Applied Surface Science 565 (2021) 150482

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Two-dimensional nanosheets constituted trimetal Ni-Co-Mn sulfide

nanoflower-like structure for high-performance hybrid supercapacitors
Jiaying Zhang a, Chao Li a, *, Meiqiang Fan a, Tingli Ma a, Haichao Chen b, *, Hongxia Wang c
a
College of Materials Science & Chemistry, China Jiliang University (CJLU), Hangzhou, 310018, China
b
Institute of Materials for Energy and Environment, School of Materials Science and Engineering, Qingdao University, Qingdao, 266071, China
c
School of Chemistry and Physics, Science and Engineering Faculty, Queensland University of Technology, 2 George Street, Brisbane, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Trimetal NiCoMn-based sulfides with two-dimensional (2D) nanosheets constituted flower-like structures have
Trimetal sulfides been synthesized using an anion exchange approach, which exhibit excellent performance as electroactive
Two-dimensional nanosheets battery materials for hybrid supercapacitors. These NiCoMn-based sulfides were transformed from layered hy­
Ni-Co-Mn sulfide
droxides while well maintaining 2D nanosheets constituted flower-like structure. The amounts of Mn constitution
Hybrid supercapacitors
have been tuned to control performance of sulfides. It is found that Mn doping causes formation of pure phase
sulfide while maintaining same flower-like structure. Mn-doping can enhance specific capacity and cycling
stability of sulfides, and resulting sulfides maintain a low charge transfer resistance. Mn-doped sulfides display a
maximum specific capacity of 657.7C g− 1 at 1 A g− 1, and a specific capacity of 339.5C g− 1 has been achieved
when the specific current increases by 50 times to 50 A g− 1. More significantly, the NiCoMn-based sulfide has
been used to assemble hybrid supercapacitors with reduced graphene oxide, which achieves a maximum specific
energy of 36.3 Wh kg− 1 combined with long-term cycling stability.

1. Introduction long life time and high power performance are ensured thanks to the
contribution of the EDLC materials in the HSCs [8].
With the increasing energy demand for social society and the global Transition metal sulfides have been extensively investigated as
climate issues caused by burning fossil fuels, developing efficient tech­ competitive battery-type electrode materials for HSCs because of their
nologies for renewable energy conversion and storage have become an remarkable electrochemical properties [9–11]. Compared with transi­
imperative mission in the world to address current global issues [1]. tion metal oxide or hydroxides, sulfides can realize higher electron
Supercapacitors have attracted great research attentions in the past two conductivity and provide more effective active sites [12–15]. For
decades owing to their complimentary merits of high power and ultra- example, NiCo2S4 exhibited considerable electron conductivity as high
long cycling lifespan compared to other energy storage technologies as 100 times that of NiCo-OH [16,17]. Qin et al. prepared H-
such as batteries [2,3]. However, traditional supercapacitors use porous 3DRG@NiCo-LDH and H-3DRG@NiCo2S4, and verified that the latter
carbon based electrode materials for energy storage, which still suffer offered higher electrochemical activity and its redox peaks locate at a
from low charge storage ability and thus low energy density due to the higher potential [18]. More significantly, recently investigation found
limited electrical double layer capacitance (EDLC) [4,5]. To solve this that the sulfides with three types of transition metal constitutions show
problem, hybrids supercapacitors (HSCs) are designed to enhance en­ higher specific capacitance and better rate performance than single
ergy density of supercapacitors without significantly compromise their metal sulfides or binary metal sulfides [10,19,20]. Rahimi et al. pre­
power density [6]. The HSCs are constructed using a battery electrode pared Ni-Co-Fe sulfides supported on 3D Ni nanocone and realized a
with a capacitive electrode, which in principle combine both merits of high specific capacitance (2159.7F g− 1) [21], which is much better than
batteries and supercapacitors for high energy and high power energy single metal counterpart such as NiS [22], CoS [23], and FeS2 [24]. The
storage. Wherein, battery-type electrode material experiences phase different transition metals exhibit different redox reactions for energy
change during charge and discharge processes which significantly en­ storage, and thus multi-metal sulfides combines the merits from each
hances the charge storage capability of the device [7]. Simultaneously, transition metal, resulting in a synergistic effects for enhanced energy

* Corresponding authors.
E-mail addresses: lichao@cjlu.edu.cn (C. Li), chenhchust@126.com (H. Chen).

https://doi.org/10.1016/j.apsusc.2021.150482
Received 11 January 2021; Received in revised form 21 June 2021; Accepted 24 June 2021
Available online 27 June 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
J. Zhang et al. Applied Surface Science 565 (2021) 150482

storage performance [25–29]. On the other hand, layered metal sulfides Halenda (BJH) methods. Elemental ratios of sulfides were tested using
can accommodate volumetric expansion preferably during redox reac­ the X-ray fluorescence probe (XRF, EDAX Inc. Eagle III) technique. X-ray
tion, leading to excellent mechanical stability [30–32]. However, syn­ photoelectron spectroscopy technique (XPS; AXIS-ULTRA DLD-600 W)
thesis of layered sulfides with multi-metals is still a big challenge as the was used to collect the elemental composition and their chemical states
different coordination mode of transition metals with S2- may give rise to of the sample surface.
a different crystal structure.
Herein, NiCoMn-based sulfides with 2D nanosheets-constituted
nanoflower-like structure have been synthesized using an ion ex­ 2.4. Electrochemical measurements
change approach. The NiCoMn-based hydroxides were synthesized as
the precursor for the conversion of sulfides. Owing layered the structure The electrochemical tests were performed in a three-electrode sys­
of these hydroxides, the precursor is constituted by 2D nanosheets which tem using a CHI660E electrochemical workstation. The electrode was
interconnected to form a flower-like structure. The hydroxides serve as prepared in the following procedure. Initial mass of nickel foam was
self-sacrificial template for ion exchange reaction, resulting in its con­ weighed. The electrode materials, acetylene black and polytetrafluoro­
version to sulfide maintaining 2D nanosheets structure. In addition, ethylene (PVDF) were dispersed in anhydrous ethanol with a mass ratio
amounts of Mn constitution have been tuned to control the performance of 8: 1: 1, which was coated onto the nickel foam and dried at 60 ◦ C in a
of sulfides. The contribution of Mn element on phase structure, vacuum. Then the electrode sheet was pressed at 10 MPa. The mass
morphology and electrochemical performance of the NiCoMn-S was loading on each electrode was approximate 3.0 mg. The electrolyte was
investigated and discussed. It is found the sulfides shows better perfor­ 6 M KOH aqueous solution. A platinum foil (1 × 1 cm) and Hg/HgO
mance than with Mn doping and excellent performance has been ach­ electrode were used as the counter electrode and reference electrode,
ieved for the NiCoMn-S based HSC. respectively.
The cyclic voltammetry (CV) curves of the as-synthesized materials
2. Experiment were obtained in a potential window of 0–0.56 V at scan rates ranging
from 3 to 50 mV s− 1. The electrochemical impedance spectroscopy (EIS)
2.1. Synthesis of Ni-Co-Mn sulfide nanosheets was performed at an open circuit potential in the frequency region from
0.01 Hz to 100 kHz. The galvanostatic charge-discharge (GCD) tests
NiCoMn-based sulfides were prepared via an anion exchange reac­ were performed to test the specific capacity, cycling stability, energy
density and power density at specific currents ranging from 1 A g− 1 to 50
tion of NiCoMn-based hydroxides with Na2S⋅9H2O. The NiCoMn hy­
droxides were synthesized according to the hexamethylenetetramine A g− 1. The specific capacity (C, in C g− 1) of active material was calcu­
lated from the GCD curves using the following equation [35]:
(HMT) assisted hydrothermal method [33]. In a typical procedure,
NiCl2⋅6H2O, CoCl2⋅6H2O MnCl2⋅4H2O with a total molar weight of 6 I × Δt
C= (1)
mmol was dissolved in 60 mL deionized water, and then 6 mmol of HMT m
was added under stirring. The molar weight ratio of between Ni and Co
precursors was kept at 1:2 and the amount of Mn was changed from 0.5 where I (A), Δt (s) and m (g) represent the discharge current, discharge
to 3 mmol. Hydrothermal reaction was performed at 90 ◦ C for 6 h. After time and active material mass, respectively.
cooling down to room temperature, NiCoMn-based hydroxides can be The HSC cell was assembled in 6 M KOH electrolyte with the sulfide
collected. The hydroxides were dispersed into 60 mL of deionized under as the positive electrode materials and the RGO as the negative electrode
ultrasonic treatment, and then Na2S⋅9H2O was added. Weight ratio be­ materials. The mass ratio between the positive and negative electrodes
tween hydroxide and Na2S⋅9H2O was 1:3. The solution was transferred was controlled based on the balanced charge principle [33]:
into an 80 mL of Teflon-lined stainless steel autoclave and heated at m + C − × V−
160 ◦ C for 6 h. After hydrothermal reaction, the products were collected = (2)
m− C + × V+
and washed with deionized water and alcohol for several times.
NiCoMn-based sulfides were named as NiCoMn-S-n (n = 0, 1, 1.5, 2 and The specific energy (E, in Wh kg− 1) and specific power (P, in kW
− 1
3 mmol), where n represents the molar weight of MnCl2⋅4H2O. kg ) of the HSC were calculated from the GCD curves according to the
following equations [32,36].
2.2. Synthesis of reduced graphene oxide 1
∫ Vmax
E= Is Vdt (3)
3.6 0
The reduced graphene oxide (RGO) was synthesized by a modified
Hummers method [34]. Briefly graphene oxide was dispersed in 3.6E
deionized water and its concentration was 2 mg mL− 1. The mixture was P= (4)
Δt
transferred to a Teflon-lined stainless steel autoclave and hydrother­
mally heated to 180 ◦ C and kept for 6 h. Finally, RGO samples were where Is (A g− 1) is the specific current, V (V) is the voltage, Δt (s) is the
collected by freeze drying. discharge time.

2.3. Materials characterizations 3. Results and discussion

X-ray diffraction analysis (XRD; AXS D2 Phaser; Cu Kα, λ = 0.1542 The NiCoMn-based sulfides are transformed from the hydroxides by
nm) was used to test the diffraction pattern of the samples at a scan rate an anion exchange reaction with the synthesis process illustrated in
of 5◦ min− 1. The scanning electron microscopy (SEM; HITACHI SU8010) Fig. 1a. The NiCoMn-based hydroxides were synthesized under hydro­
and transmission electron microscope (TEM; FEI Tecnai G2 F20) were thermal condition while using hexamethylenetetramine as the precipi­
used to collect the microstructure and diffraction pattern, and high- tant for the precipitation of transition metal ions. Owing to layered
resolution TEM (HRTEM) was used to collect lattice fringe of NiCoMn- microstructure of hydroxides, these NiCoMn-based hydroxides demon­
S. The elemental distribution was obtained by energy-dispersive X-ray strate a 2D nanosheets-constituted flower-like structure. Then, the an­
spectroscopy (EDS) mapping. N2 adsorption/desorption isotherms were ions of hydroxides were exchanged with the S2-, resulting in the
measured by a Quantachrome Autosorb-IQ-MP/XR surface area and hydroxides converted to sulfides. In traditional precipitation methods,
pore analyzer at 77 K, and pore size distribution cures were calculated Co-containing sulfides mainly grow into bulk particles owing to their
from desorption branches of isotherms according to Barrette-Joynere- cubic crystal structure, and thus synthesis of sulfides with 2D

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J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 1. (a) Schematic illustration of synthesis process of NiCoMn-based sulfides. SEM images of (b,c) NiCoMn-S-0 and (d,e) NiCoMn-S-1.5. (f) EDS mapping images of
NiCoMn-S-1.5.

nanosheets- constituted flower-like structure is still very challenging. Co9S8 (JCPDS No. 73–1442). Diffraction peaks located at 31.6◦ , 38.3◦ ,
Layered hydroxides serve as sacrificial templates in the anion exchange and 55.3◦ can be assigned to diffraction peaks from NiCo2S4 phase, and
reaction, and the resulting sulfides fully maintain overall structure of diffraction peaks located at 29.8◦ , 39.5◦ and 51.9◦ can be attributed to
hydroxides, making the synthesis of 2D sulfides possible. those of (Ni,Co)9S8 phase. With the introduction of manganese to these
Fig. 1b shows SEM images of NiCoMn-S-0. It can be found that the sulfides, (Ni,Co)9S8 phase gradually disappears. Diffraction peaks of
sulfide displays a flower-like overall structure, which is constituted by NiCoMn-S-n (n = 1, 1.5, 2 and 3) are consistent with those of NiCo2S4
interconnection of 2D nanosheets (Fig. 1c). SEM images of NiCoMn-S- phase. According to calculation result, the lattice parameter of NiCoMn-
1.5 (Fig. 1d and e) demonstrate same structure. EDS mapping images S-1.5 phase is a = b = c = 9.389 Å, which is very close to the theoretical
in Fig. 2f show the uniform distribution of Ni, Co, Mn and S elements in structure of NiCo2S4 phase. Therefore, introduction of manganese pro­
NiCoMn-S-1.5 sample, verifying successful doping of sulfide with Mn motes the formation of M3S4 pure phase, where M = Ni, Co and Mn. The
elements. More significantly, this synthesis method has been used to XRF results (Fig. S1) show the chemical formulas are Ni1.11Co1.89S4.28,
prepare sulfides with different Mn doping contents. As shown in Fig. 2, Ni1.25Co1.67Mn0.08S3.93, Ni1.15Co1.71Mn0.14S3.95, Ni1.17Co1.65Mn0.18S3.87
resulting sulfides NiCoMn-S-n (n = 0.5, 1 and 2) also maintain same and Ni1.13Co1.60Mn0.27S3.83 for NiCoMn-S-n with n = 0, 1, 1.5, 2 and 3,
flower-like structure connected by two-dimensional nanosheets, indi­ respectively. N2 adsorption/ desorption isotherms of NiCoMn-S-0 and
cating our synthesis method is very robust for preparing sulfides with 2D NiCoMn-S-1.5 are compared in Fig. 3b. The isotherms both exhibit
structure. However, flower-like structure collapses with the molar mass hysteresis loops at a relative high pressure owing to existence of meso­
of Mn increasing from 1.5 to 3 mmol, reflecting that the content of Mn porous structures, and pore size distribution curves shown in inset of
affects the stability of the structure. Fig. 3b indicate their similar mesoporous structures. The Brunauere-
Fig. 3a shows XRD patterns of NiCoMn-based sulfides doped with Emmette-Teller (BET) surface areas are 30.2 and 27.4 m2 g− 1 for
different amounts of Mn. It is found that XRD pattern of NiCoMn-S-0 can NiCoMn-S-1.5 and NiCoMn-S-0, respectively. Therefore, Mn doping
be matched with mixed phases of NiCo2S4 (JCPDS No. 43–1477) and enhances specific area of sulfides.

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J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 2. SEM images of the (a) NiCoMn-S-0.5, (b) NiCoMn-S-1, (c) NiCoMn-S-2 and (d) NiCoMn-S-3.

The elemental constitutions and chemical valances of each element No.20–0782), which is lower than 0.338 nm and 0.576 nm of NiCoMn-S-
for the NiCoMn-S-1.5 are characterized using the XPS test. Survey XPS 0 in Fig. 4c at the similar conditions, respectively. It is explained that Mn
spectrum of NiCoMn-S-1.5 displays photoelectron signals from Ni, Co, replaces Co and Ni partially and shortens the atom distance between Ni,
Mn and S elements (Fig. S2). High-resolution Ni 2p and Co 2p spectra Co and Mn.
can be best fitted into two spin-orbit doublets and two shake-up satel­ Electrochemical properties of NiCoMn-based sulfides were measured
lites (identified as “Sat.”). As demonstrated by the high resolution Ni 2p in a three-electrode configuration using an aqueous 6 M KOH solution as
spectrum, the fitted peaks locate at 855.7 and 873.5 eV can be attributed the electrolyte. CV and GCD curves at different rates of NiCoMn-S-0 and
the Ni 2p3/2 and Ni 2p1/2 photoelectron signals of Ni2+, respectively NiCoMn-S-1.5 are shown in Fig. 5 to compare their charge storage
[37,38]. In the meantime, the peaks located at 852.9 eV in Ni 2p3/2 mechanism. Fig. 5a and b shows CV and GCD curves of NiCoMn-S-0,
spectrum and 870.1 eV in Ni 2p1/2 spectrum indicate the presence of respectively. CV curves at each scan rate exhibits a pair of redox
Ni3+ [39,40]. In addition, the fitted peaks at 780.9 and 796.8 eV in the peaks. Overall shape of each CV curve is largely unchanged when the
Co 2p3/2 and Co 2p1/2 photoelectron spectra, respectively, indicate the scan rate increased from 3 mV s− 1 to 50 mV s− 1, which demonstrates
presence of Co2+ [41–43]. The electronic coupling splitting peaks in high rate performance. GCD curves also exhibit charge/discharge pla­
Fig. 3e at 82.4 and 89.1 eV can be ascribed to Mn 3 s and Mn 3d valence teaus at each specific currents, which can be well maintained even at
band with a splitting binding energy difference of 6.7 eV, suggesting that high specific currents of 20 A g− 1. These results indicate that NiCoMn-S-
the Mn element exists as Mn2+ [33]. With respect to S 2p XPS spectrum 0 shows high-rate battery charge storage behavior. CV and GCD curves
shown in Fig. 3f, the peaks from the metal sulfides can be positively of NiCoMn-S-1.5 are also presented in Fig. 5c and d, respectively. The
observed, confirming the synthesis of metal-sulfides [44]. In the mean­ NiCoMn-S-1.5 exhibits similar CV and GCD curves but shows lager
time, the XPS signal from metal sulfate can be also found owing to the circulated areas and longer charge/discharge time than NiCoMn-S-
unavoidable retention of oxygenated functional groups in the surface 0 with at a given rate for the CV and GCD curves, respectively. There­
region. fore, it can be concluded that sulfide within Mn doping shows higher
Fig. 4 shows TEM images, selected-area electron diffraction (SAED) charge storage capacity. Indicated by redox peaks displayed in CV
patterns and HRTEM images of NiCoMn-S-0 and NiCoMn-S-1.5 to curves and charge/discharge platforms in GCD curve, NiCoMn-S-1.5
further understand the effect of Mn doping. Fig. 4a and d displays the presents a battery-type energy storage behavior when used as an elec­
layer structure change of the NiCoMn-S-0 and NiCoMn-S-1.5. Fig. 4b and trode material. Transition metal ions store or release charges by per­
e exhibit NiCoMn-S-1.5 has more significant diffraction spot and better forming redox reactions with OH– within a certain voltage window.
crystal degree than NiCoMn-S-0, which means Mn doping enhances the Redox reactions of NiCoMn-S-1.5 can be described by following equa­
crystallinity of NiCoMn-S. In addition, Fig. 4f shows the HRTEM image tions [10,45]:
of NiCoMn-S-1.5 with the lattice fringes of 0.329 nm and 0.541 nm
NiS + OH− NiSOH + e− (5)
corresponding to (2 2 0) and (1 1 1) planes of NiCo2S4 (JCPDS

4
J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 3. (a) XRD patterns of the NiCoMn-S-n (n = 0, 0.5, 1, 1.5, 2 and 3). (b) N2 adsorption/desorption isotherms and pore size distribution curves (inset) of NiCoMn-
S-0 and NiCoMn-S-1.5. High-resolution (c) Ni 2p, (d) Co 2p, (e) Mn 3 s and (f) S 2p XPS spectra in NiCoMn-S-1.5.

CoS + OH− CoSOH + e− (6) decreases with the further increase of Mn content. The NiCoMn-S-1.5
maintains a specific capacity of 339.5C g− 1 when the specific currents
MnS + OH− MnSOH + e− (7) increase from 1 to 50 A g− 1, indicating its superior rate performance.
Nyquist plots and equivalent circuit for the electrochemical impedances
CoSOH + OH− CoSO + e− (8) (EIS) of NiCoMn-S-1.5 and NiCoMn-S-0 have been shown in Fig. 6c.
Their charge-transfer resistances (Rct) at interface of electrolyte/elec­
Charge storage performances of NiCoMn-based sulfides with trode are fitted using the semicircle in the high-frequency region. Chi-
different Mn-doping contents are compared in Fig. 6. Fig. 6a shows CV Squared values of NiCoMn-0 and NiCoMn-S-1.5 are 0.0036 and
curves at a scan rate of 5 mV s− 1 of these sulfides. It can be found that 0.0020, indicating fitting results are basically close to experimental
their performances can be tuned by different Mn-doping amounts, and impedance. The Rct of NiCoMn-0 and NiCoMn-S-1.5 is 0.18 Ω and 0.15
therefore CV curves show different circled areas under different Mn Ω, respectively. The comparable low charge transfer resistance makes
doping. Specific capacity is proportional to specific area of CV curves the NiCo sulfide doped with Mn also very suitable for high-rate appli­
∫
according to the formulaC = IdV/(νm) = S/(2νm). Fig. 6b shows the cations. More significantly, the straight line of EIS spectrum for NiCoMn-
dependence of specific capacity as a function of specific current of these S-1.5 demonstrates higher slope than that of NiCoMn-S-0, indicating
sulfides. The specific capacities of Ni-Co-Mn sulfides are calculated as higher ion adsorption/desorption rates at the electrode/electrolyte in­
526.2, 623.2, 657.7, 576.8, 543.3C g− 1 at a specific current of 1 A g− 1 terfaces. Fig. 6d shows the cycling performances for both NiCoMn-S-1.5
for NiCoMn-S-n with n = 0, 1, 1.5, 2 and 3, respectively. The specific and NiCoMn-S-0. It can be found that the NiCoMn-S-1.5 shows better
capacity first increases to the highest value at NiCoMn-S-1.5, and then it

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J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 4. TEM images, SAED patterns and HRTEM images of (a-c) NiCoMn-S-0 and (d-f) NiCoMn-S-1.5.

Fig. 5. (a) CV and (b) GCD curves of the NiCoMn-S-0, and (c) CV and (d) GCD curves of the NiCoMn-S-1.5.

cycling stability than the NiCoMn-S-0. After cycled at a specific current constituted flower-like structure provide two sides for reduced diffu­
of 7 A g− 1 for 1100 cycles, the NiCoMn-S-1.5 retains a specific capacity sion distance of electrolyte, and the interconnection of these nanosheets
of 97.8%, which further confirm its excellent cycle stability. can maintain the electroactive sites of nanosheets for stable energy
According to above analysis, it is obvious that the NiCoMn-S-1.5 storage; second, the NiCoMn-S-1.5 inherits the low charge transfer
shows the best performance for charge storage, which can be attrib­ resistance of Ni-Co sulfides for high rate energy storage; lastly, the Mn
uted to the specific structure and combined contributions from Ni, Co element can tune the performance of sulfides, resulting in high specific
and Mn elements. First, as illustrated in Fig. 6e, the 2D nanosheets- capacity and cycling stability.

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J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 6. (a) CV curves at 5 mV s− 1 and (b) specific capacity vs specific current curves of NiCoMn-based sulfides with different doping amounts of Mn. (c) Nyquist plots
of electrochemical impedance spectra and (d) cycling performance of NiCoMn-S-1.5 and NiCoMn-S-0. (e) Schematic illustration for ion diffusion and electron
transportation pathways of the flower-like NiCoMn-based sulfides.

NiCoMn-S-1.5 has been used as the positive electrode and RGO used specific current of 15 A g− 1. Nyquist plot of HSC (Fig. S4) was measured
as the negative electrode material to assemble hybrid supercapacitor in the frequency range from 10-2 Hz to 105 Hz at 5 mV AC potential
(HSC). The HSC cell combines the advantages of NiCoMn-S-1.5 with amplitude. The fitted results can well-match the experimental data with
battery-type charge storage characteristics and RGO with electric double a low Chi-Squared value of 0.0025 delivered. Charge-transfer resistance
layer capacitive characteristics [46]. CV curves at different potential and the ion diffusion resistance of the HSC cell is 1.19 Ω and 1.43 Ω
windows of HSC cell were tested (Fig. S3), and its operating potential respectively, indicating low resistance and excellent charge transfer
window is determined to be 0–1.56 V. This wide potential window of capabilities. Cycling performance of the HSC is shown in Fig. 8c with a
HSC cell can be ascribed to combination of different potential windows testing specific current of 5 A g− 1. The initial specific capacitance of the
between the NiCoMn-S-1.5 and RGO electrodes, as shown in Fig. 7. HSC cell is 84.6F g− 1, and then it increased to 94.9F g− 1 after 30 cycles
Fig. 8a shows GCD curves of the NiCoMn-1.5//RGO HSC. Its specific owing to the initial activation and better wetting of the electrode with
capacitances at different specific currents can be calculated from these electrolyte. After 3000 cycles, the specific capacitance of the HSC still
GCD curves, as plotted in Fig. 8b. The specific capacitances and specific remains 78.8F g− 1, indicating good cycle stability of the HSC.
currents are both calculated referring to the total mass of NiCoMn-S-1.5 The Ragone plot (specific energy vs specific power) of the HSC is
and RGO. This HSC cell displays a specific capacitance of 111.6F g− 1 at a shown in Fig. 8d. The HSC cell delivers a specific energy of 36.3 Wh kg− 1
specific current of 1 A g− 1, and it maintains 44.9F g− 1 at a much larger at 0.75 kW kg− 1 and 14.5 Wh kg− 1 at 11.3 kW kg− 1, which are higher
than Co-Mn-S-2.5//RGO (22.3 Wh kg− 1 at 0.75 kW kg− 1 and 11 Wh
kg− 1 at 30 kW kg− 1) [47], α-MnS/N-RGO //N-RGO (27.7 Wh kg− 1 at 0.8
kW kg− 1 and 16.1 Wh kg− 1 at 20 kW kg− 1) [48], Ni-Mn sulfides//RGO
(36 Wh kg− 1 at 0.775 kW kg− 1 and 16.9 Wh kg− 1 at 15.5 kW kg− 1) [49],
Ni-Co sulfide nanowires//AC (25 Wh kg− 1 at 0.447 kW kg− 1 and 17.8
Wh kg− 1 at 3.57 kW kg− 1) [50]. Significantly, both high energy and high
power performance have been achieved in the NiCoMn-S-1.5//RGO
HSC.

4. Conclusions

2D nanosheets-constituted flower-like NiCoMn sulfide has been

synthesized by a combined hydrothermal reaction and subsequent anion
exchange reactions, which exhibits excellent performance in hybrid
supercapacitors. The Mn dopping affects the 2D nanosheets-constituted
flower-like structure and crystallinity degree, which are consistent to the
electrochemical performance of NiCoMn-S. The NiCoMn-S-1.5 exhibits a
maximum specific capacity of 657.7C g− 1 at 1 A g− 1 and a specific ca­
pacity of 339.5C g− 1 has been achieved when the specific current in­
creases from 1 to 50 A g− 1. The NiCoMn-based sulfide has been used to
1
assemble hybrid supercapacitors with RGO, which achieves high specific
Fig. 7. CV curves of the Mn-1.5 and RGO electrodes at a scan rate of 5 mV s−
energy combined with long-term cycling stability. Although the
and the NiCoMn-1.5//RGO HSC different scan rates.

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J. Zhang et al. Applied Surface Science 565 (2021) 150482

Fig. 8. (a) GCD curves at different specific currents, (b) specific capacitance vs specific current curves, (c) cycling performance, and (d) Ragone plot of the NiCoMn-S-
1.5//RGO HSC compared with other works.

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