both rely on electrochemical processes, their charge-​storage mechanisms
are dissimilar, giving rise to different energy and power densities. Pseudocapacitive materials
store charge through battery-​like redox reactions but at fast rates comparable to those of
electrochemical double-​layer capacitors; these materials, therefore, offer a pathway for
achieving both high energy and high power densities. Materials that combine these properties
are in demand for the realization of fast-​charging electrochemical energy-​storage devices
capable of delivering high power for long periods of time. In this Review, we describe the
fundamental electrochemical properties of pseudocapacitive materials, with emphasis on
kinetic processes and distinctions between battery and pseudocapacitive materials. In addition,
we discuss the various types of pseudocapacitive materials, highlighting the differences
between intrinsic and extrinsic materials; assess device applications; and consider the future
prospects for the field.

1
Department of Materials
Science and Engineering,
University of California,
Los Angeles, Los Angeles,
CA, USA.
2
Sandia National Laboratories,
Livermore, CA, USA.
3
Energy Storage and
Distributed Resources
Division, Energy Technologies
Area, Lawrence Berkeley
National Laboratory,
Berkeley, CA, USA.
4
These authors contributed
equally: Christopher Choi,
David S. Ashby, Danielle
M. Butts
*e-​mail: bdunn@ucla.edu
https://doi.org/10.1038/
s41578-019-0142-z
Electrochemical energy-​storage (EES) technologies power
the portable, electronic devices that are an indispensable
part of our daily lives. All evidence indicates that the
growth of EES technologies will continue almost unabated
in the near future, driven by expanding markets for mobile
consumer electronics, the electrification of transportation
and the need for wireless communication1,2. In addition,
substantial growth for stationary EES is projected, owing
to the increasing integration of renewable technologies
into the energy grid3,4. Although batteries are the fore-
most devices used for EES, electrochemical capacitors,
known as supercapacitors, generally have charge-​storage
properties that complement those of batteries, and their
usage has increased substantially over the past 10 years5.
The energy-​storage processes within the two types of
devices derive from fundamentally different mechanisms,
leading to the different charge-​storage properties. Battery
materials store large amounts of energy (~200 Wh kg–1)
through diffusion-​limited redox reactions, which results
in slow charging (on the order of hours)3. By contrast,
capacitive materials store much smaller amounts of
energy (~5 Wh kg–1) very rapidly (on the order of seconds)
through the formation of electrical double layers6.
This Review addresses the question of whether there
are energy-​storage materials that can simultaneously
achieve the high energy density of a battery and the high
power density of a supercapacitor. There is a clear need
for such materials to enable fast charging and to deliver
high power for long periods of time to enhance the capa-
bilities of mobile power sources. Pseudocapacitance pro-
vides an opportunity to achieve high energy density at
high power density, and an increasing number of studies
show that pseudocapacitive materials can fulfil this goal.
Pseudocapacitive materials exhibit battery-​like redox
reactions that occur at rates comparable to those of
double-​layer formation in a capacitive material7 (Box 1).
As a consequence, pseudocapacitive materials gener-
ally charge much faster than battery materials, on the
timescale of a few minutes. Although pseudocapaci-
tive behaviour in materials such as hydrated RuO2 and
MnO2 has been known since the 1970s (Box 2), the field
has received renewed interest, owing to the increased
demand for EES and the greater understanding of the
electrochemical properties of nanoscale materials.
Consequently, the diversity of pseudocapacitive mate-
rials has expanded to include perovskite, non-​oxide,
polycationic and 2D materials.
This Review begins with a discussion of the kinetic
signatures and charge-​storage mechanisms of pseudo-
capacitance, with a focus on establishing the distinc-
tions between pseudocapacitive and battery materials.
The characterization techniques that can be used for

Nature Reviews | Materials

Reviews
Box 1 | electrochemical charge-​storage mechanisms
a Li-​ion battery material stores charge through diffusion-​limited, faradaic reactions
throughout the bulk of the active material. Diffusion-​limited redox is often slow
and, although the redox reactions lead to high energy density, the electrochemical
performance of these devices is characterized by low power density and charging
requires tens of minutes to hours. supercapacitor devices, also known as electrical
double-​layer capacitors (eDLCs), do not involve faradaic charge storage and only
store charge through surface-​controlled ion adsorption (see panel a of the figure).
this capacitive charge-​storage mechanism leads to high power and rapid charging
on the order of minutes. a pseudocapacitive material exhibits a second mechanism
for capacitive charge storage. these materials undergo surface-​controlled, faradaic
reactions, which, because they are confined to the surface (or near the surface),
occur at rates comparable to those of double-​layer formation in eDLCs (see panels b
and c of the figure). thus, pseudocapacitive materials differ from eDLCs because
they undergo faradaic redox reactions. However, pseudocapacitive materials also
differ from traditional Li-​ion battery materials because the kinetics of the redox
reactions are dramatically faster and are not limited by semi-​infinite diffusion.
within pseudocapacitive materials, there are two main mechanisms of charge
storage: surface redox pseudocapacitance and intercalation pseudocapacitance.
with surface redox materials, the charge-​storage mechanism is attributed to charge
transfer occurring at or near the surface of the material (see panel b of the figure,
where O and r are the oxidized and reduced forms of a redox couple, respectively),
where ions are electrochemically adsorbed, creating short diffusion distances and,
subsequently, short diffusion times. By contrast, intercalation pseudocapacitance (see
panel c of the figure) involves the rapid diffusion of ions in and out of ion-​conduction
channels or layers within a host material, without the material undergoing a phase
change. these two mechanisms may occur in intrinsic pseudocapacitive materials or
can be achieved by engineering materials to elicit a pseudocapacitive response and
are, thus, termed extrinsic pseudocapacitive materials.
a EDLC b Redox c Intercalation
pseudocapacitance pseudocapacitance
– – + O + ze ↔ R
– a changing potential. By contrast, a battery material dis-
– – Li+ Li+
+ + + plays a defined voltage plateau (Fig. 1a) and, therefore,
– –
– Li+ Li+
– +
+ + + + Li+ Li+
– E = QV when incremental charge is added at a constant
–
– – + Li+
+ – –
–
Carbon Anion Cation Redox-active material Redox host material
Figure adapted from ref.55, courtesy of Kristy Jost, 3M, Minnesota, usa.
the analysis and identification of pseudocapacitive
materials are also discussed. Although the fundamen-
tals of pseudocapacitive behaviour have been well stud-
ied, understanding continues to evolve as the range of
pseudocapacitive materials expands. The second part
of this Review illustrates the current inventory of pseudo­
capacitive materials. In particular, we highlight the dif-
ferences between intrinsic pseudocapacitive materials,
which exhibit inherent capacitor-​like charge storage, and
extrinsic pseudocapacitive materials, which need to be
nanostructured to exhibit pseudocapacitive behaviour.
In addition, we briefly consider the nascent integration
of pseudocapacitive materials into EES devices and the
direction of this research. Finally, we provide our per-
spective on the role of pseudocapacitive materials in the
future energy landscape.
Pseudocapacitive charge storage
Pseudocapacitive materials exhibit a combination
of characteristics that distinguish them from battery
materials. The mechanisms that underpin pseudo­
capacitive processes in materials are discussed in Box 1.
In this section, we discuss the fundamental aspects of
the electrochemical, chemical and structural signa-
tures of pseudocapacitive materials and the various
characterization techniques used in their analysis.
Electrochemical signatures
The charge-​storage mechanisms of pseudocapacitive
materials are based on battery-​like redox reactions,
which occur at rates comparable to that of electrical
double-​layer charge storage in capacitive materials, and
display an electrochemical response similar to that of a
capacitor. The capacitance, C (F g–1), can be defined as
a function of the potential, V (ref.6):
Q  nF  X
C[F g −1] = =  (1)
V  m  V
where X is the extent of fractional coverage on the sur-
face or inner surface of the active material, m is the
molecular weight of the active material, n is the number
of electrons and F is the Faraday constant. For a pseudo­
capacitive material, the stored charge, Q, is expected
to increase linearly with an increase in potential. Thus,
a nearly linear dependence of charge storage within
the potential window is a defining feature of a pseudo­
capacitive material and indicates that the faradaic
charge storage is not limited by diffusion (Fig. 1a). The
energy stored in a pseudocapacitive material is there-
fore given by E = ½CV2 = ½QV (ref.8), with E continu-
ously increasing as charge is added incrementally with
Li+
Li+ the majority of the charge is stored at a constant poten-
tial. The energy stored in a battery material is given by
Li+
Li+ potential7. Characterization of the charge-​storage prop-
erties of a pseudocapacitive material should establish
the possible processes (for example, surface adsorp-
tion or ion intercalation) that occur over the operating
potential range. For this reason, it is more appropriate
to describe pseudocapacitive materials using gravimet-
ric capacity (C g–1 or mAh g–1), rather than gravimetric
capacitance (F g –1), which can lead to higher than
theoretical values9.
Experimentally, the cyclic voltammetry (CV) res­
ponse for a pseudocapacitive material resembles that
of a capacitive material. Pseudocapacitive voltammo-
grams can be quasi-​rectangular (as for hydrated RuO2,
top-​left part of Fig. 1b) but will often have broad fara-
daic charge-​transfer peaks superimposed over a ‘box-​
like’ profile10 (as for orthorhombic Nb2O5 (T-​Nb2O5)
or extrinsic MoS2, top-​right and bottom-​left parts of
Fig. 1b, respectively). The separation between the broad
anodic and cathodic peaks is small, indicating that there
is only a small amount of polarization in the charge-​
storage process and that the charged and discharged
states have a similar free energy. The parameters that
lead to broad faradaic peaks and quasi-rectangular
shapes in CV have been investigated computationally
using numerical methods and multiphysics models11.
It has been suggested that peak broadening is due to
concentration-​dependent activity coefficients and the
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interactions between reactant molecules according to
Eq. 2 (ref.12):
 RT   2Γ 
o
E * = E app +  (a R + a O − 2a RO)1 − R  (2)
 F   Γm 
where E* is the standard potential for an ideal couple; aR,
aO and aRO are interaction coefficients (where R and O
indicate the reduced and oxidized forms of a redox couple,
respectively); ΓR is the surface concentration of the redu­
ced species; Γm is the maximum surface concentration;
o
and E app is the apparent standard potential, which
o RT
is given by E app = E o + ( F )(a O − a R ). Peak broadening
occurs when the interaction parameter (aR + aO – 2aRO) is
positive12. In addition to voltammetry, electrochemical
impedance spectroscopy (EIS) provides a specific pseudo­
capacitive electrochemical signature. Namely, 3D Bode
plots of frequency, potential and either real/imaginary
impedance (Zʹ/Zʺ), real/imaginary capacitance (Cʹ/Cʺ) or
phase angle (ϕ) as the third axis can distinguish between
capacitive, pseudocapacitive or battery-​like materi-
als (Fig. 1c–e). 3D Bode representations offer a means
of deconvoluting the faradaic contribution to the total
capacitance on top of double-​layer capacitance across
the operating potential window and calculating the
corresponding relaxation time constants13–16.
Analysis of electrochemical kinetics
The kinetics of charge storage provide insight into the
charge-​storage mechanisms as well as information
about device operation. In general, EES processes can
be divided into diffusion-​controlled (that is, battery-​like)
and surface-​controlled (that is, capacitor-​like) responses
Box 2 | ruO2 as a pseudocapacitive material
the idea of pseudocapacitive charge storage was addressed as early as 1962 by
Conway and Gileadi to explain the underpotential deposition of hydrogen adatoms on
noble-​metal surfaces174. the prototypical pseudocapacitive charge-​storage material,
namely ruO2, was shown to be “a new interesting electrode material” in a preliminary
report in 1971 (ref.63), with a follow-​up study in 1974 (ref.64); subsequently, ruO2
has become the benchmark for an ultrafast, high-​capacity charge-​storage material.
although redox reactions were clearly observed, the exact nature was elusive
until trasatti and Buzzanca accurately theorized that ruO2 is a hydrous oxide that
undergoes protonation in mildly acidic aqueous solutions63,66. the mechanism of
electron charge transfer in hydrated ruO2 (see the figure) is mediated by facile
transport of H+ through the hydrous boundaries of ruO2 as the ru valence changes
from ru4+ to ru3+ to ru2+. without abundant hydrous boundaries throughout
the nanoporous ruO2 network, proton diffusion becomes sluggish and redox is
restricted to the outermost surface, resulting in low capacities. Hydrated ruO2
exhibits electrochemical signatures
similar to those of a capacitor, such Aqueous electrolyte (e.g. H2SO4)
as multicycle repeatability and
box-​like voltammograms, despite Ru 2+
↔ Ru3+ ↔ Ru4+ Hydrous
boundary
the faradaic charge-​storage H +
mechanism, making ruO2·xH2O
a unique redox pseudocapacitive
e–
material65,67. although there were
efforts in the mid-1970s to early 1980s
to commercialize ruO2 capacitors,
the prohibitively high cost of ru has
largely restricted the use of these Nanoporous RuO2·xH2O
devices to military applications7.
Nature Reviews | Materials
Reviews
(Box 1). Electrochemical methods, such as CV and EIS,
have been widely used in an attempt to deconvolute the
kinetic responses and identify charge-​storage mecha­
nisms in materials. In a CV experiment, the current
response i upon varying the sweep rate (υ) is dependent
on the charge-​storage process. Specifically, a power-​
law relationship can be used to correlate the current
dependence17:
i(υ) = aυ b (3)
where a is a constant and b is the power-​law exponent.
The b value can be obtained from the slope of the plot of
log(i) versus log(υ) for the cathodic and anodic peaks.
On the basis of the experimental b values, the kinetics
of the charge-​storage mechanism can be determined
qualitatively.
For a redox reaction limited by semi-​infinite diffu-
sion, the relationship between the peak current, ip, and
the sweep rate follows the Randles–Sevcik equation18,19:
1∕2
 αnF 
i p = 0.4463nFAcD 1∕2υ1∕2 (4)
 RT 
where c is the surface concentration of the electrode
material, α is the transfer coefficient, D is the chemical
diffusion coefficient, A is the surface area of the elec-
trode material, R is the molar gas constant and T is the
temperature. The redox peak current for a diffusion-​
controlled process is, thus, proportional to the square
root of the sweep rate, hence b = 0.5. This value indicates
a faradaic charge-​storage process, as occurs in battery
materials. By contrast, for a non-​faradaic, capacitive
charge-​storage mechanism, the peak current has a linear
relationship with the scan rate υ (ref.7), resulting in b = 1:
i p = υCA (5)
Although the charge-​storage mechanisms in pseudo­
capacitive materials are faradaic in nature, these mate-
rials also display b = 1, owing to their capacitor-​like
(surface-​c ontrolled) electrochemical response. On
the basis of the different current dependencies, capac-
itive processes, rather than faradaic processes, dom-
inate the peak current response at high sweep rates,
owing to the linear relationship. Experimentally, the
well-​known battery material LiFePO4 has a b value of
0.5, whereas orthorhombic Nb2O5, a pseudocapacitive
material, shows a b value of 1.0 over a wide range of
sweep rates20,21. For several other battery materials, b
values between 0.5 and 1.0 have been observed, which
suggests a mixture of diffusion-​controlled and capacitor-​
like responses22–24. For example, cyclic voltammograms
of nanostructured (extrinsic) MoS2 (bottom-​left part of
Fig. 1b) exhibit broad redox peaks superimposed on a
box-​like profile, which suggests that nanostructured
MoS2 is pseudocapacitive. In addition, the b values for
these redox peaks are ~1 (ref.25). By contrast, the cyclic
voltammograms of bulk MoS2 present well-​defined
redox peaks (bottom-​right part of Fig. 1b). Although
Eq. 4 was derived for redox molecules in solution with
a fixed, single-​redox peak potential, the extension to
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a 1.0 b Redox pseudocapacitance Intercalation pseudocapacitance

(RuO2·xH2O) (T-Nb2O5)
0.9 4
30
3

Current (mA cm–2)

0.8 20

Current (A g–1)
2
Normalized potential (V/V0)

0.7 10 1
0
0
0.6 –1
–10 –2
0.5 –3
–20
–4
0.4 –30 –5
0.0 0.2 0.4 0.6 0.8 1.0 0.0 1.2 1.5 1.8 2.1 2.4 2.7 3.0
0.3 Potential (V vs SCE) Potential (V vs Li/Li+)
0.2
Extrinsic pseudocapacitance
0.1 (nano-MoS2) Battery material (bulk MoS2)
0.6 0.6
0.0
0.4 0.4

Current (mA)

Current (mA)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Normalized capacity (Q/Q0) 0.2 0.2
0.0 0.0
Battery material (bulk LCO)
Extrinsic pseudocapacitance (nano-LCO) –0.2 –0.2
Redox pseudocapacitance (RuO2·xH2O)
–0.4 –0.4
Intercalation pseudocapacitance (T-Nb2O5) 0.0 1.0 1.5 2.0 2.5 3.0 0.0 1.0 1.5 2.0 2.5 3.0
Potential (V vs Li/Li+) Potential (V vs Li/Li+)

c Capacitive d Pseudocapacitive e Battery-like

2.5 1.4 1.4
1.2 0.01 Hz 1.2
2.0 0.01 Hz
1.0 1.0
C′ (F cm–2)
C′ (F cm–2)

C′ (F cm–2)
1.5
0.8 0.8 0.03 Hz
1.0 0.6 0.03 Hz 0.6
0.4 0.4
0.5 0.1 Hz
0.01 Hz 0.2
0.03 Hz 0.1 Hz 0.2
0.0 0.1 Hz 0.0 0.0
0.01 0.01 1 Hz 0.01 1 Hz
Fr

1 Hz Fre Fre
eq

0.1 q ue 0.1 1.8 2.0 q ue 0.1 1.8 2.0

ue

1.2 nc 1.4 1.6 nc 1.4 1.6

nc

0.8 1.0 y (H Zn )
1 2+ )
1.0 1.2 y (H
2+
0.6 1
0.4 n / 1 1.0 1.2 s /Zn
n
y(

0.2 s Z
l (V v Z
Potential (V vs
Ag/AgCl) z) ia z ) ial (V v
Hz

Potent Potent
)

Fig. 1 | representative characteristics of electrochemical energy-​storage materials. a | Illustrative galvanostatic

discharge curves for various kinds of pseudocapacitive materials (surface redox, intercalation pseudocapacitance
and a nanostructured extrinsic pseudocapacitive material) and, for comparison, a battery material, bulk LiCoO2 (LCO).
The pseudocapacitive materials have capacitor-​like electrochemical features, showing linear potential versus capacity
responses during galvanostatic discharging, whereas the battery material shows a potential plateau. Data from refs26,70,108.
b | Cyclic voltammograms for various pseudocapacitive materials: surface redox, RuO2 (500 mV s–1 at a mass loading of
1 mg cm–2)68; intercalation pseudocapacitance, Nb2O5 (10 mV s–1, 1 M LiClO4 in propylene carbonate, 40 µg cm–2)95; and
an extrinsic pseudocapacitive material, nano-​MoS2 (1 mV s–1, 1 M LiPF6 in ethylene carbonate:dimethyl carbonate 1:1,
5.8 mg cm–2)25; as well as a battery material, bulk MoS2 (1 mV s–1, 1 M LiPF6 ethylene carbonate:dimethyl carbonate 1:1,
3.4 mg cm–2)25, highlighting the variation in peak broadening. c–e | Examples of 3D Bode plots showing the normalized
capacitance (C′) versus frequency and potential for capacitive (carbon nanofoam (CNF)15; panel c), pseudocapacitive
(MnOx@CNF in a NaSO4 electrolyte; panel d) and battery (MnOx@CNF in a 3:1 NaSO4:ZnSO4 electrolyte; panel e)
materials16. MnOx@CNF electrodes can display either battery-​like (Zn-​ion insertion) or capacitor-​like (pseudocapacitive
from Na-​ion insertion) character, depending on the cations in the electrolyte. The capacitive and pseudocapacitive
materials exhibit near-​constant capacitance values across the potential range, whereas the battery material shows peak-​
like features near the redox potential at low frequency. SCE, standard calomel electrode. Panel a curve for bulk LCO is
adapted with permission from ref.108, ACS. Panel b top-​left part is adapted with permission from ref.68, ACS. Panel b
top-​right part is adapted with permission from ref.95, Wiley-​VCH. Panel b bottom parts are adapted with permission from
ref.25, ACS. Panel c is adapted with permission from ref.15, Elsevier. Panels d and e are adapted with permission from ref.16, RSC.

solid-​phase pseudocapacitive systems, in which both way, the variation in b value can be determined across
faradaic and non-​faradaic phenomena occur over a the entire operating potential range. Thus, it is possi-
range of potentials due to peak broadening, suggests ble to ascertain whether materials, pseudocapacitive
that b values can also be obtained at potentials other or battery-​like, show a transition between capacitor-​
than that at which the peak current is observed. In this like and diffusion-​controlled processes, depending on

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potential26. For pseudocapacitive materials at potentials
far from the redox regime, it is also possible to observe
b = 1, which is representative of electrical double-​layer
processes. For example, multiphysics modelling studies of
Nb2O5 have shown that b = 1 above 2.4 V (versus Li/Li+)
and arises from non-​faradaic electrical double-​layer
formation11. Indeed, this analysis shows that, although
the charge-​storage mechanism in Nb2O5 is surface con-
trolled throughout the potential range, there is a change
in the dominant charge-​storage mechanism between
pseudocapacitive faradaic (b = 1) and electrical double-​
layer capacitive (b = 1). The transition between regimes
is indicated by an abrupt dip in the b value2,11, which
arises from Li-​ion depletion at the electrode–electrolyte
interface11,26.
In a related analysis approach, the current response at
a fixed potential is expressed as the combination of two
separate contributions: surface capacitive and diffusion
controlled27,28:
i(υ) = k 1υ + k 2υ1∕2 (6)
where k1 and k2 are the proportionality constants that
describe the surface-​controlled and diffusion-​controlled
processes, respectively. This method is qualitative, giving
an indication only as to the fraction of the current car-
ried by the two processes. Moreover, this approach is not
applicable if there are other charge-​storage mechanisms
(for example, conversion reactions). In order to more
accurately evaluate the surface-​controlled component,
this analysis is often carried out using slow sweep rates
(<1 mV s–1) to enhance the contribution from the slower
diffusion-​controlled process.
Electrochemical analytical methods based on the
potentiostatic intermittent titration technique (PITT)
have recently been developed to elucidate the behav-
iour of pseudocapacitive materials. These analytical
methods include step potential electrochemical spec-
troscopy (SPECS)29 and multiple-​step chronoampero­
metry (MUSCA)30. PITT was initially developed for
determining the diffusion coefficients of intercalation
species and to identify whether ion diffusion is confined
by finite space or is governed by semi-​infinite diffusion,
as in classical electrochemical cells31,32. In PITT experi-
ments, small potential pulses of specified increments are
applied, each followed by a relaxation period intended
to allow the system to reach pseudo-​equilibrium at each
given state of charge. The pertinent diffusion properties
can then be obtained from current transients monitored
during the incremental titration.
The SPECS and MUSCA analytical methods enable
further interpretation of PITT data but have only been
demonstrated for a few pseudocapacitive materials thus far.
With the SPECS method, the transient current response
iD of the diffusion-​controlled process is defined by the
Cottrell equation for semi-​infinite planar diffusion33:
 D 1∕2
iD = nFAc  (7)
 πt 
where t is the time elapsed at the applied potential. By
contrast, for the capacitive-​like process, the transient
Nature Reviews | Materials
Reviews
current iC decays exponentially in response to a potential
step of magnitude, ΔV (ref.34):
ΔV −t ∕ R sC
iC = e (8)
Rs
where Rs is the series resistance. A few studies using
activated carbon and MnO2 have demonstrated practi-
cal applications of the SPECS model35,36. The MUSCA
method has been used to examine the energy-​storage
mechanism of Ti3C2Tx (where T is the surface termi-
nation functional group, such as OH, O or F) MXene
materials30. With the MUSCA technique, the influence
of polarization from the ohmic drop is minimized, as the
mean current during the titration experiment is calcu-
lated by integrating transient currents at each incremental
potential step. The voltammogram is then reconstructed
using the mean current to deconvolute the surface and
bulk diffusion processes with a minimal ohmic contribu-
tion. This analysis will be particularly useful for material
systems with limited electronic conductivities, for which
the ohmic drop can be substantial.
Another electrochemical signature that might pro-
vide insight into charge-​storage mechanisms is the rate
of reaction. In terms of electrochemical redox reaction
kinetics, pseudocapacitive charge storage is an electro-
chemically reversible or quasi-​reversible process (that
is, has fast reaction rates), owing to a small separation
between the anodic and cathodic peaks, stemming from
the minimal polarization in the charge-​storage process.
The effect of reaction kinetics on the pseudocapacitive
charge-​storage mechanisms for Nb2O5 has been studied
computationally using numerical methods37. Results
from this study suggest that the rate constant for hetero­
geneous electron transfer, ko, has to be sufficiently
high to maintain a faradaic process and to avoid the
non-​faradaic electrical double-​layer process from dom-
inating, especially at a high scan rate (that is, at 1 V s–1).
When the electrochemical storage capabilities of Nb2O5
are not limited by the rate of charge transfer, ko had a
minimal effect on the charge-​storage process.
A well-​known kinetic analysis based on Nicholson’s
parameter (Ψ)38 has also been applied to experimentally
determine the reaction kinetics of faradaic charge trans-
fer for pseudocapacitive materials39. Nicholson’s param-
eter was initially derived for redox molecules in solution
in the quasi-​reversible regime to qualitatively describe
how a system evolves from displaying a reversible to
an irreversible reaction. This parameter can be deter-
mined by correlating changes in peak-​to-peak separation
with respect to varying CV sweep rates; ko can then be
calculated using Eq. 9 (ref.38):
1∕2
 RT  −1∕2
Ψ = ko  υ (9)
 πnFD 
A higher ko value indicates that the system is able to
reach equilibrium more rapidly through faster redox
reactions. In a study of the extrinsic pseudocapacitive
behaviour of MoS2, the ko value of nanoscale MoS2 on
reduced graphene oxide (rGO) was roughly two orders
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of magnitude greater than that of bulk MoS2 (ref.39).
Although there remain questions regarding the appli-
cation of Nicholson’s parameter to solid-​state systems,
it may provide a qualitative method for determining
the difference in the rate of reaction between bulk and
nanostructured materials in extrinsic pseudocapacitive
systems.
Chemical and structural signatures
The ability to track changes in the valence state of a
metal ion can be useful in characterizing pseudocapaci-
tive materials. Monitoring changes in the oxidation state
of the materials using X-​ray techniques, such as X-​ray
absorption near-​edge structure40 and X-​ray photo­electron
spectroscopy41, combined with the electrochemical
kinetic analyses described above further enables decon-
volution of the charge-​storage mechanisms. In pseudo-
capacitive materials, the total capacitance (Ctotal) has a
non-​faradaic electrical double-​layer contribution (CNF)
and/or a faradaic pseudocapacitive contribution (CF).
The faradaic pseudocapacitive contribution is directly
proportional to the change in oxidation state, [Ox], and
the theoretical capacity per valence state change, ξ:
C total = C NF + C F = C NF + ξ[Ox] (10)
Recently, this approach was used to determine the
capacitive charge-​storage contributions from fara-
daic and non-​faradaic processes in bronze-​phase TiO2
(TiO2(B)) nanotubes42. On the basis of the quantitative
charge-​storage analysis using in situ, dynamic valence-​
state monitoring, the decrease in the specific capacity
with increasing sweep rate was attributed to a decrease
in battery-​like, diffusion-​limited contributions. Thus, in
a material with multiple charge-​storage processes, such
as TiO2(B), charge-​storage contributions from diffusion-​
limited, pseudocapacitive and non-​faradaic reactions can
be precisely evaluated using the valence-​state monitor-
ing technique in conjunction with the aforementioned
kinetic analyses.
A structural feature that seems to correlate with the
electrochemical characteristics discussed above is that
faradaic charge transfer occurs without a phase tran-
sition in pseudocapacitive materials. For example, the
pseudocapacitive response of orthorhombic Nb2O5
arises from fast 2D Li-​ion transport through empty
octahedral sites between (001) planes. This structural
arrangement provides tunnels in the a–b crystallo-
graphic plane to accommodate the ions; thus, the Li+
insertion–deinsertion process does not cause phase tran-
sitions in LixNb2O5 when x ≤ 2 (refs10,43). When structural
changes need to be considered, X-​ray diffraction (XRD)
should be used to confirm that a phase change does not
occur upon varying the Li+ content. If no changes in
the lattice parameters are observed, redox reactions are
likely confined to the surface of the material.
Thin-​film electrochemistry
The charge-​storage kinetics in pseudocapacitive materi-
als are not characterized by semi-​infinite diffusion; that
is, the ion diffusion length l and the diffusion coefficient
D are related by l « (Dtd)1/2, where td is the diffusion time.
This requirement can be satisfied by having either a very
short diffusion length or a large diffusion coefficient.
It is difficult to establish the materials that have a large
mobile-​ion (typically Li+) diffusion coefficient, owing
to the dependence of this value on the measurement
method and the mobile-​ion concentration. By contrast,
there has been considerable success in creating nanoscale
materials that exhibit pseudocapacitive properties. One
reason for this success is that, when the electrode film
is very thin — that is, less than the characteristic diffu-
sion length — diffusion of the species involved in the
redox reactions is governed not by conventional electro­
chemistry but by thin-​layer electrochemistry44,45. In
thin-​layer electrochemistry, the faradaic reactions occur
within a finite diffusion space within which the concen-
tration gradients that occur in the bulk electrode are neg-
ligible and the redox kinetics begin to resemble capacitive
processes (b = 1). This behaviour is shown by the propor-
tional relation between i and υ in the following equation,
which considers no mass transport limitations34:
 2 2 1
 n F υVAcD 2
i = 



( )
exp RT (E − E 0′)

nF

(11)
{ }
 2
 RT
( )
 nF 0′ 
1 + exp RT (E − E )
 
where E is the potential of an electrode and E0′ is the
formal potential of an electrode.
Early studies on finite diffusion primarily focused
on the mechanism of redox processes in conducting
polymer films46–48. The electrochemical features of thin
conducting polymers resemble those of capacitive redox
systems, with both demonstrating changes in oxidation
state with increasing electrode potential and reversible
charge-​transfer redox processes. Consequently, these
polymers exhibit nearly mirror-​image voltammograms
and a linear relationship between the current and the
scan rate. Electron propagation through a polymer film
occurs between immobile redox centres during the
faradaic process. Furthermore, the sweep-​rate depend-
ence of the peak current has been explained in terms
of 1D diffusion and surface-​confined redox processes46.
Thus, with an increase in film thickness, mass transport
within the polymer film becomes limiting and the cyclic
voltammetric response deviates from a mirror image
to the classic, asymmetrical shape, with the current
proportional to the square root of the sweep rate49.
The reaction kinetics of thin-​film electrodes have
been evaluated using different electrochemical tech-
niques, such as chronopotentiometry39, cyclic voltam-
metry49,50, staircase voltammetry51 and square-​wave
voltammetry52–54. These studies show that, in thin-​film
electrochemistry, the mass-​t ransport dynamics are
determined primarily by a few key kinetic parameters.
For example, a finite diffusion parameter, w, was pro-
posed to describe the reaction kinetics of thin-​film elec-
trode materials and is dependent on variables such as
the electrode thickness, the diffusion coefficient and the
potential sweep rate49:
nFl 2υ
w= (12)
RTD
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Depending on the value of the finite diffusion
parameter, the voltammetric response of the reaction
is characteristic of a surface redox process (w < 0.2),
an electrode reaction controlled by restricted diffusion
(0.2 < w < 10) or a faradaic process occurring under
semi-​infinite diffusion (w > 10). Thus, it is evident that
thin-​film electrochemistry, as described by surface-​
confined redox processes and finite diffusion, will
produce a pseudocapacitive electrochemical response.
However, the interpretation of such a response at the
thin-​film length scale is not straightforward. It is diffi-
cult to discern whether the finite diffusion response in
a thin-​film electrochemical measurement comes from
the intrinsic or extrinsic material properties because
both factors contribute to the emergence of pseudo­
capacitance in materials as the electrode dimensions
reach the thin-​film regime.
The occurrence of extrinsic pseudocapacitive behav-
iour in materials is influenced significantly by thin-​film
electrochemistry55. Nanostructuring materials can sup-
press crystallographic phase transitions by decreasing
intercalation stress, leading to fast kinetics that are not
limited by the reaction rates of phase transitions. This
behaviour has been observed experimentally in sev-
eral materials, including MoO2 (ref.56), LiMn2O4 (ref.57)
and MoS2 (ref.25), which exhibit battery-​like behaviour
in bulk form. The fast kinetics and pseudocapacitive-​
like responses of these materials arise primarily from
thin-​layer electrochemistry, as the condition l « (Dtd)1/2
is satisfied for nanoscale dimensions. The experi­mental
phenomenon of extrinsic pseudocapacitive nano­scale
materials has also been observed using numerical
model­ling simulations58. Thus, nanostructuring of the
electrode materials to the thin-​layer electrochemistry
regime is one important consideration for obtaining
extrinsic pseudocapacitive behaviour.
Classifying pseudocapacitive materials
For many years, RuO2 and MnO2 dominated the field of
pseudocapacitive materials. Over the past 10 years, the
field has broadened considerably following the discovery
that several battery materials exhibit pseudo­capacitive
responses when nanostructured or engineered into a
nanoscale form. To account for this ability to modify
charge-​storage behaviour, it has been proposed that mate-
rials should be classified as either intrinsic or extrinsic,
depending on whether pseudocapacitance is inherent to
the material in its bulk form or arises upon nanostructur-
ing, respectively59. This distinction is used in the following
as we review model intrinsic pseudocapacitive materials
and the design of extrinsic pseudocapacitive materials.
We also discuss the emergence of pseudocapacitive
non-​oxide systems.
Selected properties of model intrinsic and extrinsic
pseudocapacitive materials are provided for reference in
Table 1 and compared in Fig. 2. Table 1 highlights the
representative electrochemical performance expected
for several common pseudocapacitive materials and
their inherent advantages and disadvantages. It should
also be noted that the group of materials identified here
is not intended to cover all pseudocapacitive materials.
In particular, we have not reviewed systems that have
Nature Reviews | Materials
Reviews
more than one transition-​metal ion, an area of increas-
ing interest60. More extensive lists of pseudocapacitive
materials have been reported elsewhere59,61,62.
Intrinsic pseudocapacitive materials
RuO2·xH2O. RuO2 is considered the archetypal pseu-
docapacitive material, owing to its well-​understood
charge-​storage mechanism, historical significance and
high theoretical capacity7,63–70 (Box 2). In early investi-
gations, the redox reaction was found to be localized
on the surface and, thus, pseudocapacitive charge stor-
age was thought to be dependent on surface area71,72.
Further analysis revealed the importance of the elec-
trolyte and the surface chemistry, as only hydrated
RuO2 (RuO2·0.5H2O, which has a theoretical capacity of
375 mAh g–1 at 1 V) displayed high-​rate pseudocapaci-
tance73,74 (Table 1). Anhydrous RuO2 does demonstrate a
pseudocapacitive response but the capacitance and rate
capability are severely limited3. The discrepancy between
the hydrated and anhydrous forms is due to the hydrated
state acting as a proton lubricator and, therefore, facil-
itating fast proton conduction along the surface and
through grain boundaries3. This storage of protons in
hydrated RuO2 can be expressed as:
RuOx (OH)z + δ H + + δ e − ↔ RuOx − δ (OH)z + δ
Density functional theory analysis of the charge-​
storage mechanism supports that proton migration
through the bulk is unfavourable (with an energy
barrier of 1.62 eV for proton intercalation into bulk
RuO2), confirming that redox is confined to the sur-
face of RuO 2 (ref. 75) . The rutile phase of RuO 2 is a
metallic conductor, enabling fast electronic transport
through the bulk, while chemisorption or physisorp-
tion of water on the RuO2 surface is responsible for
facile proton insertion. Thus, a hydrated RuO2 material
can accommodate rapid charge transfer at the inter-
face between the RuO2 nanocrystal and the boundary
water76. Moreover, there is a key relationship between
the electrolyte and available capacitance. Protons have
been shown to be the dominant charge-​carrying ions
over hydroxides. Similarly, a direct relationship has been
shown between cation concentration in the electrolyte
and capacitance77. In many respects, the electrochemical
signatures of RuO2 provide a model system for pseudo-
capacitive materials in aqueous electrolytes. The high
electronic conductivity (10 4 S cm–1 in single-​crystal
RuO 2) 7 coupled with the rapid proton migration
in hydrated systems provides a basis for understanding
pseudocapacitive materials when the redox processes
are confined to the surface.
MnO2. Since the discovery in 1999 that amorphous
MnO2 displays a faradaic, rectangular voltammogram
in aqueous electrolytes, MnO2 has been explored as
an inexpensive alternative to RuO2 (ref.78). In general,
charge storage in MnO2 occurs through a pseudo­
capacitive faradaic reaction between Mn4+ and Mn3+ in
aqueous electrolytes:
MnO2 + δ M + + δ e − ↔ M δ MnO2
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Table 1 | summary of representative intrinsic, extrinsic and non-​oxide pseudocapacitive materials

Classification Material electrolyte Capacity (mah g–1) Cycle life Cell advantages Disadvantages refs
(C-​rates) (no. of cycles) potentiala
Intrinsic pseudocapacitive
Surface redox RuO2•xH2O Aqueous 172 (C/3), 139 (80C) 5,000 (82% 1-V High σe; fast H+ High cost; 69

retention) window diffusion; high performance

theoretical dependent on extent
capacity of hydration
Surface redox MnO2 Aqueous 50 (20C), 40 (720C) 10,000 (100% 0.9-V High theoretical Low σe; non-​aqueous 91

(thick film) retention) window capacity; low cost instability

MnO2 263 (15C), 124 (80C) – 1.2-V 81

(thin film) window

Intercalation T-​Nb2O5 Non-​aqueous 140 (1C), 110 (100C) 1,000 (100% 1.2–3.0 V Fast bulk diffusion Low σe; high anodic 21

pseudocapacitance retention) vs Li/Li+ voltage

Intercalation TiO2(B)b Non-​aqueous 230 (1C), 160 (30C) 1,000 (100% 1–3 V vs Fast bulk diffusion; Low σe; high anodic 99

pseudocapacitance retention) Li/Li+ high theoretical voltage

capacity
Extrinsic pseudocapacitive
Size dependence Nano-​LiCoO2 Non-​aqueous 120 (1C), 75 (100C) 20 (75% 3.0–4.3 V High σi and σe; Inactive surface 108

retention) vs Li/Li+ 2D diffusion sites; poor cyclability

Bulk LiCoO2 145 (1C), 40 (100C)
Dopant chemistry MoO3–x Non-​aqueous 270 (1 mV s–1), 50 (97% 1.5–3.5 V 2D diffusion; Initial phase change; 118

150 (100 mV s–1) retention) vs Li/Li+ high σe; fast bulk poor cyclability
diffusion
MoO3 250 (1 mV s–1),
78 (100 mV s–1)
Anion intercalation LaMnO3–x Aqueous 200 (1 mV s–1), – 1.27-V Fast O2– diffusion; High cost; cyclability 122

127 (100 mV s–1) window high volumetric dependent on

capacity O2– stability
Non-​oxide
Nitride VN Aqueous 100 (10 mV s–1), 10,000 (95% 1.2-V 2D diffusion; Capacity dependent 125

73 (100 mV s–1) retention) window high σe on the degree of

surface oxidation
Sulfide Nano-​MoS2 Non-​aqueous 180 (1C), 90 (100C) 3,000 (80% 1–3 V vs High σe; Li+ and Initial phase change; 129

retention Li/Li+ Na+ insertion high anodic voltage

at 20C)
Carbide Ti3C2Tx Aqueous 110  (2 mV s–1), 10,000 (98% 0.9-V High σe; easy Performance 138

63  (1,000 mV s–1) retention) window fabrication dependent on

surface functional
group
Summary of useful parameters and performance metrics for intrinsic, extrinsic and non-​oxide pseudocapacitive materials, as well as the main advantages and
disadvantages of the materials. σe, electronic conductivity; σi, ionic conductivity; TiO2(B), bronze phase of TiO2; T-​Nb2O5, orthorhombic phase of Nb2O5; Tx, surface
termination functional group. aThe cell potential is the operating potential range in which redox occurs versus Li/Li+ for non-​aqueous electrolytes or the voltage
stability window for aqueous electrolytes. bElectrochemical data are for TiO2(B) nanosheets.

where M+ is an alkali metal cation or H+. Assuming a
one-​electron redox reaction (δ = 1), a theoretical capacity
of 308 mAh g–1 (over 0–0.9 V) can be obtained. However,
several studies have shown that the electrochemical
behaviour of bulk MnO2 is dependent on the phase as
well as the charge-​carrying cation in the electrolyte79,80.
Unlike RuO2, MnO2 shows high ion-​diffusion rates,
enabling bulk redox, but the low electronic conductiv-
ity (on the order of 10–7 S cm–1) limits redox reactions to
the near surface. Thin films have achieved high specific
capacities (263 mAh g–1) but increasing the electrode
thickness limits the obtainable capacity, typically to
40–90 mAh g–1 (refs81–84) (Table 1). Through careful con-
trol of the synthesis conditions, it is possible to fabricate
MnO2 with a specific morphology and crystal struc-
ture85,86. The crystal structure influences key material
properties, such as conductivity, diffusivity and capacity,
and, thus, the performance of MnO2 is dependent on the
polymorph79,80. Increasing the number of diffusion path-
ways and the size of the intercalation channels, which
depend on the crystal structure, increases the ionic
conductivity and thus the obtainable capacity. Owing to
the variations in testing conditions, a verdict has not yet
been reached on which phase of MnO2 has the high-
est capacity (λ-​MnO2 achieves a capacity of 68 mAh g–1
after 2.7 min charging in 0.5 M K2SO4 (ref.84), whereas α-​
MnO2 achieves 83 mAh g–1 after 5 min charging in 0.1 M
Na2SO4 (ref.79)). In contrast to the effects of the crystal
structure on MnO2 properties, the surface area does not
influence the performance. The absence of a surface-​
area dependence is an indication that bulk redox con-
tributes significantly to the capacity, and this has been
further confirmed using in situ Raman spectroscopy87
and in situ XRD88. In neutral aqueous electrolytes that
contain alkali metal salts, charge storage is dominated
by the proton contribution (>60%), stemming from

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the high proton mobility and ease of proton insertion
into the bulk88. With aprotic solvents, the capacitance
is lower and there is a capacity loss upon cycling com-
pared with that in aqueous electro­lytes89–91. To increase
the potential window and, thus, the energy density, the
‘water-​in-salt’ approach has been explored, leading to an
increased capacity (106 mAh g–1 at 1.7 V in 5 M LiNO3)92.
However, the low ion mobility of the electrolyte limited
the achievable capacity at higher scan rates.
T-​Nb2O5. Nb2O5 has been of interest as an electro­
chemical energy-​storage material since the 1980s, when
Li-​ion solid-​s olution intercalation was observed in
Nb2O5 at potentials <2 V versus Li/Li+ (refs93,94). This
intercalation behaviour produces broad faradaic charge-​
transfer peaks in the cyclic voltammogram, which dis-
plays a notable surface-​charge-storage contribution
(>80%) with ion-​diffusion kinetics that are not limited
by semi-​infinite diffusion (b = 1)10,95. There are several
polytypes of crystalline Nb2O5, with the orthorhombic
phase (T-​Nb2O5) displaying the highest capacity, cycling
stability and power density59 (140 mAh g–1 at 1C over
1.2–3 V versus Li/Li+; Table 1). The amorphous phase
has also displayed pseudocapacitive behaviour, albeit
at much lower capacities (69 mAh g–1 after 4 min charg-
ing), owing to the lack of intercalation channels in non-​
crystalline Nb2O5 (ref.95). Li-​ion-based charge storage
occurs in Nb2O5 through an intercalation reaction:
Nb 2O5 + x Li+ + x e − ↔ Li x Nb 2O5
where x ≤ 2. Fast intercalation was calculated to occur
in the (001) plane because the large oxygen–oxygen dis-
tance (3.9 Å) results in a low-​energy diffusion barrier
for hopping between adjacent NbO6 octahedra96. In situ
X-​ray absorption fine structure and XRD analysis of
T-​Nb2O5 during intercalation confirm that Li+ interca-
lates as a solid solution with a linear change in its oxida-
tion state with voltage, reducing Nb5+ to Nb4+ and giving a
180
160 TiO2(B)
140 RuO2·xH2O
Capacity (mAh g–1)
LaMnO2.91
120
T-Nb2O5 Charge time
100
MoS2 Aqueous
80
VN
60 Ti3C2 1s 120 s
40
MnO2 Non-aqueous
20
1s 120 s
EDLC
0
–2.5 –2.0 –1.5 –1.0 –0.5 0.0 0.5 1.0 1.5 2.0
Potential (V vs SHE)
Fig. 2 | electrochemical performance of selected pseudocapacitive materials.
The capacity of various aqueous (blue) and non-​aqueous (green) pseudocapacitive
material thick films with the corresponding operating potential range versus the standard
hydrogen electrode (SHE). The properties of these materials are summarized in Table 1.
The colour intensity indicates the time needed to charge, with a darker colour indicating
a faster charging time. The benchmark electrical double-​layer capacitor (EDLC) capacity
(20 mAh g–1 in ~1 s) is displayed in red. All materials have mass loadings above 0.5 mg cm–2.
TiO2(B), bronze phase of TiO2; T-​Nb2O5, orthorhombic phase of Nb2O5.
Nature Reviews | Materials
Reviews
linear dQ/dV response10,43. Although T-​Nb2O5 retains
a high energy density at high rates of charge and dis-
charge, poor electronic conductivity necessitates nano-
structuring and a conductive network to achieve fast
charge-​transfer reactions for thick electrodes26.
TiO2(B). Another promising intercalation material is
the bronze phase of titanium dioxide, TiO2(B)97. This
phase of TiO2 can intercalate up to one Li ion into its
structure, giving a theoretical capacity of 335 mAh g–1
between 1.2 V and 3.0 V. Owing to its low structural
density and layered structure, fast Li+ diffusion is possi-
ble in bulk TiO2(B) through channels between edge and
corner-​sharing [TiO6] octahedra parallel to the b axis.
CV analysis of bulk TiO2(B) particles indicated a nearly
linear dependence of the peak current on the sweep rate
(b = 1), signifying a surface-​controlled redox reaction98.
The morphology of TiO2(B) also has a strong effect on
the Li+ insertion mechanism and cycling kinetics. For
example, nanosheets99 (with a capacity of 230 mAh g–1
at 1C; Table  1 ) display improved Li-​i on insertion
kinetics over nanoparticles or nanowires (150 mAh g–1
at 1C for nanowires)100. This improvement originates
from the decreased confinement in the c axis, which
reduces the repulsion between neighbouring axial oxy-
gen sites and channel sites100–103. Interestingly, NMR
analyses of Li+ diffusion in these various morphologies
do not corro­borate the experimental results104,105; how-
ever, the inclusion of anatase impurities could mask
the true kinetics and capacity of the different morpho­
logies106,107. Similar to Nb2O5, the fast Li-​ion intercala-
tion within TiO2(B) makes this material promising for
high-​rate devices, but the poor electronic conductivity
restricts its incorporation into EES designs.
Extrinsic pseudocapacitive materials
Size dependence. Decreasing the size of the active mate-
rial is the most commonly investigated route to engineer
extrinsic pseudocapacitive materials. This approach has
been widely explored with battery materials as a route
for increasing power density. With some battery materi-
als, however, the electrochemical characteristics change
significantly and the materials exhibit a pseudocapac-
itive response. One of the more dramatic examples is
LiCoO2, the well-​known cathode material for Li-​ion bat-
teries. When the nanoscale material (with a particle size
of <10 nm) is subjected to constant-​current (galvano­
static) conditions, the voltage profile changes from that of
a typical battery, for which the majority of the charge is
stored at a constant potential, to a capacitive profile with
a linear dependence of charge storage within the poten-
tial window108 (Fig. 1a). The change in electrochemical
characteristics leads to a notable increase in the retention
of capacity as the charging rates increase (Table 1). This
capacitive electrochemical signature has been associated
with a decrease in the ionic and electronic diffusion dis-
tances (as the system enters the thin-​film electrochem-
istry regime), suppression of phase transitions and an
increase in the number of available surface sites for Li+.
The size dependence for pseudocapacitive materials
has been demonstrated for several systems25,28,57,109. For
example, decreasing the particle size of MoO2 to 20 nm
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suppresses the monoclinic–orthorhombic phase tran-
sition that occurs upon lithiation. The capacity of the
nanomaterial at 10C (120 mAh g–1) is three times greater
than that of the micro-​sized powder (40 mAh g–1)56.
Moreover, by anchoring the MoO2 particles on a rGO
scaffold, the charge-​transfer properties improve greatly
and the MoO2–rGO material achieves a high capacity
(150 mAh g–1) at a charge–discharge rate of 50C.
Dopant chemistry. Among energy-​storage materials,
doping is routinely used to increase the electronic or
ionic conductivity of a material and improve its electro-
chemical kinetics. One approach developed for layered
materials is to increase the interlayer spacing by doping
large moieties, such as polyoxometalates110, carbon111,
polymer chains112 or metal cations113,114, into interca-
lation channels. This approach has been examined for
materials such as MnO2, VS2 and Ti3C2, for which the
increase in interlayer spacing can drastically increase
2D conduction115,116. Note that the choice of insertion
species is important, as it must not impede diffusion
through the channel117. Another route to improving the
electrochemical kinetics is to introduce oxygen vacan-
cies. For example, by introducing vacancies in MoO3,
the b-​axis spacing increased, allowing for faster Li-​ion
insertion kinetics without a phase change and, thus, sub-
stantially higher charge-​storage contributions and rate
capabilities118 (Table 1). The introduction of vacancies
has the additional benefit that these sites act as shal-
low donors, forming localized midgap states that can
increase the electronic conductivity, but they can also
lead to instability of the structure during cycling. A simi­
lar improvement to the kinetics has been observed with
anatase, for which partial reduction increased the electro­
nic and ionic conductivity, leading to an enhanced rate
capability119.
Anion-​intercalation pseudocapacitance. Another route
to increase pseudocapacitive-​b ased charge storage
is through redox reactions based on anion intercala-
tion. In this approach, an anion (for example, oxygen),
is intercalated into a host material, causing cationic
charge transfer. Anion-​intercalation pseudocapacitive
materials should not be confused with anionic redox
materials, such as Li-​rich oxides, which undergo anionic
charge transfer120,121. Non-​traditional systems such as
oxygen-​d eficient perovskites have been shown to
display pseudo­c apacitive behaviour through anion
intercalation in aqueous solutions. For example, for
pseudocapacitive LaMnO3 (ref.122), anion intercalation
was proposed to occur through the insertion of O2– from
electrolyte OH– ions; the protons released during this
process combine with OH– ions in the electrolyte to
form water:
A(B 22+x ,B1−2
3+
x )O3−x +2x OH
−
↔ AB3+ O3+2x e − + x H 2O
where A is La and B is Mn. The oxygen vacancies in
perovskite structures enable oxygen-​ion intercalation
and hopping of O2– ions between adjacent vacancies.
The intercalated charge is compensated by the oxida-
tion of Mn3+ to Mn4+, which diffuses towards the sur-
face, maintaining a stable system122,123. The intercalation
of excess oxygen ions promotes high capacities that are
retained at high rates122 (Table 1). However, the capac-
ity is highly dependent on the electrolyte composition,
with hydroxide-​rich solutions (high pH) increasing
the capacitance in comparison with acidic electrolytes
as the Mn2+/Mn3+ redox couple becomes dominant.
SrCo0.9Nb0.1O3–x and PrBaMn2O6–x also possess the per-
ovskite structure and demonstrate excellent capacitive
storage and stability at high specific currents (147 mAh g–1
at 10 A g–1 for SrCo0.9Nb0.1O3–x and 132 mAh g–1 at 10 A g–1
for PrBaMn2O6–x), demonstrating a b value of 0.9, which
indicates a surface-​controlled reaction123,124.
Non-​oxides. In addition to the oxide systems, pseudo-
capacitive responses have also been reported for vari­
ous nitrides, sulfides and carbides. One interesting
pseudocapacitive nitride is thin-​film vanadium nitride
(VN), which has an electronically conductive rock salt
structure that develops an oxy-​VN surface in aqueous
electrolytes. The charge-​storage mechanism is pro-
posed to involve the simultaneous redox of V3+ to V2+
with that of an oxy/oxyhydrate couple at the surface. For
thin films, this reaction gives a broad CV response with
capacities of up to 446 mAh g–1 over a 1.2-V window125.
In general, the charge-​storage properties of nitrides are
strongly dependent on the electrolyte; for example, the
highest pseudocapacitive contributions occur with basic
electrolytes126,127.
Another class of non-​oxide pseudocapacitive materi-
als is the transition-​metal dichalcogenides (MX2). These
materials, which typically have trigonal prismatic (H)
or octahedral (T) phases, are of considerable interest for
energy storage, as their layered structure allows for facile
ion access and high electronic conductivity128. One of
the most well-​studied systems is MoS2. During electro­
chemical cycling, Li+ inserts within the van der Waals
gap, enabling MoS2 to intercalate 1 mol of Li+ (corre-
sponding to a capacity of 167 mAh g–1) between 0.8 V
and 3.0 V versus Li/Li+. At lower voltages (<0.8 V), MoS2
is converted into metallic Mo, which limits the electro-
chemical stability of the cell129. Li+ insertion into the lay-
ered structure has been demonstrated computationally
and experimentally, confirming facile 2D ion conduc-
tion128,129. Upon Li+ intercalation in bulk MoS2, the metal-
lic 1T phase undergoes a reversible structural change to
the triclinic phase (LixMoS2), owing to the low solubility
of Li+ in the 1T phase. Recent operando XRD studies
have indicated that the intercalation mechanism depends
on the size of the MoS2 particles. When the particle size
is reduced to tens of nanometres, intercalation of Li+
occurs by a solid-​solution mechanism without a phase
change. This process enables increased energy storage at
high charge–discharge rates (the capacities of nanostruc-
tured and bulk MoS2 are 115 mAh g–1 and 40 mAh g–1,
respectively, at 60C)25. Selected data for a nano-​MoS2
are provided in Table 1. Similar electrochemical behavi­
our has also been reported for other layered dichalco-
genides, such as WS2 and TiS2; both materials show high
surface capacity contributions of 85% at slow rates130,131.
www.nature.com/natrevmats

The intercalation kinetics of layered dichalcogenides
are greatly affected by the interlayer spacing and multi-
ple methods are being explored in an effort to increase
the spacing to ultimately improve solid-​state ion diffu-
sion and rate capability132,133. Although the ion diffusion
coefficient can be tuned, there is still a need for short ion
and electron conduction pathways to obtain apprecia-
ble capacities at high charge–discharge rates, as demon-
strated for nano-​MoS2 versus bulk MoS2 (refs25,129). The
prospect of aligning the intercalation pathways of layered
materials may enable a significant improvement in the
performance and use in commercial-​sized devices.
Carbides constitute a third class of non-​oxide pseu-
docapacitive materials. Over the past decade, pseudo-
capacitive carbides, based on the 2D layered MXene
family of materials (for example, Ti3C2, Ti2C, V2C, Nb2C
and Ti3CN), have been the subject of intense research134.
MXenes consist of 2D hexagonal sheets with an electron-
ically conductive carbide core and a transition-​metal (M)
surface produced from etching the A atoms from MAX
(where A is typically a group 13 or 14 element and X is
carbon and/or nitrogen) phase materials. MXenes have
high surface areas and can undergo faradaic reactions,
leading to theoretical capacities of up to 320 mAh g–1
between 0.05 V and 2.5 V versus Li/Li+ for Li2Ti3C2.
This family of materials is amenable to the intercalation
of various ions between the 2D layers135, including Li+
(in Ti3CNTx; 190 mAh g–1 at 50 mA g–1)136, Na+ (Ti3C2Tx;
140 mAh g–1 at 50 mA g–1)137, K+ (Ti3C2Tx; 100 mAh g–1 at
50 mA g–1)137 and H+ (Ti3C2Tx; 110 mAh g–1 at 1 mV s–1
Table 1)138; these intercalated materials all display broad
faradaic peaks in the CV response. MXenes are typically
cycled in aqueous environments, in which the charging
mechanism can be controlled by changing the pH of the
electrolyte. In acidic electrolytes, redox is centred on
the M=O/M–OH couple; the redox couple is induced
by the adsorption of H3O+ from the electrolyte onto the
surface of the MXene, shifting the valence state of
the transition metal139. An important consideration with
MXenes is the correlation between the charge-​storage
mechanism and etching processes, which determines the
surface termination groups. Etching using hydrofluoric
acid leaves a surface terminated with either –F or –OH
groups that hinder ion access to the transition metal,
while also increasing the charge-​transfer barrier. For
Ti3C2, –OH termination was found to be more detrimen-
tal than –F termination, resulting in diffusion barriers
that are several times larger than those for F-​terminated
and bare Ti3C2 (0.9 eV (–OH) > 0.36 eV (–F) > 0.07 eV
(bare))140. Although MXenes have promising electronic
and ionic kinetics, further study is needed to understand
how the surface functionalization and interlayer spacing
affects the charge mechanism and kinetics.
The selected intrinsic and extrinsic pseudocapacitive
materials discussed above display the various electro-
chemical signatures of pseudocapacitance. It is apparent
that there are underlying structural characteristics that
are typically displayed in a pseudocapacitive material:
an open crystal structure with multiple diffusion path-
ways that enable fast ion conduction (as in α-​MnO2
or TiO2(B)), high electronic conductivity (as in RuO2) or
a means of enhancing electron transport (for example,
Nature Reviews | Materials
Reviews
MoO2–rGO) and a stable phase that allows for solid-​
solution intercalation (for example, T-​Nb2O5). Intrinsic
pseudocapacitive materials inherently display these
characteristics. For extrinsic pseudocapacitive materi-
als, one or more of these criteria are addressed through
materials engineering strategies, such as nanostructuring
and dopant chemistry. Although a material exhibiting
these properties does not guarantee pseudocapacitive
electrochemical signatures, these criteria can provide
some guidance as to whether a new material should
be evaluated for a pseudocapacitive response.
Integration into hybrid EES devices
Early efforts in integrating pseudocapacitive materials
(such as MnO2 and RuO2) into EES devices centred
on the development of hybrid devices with aqueous
electro­lytes141–144. A hybrid device comprises two dif-
ferent electrodes; one electrode is a redox material and
the other is a carbon-​based electrical double-​layer elec-
trode, typically activated carbon (Fig. 3a). By contrast,
an EDLC comprises two activated-​carbon electrodes
(Fig. 3b). Hybrid devices were designed with the intent of
operating at power levels comparable to those of EDLC
devices but with much higher energy densities through
the incorporation of redox-​active materials145. Although
these early aqueous devices did not significantly sur-
pass EDLC performance (5 Wh kg–1 at 10 kW kg–1 (note
that the specific energies and powers listed here are
based on the total mass of the device unless otherwise
indicated))146,147, they laid the groundwork for further
development of hybrid devices.
Hybrid devices based on non-​aqueous electrolytes
can achieve much higher capacities and operating volt-
ages (~4 V) and, therefore, higher energy densities, than
those based on aqueous electrolytes. Indeed, hybrid
supercapacitors with non-​aqueous electrolytes have
achieved higher energy densities than symmetric EDLC
devices (Fig. 3c). Li-​ion capacitors (LICs) are prominent
hybrid devices based on Li-​ion battery electrode mate-
rials paired with activated carbon. High-​rate LICs based
on Li4Ti5O12 were the first established LIC anodes and
undergo redox reactions at 1.55 V versus Li/Li+, which
is within the electrochemical stability window of most
common non-​aqueous, organic electrolytes148. LICs
based on Li 4Ti5O12 have demonstrated gravimetric
energy densities 3–4 times higher than those of conven-
tional EDLCs, up to 40 Wh kg–1 at a specific power of
5 kW kg–1 (refs149,150). Li4Ti5O12 remains one of the few
materials that can cycle more than 10,000 times without
considerable degradation, as it undergoes only a small
volume change and has a limited potential window.
Modern devices commonly use graphite as the faradaic
anode (owing to its higher specific capacity and lower
potential compared with Li4Ti5O12), which results in
an increased working voltage and energy densities of
40–60 Wh kg−1 (based on the total mass of the electrode
materials)151. Unfortunately, graphite-​based LICs are
limited by the sluggish diffusion of Li+ in graphite, the
formation of a solid-​electrolyte interphase and the need
for pre-​lithiation of the graphite electrode152,153.
The next step in the evolution of hybrid devices is
the incorporation of non-​aqueous pseudocapacitive
 Reviews

materials as a route for maintaining high power den-
sities while simultaneously increasing energy densities.
Prototypes of hybrid devices based on the intrinsic
pseudocapacitive materials T-​Nb2O5 and TiO2(B) have
demonstrated energy densities at high-​p ower lev-
els comparable to those of the LICs that use Li4Ti5O12
(refs21,154–156) (Fig. 3d). Moreover, thick Nb2O5 electrodes
(with mass loadings >10 mg cm–2) have demonstrated
that intrinsic pseudocapacitive materials can deliver
high-​rate performance at practical mass loadings for
commercialization157. In the progression towards high-​
energy-density devices, positive-​electrode pseudoca-
pacitive materials with high voltages versus Li/Li+ still
present a challenge for hybrid devices, owing to the lack
of identified materials and the difficulty of nanostruc-
turing158. Asymmetric pseudocapacitor devices with
two pseudocapacitive electrodes would increase the
a + – c 5 power density of capacitive materials. The interest in
Anion Oxidative decomposition of electrolyte
– Li+ AC
achievable energy density and greatly expand device
applications for mobile power.
Na-​ion capacitors are a future area of development
that can take advantage of high-​rate pseudocapacitive
materials. Despite the obvious size disadvantage of Na+
compared with Li+, the lower desolvation energy of
Na+ may enable the development of high-​rate devices159,160.
Although there are few reports on pseudocapacitive
materials for Na-​ion capacitors, MXenes are promising
candidates, and Na-​ion capacitors may yet turn out to be
an area in which significant progress can be made161,162.
Future perspectives
Pseudocapacitive materials exhibit a unique combi-
nation of properties: redox reactions that occur with
kinetics similar to those of charge storage in EDLC
materials. These materials fill an important gap in the
energy-​storage field, namely the lack of materials that
have the energy density of battery materials and the
pseudocapacitive materials spans from fundamental
AC
studies to EES devices. It is certain that the allure of

Electrolyte stability window

4
– Li+ these materials will become more widespread because
Potential (V vs Li+/Li)

their unique combination of properties is suitable for

– Li+ 3 several of the expected growth areas for energy storage.
AC MOx Looking ahead, there are key questions regarding new
AC materials, energy densities and device performance that
b + – 2
Anion Cation have to be addressed before practical applications of
Nb2O5
– + pseudocapacitive materials are realized.
1 An apparent question to ask is whether any poten-
– + Reductive decomposition of electrolyte and tial classes of materials have been overlooked during
SEI formation
– + the exploration of pseudocapacitive materials. One
0
0 25 50 75 100 125 150 175 200 class of materials that seems to have gone unnoticed in
AC AC Capacity (C g–1) the context of pseudocapacitive materials is those that
d Pseudocapacitive hybrid devices exhibit anionic redox, an approach that has already led to
EDLC LICs Aqueous Non-aqueous increased capacity with battery materials163. In this regard,
80
sulfides provide an interesting opportunity. Owing to
their covalent nature, sulfides are better understood than
Specific energy (Wh kg–1)

70
60 oxides with regard to anionic redox behaviour164–166. It is
50 also interesting to note that amorphous pseudocapaci-
40 tive materials, which may have differing ionic and elec-
30 tronic properties from the bulk, have received limited
20 study. Although there has been some work with aqueous
10 systems167,168, to the best of our knowledge, there have
0 yet to be reports of amorphous pseudocapacitive mate-
AC Graphite Li4Ti5O12 MnO2 RuO2 TiO2(B) T-Nb2O5 Ti3C2
rials for non-​aqueous EES. Extrinsic pseudocapacitive
Maximum Specific energy Specific energy materials can be synthesized by numerous modifica-
specific energy at 1 kW kg–1 at 5 kW kg–1 tions and nanostructuring routes, and it is likely that
this area will continue to expand as researchers develop
Fig. 3 | Comparison of hybrid device architectures and performance. a, b | Architecture new approaches for synthesizing nanoscale materi-
of a hybrid device with one activated carbon (AC) electrode and one metal oxide (MOx) als. In addition, new scientific directions may begin
electrode (panel a) and an electrical double-​layer capacitor (EDLC) with two AC electrodes to emerge, as there are fundamental questions of ther-
(panel b). c | The electrochemical voltage profiles of a typical EDLC and a hybrid device modynamic metastability and the possibility to achieve
with a Nb2O5 electrode. The area between the curves of the hybrid device (yellow) is greater than one-​electron redox with materials on the
much larger than that between the curves of the EDLC (blue), indicating that the hybrid nanoscale. Colloidal chemistry, for example, offers new
device has a higher available energy density within the electrolyte stability window. synthetic routes for extrinsic pseudocapacitive materi-
d | Comparison of the maximum specific energy, specific energy at a specific power of
als and the ability to form compositional gradients to
1 kW kg–1 and specific energy at a specific power of 5 kW kg–1 for EDLCs147, Li-​ion capacitors
(LICs)149,151 and pseudocapacitive hybrid capacitors142,143,155,156,162, all versus an AC electrode improve the electrochemical performance169–171.
with mass loadings above 1 mg cm–2. Pseudocapacitive hybrid devices show promise for The second question to consider is how to close the
increasing the maximum specific energy of mobile power devices145. SEI, solid electrolyte energy-​density gap between batteries and pseudocapac-
interphase; TiO2(B), bronze phase of TiO2; T-​Nb2O5, orthorhombic phase of Nb2O5. itors. Although techniques such as nanostructuring can
Panels a–d are adapted with permission from ref.150, RSC. produce capacitor-​like kinetics, the energy density of

www.nature.com/natrevmats
 Reviews

nanomaterials is limited by the inherent properties or high-​voltage pseudocapacitive materials. There is

of the bulk material. Although there are several pseudo-
capacitive materials that operate between 2.5 V and 1.0 V
(versus Li/Li+) that can achieve high energy densities at
high power densities, there are very few that operate at
potentials >3.5 V (Table 1). High-​voltage pseudocapac-
itive materials would enable the replacement of carbon
in hybrid devices, thus producing asymmetric pseudo-
capacitors with increased energy densities159. Layered
transition-​metal oxides, such as LiNi0.8Co0.15Al0.05O2 and
LiNixMnyCo1–x–yO2, have high achievable capacities that
arise from the substitution of nickel and present a prom-
ising research direction, as these materials exhibit solid-​
solution intercalation above 3.8 V after the first charge,
as verified by operando XRD172,173.
The last question we consider is the practical advan-
tages of pseudocapacitive materials and whether their
properties will lead to tangible improvements in EES
device performance. Hybrid pseudocapacitive devices
are currently comparable to Li4Ti5O12-based LICs in
terms of retaining high energy density at high power
density. The ability to surpass present performance levels
will depend on advances in designing new high-​capacity
every reason to believe that the hybrid device field will be
a robust one that achieves an energy density equal to half
that of a Li-​ion battery at power densities on par with
carbon-​based supercapacitors. Further progress could
lead to a Li-​ion battery based on two intercalation-​type
electrodes, both of which are pseudocapacitive materials
(an example of an asymmetric pseudocapacitor), with
each electrode capable of achieving capacities well above
100 mAh g–1 and being charged in minutes.
The development of EES devices that exhibit the
energy density of a battery at the high power density of
a supercapacitor has yet to be realized. Using existing
materials and architectures as a starting point, however,
we now have various pathways to design novel materi-
als that can help reach the desired performance of high-​
energy, high-​power devices. Although the best materials
and devices have yet to be achieved, pseudocapacitive
materials offer glimpses of a new generation of energy-​
storage materials that will lead to unmatched energy for
high-​power devices.
Published online xx xx xxxx

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Acknowledgements
The authors are grateful to the US Office of Naval Research
(grants nos. N00014-17-1-2244 and N00014-16-1-2164)
for supporting their research.
Author contributions
All authors researched data for the article. C.C., D.S.A., D.M.B.,
R.H.D. and B.D. contributed to the discussion of content and
writing and editing of the article prior to submission.
Competing interests
The authors declare no competing interests.
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