Niquel PDF

Materials Today d Volume xxx, Number xx d xxxx 2018 RESEARCH
RESEARCH Review
Nickel-based materials for
supercapacitors
Liuyang Zhang 1, Diwen Shi 2, Tao Liu 1, Mietek Jaroniec 3, Jiaguo Yu 1,⇑
1
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 122 Luoshi Road, Wuhan 430070,
PR China
2
Department of Materials Science and Engineering, National University of Singapore, Singapore 117576, Singapore
3
Department of Chemistry and Biochemistry, Kent State University, Kent, OH 44242, USA
A clear understanding of energy and environmental problems stimulates exploration of clean and
versatile energy sources. The majorities of sustainable energy sources are intermittent and therefore
need compatible energy storage technologies. Supercapacitors have stimulated a great scientific
interest due to their importance for energy storage. Electrode materials, as the key part of
supercapacitors, determine their performance. Nickel oxide/hydroxide, characterized by ultrahigh
theoretical capacitance and other intriguing features, has drawn considerable attention. However, its
poor rate capability and low conductivity hinder its widespread application. Recently, tremendous
efforts have been devoted toward resolving those issues. This review presents a concise compilation of
the recent progress in the area of nickel-based materials by categorizing them into several groups based
on chemical composition. Important issues associated with the fabrication and properties of these
materials as well as with the improvement of their performance are discussed. The underlying reasons
for the observed synergistic effects are analyzed and highlighted. Finally, the challenges and possible
solutions are briefly presented with some perspectives toward future development of this group of
materials.
Keywords: Nickel-based materials; Electrode materials; Electrochemical energy storage
Introduction terms of the specific energy (energy density) and specific power
Environmental and energy-related problems are among top con- (power density) is shown in the form of the well-known Ragone
cerns facing humanity. Currently, the use of green energy plot in Fig. 1. Energy density (ED) is defined as the amount of
sources such as solar or wind energy is rapidly growing. Further energy stored per unit. In the electrochemical storage field, it
progress in this area requires smart and versatile energy storage usually refers to the energy per unit of mass. Similarly, power
devices. Thus, energy storage becomes one of the key issues in density (PD) is commonly defined as a measure of power output
the energy generation. per unit mass. It is clear from Fig. 1 that supercapacitors can be a
All sorts of energy storage devices have distinctive features [1]. tradeoff between traditional capacitor and battery in terms of ED
Supercapacitors, also known as electrochemical capacitors (ECs), and PD. The similarities between supercapacitors and batteries
which can buffer the unsteady nature of wind/solar energy include two aspects: (1) the energy storage occurs at the elec-
sources, are newly emerged stand-alone or supplementary energy trode/electrolyte interface. And (2) ion transport and electron
storage devices [2]. A comparison of the common devices in transport are isolated from each other. The intrinsic difference
between batteries and supercapacitors refers to the free energy:
⇑ Corresponding author. an ideal battery has a single-value free energy, whereas superca-
E-mail address: Yu, J. (yujiaguo93@whut.edu.cn).
1369-7021/Ó 2018 Elsevier Ltd. All rights reserved. https://doi.org/10.1016/j.mattod.2018.11.002

1
Please cite this article in press as: L. Zhang et al., Materials Today, (2018), https://doi.org/10.1016/j.mattod.2018.11.002
RESEARCH Materials Today d Volume xxx, Number xx d xxxx 2018
Supercapacitors have already entered a specific market niche.

Apart from simple charge storage principle and mode of con-
struction, the merits of supercapacitors comprise high power
density and a long lifespan. Moreover, supercapacitors are safe,
cheap, and almost maintenance-free [6]. Their virtues are encap-
sulated in Fig. 2.
Overall, supercapacitors can be divided into two types, i.e.,
electrochemical double-layer capacitors (EDLCs) and pseudoca-
pacitors (PCs) [7]. In EDLCs, two layers of ions with opposite
charges (i.e., cations and anions) are physically adsorbed/des-
RESEARCH Review
orbed at the electrode/electrolyte interfaces. In this case, electro-

static surface charge storage ensures better power density [8–10].
In contrast, in PCs, fast and reversible faradic reactions occur at
the surface or near-surface of the electrode materials. Nowadays,
there is a great interest in hybridization of EDLC and PC materi-
als. Besides, asymmetric configuration, which is used in PC and
EDLC as positive electrode and negative electrode respectively,
becomes a wise solution to overcome the hurdle of poor energy
density of supercapacitors. Schematic illustrations of the classical
electrostatic capacitor and EDLC are shown in Fig. 3.
As mentioned above, the capacitance is an important indica-
tor in evaluating the performance of a supercapacitor. Two com-
mon methods for estimation of the capacitance are briefly
FIGURE 1 introduced here since the word “capacitance” will be frequently
Ragone plot showing a comparison of common electrochemical energy encountered in the following sections. One of them is the cyclic
storage devices. Reproduced with permission [5]. Copyright 2008, Nature voltammetry (CV), which applies a linearly changed potential
Publishing Group. between the working electrode and the reference electrode. The
speed of change is called as sweep rate or scan rate. The instanta-
pacitor theoretically exhibits a continuous change in the free neous current response is recorded. The specific capacitance
energy according to the degree of material conversion or extent obtained from the CV curves can be calculated using Eq. (1),
of the charge possessed [3,4]. In a battery, chemical reactions where I, v, m, U1 and U2 denote current (A), scan rate (mV/s),
release electrical carriers that can be extracted into a circuit. In mass (g), starting and ending voltage (V), respectively. Eq. (2)
contrast, in a supercapacitor, charges are mainly stored electro- describing the relationship between current and scan rate is
statically. Surface confined chemical reactions may also take sometimes used to differentiate supercapacitor and battery. If b
place in supercapacitors. The potential of a supercapacitor is a equals 1, EDLC is the dominating mechanism. If b equals 0.5,
continuous function of the degree of material conversion, while then the semi-infinite diffusion controlled mechanism becomes
that of a battery is fixed at a certain value, which is determined the leading mechanism. In most cases, both these two mecha-
by the Gibbs free energy of the specific phase. Therefore, a pla- nisms coexist and the contribution from each type can be sepa-
teau is observed in the potential-time profile of the battery. A rated. However, due to similar time scale of EDLC and PC, it is
brief comparison of batteries and supercapacitors is summarized difficult to distinguish them. The other method is galvanostatic
in Table 1. These two systems are targeted at different applica- charge–discharge (GCD) testing. The potential–time curve is
tions. Each one has its own priority and scope. They can be used recorded at a constant current. The gravimetric capacitance
in combination or separately depending on the application based on the GCD curve can be calculated from Eq. (3), where
requirements. I represents current and t is the discharging time. Rate capability
can be appraised by selecting different currents and cycling
stability can be assessed by elongating the time period.
TABLE 1
R U2
Comparison of supercapacitors and batteries. Ivdv
C¼ U1
ð1Þ
Supercapacitors Batteries 2vmðU 2 U 1Þ
Continuous variation of the free Single-value free energy

energy with degree of the material I ¼ avb ð2Þ
conversion
Intrinsically sloping charge–discharge Constant charge/discharge It
curve potential C¼ ð3Þ
mU
High degree of reversibility Irreversibility
Little or no polarization Temperature dependent Electrode materials, as core elements in the EDLC and PC
polarization devices, need to be carefully designed and tuned [5,11]. Despite
Excellent power density and mediocre Good energy density and the attractive features of carbon-based EDLC electrode materials
energy density moderate power density
[12], the high PD is at the expense of ED. It is impossible to find
2
Materials Today d Volume xxx, Number xxx d xxxx 2018 RESEARCH
RESEARCH Review
FIGURE 2
Advantages of supercapacitors.
FIGURE 3
Schematic diagrams of (a) an electrostatic capacitor, (b) an electric double-layer capacitor, (c) pseudocapacitor and (d) lithium ion capacitor.
an omnipotent material as supercapacitor electrode. A sensible materials [14] also exhibit the pseudocapacitance behavior origi-
move is to design proper composites to suit different circum- nating from the surface edge oxygen-functionalities or other
stances, maximizing the merits of each component and employ- organic groups; for another, for PC-type materials, even
ing the synergistic effects. battery-type materials, a portion of the total capacitance (proba-
Comparatively, pseudocapacitive materials possess higher bly 5–10%), which is proportional to their electrochemically
capacitance and higher energy density than EDLC-type materi- accessible interfacial area, can be attributed to EDLC behavior.
als. The electrons involved in EDLCs are peripatetic Several criteria should be taken into account for boosting the per-
conduction-band electrons of the metal or carbon electrode formance of electrode materials:
[13]; while the electrons involved in PCs originate from
valence-orbitals, which take part in the redox reactions. (1) High specific capacitance (SC) achieved at a high amount
However, we should bear in mind that a complete differentia- of mass loading to achieve high energy;
tion between these two categories of devices for certain electrode (2) wide potential window and chemical stability of the elec-
materials is difficult. For one thing, the carbon-based EDLC-type trolytes used;
3
(3) high permeability for rapid ion and electron transport, published on the nickel-based supercapacitors is shown in
along with large surface area for ion adsorption and redox Fig. 4. The data are retrieved from the Google scholar database.
reactions to assure high power; Most of these papers demonstrate that the achievable capaci-
(4) high reversibility of the surface/near-surface redox reac- tance is around 500–2500 F g1 (250–1250 C g1). To the best
tions to assure high rate capability; of our knowledge, the highest value reported so far is
(5) stable electrode structure and robust electrode/electrolyte 4172.5 F g1 (1669 C g1) at a current density of 1 A g1 [26];
interface to achieve high cycling retention; however, this value was achieved for a very small loading mass
(6) facile preparation, low-cost, and environmental (only 1 mg) on a nickel foam.
friendliness; The fundamental difference between nickel-based batteries
(7) high energy density and power density when the electrode and electrochemical capacitors is that the redox reactions in bat-
RESEARCH Review
materials are assembled into devices. teries occur in the bulk phase; while the energy stored in super-
capacitors is mainly due to the surface-involved processes. This
Nonetheless, hardly any existing single material can fulfill all disparity leads to the different theoretical limits of the stored
of these criteria. energy. There is still a controversy whether “nickel hydroxide”
Pseudocapacitive materials can integrate the merits of both or “nickel oxide” can be designated as “pseudocapacitive” mate-
battery materials and EDLC-type materials. They can fulfill the rials. Brousse et al. suggested that nickel hydroxide the cyclic
balance between decent energy density and acceptable power voltammetry (CV) curves of which show obvious peaks, should
density. Among them, transition metal oxides/hydroxides have not be classified as “pseudocapacitive” electrode material [27].
be proven to achieve much higher specific capacitance (SC) than Only materials with electrochemical behavior similar to that of
other types of electrode materials based on their high theoretical EDLC-type carbon electrodes in a mild aqueous electrolyte, such
capacitance, relatively good cycling stability and easy modifica- as RuO2 and MnO2, belong to the “pseudocapacitive” family.
tion [15–17]. That is to say, the CV curves of a pseudocapacitive material
Among all the pseudocapacitive materials, beyond all doubt, should also be nearly rectangular. Meanwhile, the GCD curves
ruthenium oxide with wide potential window (more than 1 V), should be symmetrical and linear. Brousse claimed that the rela-
high capacitance, and great electrical conductivity, is recognized tionship between the charge accumulated/released and the
as the most promising material. However, its scarcity limits its potential change in nickel or cobalt compounds is not capacitive.
large-scale applications. There are ongoing efforts to substitute However, in regard to electrode materials, this obvious boundary
ruthenium oxide by other inexpensive transition metal oxides has become vague because of the recent progress in nanoscience
such as manganese oxide/hydroxide [18,19], cobalt oxide/ and appearance of new electrode materials with concurrently
hydroxide [20–22], iron oxide/hydroxide [23], and their high power and energy density. The terminology of “supercapat-
composites [24,25]. Meantime, nickel-based materials have been tery” is even used in some reports [28,29]. Hundreds of papers
intensively investigated and evaluated as potential pseudocapac- related to the nickel-based materials consider them as
itive electrode materials due to their high theoretical specific supercapacitor-type materials. Noteworthy, it is still under debate
capacitance, thermal and chemical stability in various elec- on the capacitive behavior of nickel-based materials. In this
trolytes, facile fabrication protocols, as well as low-cost and envi- manuscript, capacity (expressed in C g1) and capacitance
ronmental benignity. A graphical overview of numerous papers (expressed in F g1) are both given since the original cited papers
adopted capacitance. The capacity value is calculated based on
the result of multiplication of the reported capacitance and the
potential window of the materials. Herein, these papers are sum-
marized. It is a pity that the performance of pristine nickel oxide
and nickel hydroxide themselves is not satisfactory. The major
issues of these materials are as follows:
(1) The inherent relatively narrow potential window (0.4–

0.6 V) restricts their application.
(2) They suffer from low conductivity (103–102 S cm1) orig-
inating from the intrinsic semiconductor or insulator nat-
ure, which limits their electrochemical kinetics through a
polarization resistance.
(3) Their cycling stability is mediocre due to the irreversibility
and the volume expansion/contraction during Faradic
redox reactions.
To eliminate the aforementioned shortcomings, various

FIGURE 4 attempts have been undertaken. In this review, by categorizing
Graphical overview of papers published on the nickel-based supercapac- the nickel-based materials into several groups based on their
itors within the last decade. (The data for 2018 only cover the papers chemical composition, we present a summary of recent achieve-
published before June 2018.) ments in this exciting area of research. Moreover, this review
4
highlights the major research activities and provides a critical Nickel-based electrode materials
appraisal of the recent developments in the area of nickel- Pristine nickel oxide/hydroxide
based electrode materials. Nickel oxide and nickel hydroxide are competent as supercapac-
The history, applications, detailed principles and fabrication itor electrode materials, including high theoretical capacitance,
of supercapacitors have already been comprehensively reviewed low cost and low environmental impact [30]. Besides, their facile
elsewhere. So far, a thoughtful review paper devoted to the synthesis and favorable chemical stability also foster their wide-
nickel-based materials for supercapacitor applications is not spread use. Nickel oxide, as a p-type semiconductor with a high
available. The growing amount of research reports on this topic theoretical capacitance of 2584 F g1 (1292 C g1 within 0.5 V)
indicates that a comprehensive review on this topic is necessary has been investigated as a supercapacitor material since 1996.
and timely. Hence, the focus of this review is merely on the At that time, the synthesized porous nickel oxide film showed
RESEARCH Review
nickel-based materials with special emphasis on their fabrication only a SC value between 200 and 256 F g1 (100–128 C g1) [31].
and performance. An extensive survey on the nickel-based mate- Later, Abdalla et al. synthesized nickel oxide nanotubes fea-
rials is the essence of this review. Since the quantity of the papers turing the gravimetric capacitance of 245.3 F g1 (123 C g1)
published in this area is large, we could not cover all of them. only and the area capacitance of 3.28 F cm2 at 2 mV s1 [32].
Only essential works devoted to doped or modified nickel Also, nickel oxide nanowires with uniform size distribution were
oxide/hydroxide materials are discussed; namely, our focus is prepared by electrospinning with diameters of ranging from 50
on the papers dealing with: to 70 nm. As compared to nanotubes, the capacitance of these
nanowires was much higher, i.e., 670 F g1 (335 C g1) at
(1) pristine nickel oxide/hydroxide, 1 A g1 [33]. However, this value is still relatively low. Another
(2) nickel oxide/hydroxide with incorporated or decorated car- strategy to elevate the capacitance is by maximizing the effective
bonaceous materials, active surface area, which can be achieved in the case of well-
(3) nickel-based bimetallic materials, developed nanostructures. Wang et al. utilized rape pollen to
(4) nickel-containing metal–organic frameworks (MOF), construct elliptical NiO (Fig. 6d–f) [34]. The reported porous hol-
(5) nickel-sulfide-based materials, low ellipsoids were composed of a large number of nanosheets.
(6) nickel-phosphide-based materials The abundant cavities in this material assured a lot of free space
(7) multi-component nickel-containing materials. for ion storage. Therefore, capacitance of this pollen-templated
The arrangement of different sections is shown in Fig. 5. The NiO (P-NiO) reached the value close to 1589 F g1 (715 C g1)
design methods, optimization strategies, as well as interaction at 1 A g1, which is much higher than that for NiO synthesized
with other components (not limited to the current collector, without pollen (W-NiO). Another example also shows a success-
electrolyte and binders) are also discussed, including major chal- ful effort to enlarge accessible surface area. Qi and co-workers
lenges in this area. Several scientific issues related to scaling-up were able to design a multi-shelled NiO using resin spheres as a
laboratory research into industrial level are presented too. Anal- template. They carefully controlled the calcination rate and
ysis and constructive comments on the key problems in this area adjusted the ion concentration and reaction time as illustrated
are given. We believe that this updated overview can provide in Fig. 7. The formation of multi-shelled NiO was dependent
some guidelines for the future development of these materials on the temperature-gradient-induced two forces: the adhesion
for energy-related applications. force directing outward, and the contraction force directing
FIGURE 5
Nickel-based materials discussed in this review.
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RESEARCH Review
FIGURE 6
Fabrication scheme and the corresponding SEM images of (a, d) Rape pollen grains without treatment; (b, e) pretreated rape pollen grains; (c, f) P-NiO; (g, h)
TEM images and (i) HRTEM image of P-NiO. Electrochemical performance: (j) CV curves measured at 10 mV s1, (k) GCD curves at 10 A g1 (inset: at 1 A g1)
and (l) rate capability performance of W-NiO (without the addition of rape pollen grains), P-NiO (pollen templated NiO), Ni foam, Pollen-A (natural pollen
grains) and Pollen-C (treated pollen grains). Reproduced with permission [34]. Copyright 2017, Elsevier.
inward. The hollow NiO with triple-shell and internal voids literature. Lately, the Ni(OH)2 ink with a concentration as high
delivered the highest capacitance value of 1280 F g1 as 50 mg mL1 has been prepared through a facial co-
(576 C g1), possibly due to the proper pore volume and abun- precipitation and ultrasonication method [36]. This ink can be
dance of active sites [35]. re-dispersed in various electrolytes. The capacitance of the mate-
Ni(OH)2, the history of which as a battery material dates back rial coated on carbon fiber yarn reached more than 1000 F g1
to 19th century, with a high theoretical capacitance of (500 C g1) for the thickness of several tens of nanometers. This
2081 F g1 (1040 C g1) (within 0.5 V), is another potential can- proof-of-concept research confirms the feasibility of nickel
didate as a supercapacitor electrode. Two commonly used phases hydroxide as a promising electrode for real-life device fabrication
of this material are a-Ni(OH)2 and b-Ni(OH)2. The former has and applications. Deng et al. pioneered the in-operendo study of
higher capacitance due to the higher oxidation state of nickel. Ni(OH)2 nanosheets via electrochemical atomic force micro-
However, the former is not stable and can be easily transformed scopy. They found that the increase of the potential led to an
into the latter when alkaline electrolytes are used. The com- increase in the porosity, and nanoparticles replaced nanosheets
monly used electrolytes for nickel oxide and nickel hydroxide because of the transformation of Ni(OH)2 into NiOOH [37]. Fur-
are aqueous alkali solutions, such as KOH. Although they show ther mechanic studies are needed to reveal more in-depth rea-
similar reaction with OH, the charge storage mechanism varies sons for the phase reconstruction.
as presented in Eq. (4) and (5), which is often oversimplified in NiO þ OH $ NiOOH þ e ð4Þ
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RESEARCH Review
FIGURE 7
TEM images of (a) double-, (b) triple-, and (c) quadruple-shelled hollow NiO microspheres with closed exterior double-shells; TEM images of double-, triple-,
and single-shelled NiO hollow microspheres. Electrochemical performance: (g) Cyclic voltammetry (scan rate: 50 mV s1), (h) galvanostatic charge/discharge
curves, and (i) rate performance under different current densities of the previous multi-shelled NiO. Reproduced with permission [35]. Copyright 2016, Nature
Publishing Group.
NiðOHÞ2 þ OH ! NiOOH þ H2 O þ e ð5Þ disparity between pristine nickel oxide/hydroxide and other
The CV curves of nickel-containing electrode materials are nickel-based materials.
quite similar, indicating that the redox reaction involved Ni2+ For nickel oxide, its charge storage mechanism is mainly due
and Ni3+. The CV curves are given and discussed to show the to the surface adsorption and redox reaction with OH; whereas
7
for nickel hydroxide, the mechanism involves the intercalation

and de-intercalation of H+ between the layers. Since the size of
H+ is smaller than that of OH, it is easier for H+ to diffuse into
Ni(OH)2, making the bulk properties of Ni(OH)2 better than
those of NiO [38]. However, both of them suffer from low con-
ductivity (ca. 105–109 S cm1) [39]. To ameliorate this short-
coming, the construction of nano-sized and porous structures
is a good strategy. When the size scales down to nanometers,
the specific surface area becomes higher, and the diffusion path
becomes shorter, which guarantees high transfer rate of electrons
RESEARCH Review
and/or ions.
Incorporation and decoration with carbonaceous materials

Despite significant progress made in the modification of pristine
nickel oxide and hydroxide materials, up to now there is a great
challenge to simultaneously achieve high specific capacitance, FIGURE 8
rate capability and cycling stability. Accordingly, scientists have Advantages of using carbonaceous materials.
tried to couple carbon-based materials with nickel oxide/hydrox-
ide or grafting nickel oxide/hydroxide on these materials to form groups of graphene can attract nickel oxide/hydroxide on its
composites [40]. The carbon-based materials themselves are basal planes or edges, which assure uniform distribution of nickel
superb electrode materials [10,41]. The introduction of carbona- oxide/hydroxide species and enhance the electrochemical per-
ceous materials brings plenty of benefits. formance of the composite. Besides, the flexibility of graphene
makes it a good candidate as a substrate for assembly of flexible
(1) Carbonaceous materials can govern the growth of nickel- supercapacitors. The preparation methods of nickel-based com-
based materials and reduce the size of the overall posites with incorporated/decorated carbon together with their
composite. performance are summarized in Table 2. The capacitance values
(2) It can suppress the agglomeration of nickel oxide/hydrox- and the potential range provided in this table are calculated from
ide. Nano-structured nickel oxide/hydroxide has high sur- the GCD curves unless otherwise indicated. Columbic efficiency
face energy and tends to aggregate to form bulky particles and the performance of asymmetric supercapacitors are not
in the absence of carbonaceous materials. included in Table 2. However, their importance cannot be
(3) Carbonaceous materials can be used as scaffolds to pin- overlooked.
point nickel-based materials; therefore their movements Owing to the fact that the specific capacitance (SC) of elec-
during the charge–discharge cycles are minimized. trode materials is strongly correlated to the electrolyte and scan
(4) The volume change during the cycling tests is also rate/current density, the corresponding parameters are provided
mediated. for comparison at the same time. The reported performance of
(5) The electrical conductivity of the overall composite is nickel-based composites is quite encouraging. For instance, gra-
enhanced, facilitating the charge transfer process. phene nanoflakes decorated with nickel oxide quantum dots
The specific surface area is tremendously increased. Concur- were shown to have a specific capacitance of 1181.1 F g1
rently, the high porosity and interconnectivity are also desirable. (590 C g1) and rate capability of 66.2% at 42 A g1 [44]. Tang
These six merits are illustrated in Fig. 8. et al. directly fabricated Ni(OH)2 on CNTs, which were grown
Among various carbon materials (graphene, rGO) and carbon on Ni foam by CVD method. The aligned composite forest
nanotubes (CNTs) are most often used. Carbon aerogels, ordered achieved a strikingly high specific capacitance of 3300 F g1
carbon frameworks, carbon quantum dots are also used [42,43]. (1320 C g1) and a high areal capacitance of 16 F cm2 [45]. To
CNTs can be either conducting materials like metals due to the further increase conductivity, Ma et al. used nickel-coated carbon
free movement of delocalized p electrons or semi-conducting. nanotubes (Ni-CNTs) as the conductive substrate for growing b-
They are resistant to chemical corrosion or physical force. Hence Ni(OH)2. The composite demonstrated a high SC value of
they are expected to have high strength and stability. When 1815 F g1 (907 C g1) and good capacitance retention of 97%
combined with nickel-based materials to form composites, the after 2000 cycles at a relatively high charge density (10 A g1)
unique one dimensional structure of CNTs endows the compos- [46]. Except for incorporation of carbon nanotubes or graphene,
ite with remarkable electronic conductivity and ultrahigh speci- carbon spheres have also been used to form NiO/C composites
fic surface area. Therefore, in some rational designs, CNTs are [47]. The morphology is illustrated in Fig. 9b–d. The hollow
used as the scaffolds to grow nickel-based materials. The remark- spheres anchored with the lacy nanosheets endowed the com-
able two dimensional structure of graphene renders its compos- posite material with high capacitance of 686 F g1 (343 C g1)
ites with nickel oxide/hydroxide with ultrahigh specific surface at 1 A g1. The synthetic procedure of this composite is also dis-
area due to the extremely high theoretical surface area of exfoli- played in the same figure. SiO2/C spheres were used as the semi-
ated graphene, which is around 2630 m2 g1. The functional sacrificial templates for growing Ni(OH)2 nanosheets, which was
8
method; MPCVD; microwave plasma enhanced chemical vapor deposition; QD: quantum dot. The potential window and the specific capacitance are based on the galvanostatic charging–discharging tests. And the potential window from CV curves is also
SBET: BET specific surface area; U: electrochemical potential window; Cs: gravimetric specific capacitance; D: direct growth method without the usage of binder or other additive; S: slurry-coated/doctor-bladed method; NF: nickel foam; HT: hydrothermal
transformed into nickel oxide after calcination. The in-situ
Ref.
[46]
[49]
[50]
[51]
[52]
[53]
[44]
heterogeneous nucleation of Ni(OH)2 and in-situ dissolution of
SiO2 by OH released from urea due to its controlled decomposi-
tion at high temperatures are responsible for the formation of
Rate Capability
( F g1/C g1)
this intriguing morphology. Instead of being a scaffold or sup-
(10 mV s1)
1902/1046
port, carbon can also be used for the surface modification via
(20 A g1)
(10 A g1)
(30 A g1)
(15 A g1)
(25 A g1)
(42 A g1)
1226/552
1000/600
857/429
403/202
938/563
781/391
coating or wrapping nickel-based materials, which has been also
demonstrated as an effective strategy and will be discussed in the
sections associated with other nickel-based materials.
97% (2000th, 10 A g1)
84% (4000th, 10 A g1)
81% (5000th, 15 A g1)
98% (2000th, 10 A g1)

Cycling Stability (%)
There are two main reasons for the enhancement of graphene-
RESEARCH Review
nickel-based hybrid materials: (1) graphene has good
Properties, characteristics and supercapacitor performance of nickel oxide/hydroxide materials with incorporated carbon via various preparation methods.
94.9% (5000th,
83.5% (1000th,
conductivity, which enhances its interfacial contact with nickel
95% (10000th,
oxide/hydroxide, and nickel-based materials act as spacers to

10 mV s1)
2.1 A g1)
10 A g1)
prohibit the restacking of graphene. The interlayer spacing can

be effectively utilized as an ion-buffering reservoir. Although
good results in this case have been attained, several critical points
should be taken into account. To date, the most popular strategy
Cs ( F g1/C g1)
for the fabrication of supercapacitor electrodes is the

slurry-casting method. If this method is exploited for nickel
2287/1258
1829/1097
(2.1 A g1)
(1 mV s1)
1815/907
1016/508
1768/756
1283/770
1181/590
(2 A g1)
(1 A g1)
(7 A g1)
(2 A g1)
(3 A g1
oxide/hydroxide decorated with graphene, the superiority of

the high surface area of graphene or CNTs becomes pointless.
The underlying reason is a strong tendency of nano-sized carbon
materials to agglomerate when mixed and pasted on the current
0–0.55 vs. Hg/
collectors. Moreover, homogeneous dispersion of graphene or

CNTs on the current collector is difficult. Hence, direct growth
0–0.45
U (V)
0–0.5
0–0.5
0–0.6
0–0.6
0–0.5
of nickel oxide/hydroxide on the carbon-based skeleton, instead

HgO
of mechanical mixing is favorable.

(m2 g1)
Nickel-based bimetallic materials

SBET
274
227
Another remedy for improving performance of pristine nickel

30
62
/
oxide/hydroxide is through the fabrication of ternary oxides.

listed in the brackets. The reference electrodes are saturated calomel electrodes (SCE), otherwise they are specified.
Electrolyte
To circumvent the drawbacks of mono metal oxides/hydroxides,

1 M KOH
2 M KOH
6 M KOH
6 M KOH
1 M KOH
1 M KOH
2 M KOH
bimetal oxides/hydroxides have emerged with desired properties,

stemming from the co-existence of two different cations in one
structure. The merits of bimetal oxide/hydroxide embrace several
aspects.
HT + Electrochemical
(1) The presence of metal ions with multiple oxidation states

Synthetic Method
(valence states) grants the ternary materials with rich redox

Electrochemical
MPCVD + HT
Two-step HT
Precipitation
reactions.
activation
approach
(2) Ternary metal oxides/hydroxides exhibit higher electronic

conductivity than their binary counterparts.
HT
HT
(3) The electrochemical performance of the bimetallic nickel-

based materials is not exactly the same with that of nickel
oxide/hydroxide. The reversibility of the compounds is
enhanced, which can be justified by the shape of the CV
Dots on flakes
3D flower-like
Morphology
Tremella-like
Honeycomb
curves or the reduced peak separation. Sometimes CV

Nanoflakes
Nanoflakes
Structure/
Core–shell
spheres
curves become rectangular, such as nickel cobalt oxide;

whereas in other cases, the peak separation becomes smal-
ler, the distinct transition points in the GCD curves are not
g-C3N4@Ni(OH)2/(S)NF
so obvious.
b-Ni(OH)2/GO/CNTs/
Ni-CNTs@b-Ni(OH)2/
Material/Substrate
Graphene/(D)NF
NiC2O4@NiO/(D)NF
(4) Various combinations of different cations offer abundance

NiO QD/G/(S)NF
of choice for manipulating potential candidates.

NiO/rGO/(S)NF
The physical and electrochemical properties can be tuned by

(S)NF
(S)NF
NiO-3D
tailoring the composition and structure. This review will be con-

TABLE 2
centrated on the ternary metal oxides/hydroxides, which con-

tain nickel as one of the cations.
9
RESEARCH Review
FIGURE 9
(a) Schematic illustration and (b) the corresponding TEM images of the precursor SiO2/C, intermediate Ni(OH)2/C-HS and the final product NiO/C-HS.
Reprinted with permission [48]. Copyright 2018, Royal Society of Chemistry.
Nickel–aluminum (Ni–Al)-based materials et al. synthesized graphene nanosheet/Ni-Al LDH and the result-
Nickel-aluminum-based supercapacitors are primarily NiAl-lay- ing composite delivered a SC of 781.5 F g1 (367 C g1) [60]. Silver
ered double hydroxide. Layered double hydroxides (LDH), with nanowires have been selected as the conductive backbone to sup-
the general formula of [MII III x+
1xM x(OH)2] [A
n
]x/n and generally port Ni–Al LDH material, and a SC of 1247 F g1 (1247 C g1) at
surrounded by hydroxyls, where M and MIII are divalent and
II
1 A g1 was obtained for this novel architecture [61]. In addition
trivalent cations and A is inorganic or organic anion, have grasped to the typical examples presented above, other composites con-
great attention. The layered or two-dimensional structures, taining Ni-Al LDH have been explored too (see Table 3).
together with multiple options of cations and anions, have pro- However, we should be aware that since the valence of alu-
vided myriad of LDHs under consideration. The effect of Al doping minum (Al) is fixed to be +3, Al is not involved in any redox reac-
on the electrochemical performance has been scrupulously inves- tions. The active reaction sites are purely Ni sites themselves,
tigated by Huang and co-workers [54]. At an optimal Al ratio where the insertion and extraction of OH ions occur. Further-
(3.4%), an outstanding SC of 2122.6 F g1 (849 C g1) at 1 A g1 more, only a part of the inner surfaces between layers is accessi-
was attained. Verwey et al. have reported that the conductivity ble to the electrolyte ions. Although unilamellar nanosheet is
of nickel oxide is proportional to the concentration of Ni3+ ions acquired via exfoliation, the elegant design and exfoliation can
in the lattice [55]. Inspired by their findings and the fact that alu- become useless if the electrode fabrication process is still the
minum can be etched away in alkali solutions, the adjustment for slurry-coating. To maximize the utilization, the structures, pore
the amount and valence state of nickel has been tried. Al, ampho- size distribution, and the thickness of the Ni-Al LDH materials
teric in nature, can be easily displaced; while nickel remains intact. need to be attentively modulated.
In principle, a decrease of Al3+ in the Ni–Al LDH increases auto-
matically the ratio of Ni in the LDH. Simultaneously, the loss of Nickel–cobalt (Ni–Co)-based materials
charge is compensated by converting Ni2+ into Ni3+. Meanwhile, Cobalt oxide/hydroxides themselves have been recognized as a
plentiful amounts of pores are also created. A similar approach class of the most promising supercapacitor electrode materials.
has been widely used in relation to Co–Al LDH materials by The reversible redox processes between Co2+/Co3+/Co4+ bring
removal of Al [56–58]. To date, the studies of Ni–Al LDH and the extra capacitance. Therefore, among all the ternary oxides/
etching of Al are scarce. At present, apart from using LDH alone hydroxides, nickel cobalt-based materials are the most popular,
as supercapacitor electrode, its decoration with carbon and other which is corroborated by the fact that there is a huge surge in
kinds of hybridization has been simultaneously explored to developing them. This review does not cover all the papers deal-
enhance the overall performance. The interlayer spacing in LDHs ing with nickel–cobalt-based materials. Only some archetypes are
can be controlled by exchanging interlayer anions. Moreover, selected for discussion. Spinel nickel cobaltite [80–82] and nickel
LDHs can also be exfoliated into monolayer nanosheets with ultra- cobalt double hydroxide [83] are the two main promising mate-
high specific surface area. Ge et al. have devised a protocol to rials. Other composite, e.g., CoO nanowire@Ni(OH)2 with NO 3
assemble stacked Ni–Al LDH/graphene superlattice [59]. This was intercalation has also been prepared [84].
achieved by chemical exfoliation of LDH in formamide and elec- Nethravathi et al. synthesized mixed nickel cobalt hydroxide
trostatic attraction between the positivelycharged LDH and nega- rings grafted on graphene. The acidic groups on the graphene
tivelycharged graphene. Instead of reporting the SC values, they etched the nanoplates successfully and thus the rings were cre-
provided a battery-related capacity of 129 Ah g1 at 1 A g1. Gao ated. The procedure in synthesizing Co3O4/CoO–graphene
10
Materials Today
TABLE 3
Nickel–aluminum-based materials prepared using different methods and their supercapacitor performance.
d
Cs ( F g1/C g1)
Volume xxx, Number xxx

Material/substrate Structure/morphology Synthetic Electrolyte SBET U (V) Cycling stability Rate Capability Ref.
method (m2 g1) (%) ( F g1/C g1)
NiAl-LDH@CNP/(D) CF Hexagonal nanoplatelets HT 1 M KOH / 0–0.6 1146/688 / 478/287 (200 mV s1) [62]
(2 mV s1)
rGO/Ni2Al1–LDH/(S)NF Nanosheets LBL + HT 6 M KOH 184 0–0.37 1329/492 91% (500th, 851/315 (17.86 A g1) [63]
(3.57 A g1) 15.30 A g1)
G/Ni–Al LDH/(S)NF Layered sheets HT + DL 3 M KOH / 0–0.48 915/439 95% (1500th, 10A 154/74 (10 A g1) [64]
(2 A g1) g1)
NiAl-LDH + CQDs/(S)NF Ultrathin HT + mixing 6 M KOH 77 0–0.42 1794/753 93% (1500th) 967/899 (20 A g1) [65]
d
(2 A g1)
xxxx 2018
nanoplates
Ni-Al LDH/(S)NF Rosette (nanosheets) HT 6 M KOH / -0.2–0.4 891 C g1 82.9% (1000th, 625 C g1 (10 A g1) [66]
(0.5 A g1) 2 A g1)
Al-doped Ni(OH)2/(D)NF Nanosheets HT 6 M KOH / -0.2–0.5 2123/1486 78% (500th, 1 A g1) 1389/972 (6 A g1) [67]
(1 A g1)
Fe3O4@C–Ni–Al LDH/(S) NF Flower-like HT + LBL + HT 6 M KOH 792 0–0.37 767.6/284 85% (1000th, 406/150 (10 A g1) [68]
(1 A g1) 8 A g1)
CoxNi1xAl LTH/(S)/NF Flower-like HT 1 M KOH / 0–0.5 1375/688 93.3% (1000th, 962/481 (6 A g1 [69]
(0.5 A g1) 2 A g1)
GNS/Ni–Al LDH/(S)NF Agglomerated sheets In situ- 6 M KOH 87 0–0.47 781.5/367 122% (200th, / [60]
crystallization 10 mA cm2)
Al-substituted Ni(OH)2/(D)NF Nanoflakes HT 3 M KOH / 0–0.45 vs. Ag/ 3492/1571 81% (2000th, 1142/514 (32 A g1) [70]
AgCl (4 A g1) 10 A g1)
rGO/Ni0.75xCoxAl0.25–LDH/ disk-like ultrathin flakes ST 3 M KOH / 0–0.5 vs. Hg/ 1544/772 100% (2000th, 1343/672 (40 A g1) [71]
(S)Ni foam HgO (1 A g1) 10 A g1)
Zn–Ni–Al–Co oxide/(D)NF Flower-like nanosheets CBD + A 2 M KOH 83 0–0.5 vs. Hg/ 839 C g1 100% (2000, 688 C g1 (1 A g1) [72]
HgO (1 A g1) 10 A g1)
Ag NW@ 1D core–shell SG + HT 6 M KOH 36.7 0–0.5 1246.8/623 80.3% (5000th, 760/380 (10 A g1) [73]
NiAl LDH/(S)NF (1 A g1) 10 A g1)
rGO/Ni1xCoxAl–LDH/(S)NF Sandwich LBL + HT 6 M KOH 171.5 0–0.37 1902/704 62% (1500th, 1422/526 (10 A g1) [74]
(1 A g1) 10 A g1)
LDH/CNT/GNS/(S)NF Flowers on sheets ST 6 M KOH / 0–0.42 1896/796 96.5% (1000th, 713/299 (100 mA cm2) [75]
(1 mA cm2) 10 A g1)
Grapheme/Ni–Al LDH/(S)NF Nanowires LBL + HT 6 M KOH 230 0–1 268 (0.43 A g1) 100% (1000th, / [76]
(symmetric) 3 A g1)
CoNiAl LTH/(DNF Nanofiber-composed HT 3 M KOH / 0–0.45 vs. Ag/ 1344/605 85% (2000th, 1344/605 (50 mV s1) [77]
dandelion-like AgCl (50 mV s1) 1.47 A g1)
Ni–Al LDH/CNTs/(S)NF Nanoflakes LBL + HT 6 M KOH / 0–0.6 2143/1071 88% (1000th, 1825/1095 (10 A g1) [78]
(1 A g1) 2 A g1)
Ni–Al LDH Petal-like CBD + HT 1 M KOH / 0–0.5 795/398 80% 1000th, 220/110 (10 A g1) [79]
(0.5 A g1) 2.5 A g1)
U: potential window tested by GCD; CF: conductive fabric; G: grapheme; CQD: carbon quantum dots; LDH: layered double hydroxide; LTH: layered triple hydroxide; GNS: grapheme nanosheets; CBD: chemical bath deposition; 1D: one-dimensional; SG:
seed-growth technique; IE: ionic-exfoliation; FD: freeze drying; LBL: layer-by-layer; DL: delaminated by ultrasonication; PD: potentiostatic deposition; ST: solvothermal; MV: microwave; T: template-assisted.
RESEARCH
11
RESEARCH Review
hexagonal hybrid is shown in Fig. 10i. Functional groups (includ- part of the hydroxide was prone to be etched due to its larger
ing ACOOH and AOH) on the graphene oxide were used as a extent of defects. Nickel precursor was added to substitute Co
mild etching acid to dissolute the metal hydroxide, and also as with nickel to form NiCo2O4–graphene ring. Morphology of
a linking media to bind graphene oxide and the metal hydroxide. NiCo2O4 well inherited that of Co3O4/CoO (Fig. 10g). Compara-
The pH of the composite should be finely adjusted. The inner tively, conspicuous redox peaks diminished (Fig. 10a). Instead,
CV curves became the superimposition of a hump and a rectan-
gle, substantiating the improved reversibility of the composite
after the Co incorporation and graphene hybridization. NiCo2O4
graphene ring exhibited a specific capacitance of 1337 F g1
(401 C g1) at 1 A g1. The augment in capacitance was due to
RESEARCH Review
the thin nanorings and the intimate contact between the thin
nanorings and graphene through the chemical etching reaction,
which guarantees the preferable electrical contact [85]. Besides,
93% capacitance retention after 5000 charging-discharging
cycles was attributed to the graphene support.
Long et al. claimed that the amorphous nickel cobalt binary
oxide displays a specific capacitance of 1607 F g1 (854 C g1)
at 0.5 A g1. They asserted that the amorphous structure engen-
dered more surface defects, which promoted the redox reaction
[86]. Moreover, the amorphous structure induces larger channels
for ions owing to the random atomic positions. Chen et al. syn-
thesized NiCo2O4 on a carbon substrate, and assembled symmet-
ric supercapacitors with the as-obtained materials. The CV curves
were quite rectangular, and the redox peaks were non-
discernible, which demonstrated the prodigious reversibility of
this material, as shown in Fig. 11(h–k). Surprisingly, the capaci-
tance achieved was as high as 2367 F g1 (2367 C g1) at
1 A g1; and even at a high current density of 10 A g1, the capac-
itance was still intriguing (2137 F g1 2137 C g1) [87]. The rea-
son for this superb result may be the ingenious design
involving incorporation of nickel nanoparticles. Another car-
bon–nickel cobalt oxide hybrid was prepared by Zhu et al. by
employing a novel glucose coating–annealing method. The
nickel cobalt oxide was not the commonly synthesized NiCo2O4,
but rather a CoNi3O4 compound. The morphology after the car-
bon coating was well maintained without disintegration, and a
void space appeared [88].
The rate capability of nickel–cobalt-based materials is still
poor, which is curbed by their intrinsically low electronic con-
ductivity. If they are exfoliated into a thin layer with a thickness
confined to only a few atomic layers, the problem can be allevi-
ated by shortening the diffusion path and boosting the surface
area. This alternative has been demonstrated to be effective. Con-
secutive Ni(OH)2 and Co(OH)2 layers yielded a capacitance of
1524 F g1 (762 C g1), and a thrilling energy density of
101.3 Wh kg1 was achieved when it was coupled with carbon
nanofoam paper as the negative electrode [89]. Monolayer nickel
cobalt hydroxyl carbonate with an average thickness of 1.07 nm
was synthesized and a distinguished capacitance of 2266 F g1
(1133 C g1) was obtained at 0.5 A g1. When the current density
was enlarged to 20 A g1, 83.6% of the original capacitance was
FIGURE 10 maintained [90]. Both of these examples validate that the ample
Electrochemical performance: (a) CV curves, (b) GCD curves, (c) rate exposed active sites in the unilamellar layers are the principal
performance at various current densities, and (d) cycling performance of reason for the great performance. It should be mentioned that
the NiCo2O4 hexagonal ring–graphene hybrid. TEM images of (e, f) NiCo2O4
the restacking of monolayers led to the reduction of the specific
hexagonal ring and (g) NiCo2O4 hexagonal ring–graphene hybrid. (h)
HRTEM image of NiCo2O4 hexagonal ring–graphene hybrid. (i) Synthetic surface. Wang et al. reported the chemical treatment of Ni–Co–Al
processes of Co3O4/CoO hexagonal ring–graphene hybrids. Reproduced LDH to etch Al in the surface layer and simultaneously to transfer
with permission [85]. Copyright 2014, American Chemical Society. Co2+ into more conductive Co3+ [91]. All these factors were ben-
12
RESEARCH Review
FIGURE 11
SEM images of (a) CF-G, (b) CF-Ni01-G, (c) CF-Ni05-G, and (d) CF-Ni10-G. (e) TEM and (f) HRTEM of a single NiCo2O4 nanorod in CF-Ni01-G; (g) TEM and (h)
HRTEM of a single NiCo2O4 nanosheet in CF-Ni10-G. CV curves of NiCo2O4 with different amounts of nickel added (a) CF-G, (b) CF-Ni01-G, (c) CF-Ni05-G, and
(d) CF-Ni10-G. (l) Schematic representation of NiCo2O4 growth on pure CF and nickel-seeded CF. Reproduced with permission [87]. Copyright 2016, American
Chemical Society.
13
RESEARCH Review
FIGURE 12
TEM images of the (a, b) untreated and (c, d) treated nickel cobalt aluminum (NCA) layered hydroxide at different magnifications. (e) CV curves of the NCA 7–
1T sample tested in 2 M NaOH at a scan rate of 5 mV s 1. (f) The specific capacitance of different samples at different current densities. (g) Nyquist plot for
the NCA 7–1 and NCA 7–1T samples. The inset shows the enlarged Nyquist plot in the high frequency region. (h) The equivalent series resistances (ESRs) for
different samples. Reproduced with permission [91]. Copyright 2014 WILEY-VCH Verlag GmbH & Co. KGaA.
14
eficial for the specific capacitance enhancement. As shown in increase in the specific area of the whole electrode, rather than
Fig. 12, the TEM images before and after treatment were dis- the active material only. The in-situ transformation from the cur-
tinctly different. After treatment with sodium hydroxide, the sur- rent collector into the electrode material eliminated the detach-
face roughness withstood and the defects grew. The capacitance ment problem of the active material. In addition, the problem
comparison of the treated and untreated samples is shown in of the weak contact between active material and current collector
Fig. 12(e–g). The treatment was advantageous for the increment was solved. The electrochemical performance of the assembled
of capacitance. A general trend shows that the specific capaci- asymmetric supercapacitor is illustrated in Fig. 13(d–g) [96].
tance increases with increasing amount of Al etched. The reason The nearlyrectangular shape of the CV curves and the nearlytri-
is that Al was electrochemical inactive. angular shape of the GCD curves affirm the optimal match
Up to date, Nagaraju et al. have reported a flexible and light- between positive and negative electrodes (rGO). Other groups
RESEARCH Review
weight device made up of nickel cobalt hydroxide on nickel fab- also undertook studies on the incorporation of copper into nickel
ric as the positive electrode material, and activated carbon on the materials. Copper doping has been verified to be effective for the
same kind of fabric as the negative electrode material. This device performance enhancement of nickel oxide. Ni0.99Cu0.01O exhib-
delivered an areal capacitance of 1.1 F cm2 at 3 mA cm2, and ited an 86.12% increase in the capacitance in comparison to the
the corresponding PD is 2.35 mW cm2 with ED of pristine nickel oxide [97]. Copper was also adopted as the skele-
0.392 mWh cm2 [92]. ton for the growth of nickel hydroxide. Cu@Ni(OH)2 exhibited a
high capacitance of 2426 F g1 (1334 C g1) at a high current
Nickel–copper (Ni–Cu)-based materials density of 10 A g1, and a superior rate capability [98]. Nickel–
Apart from the well-established ternary metal oxide systems, the copper carbonate hydroxide has also been investigated as a
nickel copper oxide/hydroxide system is presented. Pristine supercapacitor electrode [99].
nickel oxide/hydroxide shows a mediocre rate capability and
low electronic conductivity. To tackle these issues, addition of Nickel–iron (Ni–Fe)-based materials
copper is considered. Copper is not only abundant and cost- As mentioned before, the boundary between rechargeable batter-
effective, but also highly conductive and features intriguing ies and supercapacitors is somewhat indistinct. This concept is
physiochemical properties. Besides, copper has been widely used exemplified in nickel–iron-based materials. They are bi-
to modify catalyst systems due to its high activity. In this scenar- functional electrode materials, not only for rechargeable batteries
io, modification of nickel-based materials by two approaches is but also for supercapacitors. Ni–Fe LDH, directly grown on a
considered. One approach takes advantage of the conductivity nickel foam, displayed an outstanding performance; namely,
of copper in its metallic form; while the other focuses on the the specific capacitance was 2708 F g1 (1083 C g1) at 5 A g1
design of nickel copper systems similar to other nickel-based oxi- [100]. Singh et al. adopted AAO-template-assisted electrochemi-
des/hydroxides (such as nickel cobalt oxide). We have reported cal deposition method to prepare Fe–Ni/ Fe2O3–NiO nanowire
that Cu served as a nanoconductor, increasing the conductivity core–shell structure [101]. This hybrid material demonstrated a
of nickel hydroxide. Nickel oxide cannot rival with the copper- high specific capacitance of 1415 F g1 (778 C g1) at 2.5 A g1.
decorated nickel oxide in the overall performance, including Aside from positive electrode, Xie et al. synthesized Fe–Ni alloy
the specific capacitance, rate capability, and cycling stability. nanoparticles, and used them to fabricate negative electrode.
After Cu modification, an ultrahigh areal capacitance of The resulting alloy demonstrated a potential window from 1
8.66 F cm2 has been achieved [93]. With respect to the second to 0 V, similar to that of carbon-based materials, and a capaci-
approach, we have endeavored to prepare nickel copper oxide. tance of 620 F g1 (620 C g1) at 0.5 A g1. However, this alloy
Copper and nickel are neighboring in the periodic table. They underwent a phase transition to hydroxide during the energy
share similar ionic radius and valence state. The successfullypre- storage process, deteriorating its cycling stability [102]. We also
pared nickel copper oxide has the identical crystal structure with prepared nickel iron oxide, which manifested a capacitance of
nickel oxide except for small lattice constant change. A 39% 1800 F g1 (810 C g1) at 1 A g1 [103].
increase in the specific capacitance has been achieved [94]. Ade- Since the cycling stability of nickel–iron-based materials is not
quate electrochemical sites for ion loading and charge transport satisfactory, graphene has been introduced to overcome this
may be accounted for the improvement. A follow-up study has obstacle. Fe2O3–Ni(OH)2/graphene nanocomposite showed a
been carried out by the same group to unravel the correlation nearly 100% cycling retention after 5000 cycles at 3 A g1,
between the nickel–copper ratio of this oxide and its supercapac- despite its low specific capacitance value of 855 F g1
itor performance. Interestingly, even when the amount of copper (684 C g1) at 0.5 A g1 [104]. Another research group also
in the precursor reached up to 50%, as revealed by the inductive adopted graphene as the modifier, and obtained rGO–NiFe2O4
coupled plasma (ICP) tests, the structure of this oxide did not material showing a nearly 100% cycling retention after 300
exhibit obvious change. The capacitance of nickel copper oxide cycles at 10 A g1 [105]. Both these groups showed a profound
experienced a monotonical rise and leveled off when the Cu/Ni effect of graphene on the stability of the nickel–iron-based pseu-
ratio increased to 1/3.5. Afterward the capacitance decreased doactive electrode materials.
with further increase in the Cu/Ni ratio [95]. Another approach
to synthesize nickel copper oxide was also tried. The in-situ trans- Nickel–manganese (Ni–Mn)-based materials
formation was achieved from micro-level flat copper foam into As mentioned above, layered double hydroxides (LDH) are in the
porous nanowire arrays and the morphology evolution was forefront for energy storage applications due to their tunable
clearly demonstrated in Fig. 12(a–c). This design led to an composition and morphology. Nickel–manganese (Ni–Mn)
15
RESEARCH Review
FIGURE 13
Typical FESEM images of surface morphology of (a) original copper foam, (b) after the first processing step, oxidization, and (c) after the second processing
step, i.e., hydrothermal reaction. Electrochemical performance of asymmetric supercapacitor device using 1 M L1 KOH as electrolyte (d) CV curves, (e) GCD
curves; (f) Ragone plots relate to energy and power densities; and (g) Nyquist plot for the device. Reproduced with permission [96]. Copyright 2015, American
Chemical Society.
LDH is not aloof from this backdrop; it has potential as high- between Ni and Mn, the as-attained optimal material delivered
performance electrode material. Ni–Mn LDH has an expanded a specific capacitance of 1511 F g1 (680 C g1) at 2.5 A g1,
interlayer spacing, which can expedite the ion diffusion and is and showed a fascinating rate capability (80.1% retention at
favorable for the charge-storage kinetics. Several research groups 48 A g1). This material can withstand 30,000 cycles at 15 A g1
have assessed its performance, and some merged it with carbon- with a capacitance retention of 92.8% [107]. Zhao et al. treated
based materials to enhance its performance [106]. For example, CNTs with acid, and grew Ni–Mn LDH on the CNT backbone
Guo et al. adopted a facile method to grow Ni–Mn LDH on nickel [108]. The morphology and the corresponding electrochemical
foam at room temperature. By adjusting the feeding ratio properties are shown in Fig. 14. The initial treatment of CNTs
16
RESEARCH Review
FIGURE 14
(a) Schematic illustration for the synthesis and morphology of NiMn–LDH/CNTs. Step (I): the surface modification of CNTs by functional groups, and Step (II):
the grafting of NiMn–LDH nanosheets onto CNT backbone by an in situ growth method. Electrochemical performance of NiMn–LDH/CNTs and Ni(OH)2/CNTs:
(b) CV curves, (c) galvanostatic discharge curves, (d) specific capacitance as a function of current density and (e) cycle stability. Reproduced with permission
[108]. Copyright 2014, WILEY-VCH Verlag GmbH & Co. KGaA.
was pivotal for attaining a firm contact to maximize the synergis- the superiority of the material, the density functional theory
tic effect between CNTs and the Ni–Mn LDH. The grafting of (DFT) calculations have been carried out. The density of states
pseudoactive materials was always an obstacle for achieving (DOS) results indicated that the introduction of Mn transformed
homogeneous distribution on the carbon skeleton. By virtue of the semiconductor-nature of Ni(OH)2 into half-metallic nature.
the core–shell structure and the multi-metal LDH nature, the Additionally, the introduction of Mn also facilitated desorption
material with an optimal Ni–Mn ratio showed an amazingly high of hydrogen (H2), and guaranteed a high dispersion of Ni, and
specific capacitance of 2960 F g1 (1480 C g1) at 1.5 A g1, as enhanced the utilization of Ni in the Faradaic reaction. All of
well as an excellent rate capability (79.5% retention at these factors contributed to the capacitance increment. Besides
30 A g1). This capacitance is close to the theoretical value. Sta- CNTs chosen as the modifier, graphene has also been used. To
bility tests revealed that the material only underwent a capaci- illustrate, Chen and co-workers have prepared graphene–karst
tance loss of 0.9% after 2000 cycles at 12 A g1. To elucidate cave flower-like Ni–Mn layered double oxide via a hydrothermal
17
method. The hierarchical material had a capacitance of may substantiate the merits of multicomponent electrodes. The
1538 F g1 (692 C g1) at 1 A g1. After 6000 cycles at 2 A g1, interplay or synergistic effect of three transition metals, Ni, Co,
the capacitance was still preserved at almost 96% of the original and Mo, may be responsible for the enhanced performance.
value [109]. Comparative studies of the influence of different Other than being the principal component, NiMoO4 was also
carbon-based materials on the performance of carbon-decorated opted for modification of graphene [129]. NiMoO4 nanoparticles
Ni–Mn LDHs indicated that a ternary composite, i.e., Ni–Mn and quantum dots were dispersed evenly on the reduced gra-
hydroxide, rGO and CNTs, showed the highest performance: phene oxide, which resulted in boosting the performance of
specific capacitance (1268 F g1 (634 C g1) at 1 A g1); rate capa- the composite (2327.3 F g1 (931 C g1) at 1 A g1).
bility (884 F g1 (442 C g1) at 10 A g1); cycling retention (79%
after 5000 cycles at 5 A g1) [110]. The cycling deterioration may Nickel–vanadium (Ni–V)-based materials
RESEARCH Review
be due to several aspects, including the phase transformation Vanadium owns variable valence states from II to IV, although
after consecutive charging–discharging, the dissolution or peel- vanadium oxide itself is deemed as the negative electrode than
ing off of the active material and an increase in resistance. These the positive one. The incorporation of vanadium may alter the
three factors can affect the cycling deterioration. Besides, Chen defect states of pristine nickel oxide/hydroxide according to
et al. have coated Ni–Mn LDH with carbon, and the composite the band theory, which may consequently alter its conductivity.
material had a capacitance of 1863 F g1 (671 C g1) at 1 A g1 Thus, the studies of nickel– vanadium-based materials are not
[111]. expanding in the past decades. Nickel vanadate (Ni3(VO4)2) has
Apart from Ni–Mn LDH, other Ni–Mn composites have also also become another newly explored material, albeit not widely.
been investigated. a-MnO2/Ni1xMnxOy core–shell structure has The bare nickel vanadate showed a promising capacitance of
been prepared by a two-step method: hydrothermal together 1252 F g1 (626 C g1) at 10 A g1 [130]. The mixture of nickel
with chemical bath deposition. The capacitance achieved was vanadate with nickel oxide designed by Zhang et al. demon-
657 F g1 (657 C g1) at a current density of 0.25 A g1 [112]. strated a capacitance of 1540 F g1 (616 C g1) at 8 A g1 [131].
Sun et al. fabricated another core–shell structure, employing However, another nickel vanadium oxide such as Ni1xVxO2
MnOOH as the core with NiO shell, and this composite structure has been shown to have a relatively low capacitance of
showed a high specific capacitance of 1890.5 F g1 (1040 C g1) 538.7 F g1 (538.7 C g1) at 3 A g1 [132].
at 1.7 A g1 [113]. A comparison of various Ni–Mn-based materi-
als is summarized in Table 4. Nickel-containing metal–organic frameworks (MOFs)
In 2016, Sheberla has published a paper in Nature Materials,
Nickel–molybdenum (Ni–Mo)-based materials showing that Ni3(2,3,6,7,10,11-hexaiminotriphenyle)2
Nickel–molybdenum-based materials are also flourishing. (Ni3(HITP)2 MOF) exhibits high electrical conductivity and
NiMoO4, another member of ABO4 spinel materials, can been pioneered its use as an electrode material without other additives
considered as a new candidate [123]. Moosavifard et al. synthe- and binders [133].
sized ordered NiMoO4 nanoparticles through nanocasting the Later several groups have synthesized nickel-based MOFs as
precursors using a SiO2 template. Therefore, the mesoporosity supercapacitor electrode materials. The as-prepared materials
of the material endowed it with high BET surface area of inherited the well-defined porous structure and the large surface
174 m2 g1. The electrode revealed a high specific capacitance areas of MOFs. As a result, the derived materials possess interest-
of 2351 F g1 (1411 C g1) at 2 A g1 and an attractive rate capa- ing properties. For instance, Wei’s group managed to prepare Ni–
bility of 1080 F g1 (648 C g1) at 80 A g1, attributed to its struc- MOF with a high specific capacitance of 1127 F g1 (394 C g1) at
tural feature, namely, ordered and mesoporous morphology 0.5 A g1 [134], while Wang’s group coupled Ni–MOF with con-
[124]. Xiao et al. also synthesized NiMoO4 ultrathin nanosheets ductive CNTs achieving capacitance up to 1765 F g1 at the same
instead of nanoparticles. The material demonstrated a specific current density [135]. However, the rate capability and the
capacitance of 1694 F g1 (762 C g1) at 1 A g1 [125]. Aside from cycling stability of Ni-based MOFs were unsatisfactory. Shi
the pasting approach, another work reported the direct growth of et al. have reported an ultrahigh capacitance of 2548 F g1
the same material NiMoO4 on nickel foam. The capacitance was (1147 C g1) at 1 A g1; nevertheless, when the current density
also decent, reaching 2138 F g1 (1497 C g1) at 2 mA cm2. The increased to 20 A g1, the capacitance dropped drastically to
rate capability was also comparable to the former one, which was 702 F g1 (316 C g1). After 1000 cycles at 2 A g1, the capaci-
905 F g1 (634 C g1) at 60 mA cm2 [126]. Other pseudocapacitance retention was only 39.7%. We speculate that the reason
tive materials have been selected to modify the performance of for this poor behavior is the unstable organic group in MOF that
pristine NiMoO4. CoMoO4 incorporated NiMoO4, with a 3D cannot withstand the fast charging–discharging during electro-
nanosphere structure, was directly grown on nickel foam. The chemical tests in the electrolyte. Yan et al. synthesized a novel
resulting material with hierarchical structure proclaimed a speci- Ni–MOF, the formula of which is [Ni3(OH)2(C8H4O4)2(H2O)4]
fic capacitance of 1601.6 F g1 (801 C g1) at 2 A g1 [127]. Apart 2H2O and the atomic packing is shown in Fig. 15a. They got
from CoMoO4, NiCo2O4 was another choice to hybrid with accordion-like material (Fig. 15b) through ultrasonication pro-
NiMoO4. After the growth of NiMoO4 on the scaffold of sea cess. The highest capacitance was 988 F g1 (395 C g1) at
urchin-like NiCo2O4, the composite demonstrated a high capac- 1.4 A g1. However, judging from Fig. 15c, the CV curves
itance of 2474 F g1 (1608 C g1) at 1 A g1. A surprisingly high obtained for this novel material are not symmetric. When the
capacitance of 2080 F g1 (1352 C g1) was still maintained at a scan rate increased to 100 mV s1, the sharp peak at the left side
high current density of 20 A g1 [128]. These two examples may be an indicator of hydrogen generation. Thus the Coulom-
18
Materials Today
d
Volume xxx, Number xxx
TABLE 4
Nickel-manganese-based materials prepared using different methods and their supercapacitor performance.
Material/substrate Structure/ Synthetic Electrolyte SBET Potential Cs ( F g1/ Cycling stability (%) Rate Ref.
morphology method (m2 g1) window (V vs. C g1) capability
SCE) ( F g1)
Ni–Mn LDH/CNT/rGO (S) /NF Lamellar flakes Co-precipitation 2 M KOH 0–0.5 (0–0.6 CV) 1268/634 79% (5000th,5 A g1) 884/442 [110]
d
(1 A g1) (10 A g1)
xxxx 2018
Ni–Co–Mn LDH/(D) NF Nanosheets CBD + A 1 M KOH 121.2 0–0.5 (0–0.6 CV) 751.1 C g1 / 544.9 C g1 [114]
(1 A g1) (10 A g1)
Carbon-coated Ni–Mn LDH/(D) NF Ultrathin Two-step HT 1 M KOH / 0–0.36 (0–0.5 CV) 1863/671 91% (5000th, 2 A g1) 1531/551 [111]
nanoplates (1 A g1) (10 A g1)
MnO2–Ni(OH)2/(D) NF Nanosheets Dip coating 1 M KOH 111 0–0.5 (0–0.5 CV) 1015/503 / 666.7/333 [115]
+ Seed-induced (4 mA cm2) (16 mA cm2)
HT
GrapheneNi–Mn LDH/(S) NF Flower-like HT + A 1 M KOH 139/47 0–0.45 (0–0.6 CV) 1538/692 96% (6000th, 2 A g1) 1252/563 [109]
(1 A g1) (10 A g1)
MnO2–Ni1xMnxOy Core–shell HT + CBD 0.5 M / 0–1(0–1 CV) 657/657 94.6% (1000th, 2 A g1) 400/400 [116]
nanowire- Na2SO4 (0.25 A g1) (0.7 A g1)
nanoflakes
NiMn oxide (S)/NF Hollow spiny shell HT + A 6 M KOH 112 0–0.5 969.7/485 88.9% compared to the first 560/280 [117]
framework (1 A g1) cycle after 2500th (10 A g1)
Ni–Co–Mn/rGO (S)/NF Nanoparticles Co-precipitation / 87.7 0–0.5 646.1 C g1 90% (10,000th, 5 A g1) 573 C g1 [118]
+A (1 A g1) (30 A g1)
Ni–Co–Mn (D)/NF Nanoflakes Microwave 6 M KOH / -0.3–0.45 886 m F cm2 106.5% (50000th , / [119]
irridation (5 mA cm2) 20 mA cm2)
Ni–Mn LDH/(D)/NF Nanosheets Solution method 1 M KOH / 0–0.45 1511/680 92.8% (30,000th, 15 A g1) 1222/550 [107]
(2.5 A g1) (48 A g1)
Ni–Co–Mn triple hydroxide on Nanoneedles HT 2 M KOH / 0–0.4 1400/560 117% (30,000th, 1330/532 [120]
plasma-grown graphitic petals (1 mA cm2) 10 mA cm2) (100 mA cm2)
Ni(OH)2@Mn2O3 Ranunculus / 6 M KOH / 0–0.5 1219.1 /646 90% (1000th, 2 A g1) 718.2/359 [121]
flower-like + 0.3 M (2 A g1) (6 A g1)
LiOH
Mn–Ni–Co ternary oxide (D)/NF Nanowires HT 6 M KOH / 0–0.5 609.6/305 93.6% (6000th, 2 A g1) 404/202 [122]
(2 A g1) (20 A g1)
The abbreviation rules are the same as before. In the column of potential window, the value in the bracelet means the potential window tested in CV.
RESEARCH
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RESEARCH R
view
RESEARCH Review
FIGURE 15
(a) Crystal structure and (b) TEM image of the accordion-like Ni–MOF. Its electrochemical performance in 3.0 M KOH (c) CV curves, (d) GCD curves, (e) specific
capacitance derived from the discharge curves at various current densities and (f) charge–discharge cycling test at 1.4 A g1. Reproduced with permission
[136]. Copyright 2016, Royal Society of Chemistry.
bic efficiency is disappointing [136]. Instead of using Ni–MOF Nickel–nonmetal-based materials

directly as an electrode material, the material derived from this Some researchers feel that nickel-based oxides/hydroxides run
MOF was examined. Nickel cobalt oxide with an optimal Ni/Co into a bottleneck, therefore, they started a search for other candi-
ratio of 1:1 manifested an excellent specific capacitance of dates as supercapacitor electrode materials. A myriad of research
1931 F g1 (869 C g1) at 1 A g1. After incorporation of conduc- has been carried out on these revolutionary materials.
tive graphene network, this value increased up to 2870 F g1
(1292 C g1) [137]. Nickel sulfide-based materials
The high theoretical capacitance and exceptional intrinsic con-
Multicomponent nickel-containing materials ductivity make nickel sulfide an attractive alternative to nickel
The preceding sections are devoted to binary component materi- oxide/hydroxide. Besides, the depressed electronegativity of sul-
als, namely, one of the elements is nickel, and the other is fide as compared with oxide generates more structural flexibility.
another transition metal element, albeit these materials are However, the expansion of layer after the intercalation of elec-
sometimes integrated with carbon. Moreover, various nickel- trolyte ions may disrupt the original structure and deteriorate
containing multicomponent materials have also been explored, the performance. The replacement of oxygen by sulfur may
such as nickel–cobalt–manganese (Ni–Co–Mn) and nickel– accommodate the change. The higher conductivity of nickel sul-
cobalt–zinc (Ni–Co–Zn). Since the difference between ternary fide than nickel oxide is due to the smaller bandgap. Nowadays,
and quaternary transition metal oxides is not obvious, we will selenium (Se), in the same column with oxygen and sulfur in the
not discuss them in detail. periodic table, has also been attempted to form metal selenides as
20
supercapacitor electrode materials. Most of the studied metal NiCo–glycerate spheres as the starting materials. The highest
selenides are those with two dimensional structures such as capacitance achieved at 1 A g1 was 1036 F g1 (466 C g1)
MoSe2 and VSe2. The investigation of nickel selenide just started. [146]. The authors themselves claimed that after cycling test, sul-
The growth of nickel sulfide has been well-established. One of fide would transform into whisker-like hydroxide. Other aspects
the commonly used methods is a two-step procedure via convert- of nickel sulfide composites have also been explored. Liu et al.
ing nickel hydroxide into nickel sulfide by anion exchange. The have prepared NiS nanosheets anchored on a carbon. The com-
other one is the reaction between nickel precursor and thiourea posite showed a capacitance of 1150 F g1 (518 C g1) at
or thioacetamide. Also, sulfurization of nickel metal has also 1 A g1 [147]. NixSy@CoS hollow nanocages were prepared by
been adopted [138]. template-assisted method as shown in Fig. 17 [148]. The uniform
The following example demonstrates that the high conductiv- hollow structure ensured a striking capacitance of 2291 F g1
RESEARCH Review
ity of nickel sulfide improves the charge transfer kinetics. Xiao (573 C g1) at 1.0 A g1. Nevertheless, the potential window
et al. have adopted single-crystallized NiCo2S4 nanotubes as the was only 0.25 V. Another MOF sacrificial-template-assisted
conductive core for the growth of electroactive nickel cobalt method was adopted to prepare Ni–Co LDH@Co9S8. The in-situ
hydroxide. The coaxial composite directly grown on the carbon transformation and the peripheral embedment led to the forma-
fiber paper achieved a high discharge areal capacitance of tion of superior interface. The hollow rhombic dodecahedron
2.86 F cm2 at 4 mA cm2. This remarkable performance was had a high specific capacitance of 1653 F g1 (744 C g1) at
attributed to the great conductivity of NiCo2S4, which was 4 A g1 [149]. Similarly as in the aforementioned protocols of
authenticated by the fact that the resistance of NiCo2S4 mixing carbonaceous materials with nickel oxide or nickel
(3.41 Ohm cm2) was two order of magnitude smaller than that hydroxide, the nickel sulfide-based materials have been deco-
of NiCo2O4 (498 Ohm cm2) [139]. rated or wrapped with carbon. For example, CS2 was selected as
Except for serving as the conductivity-elevating agent, nickel the unitary precursor for both sulfurization and carbonization
sulfide-based materials themselves were also used as active mate- in the presence of pentamethyldiethylenetriamine (PMDTA) as
rials. Surendran and Selvan grew spark-like b-NiS on a carbon a solvent [150]. This one-step solvothermal method generated
cloth [140]. The morphology of the petals is displayed in nickel cobalt sulfide with carbon. The composite, which partially
Fig. 16(a–d). The capacity achieved was 827 C g1 at 1 mA cm2, inherited the hollow structure of carbon and exhibited the car-
as demonstrated by the corresponding electrochemical data bon encircled morphology, exhibited a capacitance of
shown in the same figure. However, it is noteworthy that the 1722 F g1 (689 C g1) at 1 A g1. Instead of using the above
peak separation is huge, approaching 0.4 V when the scan rate one-step method, another work [151] reported the synthesis of
increases to 10 mV s1. One can speculate that when the scan nickel cobalt sulfide coated by N-doped carbon via a multistep
rate is further increased, the separation may be enlarged forward, method, which involved transformation from nickel cobalt
and the poor reversibility may hinder its application as a super- hydroxide into nickel cobalt sulfide and the dopamine coating
capacitor electrode material. with post-annealing. The hollow urchins yielded a specific capac-
Apart from using pristine nickel sulfide as an electrode mate- itance of 1404 F g1 (632 C g1) at 2.0 A g1.
rial, other attempts to enhance its performance encompass incor- Nevertheless, we have to admit that, in the alkaline elec-
poration of carbon and hybridization of pseudocapacitive trolyte, the transformation of nickel sulfide into nickel hydrox-
materials, similar to that used for boosting the performance of ide, as well as the dissolution of sulfide, impairs its stability as
nickel oxide/hydroxide. Hamid prepared graphene-wrapped an electrode material. Additionally, the use of precursors with a
nickel sulfide nanoprisms, and the resulting hybrid was used as foul odor is unavoidable. Sometimes H2S, as the toxic byproduct,
an electrode material not only for Li-ion battery but also for is also detrimental to human health and environment. There-
supercapacitor [141]. This system showed a specific capacitance fore, development of facile and environmentally friendly
of 1337 F g1 (602 C g1) at 5 A g1 [141]. Nickel cobalt sulfide method is highly desirable for the fabrication of nickel sulfide-
and its composite with carbon-based materials, similar to its based materials.
counterpart nickel cobalt oxide and derivatives, have become
popular materials nowadays [142–144]. Yang et al. have tuned Nickel phosphide-based materials
the edge-site of nickel cobalt sulfide by exploiting the etching Similar to the previous nickel sulfide-based materials, nickel
ability of S2 ions. The nickel cobalt sulfide anchored on gra- phosphide-based materials have attracted a great interest
phene delivered a specific capacitance of 1492 F g1 (716 C g1) due to the fact that Ni2+ and Pd feature rich valence. A
at the current density of 1 A g1, and 96% of the original capac- plethora of nickel phosphides is thermodynamically stable,
itance remained even when the current density increased 50 such as Ni3P, Ni2P, Ni12P5, NiP2. Some of them are n-type
times, verifying its admirable rate capability. Moreover, they also semiconductors, which is different from the p-type of pris-
assembled an asymmetric supercapacitor by employing porous tine nickel oxide, generating multiple undiscovered interest-
carbon nanosheets as the negative electrode, and the device ing properties.
showed an acceptable performance (ED: 43.3 W h kg1 at PD: One example of nickel phosphide preparations is phospho-
0.8 kW kg1). The improved performance was explained by den- rization of nickel hydroxide. The resulting material yielded an
sity functional theory calculations showing that the affinity for impressive capacitance of 3496 F g1 (1398 C g1) at 2.5 A g1,
hydroxyl ions can be enhanced by the tailored edge of nickel which ranked almost the highest among all the candidates of
cobalt sulfide [145]. Nickel cobalt sulfide ball-in-ball hollow electrode materials. This remarkable material was used to fabri-
structure was prepared by ionic exchange with uniform cate an asymmetric device, with activated carbon as the negative
21
RESEARCH Review
FIGURE 16
(a–d) SEM images of the 3D flower-like b-NiS at different magnifications. (e) Schematic illustration of the evolution of 3D flower-like b-NiS nanostructures.
Electrochemical performance of b-NiS electrode: (f) CV curves, (i) GCD curves, (j) Current density versus areal capacity plot for b-NiS electrodes, and (k) Nyquist
plot with (inset) its equivalent circuit. Reproduced with permission [140]. Copyright 2017, WILEY-VCH Verlag GmbH & Co. KGaA.
22
RESEARCH Review
FIGURE 17
(a) Schematic illustration of the formation process of amorphous NixSy@CoS double-shelled nanocages: (I) the formation of CoS polyhedral nanocages by
sulfonation reaction between ZIF-67 polyhedrons and thioacetamide (TAA), and (II) the growth of NixSy@CoS double-shelled nanocages by formation of NixSy
nanoparticles on the CoS polyhedral nanocages; and (b–d) TEM images of the materials illustrated in (a). Electrochemical performance of the NixSy@CoS
hybrid: (e) CV and (f) GCD curves. Reproduced with permission [148]. Copyright 2015, Nature Publishing Group.
electrode. It is a pity that the capacitance of the device was only The capacitance of the flower-like nickel phenylphosphonate
94 F g1 (67 C g1) at 5 mV s1, so that the ED was 26 Wh kg1 at was only 500 F g1 (250 C g1) at 1 A g1. We suspect that the
a PD of 337 W kg1, possibly retarded by the limited perfor- poor capacitance was due to the low conductivity and poor ionic
mance of the negative electrode. The universality of the phos- diffusion of the organic–inorganic framework. After calcinating
phorization protocol of other metal hydroxides and the results the phosphonated material at 600 °C, the capacitance was ele-
revealed that the phosphorization strategy enhanced the super- vated to 1100 F g1 (550 C g1) at 0.5 A g1 [156].
capacitor performance of the corresponding metal hydroxides
Ni2 P2 O7 þ 2OH $ Ni2 P2 O7 ðOHÞ2 þ 2e ð6Þ
[152]. Biphasic nickel phosphides composed of Ni5P4–Ni2P
nanoparticles interconnected into a honeycomb-like structure Moreover, Chen’s group was the first to use NH4NiPO4 nano-
giving a high specific capacitance of 2638 F g1 (1319 C g1) at plates as the electrode material. The morphology and the ele-
1 A g1 [153]. Duan et al. coated Ni12P5 on the Au core, forming mental distribution are shown in Fig. 18. The specific
the core–shell structure, which delivered a specific capacitance of capacitance of this novel material was 1513 F g1 (832 C g1) at
807 F g1 (282 C g1) at 0.2 A g1 [154]. 5 A g1, however, only 56% was retained when the current den-
Other than nickel phosphide, nickel pyrophosphate has also sity increased four times [157].
come to the forefront. For example, Senthilkumar got a Ni2P2O7
material with a specific capacitance of 1893 F g1 (1136 C g1) at Multicomponent nickel-containing electrode materials
2 A g1. The proposed redox reaction is shown in Eq. (6) [155]. Combination of various components into one single electrode
Nickel phenylphosphonate was synthesized by a hydrothermal material becomes an effective way. For example, the electrodepo-
method similar to that used in the synthesis of nickel oxide with sition of PPy on NiCo2S4 led to a two-fold areal capacitance
urea. C6H7O3P (PPA) was the extra source for P. The precise con- increase, reaching 9.8 F cm2 at 5 mA cm2 [158]. Combination
trol of pH of the solution is the key to the successful preparation. of three components, i.e., NiCo2S4, Ni–Mn LDH, and graphene,
23
RESEARCH Review
FIGURE 18
(a–c) SEM and (d) elemental mapping images of NH4NiPO4H2O/Ni foam. Electrochemical performance: (e) CV and (f) GCD curves; (g) rate capability and (h)
EIS plots for NH4NiPO4H2O/Ni foam and NH4NiPO4H2O@PPy/Ni foam (inset: enlarged curves at high frequency region). Reproduced with permission [157].
Copyright 2016, American Chemical Society.
also proved to be superior in comparison to two components. preserved at 40 mA cm2) [160]. Furthermore, the hybridization
The specific capacitance of the three-component composite of nickel hydroxide, carbon nanotube, and conducting polymer,
was even higher than the sum of the two-component composites which constitute the major three types of supercapacitor materi-
[159]. Another composite, namely FeCo2S4–NiCo2S4, was als, contributed to an astonishingly high capacitance of
designed. The synthetic procedure is illustrated in Fig. 19b: the 3262 F g1 (1957 C g1) at 5 mV s1. Besides, the rate capability,
flexible textiles with silver coating were used as the current col- i.e., 71.9% capacitance retained after increasing the scan rate
lector with the material growing atop. The binder-free electrode 20 times, was also amazing [161]. The examples or prototypes
exhibited a specific capacitance of 1519 F g1 (911 C g1) at are just a drop in the ocean. The diversity of materials offers a
5 mA cm2, and decent rate capability (85.1% capacitance was huge choice.
24
RESEARCH Review
FIGURE 19
(a) A photograph of a lab coat, (b) digital photos showing color change of a piece of pristine textile cloth cut from the coat before (left) and after sliver
sputtering (middle) as well as resulting product after sulfuration (right), (c) schematics illustrating fabrication process of FeCo2S4–NiCo2S4 on an silver-
sputtered textile cloth (SSTC). The lower schematic diagrams show the corresponding surface change of a single silver-coated fiber in SSTC. Reproduced with
permission [160]. Copyright 2017, WILEY-VCH Verlag GmbH & Co. KGaA.
Discussion and potential issues collectors (conductive substrates). The third one is vacuum filtra-
Synthetic methods tion. Namely, the active materials are mixed with conductive
Most of the aforementioned oxide-based materials undergo carbon-based materials, and they are filtrated into a piece of flex-
annealing process. This process aims to dislodge the organic resi- ible paper with the aid of pumping.
dues in the precursors, which act as the templates (morphology Each of them has disparate strengths and weaknesses. The first
directing agents) and/or the hydroxyl ion donors. At the same one applies to all sorts of materials, as long as they are in the
time, the crystallinity increases and the hydrous content powder form, and it is easy for scaling up. Nevertheless, the addi-
decreases. As for RuO2, the supercapacitor electrode with the best tion of binders may block the surface of active materials, as well
performance, hydrous content is helpful. Some papers claim that as inflict additional contact resistance. Other than that, the
the amorphous nickel hydroxide is not suitable for supercapaci- dependence on ancillary materials diminishes the electrochemi-
tor applications [162]. While others claim that it is superior to cal active surface area, which jeopardizes the electrochemical per-
a crystalline structure because of the structural disorder of amor- formance. Equally harmful outcome is the augmented grain
phous nickel hydroxide [163]. Then the question comes, boundaries, which leads to safety problems owing to the heat
whether the annealing process is necessary or detrimental? This generated at the grain boundaries during fast charging/discharg-
conflicting issue during the synthetic process deserves additional ing. In contrast, the second practice waives the need of adding
insights and in-depth clarification. ancillary additives to bind active materials and substrates
together. The robust adhesion imparts intimate interactions
between the current collector and electroactive materials, along
Assembly approaches with efficient charge transport, whereas the loading amount is
Three types of electrode assembly protocols have been well- limited. The third one permits lightweight and flexible applica-
established. The first one is the commercialized slurry-casting tions. Without the current collector, the total weight is greatly
method. Firstly, the electrode materials are mixed with reduced. The porosity decreases despite that the materials are
binders and conductive additives. Secondly, the mixture is in their solvated state, which still allows for ion diffusion and
pasted/brushed/doctor-bladed, and finally it is extruded on the penetration. This kind of electrode is not as stable as the preced-
current collector under pressure. The second one is the direct ing two kinds. The mechanical properties of these electrodes are
growth/deposition of electrode materials on the current unsatisfactory. After soaking/immersion in the electrolyte for an
25
extended period, they are liable to collapse or disintegrate. In needs to be scrutinized and the mechanism needs to be elabo-
short, intricate consideration is required when determining the rated. As stated above, the common electrolytes used for
suitable assembly method for different materials. nickel-based reactions are alkali solutions since hydroxyl ions
are necessary for the redox reactions. However, the aqueous
Current collectors alkali solutions have limited potential windows restricted by
As evidenced by the above discussion and comparison, the most the fact that the thermodynamic equilibrium potential of water
widely used current collector nowadays goes to nickel foam. In splitting is 1.23 V. In contrast, organic electrolytes have wider
contrast, in batteries, aluminum foil is the widelyused one. Other potential windows, even approaching 4 V. Nevertheless, the
metal foils or metal foams, such as titanium, stainless steel, and usage of organic electrolytes in nickel-based materials is lacking.
copper, have also been tried. As the name “current collector” Tetraethylammonium tetrafluorborate (TEABF4) in propylene
RESEARCH Review
indicates, the internal resistance of the current collector should carbonate has been reported [165]. The capacitance of NiO in
be as small as possible. Additionally, the interface between the this electrolyte was 170 F g1 (680 C g1) at 1 A g1. The poten-
current collector and active material should also be delicately tial window of the CV test was from 2 to 2 V. Unfortunately,
maneuvered. The contact between them should be intimate organic electrolytes usually suffer from high cost, poor ionic con-
enough to avoid the detachment of materials and to reduce the ductivity, flammability, and high toxicity. Therefore, if evap-
overall internal resistance. Nickel foams with several advantages orable and toxic organic electrolytes are to be used, strict
over other materials (including high conductivity, facile fabrica- encapsulation of the devices becomes crucial. This problematic
tion and low cost) have been readily commercialized. Nickel situation urges us to find a better replacement. Ionic liquids are
foams, as reticular and porous substrates, supply enough diffu- envisaged to be an ideal choice to replace hazardous/volatile
sion channels. We realized that nickel foams as inappropriate organic electrolytes. The excellent features of ionic liquids such
current collectors for nickel-based electrode materials through as large electrochemical potential window, high ionic conductiv-
our own experience. One reason is ubiquitous: based on the ity, good thermal stability, non-combustibility, and non-toxicity,
nickel Pourbaix diagram [164], nickel foam itself corrodes in enable them to become the electrolyte of choice. The
the electrolyte and nickel hydroxide is formed on its surface. This study of nickel-based materials using ionic liquids as the
brings substantial capacitance reduction, considering the mass electrolytes is deficient. Only one paper adopted 1-butyl-3-
ratio between active material and nickel foam. In other words, methylimidazolium hexafluorophosphate (BMIM-PF6) room
since the loading of an active material is small, even if only the temperature ionic liquid as the electrolyte [166]. The constituted
surface of nickel foam is converted into nickel hydroxide, the device had a potential window of 3 V and the capacitance was
overall expansion cannot be underestimated. The other reason 174 F g1 (522 C g1) at 10 mV s1. The CV curves were quite
is that it is difficult to distinguish and analyze whether nickel rectangular and identical to those of the carbon-based EDLC-
originates from active material or nickel foam substrate because type materials. This offers a new era for future research direction.
both of them contain nickel. To draw an explicit distinction When the electrolyte is aqueous, the electrode should be
between them, additional effort is needed. Nowadays, the attrac- hydrophilic. On the contrary, when it is non-aqueous, the
tive current collectors are carbon derivatives, such as carbon requirement for the electrode simultaneously changes to
fiber/graphene paper or carbon foam. Some are obtained via car- hydrophobic. Capacitance can be generated only if the pores in
bonization of cotton textiles. Lightweight and flexibility makes the electrode materials are larger than those of the electrolyte,
them unique candidates as current collectors. Moreover, the can ions penetrate or intercalate into the electrode material, gen-
advantages are complemented by their invaluable stability in erating capacitance. In aqueous electrolytes, the difference in
electrolytes, especially in aqueous electrolytes. The disadvantages cationic radius, concentration and the solvent viscosity affect
of carbon-based current collectors, e.g., incompatibility between the ionic conductivity and diffusion, and consequently, the
carbon and nickel-based materials or the hydrophobic nature of capacitance is influenced.
carbon or the low wettability in aqueous electrolytes, have been Moreover, liquid-state electrolytes may suffer from leakage if
solved by surface modification such as O3 plasma or acid treat- the packaging layer is broken. Solid-state electrolytes with better
ment. Other drawbacks include the brittleness at high tempera- safety can be integrated on a single chip, apt for portable/wear-
ture and high cost. Price cutting and enhancement of able applications. Generally, ions transfer more quickly in
structural robustness are two future directions. For flexible super- liquid-state electrolytes than their solid-state counterparts.
capacitor applications, fabrics coated with metal (such as Ag or Consequently, the kinetically hampered redox reactions are
Au) via sputtering are also promising candidates. An excellent detrimental for the rate capability of solid-state supercapacitors.
substrate, which can provide electrons and act as channel for
high-rate transfer, still needs be developed for Descriptors
commercialization. Normally, three-electrode configuration (or single working elec-
trode configuration) is adopted for the material evaluation since
Electrolytes it is very effective in analyzing redox reactions. However, the
Most researchers engage in the perfection of electrode materials. high sensitivity of this configuration may induce large errors,
However, electrolyte is also an important component since the overestimating of the capacitance of the material. While two-
electrochemical processes occur at the interface between the elec- electrode configuration mimics the real operating situation so
trode material and electrolyte. Therefore, the significance of elec- that the results objectively reflect the performance of a device
trolytes cannot be overlooked. The interplay between them in real applications [167].
26
Apparently, from the prior sections, most of the published usually conducted by electrochemical impedance spectroscopy
papers are merely concentrated on the gravimetric specific capac- (EIS). Unfortunately, some relating factors other than the con-
itance acquired from the tests using three-electrode configura- ductivity of the material alone have a strong impact on the EIS
tion. This gravimetric specific capacitance has become the results. Although equivalent circuit model is always established
universally accepted figure-of-merit. To compare the perfor- and the parameters of each component are simulated, the precise
mance quantitatively and comprehensively from different analysis is still lacking. In summary, there is still no experimental
angles, areal and volumetric specific capacitances are two other observation, which can convincingly enunciate the alteration of
important descriptors. Similarly, other than gravimetric energy performance.
density and gravimetric power density, the corresponding areal
and volumetric results should also be given. When these values Asymmetric supercapacitors
RESEARCH Review
are compared, the mass loading should also be specified. Gogotsi Several thorough reviews on the asymmetric supercapacitors
and Simon have already pinpointed that the mass loading have been published [170]. To avoid redundant discussion, only
should be at the order of 10 mg cm2 [168]. Although it is diffi- some focal points associated with nickel-based materials are
cult to meet this criterion, a high mass loading (1–10 mg cm2) mentioned and other seldom-referred issues are put forward.
is practical and also preferable for device fabrication. Except for To extend the operating potential window in aqueous elec-
miniature device, the mass loading should be at least higher than trolytes limited by the water splitting potential of 1.23 V
1 mg cm2. Otherwise, a proper comparison is difficult. The rea- (pH = 7), as well as increase the energy density, the construction
sons for not choosing high thickness are that the conductivity is of asymmetric supercapacitors has experienced a radical develop-
reduced, and poor mechanical properties lead to fragmentation ment. A battery-type material and an EDLC-type material are
of thin films. selected as the positive electrode and negative electrode, respec-
Cycling stability is another critical evaluation metrics. How- tively. Nickel-based materials have been extensively adopted as
ever, it lacks standards on the choice of current density and the positive electrode in the asymmetric configuration. The
the cycling times. To evaluate the instantaneous charging- energy density achieved ranges from several to several dozens
discharging, as well as to save time for the material evaluation, of Wh1 kg1. The power density ranges from 0.1 to
a high current density is a prerequisite. To substantiate long lifes- 100 kW kg1. For instance, asymmetric supercapacitor of nickel
pan, thousands of cycles are also required. From the aforemen- oxide//rGO delivered a maximum energy density of
tioned examples for different types of nickel-containing 45.3 W h kg1 at a power density of 1081.9 W kg1 [171], while
materials, it is obvious that the experimental values have a broad that of CNT@nickel oxide//porous carbon exhibited a maximum
distribution even if the material phase is exactly the same. Some- energy density of 25.4 Wh kg1 at a power density of 400 W kg1
times this inconsistency was due to the inconsistency in the eval- [172].The promising performance of nickel-based asymmetric
uation methods and the confusion in the metrics calculation. supercapacitors has blurred the boundary or distinction between
Several good reviews have already been published for standard- batteries and supercapacitors. A wealth of papers has chosen acti-
ization [168,169]. Stroller and Ruoff have indicated the finest vated carbon as the negative electrode material for conventional
practices for material evaluation [167]. Hopefully, the evaluation asymmetric supercapacitors because of its large surface area
methods in the future can be streamlined. Besides, this discrep- (more than 1000 m2 g1) and pore volume (exceeding 0.5 cm3 -
ancy may come from the complicated interplay of several factors g1). Nevertheless, the capacitance derived from active carbon
affecting the performance of supercapacitors. Namely, all of the is low, usually less than 200 F g1. To further advance the overall
aspects, including the preparation method, the obtained mor- performance of the asymmetric supercapacitors, exploration of
phology, the interface engineering, the specific surface area, other excellent negative electrode materials would be desirable.
the conductivity, contribute to the final performance of elec- Nowadays, the negative electrode is not restricted to activated
trodes. Research is also underway to analyze their influence on carbon, graphene, CNTs and their derivatives, together with
the electrode performance. The achievement of merely high metal oxides (i.e. iron oxide) and transition-metal dichalco-
specific capacitance is not enough. Also, the causes for the out- genides, have been attempted. Zhao et al. synthesized NiCo2-
standing or poor performance should be analyzed and O4@Ni(OH)2 on SiC skeleton as the positive electrode material
comprehended. and coupled it with Fe2O3 nanoneedle arrays to fabricate an
Coulombic efficiency (also named as Faradic efficiency) and asymmetric supercapacitor [173]. The achieved energy density
energy efficiency are two other seldom mentioned descriptors was ultrahigh, reaching 103 W h kg1 at a power density of
to weigh supercapacitor performance. The former emphasizes 3.5 kW kg1.
the ratio of output/input charge while the latter underlines the The total capacitance of the asymmetric full cell can be calcu-
ratio of output/input energy. The loss of energy may be due to lated based on the following Eq. (7):
the unwanted side reactions in the battery or the unideal accep- 1=Cf ¼ 1=Cpos þ 1=Cneg ð7Þ
tance of energy.
“Electro-active site” is a commonly encountered term in where Cf, Cpos and Cneg are the capacitances of the full cell, positive
electrode, and negative electrode, respectively. Assuming that Cpos
related papers. It is always associated with the BET specific sur-
and Cneg are 2000 F g1 and 200 F g1, respectively, thus the calcu-
face area. It is a pity that the direct proof of electro-active sites
lated total capacitance of the device is approximately 182 F g1. The
is still deficient. Not the entire surface area is electrochemically values reported by most papers do not follow this expression. The
active. Conductivity is another frequentlyused word in compar- obtained capacitance is sometimes larger than the theoretical value.
ing different materials. The characterization of conductivity is This phenomenon has hardlyever been scrutinized. Furthermore,
27
matching between these two materials needs careful consideration. material can switch between bleached and transparent state with
The reasons are that the rate capabilities of these two kinds of materi- a response time of 22.1 s. The rate capability is amazing; the
als differ much. Based on the criterion proposed for the charge equa- achieved capacitance was still 1075 F g1 at an extremely high
tion, the chosen capacitance at different current densities have a huge
current density of 100 A g1, although the mass loading was only
influence on the anticipated optimal mass loading ratio of each mate-
rial. Namely, if the Cpos is 2000 F g1 at 1 A g1, and Cneg is 200 F g1 0.048 mg cm2.
at the same current density. If the Cpos decreases to 1000 F g1 at
50 A g1, and Cneg decreases to 150 F g1, the calculated difference will
be 1.5 times for the mass loading ratio of the positive electrode to the Concluding remarks and outlook
negative electrode. It is imperative to summarize and give a timely review of the
In addition, to estimate the optimal operating potential win- explosive growth of research in nickel-based materials, validated
RESEARCH Review
dow, the evolution of hydrogen and oxygen should be mini- by hundreds of papers published in this area. Overall, the
mized. That is to say, the over potential of water splitting advances of different kinds of nickel-based materials have been
should be reduced. However, when the asymmetric supercapaci- categorized and discussed, supported by numerous examples
tor is assembled, some researchers reported a potential window and illustrations. The problems associated with nickel-based
not starting from zero. If not, the role of positive electrode and supercapacitors have been diagnosed. We cannot state that the
negative electrode is swapped. This violates the principle of con- above analysis paints an optimistic or pessimistic picture.
structing asymmetric supercapacitors. Numerous routes have been tried, including hierarchical config-
uration design, composition optimization, and hybridization,
Non-traditional supercapacitors aiming to overcome the problems, which confine their applica-
Beyond the normal supercapacitor types using nickel-based tions. Improvements in the capacitance, rate capability, and sta-
materials as electrodes, other non-traditional ones, as shown in bility of nickel-based materials are clearly visible.
Fig. 20, have come into the scene. All-solid-state, transparent, Notwithstanding the encouraging progress, the electronic con-
flexible, and lightweight supercapacitors, with exceptional prop- ductivity of the nickel-based materials is still far from that of car-
erties, can be adaptable and suitable for various applications. bons, which hinders their applications. The sluggish ion
Hybrid supercapacitor is another class of supercapacitors that transport in nickel-based materials also impedes their perfor-
combines EDLC-type material with PC-type or battery-type mance. A relatively high equivalent resistance deters the rate
materials. Two well-explored types are Li-ion capacitor and capability and power density. To ensure that a material functions
ultra-battery. The former hybrid system consists of Li-ion and effectively, further control of the synthetic parameters and
EDLC electrodes with non-aqueous Li+ containing electrolyte. experimental conditions is pivotal. By gaining vast knowledge
Its mechanism inherits the ion-adsorption/desorption of EDLC- of the elements dominating the supercapacitor performance, in
type material, as well as the Li+ intercalation/de-intercalation. the long run, we can tailor electrode materials at molecular or
While the latter one consists of lead-acid and EDLC electrodes. atomic levels.
All of the components (electrode materials, electrolytes, cur- In the design of nickel-based electrode materials, several
rent collectors and separators) should be adjusted for the specific aspects should also be taken into consideration. (1) The effect
purpose. Miniature supercapacitors integrated on a chip are fab- of oxygen or nickel vacancies on the supercapacitor performance
ricated either by delicate deposition of materials at the desig- is still unclear. Other than vacancies, the remaining defects may
nated place or by electrode-patterning and subsequent etching also affect the intrinsic properties of nickel-based materials.
process. Although most of the non-traditional supercapacitors Introduction of secondary metal species also bring defects. The
are carbonaceous materials because pseudocapacitive materials ratio between them should be delicately controlled, maybe with
such as nickel-based materials degrade the transparency or flexi- the aid of theoretical simulations. Moreover, the surface chem-
bility, progress with respect to the nickel-based non-traditional istry of the nickel-based materials is seldom investigated. Intu-
supercapacitors has also been made. For example, Grote et al. itively, adsorption of OH ions should be closely related to the
reported the nickel cobalt hydroxide anchored on reduced surface chemistry of specific materials. The surface free energy,
graphene oxide for electrochromic supercapacitor [174]. The surface tension and adsorption/desorption energies should be
calculated. The storage of energy is dependent on the phase tran-
sition of the material. Hence, the barrier or irreversibility of the
phase transition should be considered carefully. Some ingenious
experimental designs, which can reflect the intrinsic process, are
highly desirable. Other in-situ characterization techniques
should be used, for example, small angle neutron scattering,
nuclear magnetic resonance and the electrochemical quartz crys-
tal microbalance. When in-situ used, they are able to scrutinize
the behavior of ions during the phase transition of the electrode
material. Likewise, simulation of different models (one-
dimensional or three-dimensional) also provides valuable infor-
mation for designing electrode materials. These modified models
FIGURE 20 originate from the EDLC theory. The real reactions occurring
Trends in the area of non-conventional supercapacitors inside the system are invisible, similar as in a “black box”. In
28
modeling, it is possible to change one factor at one time, which However, the degree of damage the material suffers is also imper-
allows uncovering the internal distribution of the electric field, ative. In most cases, only the analysis prior to the cycling test is
interfacial phenomena and mass transport. (2) Nowadays, there conducted while the analysis after the process is always ignored.
is a trend to make the most of each material, by developing com- For nickel-based materials, the morphology and chemical state of
plex or sophisticated structures to achieve excellent results. How- nickel should be meticulously examined. For instance, the in-situ
ever, when multiple elements co-exist in one single electrode XPS or even the more sensitive electron energy loss spectroscopy
material, their distinct physical/chemical properties may induce (EELS) characterization should be performed. Other than the
inhomogeneity during the charge–discharge process. This may development of material characterization, the computational
cause the surface reconstruction of the material, and the original modeling and simulation can help to predict and explore the
structure may collapse and local strain may appear after the inter- effects of material composition on the electrochemical properties
RESEARCH Review
action between electrode material and electrolyte. Consequently, of nickel-based materials.
a caution is needed in the design and synthesis of the multicom- As elaborated in the previous sections discussing different
ponent nickel-based electrode materials. (3) Most of the current kinds of nickel-based materials, the standpoint is merely the
researches focus on the configuration or morphology. Nanos- experimental results. Encouragingly, theoretical analysis has
tructured hierarchical structures or hollow structures, ranging inaugurated for performance interpretation, however, the
from 0D to 3D, have been prepared. Undoubtedly, nanostruc- descriptors chosen are restrained to the adsorption energy of
tured hierarchical materials have many advantages. The high sur- OH, which is a physical quantity but difficult to be reflected
face area increases the likelihood of ion adsorption. Besides, the through experiments. The other metrics should also be consid-
ion diffusion length is shortened and the electron transport is ered. Understanding the mechanism for the improvement of
facilitated. However, these materials, especially those 2D lamellar the supercapacitor performance becomes a mandatory. The
sheets with small thickness, tend to aggregate or re-stack if they structure–property–performance relationship of nickel-based
are pasted on the current collector, which makes a portion of the supercapacitors is still obscure and further efforts are needed.
active material useless, generating “dead volume”. Hence, it is It should be recognized that the intrinsic energy density of
important to take the device as a whole during fabrication of supercapacitors is relatively low, which arises from its inherent
electrode materials. (4) Interfacial engineering is of paramount principle. There is still distance behind other energy storage
importance. Charge transfer of nickel-based materials occurs at devices. The pursuit of high energy density, its own merits, i.e.,
the electrode/electrolyte interface. (5) The redox reaction takes high power density, should not be sacrificed. Even if the energy
place at the outmost of the nickel-based materials. From this density cannot outperform or compete with lithium ion or
point of view, the material should be as thin as possible. How- lithium-air battery, the power density is ten to thousand times
ever, if the material is too thin and aggregation is avoided at higher.
the same time, the loading mass becomes deficient. The dilemma Since initial steps have been undertaken and a momentous
between the thickness and overall capacitance should be progress has been made, we believe that the nickel-based materi-
resolved. (6) The intrinsic narrow potential window of nickel- als with high capacitance, decent rate capability, admirable
based materials urges the development of asymmetric or hybrid cycling stability, superb energy density, and power density are
devices as well as the change in electrolytes. If the electrolyte is anticipated.
changed to organic electrolyte or ionic liquid, the mechanism
related to the redox reaction between Ni2+ and Ni3+ may some- Acknowledgments
how no longer exist. The advantage of the high capacitance of This work was supported by the National Natural Science
nickel-based materials may disappear. Thus, how to widen the Foundation of China (NSFC) (51320105001, U1705251,
potential window but at the same time preserve the high capac- 21573170 and 21433007, 21801200), the Natural Science Foun-
itance of nickel-based materials needs further consideration. A dation of Hubei Province, China (2015CFA001), and Innovative
new redox reaction between nickel-based materials with ionic Research Funds of SKLWUT (2017-ZD-4).
liquid is reasonable and conjectured. If this is true, then the
new electrochemical system with a novel mechanism may
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Materials Today d Volume xxx, Number xx d xxxx 2018 RESEARCH

Keywords: Nickel-based materials; Electrode materials; Electrochemical energy storage

1369-7021/Ó 2018 Elsevier Ltd. All rights reserved. https://doi.org/10.1016/j.mattod.2018.11.002

Supercapacitors have already entered a speciﬁc market niche.

orbed at the electrode/electrolyte interfaces. In this case, electro-

Continuous variation of the free Single-value free energy

(1) The inherent relatively narrow potential window (0.4–

To eliminate the aforementioned shortcomings, various

for nickel hydroxide, the mechanism involves the intercalation

Incorporation and decoration with carbonaceous materials

this intriguing morphology. Instead of being a scaffold or sup-

84% (4000th, 10 A g1)

81% (5000th, 15 A g1)

98% (2000th, 10 A g1)

There are two main reasons for the enhancement of graphene-

oxide/hydroxide, and nickel-based materials act as spacers to

prohibit the restacking of graphene. The interlayer spacing can

for the fabrication of supercapacitor electrodes is the

oxide/hydroxide decorated with graphene, the superiority of

collectors. Moreover, homogeneous dispersion of graphene or

of nickel oxide/hydroxide on the carbon-based skeleton, instead

of mechanical mixing is favorable.

Nickel-based bimetallic materials

Another remedy for improving performance of pristine nickel

oxide/hydroxide is through the fabrication of ternary oxides.

To circumvent the drawbacks of mono metal oxides/hydroxides,

bimetal oxides/hydroxides have emerged with desired properties,

(1) The presence of metal ions with multiple oxidation states

(valence states) grants the ternary materials with rich redox

(2) Ternary metal oxides/hydroxides exhibit higher electronic

(3) The electrochemical performance of the bimetallic nickel-

curves or the reduced peak separation. Sometimes CV

curves become rectangular, such as nickel cobalt oxide;

(4) Various combinations of different cations offer abundance

of choice for manipulating potential candidates.

The physical and electrochemical properties can be tuned by

tailoring the composition and structure. This review will be con-

centrated on the ternary metal oxides/hydroxides, which con-

Volume xxx, Number xxx

bic efﬁciency is disappointing [136]. Instead of using Ni–MOF Nickel–nonmetal-based materials

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