DOI: 10.1002/celc.

201900746 Articles

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3 Metal-Organic Frameworks-Derived NiS2/CoS2/N-Doped
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Carbon Composites as Electrode Materials for Asymmetric
6 Supercapacitor
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8 Hui Liu,[a] Hao Guo,*[a] Liguo Yue,[a] Ning Wu,[a] Qi Li,[a] Wenqin Yao,[a] Rui Xue,[b]
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Mingyue Wang,[a] and Wu Yang*[a]
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Transition metal sulfides derived from metal-organic frame- retention rate of 75 % after 5000 cycles at a current density of
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works (MOFs) have received increasing attention as a potential 5 A g 1. The good performance could be attributed to the
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energy storage electrode material. Here, a series of NiS2/CoS2/ unique rod-like structure and pore-size distribution of NiS2/
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NC-T (T = temperature) have been successfully constructed by CoS2/NC-500. Moreover, an assembled asymmetric supercapaci-
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carbonizing and sulfuring the precursor of Ni/Co-MOF. It is tor NiS2/CoS2/NC-500//AC displays a high energy density of
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worth emphasizing that N-doped carbon materials improve the 53.93 Wh kg 1 at a power density of 800 W kg 1 and good cycle
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conductivity of the electrode material. Moreover, NiS2/CoS2/NC- stability with capacitance retention of 85.71 % after 20,000
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500 maintains the rod-like structure of the precursor and cycles at 5 A g 1. In particular, a red LED can be illuminated by
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exhibits a high specific capacitance of 1325 F g 1 at a current the assembled ASC, indicating that as-synthesized NiS2/CoS2/
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density of 1 A g 1. Apart from high capacitance, the NiS2/CoS2/ NC-500 hold great potential for practical applications.
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NC-500 also demonstrated excellent cycling stability with
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1. Introduction ductive carbon materials.[11] So, if the materials of EDLCs are
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combined with pseudocapacitors, the common advantages of
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With the development of the economy, the consumption of the two charge storage mechanisms will be exerted.
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energy is increasing.[1] Supercapacitors, as one of the excellent Metal-organic frameworks (MOFs), a coordination polymer
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energy storage devices, have some attractive features such as formed by coordination of metal ions or metal clusters and
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fast charge and discharge time, high power density and long organic ligands, have received great attention from most
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cycle life, which make them a popular material in the field of researchers due to their special properties and many potential
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portable electronic devices and hybrid tram.[2–7] Pseudocapaci- applications, such as catalysis,[12] gas storage,[13] separation,[14]
33
tor, as an important class of electrochemical capacitors, stores sensors and magnetic.[15,16] Furthermore, it has been widely
34
energy by a Faraday reaction that occurs on the surface of the used in the field of energy storage, including fuel cells,[17] solar
35
electrode.[8] Another energy storage mechanism is electric cell,[18] supercapacitors,[19,20] lithium batteries,[21,22] and the like.
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double layer capacitors (EDLCs) through an ion-adsorption Recently, the application of MOFs in the field of supercapacitors
37
mechanism between the two-layer interfaces.[9] Although has also begun to receive much attention. The application of
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pseudocapacitors have high specific capacitance, they are MOFs for supercapacitor electrode materials may be divided
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generally poor in electrical conductivity and severely hinder the into two aspects. One aspect is that MOFs itself can be directly
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ability of electron transport.[10] Nowadays, it is important to used as the capacitor’s active electrode materials, because their
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synthesize appropriate porous structural materials and improve abundant pores and metal ions can provide electron transfer
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the conductivity of the electrode materials by adding con- channels and abundant redox active sites, respectively.[23–25] The
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other aspect is that the MOFs was used as a precursor to
44
synthesize metal hydroxides[26], transition metal oxides,[27] tran-
45 [a] H. Liu, Prof. H. Guo, L. Yue, N. Wu, Q. Li, W. Yao, M. Wang, Prof. W. Yang
Key Lab of Eco-Environments Related Polymer Materials of MOE,
sition metal sulfides or metal oxides/carbon composites and the
46
Key Lab of Bioelectrochemistry and Environmental Analysis of Gansu like.[28–31] The latter MOFs have received increasing attention as
47 Province, a precursor to derivatized hybrid materials.[32] Due to the
48 College of Chemistry and Chemical Engineering,
Northwest Normal University,
richness of its composition, metal ions or metal clusters in
49
Lanzhou 730070, P R China MOFs can be converted into metal or metal oxide nanoparticles,
50 E-mail: xbsfda123@126.com and organic ligands usually decompose to produce porous
51 haoguo12@126.com
[b] Dr. R. Xue
carbon .[33] For instance, a compound of Cu1.96S/C of regular
52
Laboratory of Gansu Higher Education for City Environmental Pollution octahedron is obtained HKUST-1 composites and its specific
53 Control capacitance can reach 200 F g 1.[10] Co-MOF derived Co9S8@S,N-
54 Lanzhou City University,
Lanzhou, 730070, P R China
doped Carbon shows 429 F g 1 at 1 A g 1.[34] Co/CoxSy@SNCF-800
55
Supporting information for this article is available on the WWW under is a good electrocatalyst and high power density electrode
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https://doi.org/10.1002/celc.201900746 material by pyrolysis of Co-MOF fiber at 800 °C.[35] Co-MOF
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9 Scheme 1. Preparation of NiS2/CoS2/N-doped carbon composites.
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Scheme 2. Assembly of asymmetric supercapacitor device.
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ical Reagent Co., Ltd. Sulfur powder were purchased from Shanghai
27 Chemical Reagent Co., Ltd. N,N-dimethylformamide (DMF, 99.5 %)
derived CoO@N, S-co-doped carbon composite rich in N, S for
28 was purchased from Covalent Chemical Reagent Co., Ltd. Polytetra-
lithium ion batteries.[36] The core-shell structure of ZnCoS@CoS
29 fluoroethylene (PTFE) was acquired from Sigma-Aldrich. Distilled
was obtained by carbonizing and vulcanizing ZIF-67@ZIF-8/ZIF- deionized water was used throughout.
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67 at 700 °C, and it gained a specific capacity of
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2224 mA h g 1.[11] Despite a lot of efforts to date, MOFs-derived
32 Characterization
metal sulfides/carbon composites are relatively poor as super-
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capacitors electrode materials, which constitute the reason of X-ray diffraction (XRD) patterns were obtained by an X-ray
34
the present study. diffractometer (BRUKER X-ray, Germany) using Cu Kα radiation
35
In this study, a series of NiS2/CoS2/NC-T was developed by (1.5406 Å). Scanning electron microscopy (SEM) images and Energy
36 dispersive spectrum (EDS) images of the as-prepared materials
utilizing a binary Ni/Co-MOF as a precursor. Then we used them
37 were analyzed by a Zeiss (ULTRRA Plus, Germany). Transmission
as electrode materials of supercapacitors for electrochemical
38 electron microscopy (TEM) results were tested on TecnaiG2-F20 (FEI,
performance testing. NiS2/CoS2/NC-T showed high specific USA). Brunauer-Emmett-Teller (BET) of materials was carried out in
39
capacitance and excellent cycling stability. What’s more, a liquid nitrogen atmosphere with the temperature of 196 °C.
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asymmetric supercapacitor (ASC) assembled with NiS2/CoS2/NC- Fourier transform infrared spectra (FT-IR) sample testing was carried
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500 and activated carbon has excellent electrochemical per- out on a FTS-3000 spectrometer using KBr pellets in the range of
42 400–4000 cm 1. Thermogravimetric analysis (TGA, Perkin-Elmer,
formance. The NiS2/CoS2/NC-500//AC leads to a high energy
43 SSC-5200, USA) were carried out a Dupont thermal analyzer with a
density of 53.93 Wh kg 1 at power density of 800 W kg 1. More
44 heating rate of 10 °C min 1 from room temperature to 800 °C under
importantly, this ASC also shows a long-term stability up to nitrogen flow. The X-ray photoelectron spectroscopy (XPS) meas-
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20,000 cycles. All these results indicate that the NiS2/CoS2/NC-T urement was performed on a thermoFisher Scientific (ESCALAB
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is potential and valuable for high performance electrochemical 250Xi, USA). The carbonization reaction was carried out in a GSL-
47 1600X tube furnace (Hefei Kejing Materials Technology Co., Ltd.).
energy storage devices.
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50 Synthesis of Ni/Co-MOF Precursor
Experimental Section
51 The preparation method of the precursor is slightly modified in the
52 original reference.[37] Equimolar terephthalic acid and 4,4’-bipyridine
Materials
53 (2 mmol) were dissolved in 5 mL of DMF, and a 10 mL aqueous
54 All reagents are used directly without further processing. The 1, 4- solution containing (1 mmol) of Co(NO3)2.6H2O and (1 mmol) of Ni
dicarboxybenzene and 4, 4’-bipyridyl were purchased from Aladdin. (NO3)2.6H2O was added dropwise to the previous mixed solution.
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Nickel (II) nitrate hexahydrate (98.0 %) and Cobalt(II) nitrate The resulting solution was then held at 160 °C in a 50 mL Teflon-
56 lined stainless steel autoclave for 48 hours and then was cooled to
hexahydrate (98.0 %) were purchased from Tianjin Zhiyuan Chem-
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26 Figure 1. (a), (b) X-ray diffraction patterns of Ni/Co-MOF and NiS2/CoS2/NC-500 materials, respectively. (c), (d) N2 adsorption-desorption isotherm and pore size
distribution curve, respectively.
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room temperature. It was washed several times with DMF and calomel electrode, respectively. Cyclic voltammetry (CV) was
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distilled water, filtered, and dried overnight in a vacuum oven at performed at scan rates of 5–100 mV s 1 in the potential range from
31 60 °C. 0 to 0.6 V. Galvanostatic charge-discharge (GCD) was conducted
32 within the potential window of 0–0.5 V at different current density.
33 The cycle life tests were carried out by GCD measurements with a
34 Synthesis of NiS2/CoS2/N-Doped Carbon Composites constant current density of 5 A g 1 for 5,000 cycles. Electrochemical
35 impedance spectroscopy (EIS) measurements were performed with-
Similarly, we have improved on the original method.[38] The
in a frequency range of 10 2 Hz to 105 Hz at an open circuit
36 prepared MOFs precursor was placed in a porcelain boat, and
potential with an amplitude of 5 mV.
37 carbonized by heating to 500 °C in an N2 atmosphere at a heating
38 rate of 5 °C min 1. The black powder obtained later and sulfur For an asymmetric supercapacitor (ASC), the electrochemical
powder was uniformly mixed in a porcelain boat at a mass ratio of measurements were carried out in a two-electrode electrochemical
39
1 : 2. The mixture was heated at a heating rate of 5 °C min 1 in a cell with NiS2/CoS2/NC-500 electrode (positive) and AC electrode
40 tube furnace to 350 °C for 2 hours for vulcanization. Subsequently, (negative) in a 3 M KOH aqueous electrolyte. The electrochemical
41 the tube furnace was cooled to room temperature in an N2 measurements were performed on CHI660E. The cycle performance
42 atmosphere to obtain NiS2/CoS2/NC-500. Similarly, compounds was measured using a CT2001 A-LAND cell test system (Landian,
43 NiS2/CoS2/NC-550 and NiS2/CoS2/NC-650 were obtained by chang- Wuhan, China).
ing carbonization temperature (T = 550, 650), respectively.
44
45 Calculations
46 Preparation of Electrode Materials
47 The specific capacitance of the electrode can be counted from the
The working electrode was made by mixing 80 wt% active material discharge curves on the basis of equation (1):
48 (NiS2/CoS2/NC-T), 15 wt% acetylene black and 5 wt% PTFE, then
49 dissolve the three in 60 % ethanol solution and the resulting slurry
IDt
50 was coated on foamed nickel (1 cm × 1 cm) and pressed at 10 MPa, C¼ (1)
at which time the foamed nickel served as a current collector. The mDV
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52 electrodes were dried at 60 °C for 12 hours under vacuum. The
typical mass loading of the active material was about 1.0– Where C is the specific capacitance (F g 1), m(m ¼ mþ þ m in the
53 ASC cell)is the mass of the active materials (g), I is the discharge
2.0 mg cm 1. Electrochemical measurements were carried out by a
54 CHI660E electrochemical workstation (Chenhua, Shanghai, China) in current (A) and Δt is the discharge time (s), ΔV is the range of
55 a 6 M KOH aqueous electrolyte. The counter electrode (CE) and charge-discharge voltage (V), respectively.
56 reference electrode (RE) are platinum electrode and saturated
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27 Figure 2. (a) High-resolution XPS spectra survey of NiS2/CoS2/NC-500, (b) Ni 2p spectrum of NiS2/CoS2/NC-500, (c) Co 2p spectrum of NiS2/CoS2/NC-500, (d) S
2p spectrum of NiS2/CoS2/NC-500.
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An ASC cell was assembled to estimate actual application value. In
31 order to make the positive and negative charges equal, the mass 2. Results and Discussion
32 ratio of the anode and cathode materials is calculated according to
33 equation (2) as follows:
2.1. Characterizations
34
35 mþ C � DV
R¼ ¼ (2) The diffraction peak of the Ni/Co-MOF is shown in Figure 1a.
36 m Cþ � DV þ
The crystal model was constructed by Materials Studio(Space
37
Where m, C and DV represent the mass loading, specific group C12/m1, a = 16.605 Å, b = 10.300 Å, c = 11.303 Å, α = γ =
38
capacitance and voltage range of the electrode, respectively. 90°, β = 119.05°), and the fitted XRD spectrum shows no
39
difference with the actual test spectrum. Figure 1b displays the
40 The power density (P, Wh kg 1) and energy density (E, W Kg 1) of
XRD pattern of NiS2/CoS2/NC-T obtained at three different
41 the battery were calculate according to the following equations :[39]
temperatures. All diffraction peaks are consistent with PDF
42
cards of NiS2/CoS2/NC-T (CoS2: JCPDS card number 41–1471,
43 1
E¼ CDV 2 (3) NiS2: JCPDS card number 11-0099). There are no diffraction
44 2
peaks of precursors or impurities, indicating that the precursor
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E Ni/Co-MOF has been completely converted to NiS2/CoS2/NC.
46 P¼ (4)
Dt When the carbonization temperature is raised to 650 °C, the
47
disappearance of the diffraction peak of 2θ = 31.89° is attrib-
48
Where C is the specific capacitance of the asymmetric super- uted to the sublimation of the sulfur powder resulting in failure
49
capacitor according to the galvanostatic charge-discharge curves of to bond with the metal ion center in the MOFs material. In the
50 the two-electrode system. V (V) and Dt (s) are the voltage range FT-IR spectrum, the N H bending vibration peak at 1650 cm 1
51 and discharge time, respectively.
disappeared, which proved that the N on the pyridine is
52
coordinated to the metal atom. Moreover, no absorption peak
53
was observed at 1690 to 1730 cm 1, indicating that the carboxyl
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group of terephthalic acid was present in the compound in
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deprotonated form (Figure S1a). This further proves that the
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preparation of Ni/Co-MOF is successful.[40] It can be seen TGA
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30 Figure 3. SEM images of (a) Ni/Co-MOF, (b) NiS2/CoS2/NC-500, (c) NiS2/CoS2/NC-550 and (d) NiS2/CoS2/NC-650, (e) TEM images of NiS2/CoS2/NC-500, ( f–i ) The
31 HRTEM images for NiS2/CoS2/NC-500.
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33
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curve of the precursor that the weight loss of the material is smaller pore structure ensure superior electrochemical perform-
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about 91 % at 800 °C, proving the thermal stability of the ance of NiS2/CoS2/NC-500 compared with that of Ni/Co-MOF.
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precursor is relatively poor (Figure S1b). As shown in Figure 1c, As depicted in Figure 2, elemental composition and valence
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N2 adsorption and desorption isotherms evaluate the surface of elements of NiS2/CoS2/NC-500 was characterized by XPS. The
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area of NiS2/CoS2/NC-500. The observed curves belong to the XPS survey spectrum of the NiS2/CoS2/NC-500 indicates the
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typical type IV adsorption isotherm and the H3 hysteresis curve, presence of C, N, O, Ni, Co and S elements in Figure 2a. The EDS
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and NiS2/CoS2/NC-500 obtained a high BET specific surface area mapping results also demonstrate the existence of various
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of 109.08 m2 g 1. It can be seen from the pore size distribution elements forming NiS2/CoS2/NC-500, and the various elements
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that it contains a mesoporous structure Figure 1d. This may be are evenly distributed on the prepared materials (Figure S3). By
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due to the decomposition of the sample during the porous Ni/ using a Gaussian fitting method, the Ni 2p and Co 2p spectra
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Co-MOF carbonization and vulcanization. The sharp increase in can be best fitted. Figure 2b explores that Ni 2p exhibits a
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the amount of adsorption in the high pressure region may be typical double-spin orbit, demonstrating the presence of Ni2 +
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due to the multi-layer adsorption of N2 in the pores of the NiS2/ and Ni3 +. In Figure 2c, the Co 2p spectrum has spin orbit
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CoS2/NC-500 particles. In addition, the specific surface area of doublets (2p1/2 and 2p3/2) and two satellite peaks, demon-
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the precursor was tested to be only 14.7 m2 g 1, and the pore strating that Co3 + and Co2 + are co-existing.[41] In addition, it can
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size distribution is mainly around 50 nm (Figure S2). The pore- be seen from the high-resolution S 2p spectrum (Figure 2d) that
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size distribution of NiS2/CoS2/NC-500 was consisted of hierarch- the binding energy at 162.36 and 163.64 eV are assigned to S
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ical porous composites with a narrow distribution centered at 2p3/2 and S 2p1/2, respectively. The peak at 168.34 eV is
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approximately 3 nm and a wide distribution centered at attributed to the bonding of sulfur and oxygen, which may
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approximately 8 nm. The presence of pores smaller than 20 nm come from the surface absorption of oxygenates.[42] The above
54
was beneficial in enhancing the electrochemical performances XPS test results show that the preparation of NiS2/CoS2/NC-500
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of the materials. Therefore, larger specific surface area and is successfully synthesized.
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27 Figure 4. Electrochemical performance of Ni/Co-MOF and NiS2/CoS2/NC-T. (a) CV curves were measured at 20 mV s 1, (b) GCD curves were obtained at 1 A g 1,
28 (c) The relationship between specific capacitance and current density, (d) The Nyquist curves were tested in the frequency range of 0.01 Hz to100 kHz (The
inset shows Nyquist curves the high frequency region).
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The morphology and microstructure of Ni/Co-MOF and 2.2. Electrochemical Characterization
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NiS2/CoS2/NC-T materials are shown in Figure 3. The Ni/Co-MOF
34
was synthesized by a facile solvothermal reaction as discussed Figure 4a displays CV curves of Ni/Co-MOF and NiS2/CoS2/NC-T
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later. It can be seen from Figure 3a that the Ni/Co-MOF is a rod- at 20 mV s 1. As can be seen, the four materials display a pair of
36
shaped material. As shown in the Figure 3b, NiS2/CoS2/NC-500 the redox peaks, demonstrating that these can be used as
37
maintains the appearance of the precursor well by carbonizing electrode materials of pseudocapacitor. It can be seen that the
38
and sulfuring. The unique morphology provides rich electro- NiS2/CoS2/NC-500 has a larger peak current than theirs, and the
39
active site for the redox reaction, which has superior electro- peak current of nickel foam can be negligible. As shown in
40
chemical performance. In Figure 3c, the NiS2/CoS2/NC began to Figure 4b, the GCD curves of the four materials are all triangle-
41
burst when calcination temperature was increased to 550 °C. like and accompanied by a platform, further showing that the
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Once the temperature reached 650 °C, the rod-like structure material is an electrode material with pseudocapacitor behav-
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was disappeared and nanoparticles were agglomerate. (Fig- iour. In addition, NiS2/CoS2/NC-T has a longer discharge time
44
ure 3d), which results are consistent with that of TG curve. This than the precursor at 1 A g 1, and NiS2/CoS2/NC-500 has a
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finding could be possibly attributed to the stress action under a largest discharge time among them, which may be ascribed to
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high temperature. Figure 3e is the TEM images of the NiS2/ the special rod-like morphology and pore-size distribution of
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CoS2/NC-500, which exhibit an amorphous morphology similar NiS2/CoS2/NC-500. Moreover, the contribution of nickel foam to
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to that of SEM images, and demonstrates nanocrystals with the specific capacitance of the active material is only 25 F g 1,
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diameter of ~ 12 nm. In addition, the detailed HRTEM image which can be ignored. From the relationship between the
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(Figure 3f) displays obvious lattice fringes, in which the 2.54 Å current density and the specific capacitance, it is known that
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and 2.47 Å spacing can be ascribed to the (210) interplane the specific capacitance gradually decreases as the current
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spacing of NiS2 and CoS2, respectively. It is further proved that density increases, which is attributed to the limited ion transfer
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these two phases are simultaneously present, and the result is at high current density and the insufficient utilization of the
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in accord with XRD analysis. (Figure 3g,h). The N-doped carbon NiS2/CoS2/NC-500[43] (Figure 4c). At 1 A g 1, the specific capaci-
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layer is visible in Figure 3h. tance of NiS2/CoS2/NC-500 (1325 F g 1) is significantly better
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than NiS2/CoS2/NC-550 (1229 F g 1) and NiS2/CoS2/NC-650
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27 Figure 5. Electrochemical performance of NiS2/CoS2/NC-500. (a) CV curves from 5 mV s 1
to 100 mV s 1, (b) GCD curves at different current densities, (c)
28 relationship between ip and ν1/2, (d) cyclic performance curve at a current of 5 A g 1.
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31 Table 1. Electrochemical properties of different sulfides and their compo-
(1029 F g 1). When the current density is increased to 10 A g 1, sites as electrode materials.
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the specific capacitance of NiS2/CoS2/NC-500 still reach Electrode Current Specific Electrolyte Ref.
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860 F g 1, which proves that NiS2/CoS2/NC-500 still has excellent materials density(A capacitance(F g 1)
34 g 1)
capacitive behaviour at large current densities. In addition, the
35
Nyquist curves of Ni/Co-MOF and NiS2/CoS2/NC-T are made up NiCo2S4/NCF 2.0 1231.0 6 M KOH [48]
36 Ni3S2/CNT 0.8 1024.0 2 M KOH [49]
of a straight line in the low frequency region and a semicircle in
37 Onion like 2.0 1016.0 6 M KOH [50]
the high frequency region, which correspond to the electron NiCo2S4
38
interface transfer resistance and the electron transfer resistance CoO@Co9S8 2.0 1100.0 2 M KOH [51]
39 2D CoS1.097/NC 1.5 360.1 2 M KOH [52]
inside the electrode material,[44] respectively (Figure 4d). Ob-
40 core-shell 1.0 764.2 1 M KOH [53]
viously, the small diameter of the semicircle and the linear slope Co3O4@CoS
41
in the low frequency region of NiS2/CoS2/NC-500 shows that it Co3S4 nano- 1.0 1037 2 M KOH [54]
42 sheets
has smaller internal resistance and faster electronic interface
43 NiS micro- 1.0 1122.7 3 M KOH [55]
transfer rate, which proved that NiS2/CoS2/NC-500 possess good flowers
44
capacitive properties. Fitted equivalent circuit analysis (Fig- Nickel sulfides/ 0.5 757.0 3 M KOH [56]
45 MoS2
ure S6) shows that all NiS2/CoS2/NC-T have a lower Rs value and
46 NiS2/CoS2/NC- 1.0 1325 6 M KOH This
NiS2/CoS2/NC-500 shows the lowest Rs of 0.77 Ω, and the lowest 500 work
47
Rct of 3.52 Ω.
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The electrochemical performances of the NiS2/CoS2/NC-500
49
were analyzed using CV and GCD measurements in 6 M KOH
50
aqueous solution. As the scan rate increases from 5 to Figure 5b. The plots show an obvious charging and discharging
51
100 mV s 1, the peak currents of the NiS2/CoS2/NC-500 gradually platforms, which proves that it has the characteristics of
52
increase without changing the shape of the CV curves, pseudocapacitor. The Ni/Co-MOF, NiS2/CoS2/NC-550 and NiS2/
53
indicating that the materials possess good stability (Figure 5a). CoS2/NC-650 electrodes were displayed in Figure S5a-c, respec-
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The CV plots of the Ni/Co-MOF, NiS2/CoS2/NC-550 and NiS2/ tively. Moreover, the GCD curves have good symmetry,
55
CoS2/NC-650 samples were discussed in Figure S4a-c, respec- exhibiting excellent reversible characteristics of redox reaction.
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tively. The GCD curve of NiS2/CoS2/NC-500 was shown in According to equation (1), the specific capacitance can reach
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47 Figure 6. Electrochemical performance of NiS2/CoS2/NC-500//AC ASC. (a) CV curves of NiS2/CoS2/NC-500 and AC electrodes performed in a three-electrode cell
at a scan rate of 50 mV s 1, (b) CV curves measured at 50 mV s 1 for ASC in different voltage ranges, (c) CV curves at scan rates ranging from 5 to 100 mV s 1,
48 (d) GCD curves at different current densities, (e) relationship between specific capacitance and current density, (f) histogram of charging time and power
49 density and energy density, (g) Ragone plots between power density and energy density, (h) cyclic performance curves at current density of 10 A g 1. (The
50 inset shows lit LED light)
51
52
53
1325 F g 1 at 1 A g 1. When the current density is gradually cannot be fully utilized due to rapid charging and discharging,
54
increased from 2 A g 1 to 10 A g 1, the specific capacitances are thereby its specific capacitance will be reduced.[45] In addition,
55
1247, 1161, 1048, 918.4, and 860 F g 1, respectively. It is well NiS2/CoS2/NC-500 demonstrates superior specific capacitance
56
known that at large current densities, the NiS2/CoS2/NC-500 by comparison with other materials (Table 1). By plotting the
57

ChemElectroChem 2019, 6, 3764 – 3773 www.chemelectrochem.org 3771 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Articles
peak current versus ν1/2, it can be seen that it has a linear reduces the internal resistance of the precursor. The doping of
1
relationship, indicating that NiS2/CoS2/NC-500 is diffusion- S element consolidates the skeleton structure of the precursor,
2
controlled[46] and Quasi-reversible process[47] (Figure 5c). After and the formation of sulfides also provides a guarantee for the
3
5,000 cycles of GCD tests at 10 A g 1, the capacitance retention infiltration of the electrode interface. What’s more, the prepared
4
rate was about 75 %. The abrupt drop of the capacitance may material was used as an electrode material for electrochemical
5
be caused by the deactivation and drop out of electrode surface performance test. Measurements showed that the electrode
6
active material during the long-term immersion of the material of NiS2/CoS2/NC-500 has a higher specific capacitance
7
electrode. (Figure 5d). of 1325 F g 1 and capacitance retention of 75 % after 5000
8
cycles. An assembled NiS2/CoS2/NC-500//AC with an energy
9
density of 53.93 Wh kg 1 at a power density of 800 W kg 1,
10
2.3. NiS2/CoS2/NC-500//AC Asymmetric Supercapacitors which brightens the red LED light for a few seconds. After
11
20,000 cycles, the specific capacitance remained at 85.71 %. The
12
To further verify the application performance of NiS2/CoS2/NC- above good performance is related to the unique rod-like
13
500, a NiS2/CoS2/NC-500//AC ASC was assembled. The active structure and pore-size distribution of NiS2/CoS2/NC-500. The
14
material loading is 1 mg cm 1. According to the equation (2), study found that the gratifying results may open up the
15
the AC loading is obtained, and the electrochemical data of AC possibility of manufacturing and innovating electrode materials
16
in Figure S7. At 1 A g 1, the specific capacitance of AC is for supercapacitors and other energy storage devices.
17
335.2 F g 1 calculated by GCD curves in 6 M KOH electrolyte.
18
Figure 6a shows the corresponding potential windows of the
19
NiS2/CoS2/NC-500 and AC electrodes at the same scan rate, Acknowledgements
20
testifying that the maximum potential window of the ASC could
21
reach 1.6 V. To ensure equal charge, the quality of the AC is Authors were very grateful to National Natural Science Foundation
22
calculated based on equation (2). When the voltage window of China (21665024). Northwest Normal University Young Teachers
23
increases from 0.8 V to 1.6 V, the anode polarized at 1.6 V under Research Capacity Promotion Plan (NWNU-LKQN-18-23) and Key
24
the same scan rate. The result shows that it is reasonable to set Lab of Polymer Materials of Gansu Province for their financial
25
the optimal window to 0–1.6 V (Figure 6b). As can be seen from supports.
26
Figure 6c, NiS2/CoS2/NC-500 makes better contribution to ASC
27
than the AC. The CV curves are not significantly deformed by
28
increasing the scan rate, indicating that it has good electro- Conflict of Interest
29
chemical stability. Figure 6d also discussed the GCD curves at
30
different current densities. When current densities are 1, 2, 3, 5, The authors declare no conflict of interest.
31
8 and 10 A g 1, the capacitances are 152, 130, 118, 102, 86 and
32
79 F g 1, respectively. In addition, the specific capacitance still Keywords: electrochemistry · supercapacitors · electrode
33
remains 52 % of the initial value when the current density materials · metal-organic frameworks · N-doped carbon
34
increases to 10 A g 1 (Figure 6e). According to equation (3) and composites
35
(4), obtaining a high energy density of 53.93 Wh kg 1 at a power
36
density of 800 W kg 1. At a power density of up to 16 kW kg 1,
37
the energy density can reach 19.6 Wh kg 1 (Figure 6f), demon- [1] J. Huang, J. Wang, C. Wang, H. Zhang, C. Lu, J. Wang, Chem. Mater.
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