J Mater Sci (2021) 56:13752–13762

Energy
E N E R G Y Mmaterials
ATERIALS

Melamine-assisted synthesis of cobalt–nickel

coordination polymers as electrode materials
for supercapacitors
Shuai Wang1, Meng-Di Li1, Guo-Xin Qin1, and Yu-Bin Dong1,*

1
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for
Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong
Normal University, Jinan 250014, People’s Republic of China

Received: 7 January 2021 ABSTRACT

Accepted: 13 May 2021 Coordination polymers (CPs) and/or metal–organic frameworks (MOFs) are
Published online: new active materials for supercapacitors (SC). In this study, by solvothermal
26 May 2021 route, we conduct the melamine-assisted synthesis of bimetallic CPs (Co–Ni
CPs) with controllable structures. The concentration of melamine plays an
Ó The Author(s), under important role in the morphology of Co–Ni CPs, and the CPs can be turned from
exclusive licence to Springer microspheres to nanorods. The Co–Ni CPs are used as electrode materials for
Science+Business Media, LLC, SC. The spherical Co–Ni–CP-M exhibits the highest capacitances of 677 F g-1
part of Springer Nature 2021 and 585 F g-1 at current densities of 1 A g-1 and 10 A g-1, respectively, indi-
cating an outstanding rate capability in a three-electrode system with 2.0 M
KOH electrolyte. Furthermore, the Co–Ni–CP-M//active carbon device shows
superior long-term cycling stability, i.e., approximately 92.6% of the initial
capacitance can be retained after 10,000 cycles at 10 A g-1 in 2.0 M KOH elec-
trolyte. In addition, the asymmetric SC device achieves an excellent energy
density of 28.35 W h kg-1 at a power density of 700 W kg-1.

Handling Editor: Joshua Tong.

Shuai Wang and Meng-Di Li contributed equally to this work.

Address correspondence to E-mail: yubindong@[Link]

[Link]
J Mater Sci (2021) 56:13752–13762 13753

GRAPHICAL ABSTRACT

Introduction The development of multi-metallic CPs/MOFs

enables the incorporation of different central metal
ions into the same framework, which could improve
Supercapacitors (SCs) are considered as new eco- the conductivity of CPs/MOFs by increasing in free
friendly energy storage devices with fast charge– holes [14, 15]. Meanwhile, the enhanced oxidation
discharge rate, outstanding power density, long cycle state and the synergy of the multi-metallic compo-
life, excellent reliability, etc. [1, 2]. To achieve high- nents in the CPs/MOFs electrodes improve the elec-
performance SCs, it is necessary to develop new trochemical performance [16, 17]. Recently,
electrode materials with excellent charge storage numerous bimetallic CPs/MOFs, especially Co/Ni-
properties and good cycling stability [3]. Coordina- based CPs/MOF [18–23], are widely employed in SCs
tion polymers (CPs) and/or metal–organic frame- due to their optimal redox reaction ability. Amor-
works (MOFs) are a novel class of materials phous CPs are nonspecific to metal cation species,
constructed using metal ions and organic ligands [4] which is different from crystalline MOFs; therefore,
with open metal active sites, controllable structures, they can achieve a controllable composition adjust-
ordered crystalline structures and permanent poros- ment of metal ions in one structure [24]. Therefore, it
ity [5]. Due to the charge transfer within the struc- is more conducive to study the influence of different
tures and the redox activity of their metal ions [6], central metal ratios on electrochemical behaviors
several types, including Zn-, Zr-, Cu-, Fe-, Co- and using multi-metallic CPs as the electrode material.
Ni-based CPs/MOFs have been directly used as In addition, the morphology, size and microstruc-
supercapacitors electrode materials [7–12]. However, ture of electrode materials also affect their electro-
poor intrinsic conductivity with the low capacity of chemical performance [25–27]. Up to now, CPs/
most CPs/MOFs limits their application [13]. How- MOFs with different morphologies, such as nanosh-
ever, improving the intrinsic redox activity using eets [28], spheres [29], nanoflakes, nanofibers [30] and
tunable composition/components and nanorods [31], are used in supercapacitors. However,
adjustable morphology can promote the insertion/ it is still a challenge to realize the controllable mor-
extraction of ions inside the CPs/MOFs and enhances phology of CPs/MOFs with well-defined shapes and
the electrons transport routes, which have significant sizes for improving the electrochemical performance
effects on their electrochemical performance. of SC electrodes [32].
13754 J Mater Sci (2021) 56:13752–13762

In this study, we developed a facile method to (5 mmol) are denoted as Co–Ni–CP-M and Co–Ni–
prepare Co–Ni CPs with controlled morphology and CP-5 M, respectively.
tunable Co–Ni composition. The morphology of Co– Additionally, single metal-based CPs, Co-based
Ni CPs can be turned from microspheres to nanorods CPs and Ni-based CPs were prepared using the same
with the assistance of melamine. In addition, the procedure as Co–Ni–CP-M. Notably, the Co–Ni CPs
nitrogen-rich melamine provides pseudocapacitance prepared with different amounts of nickel nitrate
and improves the electrical conductivity and wetta- hexahydrate (0.1 mmol, 0.7 mmol and 1 mmol) were
bility [33, 34]. The Co–Ni CPs exhibit a high specific prepared using the same procedure as Co–Ni–CP-M.
capacity of 677 F g-1 at 1 A g-1 and a superior rate Melamine and the two metal ions were reacted
performance in 2.0 M KOH electrolyte. The assem- with H3BTC in ethylene glycol. H3BTC (0.21 g) reac-
bled asymmetric SC, Co–Ni CPs// Active carbon ted with different amounts of melamine, 0.126 g
(AC), displayed good cycling stability (92.6% reten- (1 mmol) and 0.63 g (5 mmol), in ethylene glycol
tion after 10,000 cycles at 10 A g-1). The device pos- (40 ml) at 70 °C. The obtained products are denoted
sesses a high specific energy density of 28.35 Wh kg-1 as BTC-M and BTC-5 M, respectively. H3BTC (0.21 g)
at the power density of 700 W kg-1. Thus, it is con- reacted with 0.29 g (1 mmol) cobalt (II) nitrate hex-
sidered a promising electrode materials for SC. ahydrate and 0.29 g of nickel (II) nitrate hexahydrate
(1 mmol) in ethylene glycol (40 mL) at 180 °C by the
solvothermal route. The obtained products are
Experimental section denoted as BTC-Co/Ni.

Materials Characterization
All materials were not further purified. Cobalt nitrate The powder X-ray diffraction (XRD) patterns were
hexahydrate (Co (NO3)26H2O) was purchased from obtained using Rigaku SmartLab SE X-Ray Powder
Sigma-Aldrich Corporation, and nickel nitrate hex- diffractometer with Cu Ka line focused radiation. The
ahydrate (Ni (NO3)26H2O) and 1, 3, 5-benzenetri- galvanostatic charge–discharge (GCD), cyclic
carboxylic acid purchased from Sigma. Active carbon voltammetry (CV) and electrochemical impedance
AC was synthesized using the reported method [35]. spectroscopy (EIS) tests were performed using
Graphite powder was purchased from Sigma- CHI660E. The morphology and microstructures of
Aldrich. the samples were detected using scanning electron
microscopy (SEM, Hitachi SU800) equipped with an
Synthesis of Co–Ni CPs energy-dispersive X-ray analysis analyzer and trans-
mission electron microscopy (TEM, Hitachi 200 kV
In the typical synthesis of Co–Ni CPs, 0.21 g electron beam energy). Nitrogen adsorption iso-
(1 mmol) of 1,3,5-Benzenetricarboxylic acid (H3BTC) therms were measured at 77 K using a Micromeritics
was dissolved in 20 mL of ethylene glycol under ASAP2020 HD88 Surface Area and Porosity
stirring at 70 °C. In addition, melamine was dis- Analyzer.
solved in 20 mL of ethylene glycol at 70 °C. When the
melamine powder dissolved in ethylene glycol, Electrochemical measurements
0.29 g (1 mmol) of cobalt (II) nitrate hexahydrate and
0.145 g (0.5 mmol) of nickel (II) nitrate hexahydrate The three-electrode electrochemical experiments
was added into it. The mixed solution was poured were conducted using Hg/HgCl2 electrode and a
into the H3BTC ethylene glycol solution for 20 min, platinum counter-electrode, using 2 M KOH as the
and the mixture was transferred into an autoclave for electrolyte. The active material (80 wt%) was mixed
24 h at 180 °C. After cooling to room temperature, the with polytetrafluoroethylene (5 wt%), acetylene black
violet sediment was washed several times using (7.5 wt%) and graphite (7.5 wt%) and coated onto a
ethanol and then dried at 50 °C for 12 h. The nickel foam of 1 cm2 geometric surface area. An
obtained Co–Ni CPs prepared with different asymmetrical supercapacitor (ASC) was assembled
amounts of melamine, 0.126 g (1 mmol) and 0.63 g using the obtained sample and AC as the positive
and negative electrode, using 2 M KOH as the
J Mater Sci (2021) 56:13752–13762 13755

electrolyte. The CV and GCD curves of the ACS 200 nm in width and 500 nm in length (Fig. 1g–h). It
device were obtained using CHI660E. The long was observed that the concentration of melamine in
cycling test was conducted using Land CT2001A the system played an important role in the mor-
model (Wuhan Land Electronics, Ltd). phology of the Co–Ni CPs. The morphology of the
The specific capacities (C) of the three-electrode final product could be turned from microspheres to
system were calculated from GCD curves using the nanorods by changing the content of melamine in the
following equation: system.
C ¼ r Dt  I=DU; ð1Þ To investigate the formation of Co–Ni CPs, we
studied the morphology of the Co–Ni–CP-M at dif-
where C (F g-1) is the specific capacity of Co/Ni CPs, ferent reaction times by SEM analysis (Fig. 2). During
I (A) is the discharge current density (A g-1), Dt (s) is the experiments, white precipitates formed rapidly
the discharge time, and DU (V) is the voltage drop. after the mixing of Co(II)/Ni(II)/melamine solution
The mass ratio the two electrodes should satisfy the with the prepared H3BTC ethylene glycol solution at
following equation: 70 °C. The precipitates showed rod structures, as
mþ =m ¼ ðC  DU Þ= ðCþ  DUþ Þ ð2Þ shown in Fig. 2a. After the solvothermal reaction for
1 h at 180 °C, the prepared CPs showed a spindle-like
where m (g) is the mass of active material.
structure (Fig. 2b). When the reaction time came to
The specific capacities (Ca) of the ASC device were
1.5 h, the spindle-like structures of CPs turned into
calculated from the GCD curves using the following
microspheres (Fig. 2c). Afterward, their morphology
equations:
stopped changing with time until the end of the
Ca ¼ r Dt  I=DU ð3Þ reaction (Fig. 2d, Figure S1).
P ¼ 3600 E=Dt ð4Þ In this system, melamine and two metal ions
2
reacted with H3BTC in ethylene glycol. Melamine
E ¼ 0:5 C ðDU Þ =3:6 ð5Þ reacted rapidly with H3BTC to form reversible
-1
where Ca (F g ) is the specific capacity, I (A) is the organic compounds at 70 °C, which exhibit rod-like
discharge current density (A g-1), Dt (s) is the dis- microstructures (Figure S2). Furthermore, the length
charging time. P (W kg-1) is the power density; of the rod decreased with an increase in melamine
E (Wh kg-1) is the energy density, and DU (V) is the content. Co (II) and Ni (II) both react with H3BTC to
voltage drop. form spherical CPs by the solvothermal process
(Figure S3). It seems that the reaction rate of H3BTC
and melamine was faster than that of H3BTC and
Results and discussion metal ions in the formation of the Co–Ni–CP-M.
Therefore, the prepared CPs at 70 °C showed a rod-
The Co–Ni CPs were fabricated by a facile one-step like structure. In this solvothermal process, the con-
solvothermal route using H3BTC, melamine, Ni- and centration of melamine was not enough to maintain
Co-salts and ethylene glycol. The morphology of the the rod-like morphology. The H3BTC in the rod
Co–Ni CPs was investigated using SEM and TEM structure gradually reacted with metal ions, and the
measurements. As shown in Fig. 1a and b, Co–Ni– morphology of the CPs gradually changed from rod
CP-M shows a uniform solid spherical microstruc- to spindle-like. The spherical CPs gradually split out
ture of approximately 3 lm. The N, Co and Ni were of the spindle-like structure and changed to an
uniformly dispersed in the Co–Ni–CP-M (Fig. 1c–f). adhered-double sphere structure (Figure S4). With an
It proved the existence of melamine doped in the increase in time, CPs became a 3-lm-solid sphere
framework of Co–Ni–CP-M. Doping with heteroa- structure.
toms N enhances the electrical conductivity and The formation of the Co–Ni–CP-5 M was investi-
wettability of the materials, which is beneficial for gated at different reaction times, as shown in Fig. 2e–
improving the electrochemical properties of the h. A rod-like structure with a length shorter than that
materials [29]. When the molar ratio of H3BTC and of the Co–Ni–CP-M before the solvent thermal reac-
Melamine turned from 1:1 (Co–Ni–CP-M) to 1:5 (Co– tion formed after the mixture of Co(II)/Ni(II)/me-
Ni–CP-5 M), Co–Ni–CP-5 M showed one-dimen- lamine and H3BTC, which proved the conjecture that
sional nanorod structures, which were approximately H3BTC and melamine react before the solvothermal
13756 J Mater Sci (2021) 56:13752–13762

Figure 1 SEM and TEM images of Co–Ni-CP-M (a, b) and their mapping images (c–f), SEM and TEM images of Co–Ni–CP-5 M (g,
h).

process. Due to the high concentration of melamine, spectrum of Co–Ni–CP-5 M contains pyridinic-N
the rod-like morphology can be maintained in the (32.4%), pyrrolic-N (37.0%) and quaternary-N (30.6%)
preparation of Co–Ni–CP-5 M. The formation of CPs in the N1s. The main oxidation state of Co and Ni in
is illustrated in Fig. 3. The concentration of melamine CPs is Ni (II) and Co (II) as shown in Fig. S7c-d
affected the morphology of the Co–Ni CPs. A high [16, 21].
melamine concentration resulted in rod-shaped Co– The capacitive performance of the materials was
Ni CPs, and a low melamine concentration resulted initially tested in a three-electrode system. Cyclic
in spherical shaped Co–Ni CPs. voltammetry (CV) at different scan rates for the
Powder XRD patterns of as-prepared samples are obtained CPs in 2 M KOH electrolyte is shown in
shown in Figure S5. Co–Ni–CP-M and Co–Ni–CP- Fig. 4a. Notably, the CV curve of the Co–Ni–CP-M
5 M exhibited a broad peak located at a 2h value of had areas larger than that of the Co–Ni–CP-5 M at
approximately 25°, and no obvious peak was 10 mV s-1, which indicates that Co–Ni–CP-M has a
observed from the crystalline phases, indicating higher specific capacity than Co–Ni–CP-5 M. Addi-
amorphous features. The N2 adsorption and desorp- tionally, the distinct redox peaks of Co–Ni–CP-M and
tion isotherm plots of the Co–Ni–CP-M and Co–Ni– Co–Ni–CP-5 M may be caused by the intercalation
CP-5 M in Figure S6 reveal a microporous structure and deintercalation of OH- and the change of
with a specific surface area of 6.16 m2 g-1 and 28.52 valence state of nickel and cobalt in the charging and
m2 g-1, respectively. XPS measurements were con- discharging process [16, 19, 21, 36]. The CV curves of
ducted to demonstrate the evolution of N 1 s, Ni 2p Co–Ni-CP-M and Co–Ni–CP-5 M at 10 mV s-1,
and Co 2p in Co–Ni–CP-M and Co–Ni-CP-5 M (Fig- 40 mV s-1 and 60 mV s-1 are shown in Figs. 4b and
ure S7). The nitrogen contents of the Co–Ni–CP-M S8a. Figure 4c showed the galvanostatic charge–dis-
and Co–Ni-CP-5 M are 7.87% and 10.96% (atomic%), charge (GCD) of Co–Ni–CP-M at different current
respectively. The three peaks at * 398.7, 399.5 and densities with specific capacitances of 677 F g-1 (1 A
400.4 eV in the N1s spectrum of Co–Ni–CP-M were g-1), 629 F g-1 (3 A g-1), 606 F g-1 (5 A g-1) and 585 F
identified as pyridinic-N (29.6%), pyrrolic-N (39.6%) g-1 (10 A g-1). Figure 4d shows the constant current
and quaternary-N (30.8%), respectively. The charging and discharging of Co–Ni–CP-5 M under
J Mater Sci (2021) 56:13752–13762 13757

Figure 2 SEM images of Co–

Ni–CP-M at different reaction
time: before solution thermal:
a, 1 h b, 1.5 h c, 3 h d; SEM
images of Co–Ni–CP-5 M at
different reaction time: before
solution thermal (e), 1 h (f),
1.5 h (g), 3 h (h).

different current densities and shows specific capac- Ni–CP-M shows 94% of the initial specific capaci-
itances of 377 F g-1 (1 A g-1), 336 F g-1 (3 A g-1), tance after 1000 cycles at a current density of 10 A g-1
328.7 F g-1 (5 A g-1) and 305 F g-1 (10 A g-1). The in 2 M KOH solution Fig S8c. The specific capacitance
results of coulombic efficiency of Co–Ni CPs are of the Co–Ni–CP-M and Co–Ni–CP-5 M changed
shown in Fig. S8b. The Co–Ni CPs show a high slightly with different current densities, exhibiting a
coulomb efficiency at high current densities. The Co– good rate capability as shown in Fig. 4e. Figure 4f
13758 J Mater Sci (2021) 56:13752–13762

Figure 3 Schematic
representation of the formation
of Co–Ni CPs.

Figure 4 Electrochemical
performance of Co–Ni CPs in
the three-electrode system. CV
curves of Co–Ni–CP-M and
Co–Ni–CP-5 M at 10 mV-1
(a); CV curves of Co–Ni-CP-
M (b); GCD profiles of Co–
Ni-CP-M (d) and Co–Ni-
CP-5 M (c); specific
capacitance at different current
densities of Co–Ni-CP-M
and Co–Ni-CP-5 M (e); EIS
of Co–Ni–CP-M and Co–
Ni-CP-5 M (f).
J Mater Sci (2021) 56:13752–13762 13759

shows the EIS of the Co–Ni–CP-M and Co–Ni–CP- bimetallic CPs changed with the ratio of Co (II) and
5 M. After fitting and calculating using ZSimpWin, Ni (II), it was higher than that of the single-metallic
the total electric series resistance (Rs) of the Co–Ni– Co–CPs (182 F g-1) and Ni CPs (44 F g-1) as shown in
CP-M is 1.08 X, and the faradaic charge transfer Fig. 5. These results indicate that the mixed-metallic
resistance (Rct) is 0.94 X. The Rs and Rct of Co–Ni– CPs are conductive for improving the electrochemical
CP-5 M are 1.31 X and 0.98 X, respectively. The Co– performance. The Co–Ni–CP-M had superior specific
Ni–CP-M showed less resistance than Co–N–CP-5 M capacity with low electrochemical impedance; thus, it
indicating the ion diffusion and electrolyte perme- was used as asymmetry SC device anode materials.
ation in Co–Ni–CP-M is easier. The melamine con- An asymmetrical SC device (ASC) Co–Ni–CP-M//
tent increase decreased its specific capacitance. AC was also assembled to evaluate the practical
However, without adding melamine, the highest applications of Co–Ni CPs. The specific capacitance
specific capacity of Co–Ni CPs was 447 F g-1 of the AC electrode is 318 F g-1 at a current density of
(Fig. S9). Therefore, improvement in the electro- 1 A g-1. So, the mass ratio between the positive and
chemical performance of melamine-doped Co–Ni negative electrode is 1.2 with AC 1.3 mg. The CV
CPs was proved. curves of the ASC device at the scan rates of
Due to the tunable composition of amorphous CPs, 10 mV s-1, 20 mV s-1 and 50 mV s-1 with the scan-
we investigated the effect of different metal ion ratios ning voltage range of 0–1.4 V were shown in Fig. 6a.
on their electrochemical performance in three-elec- The ASC device shows a maximum specific capacity
trode systems. The Co–Ni CPs prepared with differ- 105 F g-1 at 1 A g-1. The GCD curves of the device do
ent molar ratios of Co (II) and Ni (II) (0:1, 1:0, 1:0.3, not possess a strong polarization phenomenon as
1:0.7 and 1:1) were prepared using the same proce- shown in Fig. 6b. Therefore, we chose a scale of
dure as Co–Ni–CP-M with the same concentration of 0–1.4 V as the best voltage range. The EIS of the Co–
melamine. These CPs exhibit spherical structures, Ni–CP-M//AC in Fig. 6c. After fitting and calculat-
which is proof that melamine influences the mor- ing using ZSimpWin, the total electric series resis-
phology of Co–Ni CPs (Fig. S10). The changes in the tance (Rs) of ASC device is 3.2 X and the faradaic
ratio of the central metal ions do not change their charge transfer resistance (Rct) is 2.1 X [37]. Figure 6d
crystallinity; thus, they still exhibit amorphous shows a long cycle of the ASC device at the current
structures (Fig. S11). Their specific capacitances at 1 A density of 10 A g-1, indicating that the specific
g-1 are shown in Figs. 5 and S12. Notably, the capacitance of the ASC device maintained 92.6% after
specific capacitance of Co–Ni CPs increased with an 10,000 cycles at 10 A g-1. This proves the stability of
increase in Ni content in the same structure. How- its cycle performance at high current density. Fig-
ever, when the molar Co/Ni ratio came to 1:0.5 (Co– ure 6e is the Ragone plot of the ASC device with the
Ni–CP-M), the specific capacitance of Co–Ni CPs highest energy density of 28.35 W h kg-1 at a power
became the highest (Fig. 5). Subsequently, the specific density of 700.5 W kg-1. Further, it can deliver an
capacitance of Co–Ni CPs decreased with the increase energy density of 22 W h kg-1 at a power density of
in Ni content. Although the specific capacity of the 7000 W kg-1, which shows better or comparable
electrochemical performance than the previously
reported Co-based MOFs, Ni-based MOFs, CO/Ni-
based MOFs ASC devices [4, 16, 18, 21, 28, 38, 39].
These results demonstrate that Co–Ni–CP-M could
be a promising electrode material for applications in
SCs.

Conclusion

Bimetallic CPs (Co/Ni CPs) with different mor-

phologies were synthesized by the solvothermal
Figure 5 The specific capacities of Co–Ni CPs with the various route. The morphology of the Co–Ni CPs, from
metal molar ratio. microspheres to nanorods, is controlled by the
13760 J Mater Sci (2021) 56:13752–13762

Figure 6 Electrochemical
performance of the Co–Ni–
CP-M//AC device. a CV
curves measured at different
scan rates, b GCD profiles
measured at different current
densities, c EIS, d Cycling
performance for 10,000 cycles
at 10 A g-1 and e Ragone
plots.

amount of melamine. The optimized Co–Ni–CP-M Acknowledgements

exhibited the highest capacitances of 677 F g-1 at 1 A
g-1 and an outstanding rate capability of 585 F g-1 at We are grateful for financial support from the
10 A g-1, in a three-electrode system having 2.0 M National Natural Science Foundation of China (Nos.
KOH electrolyte. The fabricated Co–Ni–CP-M//AC 21971153 and 21701103), the Major Basic Research
with alkaline electrolytes showed excellent cyclic Projects of Shangdong Natural Science Foundation
stability with 92.6% retention of the initial specific (No. ZR2020ZD32), and the Taishan Scholars Climb-
capacitance after 10,000 cycles at 10 A g-1. The ing Program of Shandong Province.
asymmetric SC device showed a highest energy
Declarations
density of 28.35 W h kg-1 at a power density of
700 W kg-1. Therefore, this study demonstrates that Conflict of interest There are no conflicts to declare.
mixed-metallic CPs are promising electrodes in SCs.
Supplementary Information: The online version
contains supplementary material available at http
s://[Link]/10.1007/s10853-021-06187-4.
J Mater Sci (2021) 56:13752–13762 13761

References [11] Mallick A, Liang H, Shekhah O, Jia J, Mouchaham G,

Shkurenko A, Belmabkhout Y, Alshareef HN, Eddaoudi M
[1] Ding Y, Peng Y, Chen S, Li Z, Zhang X, Falaras P, Hu L (2020) Made-to-order porous electrodes for supercapacitors:
(2019) A competitive coordination strategy to synthesize MOFs embedded with redox-active centers as a case study.
Co3O4@carbon flower-like structures for high-performance Chem Commun 56:1883–1886
asymmetric supercapacitors. Appl Surf Sci 495:143502 [12] Lee DY, Yoon SJ, Shrestha NK, Lee SH, Ahn H, Han SH
[2] Lan Y, Li M, Fan W, Deng Q, Zeng Z, Wang J, Deng S (2012) Unusual energy storage and charge retention in Co-
(2019) Functional molecules regulated and intercalated based metal–organic-frameworks. Microporous Mesoporous
nickel-cobalt LDH nano-sheets on carbon fiber cloths as an Mater 153:163–165
advanced free-standing electrode for high-performance [13] Jiao Y, Pei J, Chen D, Yan C, Hu Y, Zhang Q, Chen G (2017)
asymmetric supercapacitors. Electrochim Acta 321:134708 Mixed-metallic MOF based electrode materials for high
[3] Kazemi SH, Hosseinzadeh B, Kazemi H, Kiani MA, Hajati S performance hybrid supercapacitors. J Mater Chem A
(2018) Facile synthesis of mixed metal-organic frameworks: 5:1094–1102
electrode materials for supercapacitors with excellent areal [14] Zhang JH, Cai GF, Zhou D, Tang H, Wang XL, Gu CD, Tu
capacitance and operational stability. ACS Appl Mater JP (2014) Co-doped NiO nanoflake array films with
Interfaces 10:23063–23073 enhanced electrochromic properties. J Mater Chem C
[4] Guan BY, Kushima A, Yu L, Li S, Li J, Lou XWD (2017) 2:7013–7021
Coordination polymers derived general synthesis of multi- [15] Mai YJ, Tu JP, Xia XH, Gu CD, Wang XL (2011) Co-doped
shelled mixed metal-oxide particles for hybrid supercapaci- NiO nanoflake arrays toward superior anode materials for
tors. Adv Mater 29:1605902 lithium ion batteries. J Power Sources 196:6388–6393
[5] Salunkhe RR, Zakaria MB, Kamachi Y, Alshehri SM, [16] Wang J, Zhong Q, Xiong Y, Cheng D, Zeng Y, Bu Y (2019)
Ahamad T, Torad NL, Dou SX, Kim JH, Yamauchi Y (2015) Fabrication of 3D Co-doped Ni-based MOF hierarchical
Fabrication of asymmetric supercapacitors based on coordi- micro-flowers as a high-performance electrode material for
nation polymer derived nanoporous materials. Electrochim supercapacitors. Appl Surf Sci 483:1158–1165
Acta 183:94–99 [17] Zhang X, Wang J, Ji X, Sui Y, Wei F, Qi J, Meng Q, Ren Y,
[6] Phattharasupakun N, Wutthiprom J, Kaenket S, Maihom T, He Y (2020) Nickel/cobalt bimetallic metal-organic frame-
Limtrakul J, Probst M, Nagarkar SS, Horike S, Sawangphruk works ultrathin nanosheets with enhanced performance for
M (2017) A proton-hopping charge storage mechanism of supercapacitors. J Alloy Compd 825:154069
ionic one-dimensional coordination polymers for high-per- [18] Chen C, Wu MK, Tao K, Zhou JJ, Li YL, Han X, Han L
formance supercapacitors. Chem Commun 53:11786–11789 (2018) Formation of bimetallic metal–organic framework
[7] Zheng S, Li X, Yan B, Hu Q, Xu Y, Xiao X, Xue H, Pang H nanosheets and their derived porous nickel–cobalt sulfides
(2017) Transition-metal (Fe Co, Ni) based metal-organic for supercapacitors. Dalton Trans 47:5639–5645
frameworks for electrochemical energy storage. Adv Energy [19] Chen L, Ou D, Zhang G, Yan J, Liu J, Wang Z, Wang Y, Cui
Mater 7:1602733 J, Zhang Q, Zhang Y, Hu X, Wu Y (2020) Ni–Co coordi-
[8] Chen Y, Ni D, Yang X, Liu C, Yin J, Cai K (2018) Micro- nation hollow spheres for high performance flexible all-
wave-assisted synthesis of honeycomblike hierarchical solid-state supercapacitor. Electrochim Acta 337:135828
spherical Zn-doped Ni-MOF as a high-performance battery- [20] Ye C, Qin Q, Liu J, Mao W, Yan J, Wang Y, Cui J, Zhang Q,
type supercapacitor electrode material. Electrochim Acta Yang L, Wu Y (2019) Coordination derived stable Ni-Co
278:114–123 MOFs for foldable all-solid-state supercapacitors with high
[9] Chen L, Zhang Q, Xu H, Hou X, Xuan L, Jiang Y, Yuan Y specific energy. J Mater Chem A 7:4998–5008
(2015) Amorphous 3D nanoflake array-assembled porous 2D [21] Gao S, Sui Y, Wei F, Qi J, Meng Q, Ren Y, He Y (2018)
cobalt–oxalate coordination polymer thin sheets with excel- Dandelion-like nickel/cobalt metal-organic framework-based
lent pseudocapacitive performance. J Mater Chem A electrode materials for high performance supercapacitors.
3:1847–1852 J Colloid Interface Sci 531:83–90
[10] Ehsani A, Khodayari J, Hadi M, Shiri HM, Mostaanzadeh H [22] Wang X, Li Q, Yang N, Yang Y, He F, Chu J, Gong M, Wu
(2016) Nanocomposite of p-type conductive polymer/Cu B, Zhang R, Xiong S (2019) Hydrothermal synthesis of
(II)-based metal-organic frameworks as a novel and hybrid NiCo-based bimetal-organic frameworks as electrode mate-
electrode material for highly capacitive pseudocapacitors. rials for supercapacitors. J Solid State Chem 270:370–378
Ionics 23:131–138 [23] Rajak R, Kumar R, Ansari SN, Saraf M, Mobin SM (2020)
Recent highlights and future prospects on mixed-metal
13762 J Mater Sci (2021) 56:13752–13762

MOFs as emerging supercapacitor candidates. Dalton Trans based metal organic frameworks for supercapacitor electrode
49:11792–11818 materials. Electrochim Acta 267:170–180
[24] Shi P, Li L, Hua L, Qian Q, Wang P, Zhou J, Sun G, Huang [33] Li H, Yu C, Zhou Y, Tuo H, Zhong W (2019) Biligand
W (2016) Design of amorphous manganese oxide@multi- metal-organic coordination polymer to prepare high N-doped
walled carbon nanotube fiber for robust solid-state superca- content and structure controllable porous carbon with high-
pacitor. ACS Nano 11:444–452 electrochemical performance. Electrochim Acta
[25] Zhou S, Wang S, Zhou S, Xu H, Zhao J, Wang J, Li Y 308:263–276
(2020) An electrochromic supercapacitor based on an MOF [34] Li Q, Yue L, Li L, Liu H, Yao W, Wu N, Zhang L, Guo H,
derived hierarchical-porous NiO film. Nanoscale Yang W (2019) Metal-organic frameworks derived N, S co-
12:8934–8941 doped bimetal nanocomposites as high-performance elec-
[26] Guan X, Huang M, Yang L, Wang G, Guan X (2019) Facial trodes materials for supercapacitor. J Alloy Compd
design and synthesis of CoSx/Ni-Co LDH nanocages with 810:151961
rhombic dodecahedral structure for high-performance [35] Wang R, Lang J, Yan X (2014) Effect of surface area and
asymmetric supercapacitors. Chem Eng J 372:151–162 heteroatom of porous carbon materials on electrochemical
[27] Yang J, Ma Z, Gao W, Wei M (2017) Layered structural Co- capacitance in aqueous and organic electrolytes. Sci China-
Based MOF with conductive network frames as a new Chem 57:1570–1578
supercapacitor electrode. Chem Eur J 23:631–636 [36] Deng T, Zhang W, Arcelus O, Kim JG, Carrasco J, Yoo SJ,
[28] Du P, Dong Y, Liu C, Wei W, Liu D, Liu P (2018) Fabri- Zheng W, Wang J, Tian H, Zhang H, Cui X, Rojo T (2017)
cation of hierarchical porous nickel based metal-organic Atomic-level energy storage mechanism of cobalt hydroxide
framework (Ni-MOF) constructed with nanosheets as novel electrode for pseudocapacitors. Nature Commun 8:15194
pseudo-capacitive material for asymmetric supercapacitor. [37] Zhang Z, Huo H, Gao J, Yu Z, Ran F, Lei G, Lou S, Mu T,
J Colloid Interface Sci 518:57–68 Yin X, Wang Q, Yin G (2019) Ni-MOF derived NiO/C
[29] Qin L, Ru R, Mao J, Meng Q, Fan Z, Li X, Zhang G (2020) nanospheres grown in situ on reduced graphene oxide
Assembly of MOFs/polymer hydrogel derived Fe3O4- towards high performance hybrid supercapacitor. J Alloy
CuO@hollow carbon spheres for photochemical oxidation: Compd 801:158–165
freezing replacement for structural adjustment. Appl Catal B [38] Gao S, Sui Y, Wei F, Qi J, Meng Q, He Y (2018) Facile
Environ 269:118754 synthesis of cuboid Ni-MOF for high performance super-
[30] Tian D, Lu X, Zhu Y, Li M, Wang C (2019) Fabrication of capacitors. J Mater Sci 53:6807–6818. [Link]
two-dimensional metal-organic frameworks on electrospun 07/s10853-018-2005-1
nanofibers and their derived metal doped carbon nanofibers [39] Kang L, Sun S, Kong L, Lang J, Luo Y (2014) Investigating
for an advanced asymmetric supercapacitor with a high metal-organic framework as a new pseudo-capacitive mate-
energy density. J Power Sources 413:50–58 rial for supercapacitors. Chin Chem Lett 25:957–961
[31] Qu C, Jiao Y, Zhao B, Chen D, Zou R, Walton KS, Liu M
(2016) Nickel-based pillared MOFs for high-performance Publisher’s Note Springer Nature remains neutral with
supercapacitors: Design, synthesis and stability study. Nano regard to jurisdictional claims in published maps and
Energy 26:66–73 institutional affiliations.
[32] Ramachandran R, Zhao C, Luo D, Wang K, Wang F (2018)
Morphology-dependent electrochemical properties of cobalt-