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Ni/Co bimetallic organic framework nanosheet

Cite this: Nanoscale, 2020, 12, 10685
assemblies for high-performance electrochemical
energy storage†
Yao Chi,a Wenping Yang,a Yichen Xing,a Yan Li,a Huan Pang *a and Qiang Xu *b

Nickel–cobalt organic framework (denoted as NiCo-MOF) nanosheet assemblies are prepared through a
controllable one-pot hydrothermal synthesis procedure at 150 °C. The as-prepared samples are directly
employed as electrode materials for electrochemical energy storage (EES), and exhibit excellent electro-
chemical performance. Among these samples, NiCo-MOF-1 displays a high capacity of 100.18 mA h g−1
Received 11th March 2020, (901.60 F g−1), and obtains a capacity retention of 81.00% over 3000 cycles at 5 A g−1. Likewise, in an
Accepted 22nd April 2020
aqueous device, NiCo-MOF-1//AC delivers a discharge capacity of 83.75 mA h g−1, and also exhibits a
DOI: 10.1039/d0nr02016h good cycling life (74.14% retention after 3000 cycles). These results demonstrate that multilayer NiCo-
rsc.li/nanoscale MOF nanosheet assemblies are potential electrode materials for EES.

1. Introduction of SCs. The advantages of MOFs include unique porosity, a

large specific surface area, and an adjustable structure and
Metal organic frameworks (MOFs) are a novel class of organic– function, so they can provide various types of catalytic
inorganic compounds with intramolecular pores. This com- sites,30–33 plentiful pseudocapacitive redox centers34–36 and
pound with a periodic structure is self-assembled from organic unique adsorption properties37,38 for catalysis and EES, which
ligands and metal ions or clusters through coordination endow the MOF material with a promising EES application.
bonds.1–3 Due to the good properties of both organic and in- In particular, some MOF-based materials for EES have been
organic materials, MOFs have a broad application prospect in reported in recent years. So far, as an electrode for EES, the
many fields,4–10 especially in the EES field.11,12 EES refers to application of MOF materials can be mostly divided into two
the conversion of electrical energy into chemical energy categories. One is to employ a MOF as a template to manufac-
storage through an electrochemical reaction on the basis of ture MOF derivatives; these materials include metal
chemical elements as an energy storage medium. At present, nanoparticles,39–41 metal oxides/sulfides,42–45 porous carbon
the main EES equipment is mainly divided into batteries and compounds,46 etc. Wu et al.44 employed hetero-bimetallic zeo-
capacitors. As is known to all, the electrochemical perform- litic imidazolate frameworks (ZIFs) as a template, and
ance of the EES equipment is mainly dependent on the elec- obtained ZnxCo3−xO4 hollow polyhedra by heat treatment.
trode materials.13–15 The EES system is made up of traditional When this polyhedral material was used as an electrode for Li-
electrode materials, such as carbon-based materials,16–19 ion batteries (LiBs), it showed high capacity and excellent
metals,20 metal oxides/sulfides21–28 and conductive poly- cycling stability. They also synthesized a 3D hollow hybrid
mers.29 However, some materials have the disadvantages of a based on the structure of ZIFs; this novel composite consists
low energy density or a short cycle life. Therefore, the study of of cobalt sulfides (CoS), porous carbon polyhedra (PCP) and
new electrode materials has always been a hotspot in the field carbon nanotubes (CNTs).45 When used as an anode material
of LiBs, the CoS@PCP@CNT electrode delivered a high dis-
charge capacity of 1668 mA h g−1, and exhibited stable cyclic
a performance. In another case, a MOF is applied as an elec-
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou,
225009 Jiangsu, P. R. China. E-mail: huanpangchem@hotmail.com, trode material directly.11,47–51 Especially in recent years, the
panghuan@yzu.edu.cn; https://www.x-mol.com/groups/panghuan direct use of primary MOFs as electrodes has been rapidly
b
AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory developed, which provided more candidate materials for new
(ChEM-OIL), National Institute of Advanced Industrial Science and Technology electrode materials. Wei’s group52 employed a pristine MOF
(AIST), Yoshida, Sakyo-ku, Kyoto 606-8501, Japan. E-mail: q.xu@aist.go.jp,
(layered Zn-doped Ni-MOF) as a supercapacitor (SC) electrode.
qxuchem@yzu.edu.cn
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ It can deliver a superior capacitance of 1620 F g−1 at 0.25 A g−1,
d0nr02016h which confirmed that a MOF-based electrode was feasible. They

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also reported a Co-based MOF positive material, the capacitance a battery-like electrode, and it obtained a discharge capacity of
value of which was 2564 F g−1, and it presented a capacity reten- 100.18 mA h g−1. Additionally, an aqueous device assembled
tion of 95.8% after 3000 cycles.53 Pang’s group54 designed a Ni- from multilayer NiCo-MOF-1 nanosheet assemblies and acti-
MOF electrode for SCs, which showed a capacitance of 988 F vated carbon (denoted as NiCo-MOF-1//AC) presented a capacity
g−1 and obtained 92.8% retention after 3000 cycles. of 83.75 mA h g−1, and showed a great cycling stability during
However, the conductivity of a MOF itself is poor, so the 3000 cycles. The bimetallic multilayer NiCo-MOF nanosheet
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specific capacitance obtained by a pure MOF electrode test is assemblies can be a prospective electrode material for EES.
low. Meanwhile, this MOF electrode lacks adequate chemical
durability. According to the previous research, the method of
MOF micronano-crystallization is a very effective approach to 2. Results and discussion
improve the above conditions.55–58 In the microscale/nano-
scale MOF particles, the diffusion path of electrolyte ions can In a typical one-pot synthesis procedure, Co(NO3)2·6H2O and
be significantly shortened, and the conducting carbon contact Ni(NO3)2·6H2O were utilized as the metal sources; meanwhile,
would be better with particles, thus increasing the conductivity terephthalic acid (TPA) was the organic ligand. By adjusting
of the whole material. Thus, the improved activity of electrode the proportion of metal sources, monometallic counterparts
materials leads to better electrochemical performance. MOF and Ni/Co bimetallic MOF were obtained, and the
Additionally, the synthesis of a bimetallic MOF is also another electrochemical properties of supercapacitors were studied.
effective way to improve the performance, which has been The preparation of MOF samples is schematically illus-
demonstrated by Zeng’s group.59 In their work, the Ni/Co bi- trated in Fig. 1a, and a detailed synthesis process is provided
metallic MOF electrode displayed a specific capacitance of in the ESI.† The digital photos of the samples show the trend
1067 F g−1, which was twice as much as that of Ni-MOF. Gao of color change from one sample to another. For the monome-
et al.60 also synthesized a dandelion-like NiCo-MOF material tallic counterpart MOF, Ni-MOF is a light green powder, and
in a facile hydrothermal way, and it presented a much better Co-MOF is red. For the Ni/Co bimetallic MOF, with the increas-
rate performance and cycling life than Ni-MOF or Co-MOF in ing Co ratio, its color gradually darkens to red, and NiCo-
the SCs. The improved performance of bimetallic MOFs is due MOF-1 shows a skin color (Fig. S1, ESI†). The crystal structures
to the presence of a synergetic effect, which results in an of the obtained MOF samples were studied by X-ray diffraction
improved electronic conductivity and chemical durability. (XRD), and Fig. S2a–c† show the results. The XRD pattern indi-
In this work, we prepared microscale/nanoscale NiCo-MOF cates that we have successfully prepared a series of MOF
nanosheet assemblies with different Ni/Co molar ratios by a samples as the simulated pattern of NiCo (TPA).61,62 In
simple hydrothermal method. The sample with a Ni/Co molar addition, NiCo-MOF samples in different proportions present
ratio of 2 : 1 is denoted as NiCo-MOF-1; samples with Ni/Co a similar crystalline structure (Fig. S2c†). To further confirm
molar ratios of 1 : 1 and 1 : 2 are corresponding to NiCo-MOF-2 the results, we performed Fourier transform infrared (FTIR)
and NiCo-MOF-3, respectively. These MOF nanosheet assem- spectral tests on these samples. The same FTIR band of five
blies have a multilayer structure, which makes the surface of MOF samples is displayed in Fig. S2d,† indicating that they
the active material more exposed, and also shortens the path of have identical functional groups, which demonstrate that
charge transfer and electrolyte ion diffusion. The synergetic these samples are isostructural. According to the strong
effect of the bimetallic NiCo-MOF leads to improved electronic absorbed bands around 3409 cm−1, which are identified as the
conductivity and chemical durability. In consideration of these O–H stretching vibrations, it can be inferred that there are co-
advantages, we subsequently investigated the electrochemical ordinated water molecules in these MOFs. The presence of a
performance of NiCo-MOF-1 in a conventional three-electrode benzene ring skeleton vibration (CvC) can be inferred from
cell. In our experiments, the NiCo-MOF-1 material was used as the absorption peaks at 1627, 1620, and 1591 cm−1. In

Fig. 1 Schematic illustration of the synthesis procedure of Ni-MOF, NiCo-MOF and Co-MOF.

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Fig. 2 Microscopic characterization of NiCo-MOF-1. (a–c) SEM images, (d) TEM images, (e–i) the HRTEM image and elemental mapping of C–K,
O–K, Ni–K, and Co–K.

addition, signals at 810 and 741 cm−1 correspond to benzene is in line with the EDX elemental mapping result. From Fig. 3a,
ring pair disubstituted peaks. The observed strong peak at it can be observed that the bonding state of Ni 2p is the same in
1372 cm−1 belongs to carboxylate (COO−). two samples. The peaks at 855.2 and 872.8 eV can be associated
From the scanning electron microscopy (SEM) images, it with Ni 2p3/2 and Ni 2p1/2, and the other two broad peaks
can be obviously seen that the obtained NiCo-MOF-1 crystals located at around 861.1 and 879.3 eV are determined as their
are regular and uniform, and they have a multilayer-sheet satellites (“Sat.”), respectively. Similarly, in Fig. 3b, the typical
structure (Fig. 2a–c). This structure is further validated by peaks at 779.9 and 796.7 eV correspond to Co 2p3/2 and Co
high-resolution transmission electron microscopy (HRTEM) 2p1/2, and the corresponding satellite peaks are at 785.6 and
in Fig. 2d. Meanwhile, the energy dispersion X-ray (EDX) 802.1 eV. The above characteristic bands belong to Ni2+ and
mapping images confirm that the Co, Ni, C and O elements Co2+, respectively. Therefore, this result indicates that Ni and Co
are evenly distributed over the sample (Fig. 2e–j). The other ions in the as-synthesized MOF samples mainly exist in the
four samples are also characterized by microscopy. As can be form of Ni2+ and Co2+. Additionally, we also compare the Ni 2p
seen from Fig. S3–6,† the overall frameworks of these four and Co 2p spectra among other three NiCo-MOF samples. In
samples are similar to that of NiCo-MOF-1, with a parallelo- Fig. S7,† the bonding states of the Ni 2p and Co 2p in NiCo-
gram surface framework. However, the different morphologies MOF samples are the same, and the atomic ratio of Co/Ni is
of the five samples are relatively obvious. In detail, monome- approximately consistent with the molar ratio of Co to Ni salts
tallic counterpart MOFs have fewer sheets stacked on the by peak fitting analysis.
quadrilateral surface, especially the Ni-MOF. In the three bi- By employing Hg/HgO as the reference electrode, Pt as the
metallic MOFs, the number of nanosheets changes signifi- counter electrode, 3.0 M KOH as the electrolyte and five MOF
samples as electrode materials, we performed a series of
cantly. When the Ni/Co molar ratio is 1 : 1, the number of
electrochemical tests. In order to find the suitable potential
nanosheets in the obtained NiCo-MOF-2 is the most, which
voltage windows, we first used cyclic voltammetry (CV) to test
also indicates that the growth structure of bimetallic MOFs
five samples (scan rate 20 mV s−1), and the window voltages
can be adjusted by controlling the proportion of metals. At
ranged from 0.35 V to 0.45 V (Fig. 4a and Fig. S8†). The redox
the same time, compared with MOF-1, the thickness of other
peaks are clearly shown in the obtained CV curves, which rep-
bimetallic MOF nanosheets gradually becomes thinner with
resent Faraday behavior that occurs at these MOF material
the increase of the proportion of metal Co salt. Furthermore,
electrodes. However, the shapes of these CV curves of five
in the elemental mapping images, the corresponding
samples are different, which indicates the diverse redox reac-
elements are also uniformly distributed throughout the
tions in these different MOF materials. The faradaic features
samples.
of NiCo-MOFs were thought to be caused by the redox reac-
In order to better identify the bonding states of Ni and Co,
tions of Co and Ni anions under the action of OH−, during the
X-ray photoelectron spectroscopy (XPS) was employed to analyze
electrochemical experiment.11,61,65 And the reactions may be
the spectra of Ni 2p and Co 2p (the XPS data have been cali-
probably described as follows,
brated). The XPS survey spectrum shows that these samples
consist of C and O elements, which are the basic elements of NiðiiÞs þ OH ⇄ NiðiiÞðOHÞad þ e
the MOF materials.63,64 Additionally, Ni-MOF, three NiCo-MOFs
and Co-MOF contain only corresponding metal elements, which CoðiiÞs þ OH ⇄ CoðiiÞðOHÞad þ e

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0.4 V. Apparently, the discharge curves and the voltage

plateau show non-linear behavior, suggesting a battery-type
Faraday behavior based on the MOF electrode.67–69 These
curves are approximately symmetric, which demonstrates the
prominent capacitive performance and electrochemical rever-
sibility of the NiCo-MOF-1 electrode. At different current den-
sities (ranging from 0.5 A g−1 to 20 A g−1), the corresponding
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capacities values are 100.18, 97.92, 94.67, 87.23, 80.56, 73.33

and 66.67 mA h g−1, respectively. The GCD curves of other
four samples are shown in Fig. S9a–d.† In order to better
compare the discharge capacitance performance of each
sample, the discharge curves at 0.5 A g−1 of five MOF electro-
des are presented in Fig. 4d. Under the same conditions, the
NiCo-MOF-1 electrode presents the largest capacity of
97.92 mA h g−1, and the others present 19.36, 64.25, 47.36
and 16.17 mA h g−1, respectively. Meanwhile, Fig. 4e shows
that the specific capacity decreases with the increasing of
current density. This is due to the limited utilization of OH−
ions on the inner and outer surfaces of the active materials.66
Among five samples, the NiCo-MOF-1 electrode exhibited the
highest discharge capacity at all current densities. Moreover,
even at 20 A g−1, the NiCo-MOF-1 electrode retains 66.67 mA
h g−1, revealing an outstanding rate capability. The cyclic
stabilities of the Ni-MOF, NiCo-MOF-1 and Co-MOF electro-
des were further tested at 5 A g−1 for over 3000 cycles. It can
be observed from Fig. 4f that the NiCo-MOF-1 electrode
demonstrates the most stable performance. In detail, the dis-
charge capacity of the first cycle is 76.55 mA h g−1, and
retains 62.12 mA h g−1 at the 3000th cycle. By contrast, the
other two monometallic counterpart MOFs exhibit low initial
capacities of only 15.3 and 18.1 mA h g−1, and retain 6.7 and
9.3 mA h g−1, demonstrating their poor cycling stability. In
the process of cycling, repeated insertion and deintercalation
Fig. 3 XPS spectra: (a) Ni 2p scan of Ni-MOF and NiCo-MOF-1; and (b) of OH− at the electrode/electrolyte interface lead to the col-
Co 2p scan of Co-MOF and NiCo-MOF-1. lapse of the structure of the NiCo-MOF multilayer and hinder
the wetting of the electrode, which is the main reason for the
decrease of capacity. To further explore the electrochemical
In monometallic counterpart MOF samples, only one metal characteristics of five MOF samples, electrochemical impe-
(Co or Ni) ion undergoes redox reactions. Meanwhile, the CV dance spectroscopy (EIS) of five as-prepared electrodes also
areas of NiCo-MOF electrodes are larger than those of two was tested. From Fig. S9e,† it can be obviously seen that the
monometallic counterpart MOF samples, indicating higher slope of NiCo-MOF-1 is larger than that of other samples,
capacitances of NiCo-MOF materials. This improvement is suggesting that the NiCo-MOF-1 electrode has lower ion
attributed to the synergistic effect of two metal ions (Ni/Co). At diffusion resistance and better electrochemical performance
different scan rates (Fig. 4b and Fig. S8†), the shapes of all CV in a low-frequency region.51 The capacitances of different
curves are similar, and the peak current and curve area gradu- NiCo-based MOF electrodes are displayed in Table S1 (ESI†),
ally improve with the increasing of scanning speed. The NiCo- and the value of the NiCo-MOF-1 electrode is close to the
MOF-1 electrode, in particular, has the largest curve area com- former research results by comparison.
pared to other four samples, which also indicates the best In a bid to further study the practical application of the
charge storage characteristics and capacitive behavior. NiCo-MOF-1 material, an aqueous device was assembled by
Furthermore, even on increasing the scan rate to 100 mV s−1, employing NiCo-MOF-1 as the positive electrode and commer-
the pairs of redox peaks are still clear, which exhibits excellent cial AC as the negative electrode, which was denoted as NiCo-
rate performance and kinetic reversibility of the NiCo-MOF-1 MOF-1//AC. By estimating, 0–1.3 V is the appropriate voltage
electrode.66 range available for the device, and it can also be verified in the
To quantify the discharge capacity of these materials, CV and GCD curves. Fig. 5a presents the CV curves of NiCo-
Fig. 4c shows the galvanostatic charge–discharge (GCD) MOF-1//AC at various scanning speeds, and Fig. 5b shows CVs
curves of NiCo-MOF-1 within diverse current densities at at different potentials. The shape of these curves clearly shows

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Fig. 4 CV curves of NiCo-MOF-1 at (a) different potentials and (b) different scanning speeds. (c) Charge–discharge curves of NiCo-MOF-1 at 0.5, 1,
2, 3, 5, 10, and 20 A g−1. (d) Discharge curves at 1 A g−1 and (e) rate performance of five MOF electrodes. (f ) Cyclic performance of Ni-MOF, NiCo-
MOF-1, and Co-MOF at 5 A g−1.

the pseudo capacitive behavior. Moreover, at a high sweep (Fig. S10†). Hence, the rate capacities of three samples are pre-
speed of 100 mV s−1, the CV curve maintains a good shaped, sented in Fig. 5d. Among them, the discharge capacity of
which indicates the excellent rate performance of the NiCo- NiCo-MOF-1//AC is higher than those of other samples,
MOF-1//AC aqueous device. Fig. 5c displays the GCD curves of meaning that NiCo-MOF-1 also has good rate performance in
NiCo-MOF-1//AC, at different current densities in the range of the aqueous device system. Additionally, during a long-term
0.5 to 20 A g−1, and the corresponding discharge capacity cycle at 5 A g−1, NiCo-MOF-1 shows a discharge capacity of
values are 83.75, 72.44, 61.78, 55.58, 52.36, 56.67 and 50.43 mA h g−1 initially, as well as a capacity retention of
42.22 mA h g−1, respectively. For further evaluation of the per- 74.1% after over 3000 charging and discharging cycles. In
formance of NiCo-MOF-1//AC, Ni-MOF//AC and Co-MOF//AC Fig. S10,† the EIS spectra clearly reveal that the Ni-MOF-1//AC
devices, they were also tested under the same conditions aqueous device has the largest slope among three samples,

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Fig. 5 Electrochemical properties of the NiCo-MOF-1 aqueous device. CV curves of NiCo-MOF-1 (a) at various scanning speeds and (b) different
potentials; (c) charge–discharge curves of NiCo-MOF-1 at various current densities; (d) rate performance of Ni-MOF, NiCo-MOF-1 and Co-MOF; (e)
cyclic performance of NiCo-MOF-1 at 5 A g−1.

suggesting that it has the smallest charge transfer resistance, conductivity of the material, and lead to a good chemical
relatively. The Ragone plot shows a high specific energy of durability, which is beneficial for maintaining a stable struc-
50.25 W h kg−1 of the NiCo-MOF-1//AC device at 300 W kg−1, ture of NiCo-MOF in a good cycle life. Secondly, the as-pre-
which is competitive to many other reported aqueous devices pared NiCo-MOFs have a special multilayer sheet structure,
employing a MOF-based (Ni-MOF, NiCo-MOF or Co-MOF) elec- which affords a short pathway to ion diffusion and electrolyte
trode (Fig. S10†). penetration, and also provides plentiful pseudocapacitive
NiCo-MOF-1 exhibits the best electrochemical perform- redox centers. Moreover, among three NiCo-MOF samples,
ance among five MOF samples, both in a three-electrode cell NiCo-MOF-1 shows the best performance due to its relatively
and in an aqueous device system, for two main reasons. thicker sheet, making its structure more stable and not prone
Firstly, the synergy of Ni and Co components will improve the to collapse.

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3. Conclusion 9 J. Wei, J. Yi, M. Han, B. Li, S. Liu, Y. Wu, L. Ma and D. Li,

Chem. – Asian J., 2019, 14, 3694–3701.
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electrode system, 83.75 mA h g−1 in the aqueous device), and Chem. Front., 2019, 6, 2514–2520.
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There are no conflicts to declare. 20 J. Ma, F. Ren, G. Wang, Y. Xiong, Y. Li and J. Wen,
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21 Z. Wu and X. Zhang, Sci. China Mater., 2016, 59, 547–557.
Acknowledgements 22 M. Al-Mamun, Y. Wang, P. Liu, Y. L. Zhong, H. Yin, X. Su,
H. Zhang, H. Yang, D. Wang, Z. Tang and H. Zhao,
This work was supported by the National Natural Science J. Mater. Chem. A, 2016, 4, 18314–18321.
Foundation of China (NSFC-21671170, 21201010, U1904215 23 W. Xia, R. Zou, L. An, D. Xia and S. Guo, Energy Environ.
and 21875207), the Top-notch Academic Programs Project of Sci., 2015, 8, 568–576.
Jiangsu Higher Education Institutions (TAPP), the Program for 24 H. Lai, Q. Wu, J. Zhao, L. Shang, H. Li, R. Che, Z. Lyu,
New Century Excellent Talents of the University in China J. Xiong, L. Yang, X. Wang and Z. Hu, Energy Environ. Sci.,
(NCET-13-0645), the Six Talent Plan (2015-XCL-030), and the 2016, 9, 2053–2060.
Qinglan Project. We also acknowledge the Priority Academic 25 Y. Yuan, H. Lv, Q. Xu, H. Liu and Y. Wang, Nanoscale, 2019,
Program Development of Jiangsu Higher Education 11, 4318–4327.
Institutions. 26 S. Zheng, X. Guo, H. Xue, K. Pan, C. Liu and H. Pang,
Chem. Commun., 2019, 55, 10904–10907.
27 Y. Liu, H. Wang, K. Yang, Y. Yang, J. Ma, K. Pan, G. Wang,
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