[email protected] oxide nanosheet arrays grown on NF as binder-free anodes for lithium ion batteries

[email protected] oxide nanosheet arrays grown on NF as binder-free anodes for lithium ion batteries

Journal of Alloys and Compounds 810 (2019) 151861 Contents lists available at ScienceDirect Journal of Alloys and Compounds journal homepage: http:/...

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Journal of Alloys and Compounds 810 (2019) 151861

Contents lists available at ScienceDirect

Journal of Alloys and Compounds journal homepage: http://www.elsevier.com/locate/jalcom

[email protected] oxide nanosheet arrays grown on NF as binder-free anodes for lithium ion batteries Ruili Zhang, Xuehong Li, Yaping Zhu, Yuhua Shen*, Anjian Xie** School of Chemistry and Chemical Engineering, Lab for Clean Energy & Green Catalysis, Anhui University, Hefei, 230601, China

a r t i c l e i n f o

a b s t r a c t

Article history: Received 22 February 2019 Received in revised form 30 July 2019 Accepted 13 August 2019 Available online 13 August 2019

A novel graphene oxide encapsulated Ni3S2 multi-layer nanosheet arrays were designedly grown on Ni foam ([email protected]/NF) via a simple and low-cost method. The prepared nanocomposite was converted from a pyramid shape to a multi-layer nanosheet array because Sn4þ, Ni2þ and thioacetamide performed a coprecipitation transformation during the hydrothermal reaction. As a binder-free anode material for lithium ion batteries, the [email protected]/NF nanocomposite showed an initial charge and discharge of 797.8 and 1182.3 mA h g1 at a current density of 0.5 A g1, respectively. After 100 reversible cycles, the specific discharge capacity of the composite can still remain 1006.6 mA h g1, presenting excellent cycle stability. The enhanced electrochemical performance is due to that the multi-layer sheet array structure can increase the Liþ energy storage active site and alleviate the volume expansion caused by Liþ insertion and extraction, which was beneficial to the sufficient contact of the active material with the electrolyte, enhancing the lithium ion transmission rate. Additionally, the coating of oxide graphene on the composite further stabilized the structural morphology, thereby improving the stability of the electrochemical cycle performance of the nanocomposite. © 2019 Elsevier B.V. All rights reserved.

Keywords: [email protected]/NF Multilayer nanosheet array Binder-free anode Lithium ion batteries

1. Introduction Rechargeable lithium-ion batteries (LIBs) are now considered to be the most important source of power for electric vehicles (EVs) and hybrid electric vehicles (HEVs) [1,2]. In order to meet the growing application requirements of EV and HEV, it is urgent to explore LIBs with high energy density, high power density, and long cycle life. The anode materials of traditional and commercial lithium-ion batteries are mostly graphite. Paradoxically, the theoretical specific capacity of graphite is relatively low (372 mA h g-1), which limits its application under high energy and power density requirements. Therefore, novel anode materials have attracted intensive research attention recently [3e5]. Many metal sulfides, such as Co9S8 [6,7], Co3S4 [8], CoS2, Ni3S2 [9,10], FeS [11], FeS2 [12], MoS2 [13e16] and MnS [17], have been explored as potential alternative anode materials for LIBs because of the higher energy density, and theoretical specific capacity. Metal sulfides were considered to be a promising lithium-ion anode material due to the very rich content of sulfides in the

* Corresponding author. Tel.: þ86 15255459439. ** Corresponding author. E-mail addresses: [email protected] (Y. Shen), [email protected] (A. Xie). https://doi.org/10.1016/j.jallcom.2019.151861 0925-8388/© 2019 Elsevier B.V. All rights reserved.

natural world. However, the low intrinsic conductivity of metal sulfides caused significant irreversible capacity losses and lower cycling stability. Moreover, the pulverization of metal sulfides and subsequent detachment from the current collectors induced by volume expansion during charging/discharging processes, which also hinder their commercial application. In fact, sulfur compounds have been investigated for a long time in LIBs, and both sulfurcontaining organic compounds and inorganic compounds have been widely studied by researchers [18e24]. Currently, binary metal sulfides and spinel sulfides have attracted the attention of many scholars. Chen et al. [25] fabricated Mo-doped SnS2 nanosheet composites on carbon cloths for LIBs anode, demonstrating excellent cycling stability and good rate performance. Zou et al. [26] synthesized a CoS composite with a porous carbon tube through the curing of a hollow polyhedron ZIF-67, possessing outstanding electrochemical properties. We can conclude that the performance of the material as a anode electrode can be optimized by changing the structure of the material. Numerous attempts have been made on controlling the morphology of these materials, such as hollow spheres [27,28], nanorods [29], microboxes [30,31] et al. However, the current synthetic method for morphology controlling of materials are usually either complicated or uneconomical. In recent years, 3D multilayer nanosheet array structures have been considered to be more desirable lithium ion battery electrodes


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due to their large specific surface area, better permeability, and more active sites [32]. For example, Fan et al. prepared a multilayered electrode of TiO2 [email protected] nano-flower array structure, via a two-step method, which exhibited superior cycle performance and rate characteristics compared with powder materials [33]. Shen et al. also reported the design and synthesis of multilayer ZnCO2O4 nanowire [email protected] paper electrodes [34]. Uniform, ordered, dense multi-layered ZnCO2O4 nanowire arrays were grown on three-dimensional conductive carbon paper, exhibiting high capacity characteristics, excellent cycle stability and good rate characteristics as lithium-ion battery electrodes. Graphene has been highlighted in fabricating various functional materials devices, and also used for conductive switching, bioimaging, photocatalysis. For example, Wei et al. studied the effect of hybrid cuprous oxide/reduced graphene oxide (Cu2O/rGO) nanocomposites on the performance of light-controlled conductive switches [35]; Liu et al. researched the enhanced X-ray photon response in solution-synthesized CsPbBr3 nanoparticles wrapped by reduced graphene oxide [36]; Zang et al. discussed the tunable photoluminescence of water-soluble AgInZnS-graphene oxide (GO) nanocomposites and their applications in in vivo bioimaging [37]. In this work, we successfully designed a [email protected] composite directly grown on nickel foam, which consisted of regular and orderly multilayer nanosheets. According to the electrochemical test, the specific capacity of [email protected]/NF for the first charge and discharge can reach 797.8 and 1182.3 mA h g1 at the current density of 0.5 A g1, respectively. Evidently, the multilayer nanosheet array structure material is reasonably combined as a binderfree electrode material, which might be one of the most promising candidates for anode materials of LIBs. 2. Experimental 2.1. Materials All the reagents including SnCl4$5H2O, hydrochloric acid, thioacetamide (C2H5NS) and andydrous ethanol (C2H5OH) were purchased from Sinopharm Chemical Reagent Co. Ltd. (PR China). All reagents were of analytical grade and employed without further purification. 1 M LiPF6 in an ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) mixture (1:1:1, in wt %) was used as the nonaqueous electrolyte. 2.2. Preparation of the samples 2.2.1. NF pretreatment NF was purified and treated with 12 M HCl aqueous solution and sonicated for 30 min. Sequentially the NF was cleaned with deionized water and ethanol to remove the nickel oxide layer on the surface before use. 2.2.2. Preparation of [email protected]/NF First, a SnCl4$5H2O solution (0.1 M, 20 mL) was added to an aqueous solution of thioacetamide (0.1 M, 20 mL) with magnetic stirring for 10 min at room temperature. Then the obtained solution with NF were transferred to a 50 mL stainless-steel autoclave and then heated at 160  C for 10 h. After cooling down to room temperature, the NF was washed with deionized water and ethanol three times under ultrasonic and then vacuum-dried at 60  C for 12 h. Lastly, the NF was added into a 3 mol L1 graphene oxide solution and reacted in a Microwave-Ultraviolet-Ultrasonic machine (KQ-400KDE,China, The Trinity Synthetic Extraction Reactor combines three different energy sources, such as microwave heating, ultraviolet radiation and ultrasonic oscillation, to exert different degrees of chemical and physical effects on the separation and

synthesis of microscopic components such as molecules and electrons.) for 15 min to obtain the final [email protected]/NF. For comparison, Ni3S2/NF was synthesized using the same method without graphene oxide. 2.3. Materials characterization The phase of the [email protected]/NF was characterized by X-ray diffraction (XRD) using a DX-2700 instrument with Cu Ka radiation (l ¼ 1.54056 Å) operating at 40 kV and 60 mA. Furthermore, the composition of the surface of the as-synthesized sample was analyzed by X-ray photoelectron spectroscopy (XPS, Thermo ESCALAB 250, USA). Raman spectra were measured by a reflective laser micro-Raman spectrometer (Renishaw InVia) with an excitation wavelength of 532 nm. The specific surface area and pore size distribution of the complex were obtained via a Trstar II3020 BET surface area analyzer. The morphology and particle size were conducted using a field emission scanning electron microscope (SEM, Hitachi SU-1510, Japan) at a voltage of 10 kV. 2.4. Battery assembly and electrochemical measurement Anode electrodes was composed of [email protected]/NF composite, CR2025 type coin cells were assembled with anode electrode, lithium foil electrode, electrolyte of 1.0 M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) (EC/DMC ¼ 1:1,by volume), and a polypropylene (PP) film (diameter 18 mm), in an argon-filled glove box where oxygen and water contents were coordinated to less than 0.5 ppm. The as-prepared coin cells were used to the test system of high-precision battery cabinet to measure the chargedischarge ratio capacity, coulombic efficiency and cycle life of the battery through the galvanostatic discharge-charge tests. The cyclic voltammetry (CV) was collected from electrochemical workstation (CHI880, manufactured by Shanghai Chenhua Instrument Co. Ltd.) at the voltage scanning range of 0.01e3 V, and the scanning rate of 0.2 mV s1. The electrochemical impedance spectroscopy of coin cells was carried out on an Autolab (PGSTAT302 N) with AC signal 5 mV rms from 0.01 Hz to 0.1 MHz. All electrochemical tests were performed at room temperature. 3. Results and discussion 3.1. Phase, component and microstructure of [email protected]/NF composite Fig. 1 showed XRD patterns of [email protected]/NF and Ni3S2/NF

Fig. 1. XRD patterns of the (a) Ni3S2 @GO/NF and (b) Ni3S2/NF.

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nanocomposites. All the major diffraction peaks at 21.7, 31.1, 37.7, 38.3 , 44.3 , 49.7, 50.1, 54.6 , 55.1 and 55.3 can be assigned to (101), (110), (003), (021), (202), (113), (211), (104), (122), and (300) planes of Ni3S2, respectively(JCPDS card No. 44e1418). And the diffraction peaks of 45 , 51.8 and 76.3 , corresponding to the (111), (200) and (220) crystal faces of NF (JCPDS card NO.04e0850). No other diffraction peaks were observed in the XRD patterns, indicating the pure Ni3S2 nanosheet grew on NF by this synthetic method. XPS analysis was carried out to investigate chemical composition and electronic state of Ni, S and C in the [email protected]/NF. Fig. 2a exhibited the spectrum of XPS, revealing the presence of Ni, S, O and C elements in the sample. The chemical state of Ni was determined by high-resolution Ni 2p XPS spectrum (Fig. 2b). Fig. 2b presented two peaks at 855.7 and 873.7eV corresponding to Ni 2p3/ 2 and 2p1/2 with two satellite peaks at 861.9 and 879.9eV, indicating the formation of Ni2þ and Ni3þ, respectively. As shown in Fig. 2c, there were two peaks at 162.1 and 163.3eV, and a satellite peak at 168.0eV, arising from S in the sample. Fig. 2d presented a peak at 284.6eV, verifying the existence of the C element. The XPS results further proved that [email protected]/NF nanocomposite formed. In order to further examine the existence of GO, we used laser confocal micro-Raman spectrometer to measure the light scattering of [email protected]/NF and GO samples, respectively. It can be clearly seen from the Fig. 3 that [email protected]/NF (Fig. 3a) and GO (Fig. 3b) emerged two peaks at 1591 cm1 and 1346 cm1, respectively. The G band at 1591 cm1 was generated by the vibration of the carbon atom sp2 hybrid flat, and the peak of the disordered carbon with an aromatic structure at 1346 cm1 was the D band. By


Fig. 3. Raman spectra of (a) [email protected]/NF, (b) GO and.

comparing Fig. 3b and a, we find no significant change in the intensity of the G band to D band, demonstrating the presence of GO in the prepared sample [38]. The characteristic peaks of [email protected]/ NF (Fig. 3a) at 316 and 791 cm1 corresponded to the characteristic Raman peaks of Ni3S2, respectively. The above results demonstrated that GO was successfully coated on a foamed nickel material, which was consistent with the XPS analysis.

Fig. 2. XPS spectra of [email protected]/NF; (a) survey, (b) Ni 2p, (c) S 2p, (d) C 1s.


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Fig. 4 showed SEM images of different samples. The top right inset in Fig. 4a presented the original NF skeleton while the lowmagnification image of Ni3S2 grown on the NF substrate without adding SnCl4 was shown in bottom left inset. From the highmagnification image of Ni3S2 (Fig. 4a), we found a multi-faceted pyramid array structure. NF was used as the Ni source and substrate for the nucleation and growth in situ of Ni3S2 to form binderfree self-supported electrode. Moreover, NF was chosen as a 3D porous self-supporting conductive substrate to substitute a conventional current collector (i.e., copper foil) can increase the contact area between the electrolyte and the electrode, and all of the components could participate energy storage, maximizing the specific capacity potential [39]. Fig. 4b showed the addition of a suitable concentration of graphene oxide (GO) under the same conditions of Fig. 4a, which was still the multi-faceted pyramid array. The only difference was the surface of the pyramid that became smooth and the water chestnut was somewhat passivated due to the effect of graphene coating. We further explored the effect of the addition of the SnCl4 on the morphology of the Ni3S2. It is clearly seen from Fig. 4c and d that the morphology of [email protected]/ NF transformed from a polygon pyramid array to a nanosheet array after adding Sn4þ, which could be explained as follows. The high potential was caused by Sn4þ adsorption on the NF surface, so a planar growth of [email protected]/NF occurred in order to lower the total surface energy [40]. Therefore, the existence of Sn4þ disturbed the potential distribution and affected the growth way of Ni3S2. Lastly, the morphology changed over time into a nanosheet array structure. The multi-layered nanosheet array contributed to the Liþ energy storage active sites and enhanced its electrochemical performance, and the sheet structure can alleviate the volume expansion caused by Liþ insertion and ejection [41]. Fig. 4d presented a scanning electron image of [email protected]/NF with the addition of SnCl4. Compared with Fig. 4c, it can be found that its appearance was still a multi-layer nano-sheet array with a layer of wrinkles on its surface, which was a GO nanosheet. It explained that the GO was well coated on the surface of the Ni3S2/NF nanocomposite of the multilayer nanosheet array. This increased GO layer spacing can well buffer the volume change caused by Liþ insertion and extraction during charge and discharge process, thereby preventing material from collapse and improving battery cycle stability and cycle life [42]. The electrode material using nickel foam as a current collector facilitated sufficient contact between

Fig. 4. SEM images of (a) Ni3S2/NF with high-magnification, Ni3S2/NF with lowmagnification (the bottom left inset) and NF skeleton (the top right inset); (b) [email protected]/NF prepared without the addition of SnCl4,5H2O; (c) Ni3S2/NF and (d) [email protected]/NF prepared with the addition of SnCl4,5H2O.

the active material and the electrolyte, thereby increasing the lithium ion transmission rate. 3.2. Eletrochemical performance of [email protected]/NF composite Fig. 5a exhibited the first and second charge and discharge curves of the [email protected]/NF and Ni3S2/NF samples with a voltage range of 0.01e3.0 V at a current density of 0.2 A g 1. It can be seen from Fig. 5a that the first discharge and charge capacities of the [email protected]/NF electrode were 2488.7 and 1677.1 mA h g1, which were higher than the Ni3S2/NF (2002.3 and 1027.8 mA h g1). The excellent specific capacity of [email protected]/NF may be due to the presence of GO that has not only a large Li storage capacity (>1000 mAh g1) [43] but also high conductivity, which mainly contributed to the total capacity of [email protected]/NF. In the first discharge curve, a platform appeared at around 1.25 V, mainly due to the decomposition of the electrolyte and the formation of the solid electrolyte interface (SEI) film. The first discharge voltage platform of [email protected]/NF was higher than that of Ni3S2/NF, suggesting that the addition of GO slows down the decomposition of the electrolyte and weakens the formation of the SEI film. In the first charging curve, two platforms appeared, mainly due to the 4Liþ þ 4e þ Ni3S2 / 3Ni þ 2Li2S in the process and the phase transition occurred, after which only one platform could be observed around 2.0 V [44]. Fig. 5b showed the cycle performance curves of the [email protected]/NF and Ni3S2/NF composites at a current density of 0.2 A g1. The [email protected]/NF exhibited more better cycle stability than Ni3S2/NF at different current density of 0.2 A g1 after 100 cycles. Obviously, the multilayer nanosheet array of [email protected]/ NF sample possess higher electrochemical performance than Ni3S2/ NF, indicating that the ordered array structure can buffer the volume change and keeping the structure stable [45]. Simultaneously, the GO structure is able to increase the active sites of lithium storage [46]. After 100 reversible cycles, the specific discharge capacity of the [email protected]/NF can still remain 1006.6 mA h g1, which is much higher than the Ni3S2/NF (464.1 mA h g1). Fig. 5c was obtained by further secondary mapping of Fig. 5b, showing the difference in capacity between the samples [email protected]/NF and the sample Ni3S2/NF at a current density of 0.2 A g1 during different cycle times. It is obvious that the [email protected]/NF sample of the multilayer nanosheet array has higher electrochemical performance than Ni3S2/NF, and the sheet structure can buffer the volume change caused by the insertion and extraction of Liþ. Fig. 5d reviewed the rate performance curve of [email protected]/NF and Ni3S2/NF at different current densities. It was found that when the current density changed from 0.2 A g1 to 1 A g1, the reversible specific capacity of the [email protected]/NF is higher than the Ni3S2/NF. When the current density ranged from 1 A g1 back to 0.2 A g1, and the reversible specific capacity of the [email protected]/NF electrode material can be recovered to almost 1334 mA h g1, while that of the Ni3S2/ NF electrode was greatly lost. Improvement in conductivity of the electrode material is due to the coating of the GO, which also alleviates the volume change caused by the insertion and extraction of Liþ, therefore, the electrochemical performance of the electrode material can be well improved. We further evaluated the cycling stability and the homologous coulombic efficiency of the [email protected]/NF at a higher current density of 0.5 A g1, shown in Fig. 6a. The initial discharge and charge capacity of the [email protected]/NF were 1182.3 and 797.8 mA h g1, corresponding to the first coulombic efficiency (CE) of 67.5%, which is attributed to the likely irreversible formation of the initial SEI layer on the surface. Afterwards, the reversible specific capacity decreased to about 655 mA h g1 and remained stable. After the first cycle, the coulombic efficiency of the [email protected]/NF nanocomposite maintained almost 100%. The higher cycle efficiency at

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Fig. 5. The electrochemical performance of [email protected]/NF and Ni3S2/NF (a) charge-discharge curves in the first and second cycles at the current density of 0.2 A g1; (b) long-term cycling performance at the current density of 0.2 A g1, (c) capacity difference between [email protected]/NF and Ni3S2/NF at the current density of 0.2 A g1 and (d) high-rate capability performance.

higher current densities indicated that the as-prepared structure [email protected]/NF with multilayer nanosheet array possesses superior cycle stability. Fig. 6b showed the CV curves of the first, 10th and 101th cycles of [email protected]/NF multilayer nanosheet array with a scan rate at 0.2 mV s1 in the range of 0.01e3.00 V. During the first cycle, the voltage appeared a large reduction peak near 0e0.75 V, which may be the reduction of Ni3S2 to metal Ni. But in the 10th and 101th cycles, it is possible that the organic solvent in the electrolyte was reduced and decomposed, so reduction peaks shifted (at 1.0e1.5 V) [47]. Simultaneously, the first occurrence of the reduction peak is much larger than the reduction peak after the cycle, because the insoluble matter produce adheres to the surface of the electrode to form the SEI film [48]. Since the SEI film had been substantially stabilized during the 10th cycle, the reduction peak had a small difference from the next cycle. During the first cycle, two anode peaks appeared at 2.1 V and 2.6 V because of the generation of Ni3S2, which may be accompanied by phase transitions [49]. It is consistent with its charge and discharge curves (Fig. 5a). The anode peaks at the 10th and 101th cycles were stable at around 2.2 V, and were well combined together, revealing that the anode material possess advanced cycle stability. It can be seen from the figure that a significant redox peak appears and the position of the peak is substantially the same as the redox peak position in Fig. 5a, thus exhibiting the electrode material has good reversibility and cycle stability. Fig. 6c showed a charge-discharge curve at the first, 10th, and 50th cycles at a current density of 1 A g1. Except for the formation of SEI during the first cycle, the 10th and 50th charge-discharge curves were substantially coincident, showing the stability of the electrode, which further proved that the electrode material possesses high rate performance. Compared with Figs. 5b, 6a and c, we found that as the current density increased, the capacity faded significantly due to the cracking, pulverization and polarization of the electrode.

Fig. 6d was obtained by TGA in an air atmosphere with [email protected]/ NF nanocomposite. It can be seen from the figure that GO reacted with O2 in the air to form CO2 between 250  C and 300  C, which caused the weight loss ratio to decrease by about 2%, indicating the weight ratio of GO in the sample is only about 2%. After 400  C, the weight ratio of the sample risen due to the oxidation of Ni2S3 and O2 in the air to form nickel oxide. From above, Ni3S2 mainly contributed to the total capacity. The electrochemical impedance spectroscopy (EIS) results of the [email protected]/NF and Ni3S2/NF composites were exhibited in Fig. 7a. The both curves are composed of a semicircle and a straight line (corresponding to the high frequency region and the low frequency region, respectively). In the high frequency region, the value of the charge transfer resistance was mainly determined by the curvature in the spectrum. The Warburg impedance behavior was mainly reflected in the low frequency region, which was the solid diffusion resistance of Liþ in the electrode material [50]. Apparently, The [email protected]/NF nanocomposite exhibited considerably lower resistance than Ni3S2/NF, suggesting that the [email protected]/NF possesses enhanced charge transfer process in the electrode, The possible reason is the effect of GO, which is beneficial for Liþ transport and the conductivity of the electrode, leading to an improvement for the electrochemical performances. Fig. 7b showed the electrochemical impedance spectroscopy (EIS) results of the [email protected]/NF composite after 1, 5, and 10 cycles, and the illustration on the upper left was magnified at the high frequency region of figure. Since the EIS of [email protected]/NF was relatively low during the transfer process and diffusion process, the conduction velocity of the current and the diffusion rate of lithium ions were faster on the electrode. The impedance became smaller after 5 and 10 cycles due to the metal skeleton foam nickel directly acts as a current collector, so that the electrolyte wetted the [email protected]/NF material better, indicating that [email protected]/NF nanaosheet possess finer electrochemical properties.


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Fig. 6. (a) The cycle performance of [email protected]/NF和Ni3S2/NF Charge-discharge curves at the current density of 0.5 A g1. (b) Cyclic voltammograms of the [email protected]/NF in the first, 10th and 101th cycles at a scan rate of 0.2 mV s1 in the range of 0.01e3.00 V. (c) charge-discharge curves in the first, 10th and 50th cycles at the current density of 1 A g1. (d) TGA curve of [email protected]/NF

Fig. 7. (a) Impedance spectra of the [email protected]/NF and Ni3S2/NF in frequency rang from 0.01 to 100 kHz. (b) Impedance spectra of the [email protected]/NF electrode after cycles in frequency range from 0.01 to 100 kHz.

4. Conclusion In summary, a multi-layer [email protected]/NF nanosheet array as a binder-free anode material was obtained in situ on a nickel foam via a mild hydrothermal method and a coprecipitation principle. As the anode material of LIBs, the reversible specific capacity of

[email protected]/NF can still remain 655 mA h g1at a current density of 0.5 A g1 after 100 cycles. The outstanding conductivity of the [email protected]/NF composite originated from structural features of multilayer nanosheet arrays, coating of GO and binder-free anode materials. Furthermore, the macroporous foam nickel metal skeleton can be sufficiently wetted by the electrolyte, which can

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accelerate the transmission speed of ions and electrons, and buffer the volume change of Ni3S2 nanomaterials during charge and discharge. In general, the material exhibited excellent cycle stable performance as well as high rate performance. Acknowledgments This work is supported by the National Natural Science Foundation of China (No. 21671001 and 21571002) and Anhui Province Key Laboratory of Environment-Friendly Polymer Materials. References [1] W. Li, B. Song, A. Manthiram, High-voltage positive electrode materials for lithium-ion batteries, Chem. Soc. Rev. 46 (2017) 3006e3059. [2] A. Eftekhari, Z. Jian, X. Ji, Potassium secondary batteries, ACS Appl. Mater. Interfaces 9 (2017) 4404e4419. [3] J.L. Niu, G.X. Hao, J. Lin, X.B. He, P. Sathishkumar, X.M. Lin, Y.P. Cai, Mesoporous MnO/C-N nanostructures derived from a metal-organic framework as highperformance anode for lithium-ion battery, Inorg. Chem. 56 (2017) 9966e9972. [4] H.H. Fan, H.H. Li, K.C. Huang, C.Y. Fan, X.Y. Zhang, X.L. Wu, J.P. Zhang, Metastable marcasite-FeS2 as anew anode material for lithium ion batteries: CNFsimproved lithiation/delithiation reversibility and Li-storage properties, ACS Appl. Mater. Interfaces 9 (2017) 10708e10716. [5] S.N. Beznosov, P.S. Veluri, M.G. Pyatibratov, A. Chatterjee, D.R. MacFarlane, O.V. Fedorov, S. Mitra, Flagellar filament biotemplated inorganic oxide materials-towards an efficient lithium battery anode, Sci. Rep. 5 (2015) 7736. [6] Z. Shadike, M.H. Cao, F. Ding, L. Sang, Z.W. Fu, Improved electrochemical performance of CoS2-MWCNT nanocomposites for sodium-ion batteries, Chem. Commun. 51 (2015) 10486. [7] Y.N. Ko, Y.C. Kang, Co9S8-carbon composite as anode materials with improved Na-storage performance, Carbon 94 (2015) 85e90. [8] Q.M. Su, G.H. Du, J. Zhang, Y.J. Zhong, B.S. Xu, Y.H. Yang, S. Neupane, W.Z. Li, In situ transmission electron microscopy observation of electrochemical sodiation of individual Co9S8-filled carbon nanotubes, ACS Nano 8 (2014) 3620e3627. [9] Y.C. Du, X.S. Zhu, X.S. Zhou, L.Y. Hu, Z.H. Dai, J.C. Bao, Co3S4 porous nanosheets embedded in graphene sheets as high-performance anode materials for lithium and sodium storage, J. Mater. Chem. 3 (2015) 6787e6791. [10] C.Q. Shang, S.M. Dong, S.L. Zhang, P. Hu, C.J. Zhang, G.L. Cui, A Ni3S2-PEDOT monolithic electrode for sodium batteries, Electrochem. Commun. 50 (2014) 24e27. [11] W. Qin, T.Q. Chen, T. Lu, D.H.C. Chua, L.K. Pan, Layered nickel sulfide-reduced graphene oxide composites synthesized via microwave-assisted method as high performance anode materials of sodium-ion batteries, Power Sources 302 (2016) 202e209. [12] Z. Hu, Z.Q. Zhu, F.Y. Cheng, K. Zhang, J.B. Wang, C.C. Chen, J. Chen, Pyrite FeS2 for high-rate and long-life rechargeable sodium batteries, Energy Environ. Sci. 8 (2015) 1309e1316. [13] Y.X. Wang, J.P. Yang, S.L. Chou, H.K. Liu, W.X. Zhang, D.Y. Zhao, S.X. Dou, Uniform yolk-shell iron sulfideecarbon nanospheres for superior sodiumeiron sulfide batteries, Nat. Commun. 6 (2015) 8689. [14] X.J. Xu, S.M. Ji, M.Z. Gu, J. Liu, In situ synthesis of MnS hollow microspheres on reduced graphene oxide sheets as high-capacity and long-life anodes for Liand Na-ion batteries, ACS Appl. Mater. Interfaces 7 (2015) 20957e20964. [15] S.H. Choi, Y.N. Ko, J.K. Lee, Y.C. Kang, 3D MoS2-graphene microspheres consisting of multiple nanospheres with superior sodium ion storage properties, Adv. Funct. Mater. 25 (2015) 1780e1788. [16] Y.Y. Lu, Q. Zhao, N. Zhang, K.X. Lei, F.J. Li, J. Chen, Facile spraying synthesis and high-performance sodium storage of mesoporous MoS2/C microspheres, Adv. Funct. Mater. 26 (2016) 911e918. [17] D. Xie, X.H. Xia, W.J. Tang, Y. Zhong, Y.D. Wang, D.H. Wang, X.L. Wang, J.P. Tu, Novel carbon channels from loofah sponge for construction of metal sulfide/ carbon composites with robust electrochemical energy storage, J. Mater. Chem. 5 (2017) 7578e7585. [18] T. Stephenson, Z. Li, B. Olsen, D. Mitlin, Lithium ion battery applications of molybdenum disulfide (MoS2) nanocomposites, Energy Environ. Sci. 7 (2014) 209e231. [19] X. Zhou, L.J. Wan, Y.G. Guo, Synthesis of MoS2 nanosheet Graphene nanosheet hybrid materials for stable lithium storage, Chem. Commun. 49 (2013) 1838e1840. [20] B. Radisavljevic, M. Whitwick, B. Kis, Integrated circuits and logic operations based on single-layer MoS2, ACS Nano 5 (2011) 9934e9938. [21] H. Li, J. Wu, Z. Yin, H. Zhang, Preparation and applications of mechanically exfoliated single-layer and multilayer MoS2 and WSe2 nanosheets, Acc. Chem. Res. 47 (2014) 1067e1075. [22] X. Xie, Q. Su, J.Q. Zhang, S.X. Dou, G.X. Wang, SnS2 [email protected] nanocomposites as highcapacity anode materials for sodium-ion batteries, Chem. Asian J. 9 (2014) 1611e1617. [23] R. Zou, Z. Zhang, M.F. Yuen, M. Sun, J. Hu, Lee, S.C.W. Zhang, Three-dimensional-networked NiCo2S4 Nanosheet array/Carbon cloth anodes for highperformance lithium-ion batteries, NPG Asia Mater. 7 (2015) 195.


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