Abstract
Nowadays, it is a matter of great concern to design electrode materials with excellent electrochemical performance for supercapacitors by a safe, efficient and simple method. And these characteristics are usually related to the vacancies and impurities in the electrode. To investigate the effect of the vacancies on the electrochemical properties of the supercapacitor cathode material, the uniform reduced CoNi2S4 (r-CoNi2S4) nanosheets with sulfur vacancies have been successfully prepared by a one-step hydrothermal method. And the formation of sulfur vacancies are characterized by Raman, X-ray photoelectron spectroscopy and other means. As the electrode for supercapacitor, the r-CoNi2S4 nanosheet electrode delivers a high capacity of 1918.9 F g−1 at a current density of 1 A g−1, superior rate capability (87.9% retention at a current density of 20 A g−1) and extraordinary cycling stability. Compared with the original CoNi2S4 nanosheet electrode (1226 F g−1 at current density of 1 A g−1), the r-CoNi2S4 nanosheet electrode shows a great improvement. The asymmetric supercapacitor based on the r-CoNi2S4 positive electrode and activated carbon negative electrode exhibits a high energy density of 30.3 W h kg−1 at a power density of 802.1 W kg−1, as well as excellent long-term cycling stability. The feasibility and great potential of the device in practical applications have been successfully proved by lightening the light emitting diodes of three different colors.
摘要
如何安全、高效、简便地制备出具有优异电化学性能的超 级电容器电极材料是当前人们十分关注的问题. 这些特性通常与 电极中的空位和杂质有关. 为了研究空位对超级电容器阴极材料 性能的影响, 我们采用一步水热法制备了具有硫空位的CoNi2S4 (r-CoNi2S4) 纳米片结构电极材料. 利用拉曼光谱、X射线光电子能 谱 (XPS) 等手段对硫空位的形成进行了表征. 作为超级电容器的电 极, r-CoNi2S4 纳米片在电流密度为 1 A g−1 时具有 1918.9 F g−1 的高 容量、优异的倍率性能(在电流密度为 20 A g−1 时, 相对于1 A g−1 的 保持率为87.9%)和超常的循环稳定性. 与原始的 CoNi2S4 纳米片电 极(1 A g−1 时容量为1226 F g−1)相比, r-CoNi2S4 电极的性能显著提 高. 基于r-CoNi2S4正极和活性炭负极的不对称超级电容器具有较 高的能量密度. 通过点亮三种不同颜色的发光二极管(LED)灯, 成 功证明了该器件在实际应用中的可行性和巨大潜力.
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References
He W, Liang Z, Ji K, et al. Hierarchical Ni-Co-S@Ni-W-O core-shell nanosheet arrays on nickel foam for high-performance asymmetric supercapacitors. Nano Res, 2018, 11: 1415–1425
Kim DY, Ghodake GS, Maile NC, et al. Chemical synthesis of hierarchical NiCo2S4 nanosheets like nanostructure on flexible foil for a high performance supercapacitor. Sci Rep, 2017, 7: 9764
Li C, Balamurugan J, Kim NH, et al. Hierarchical Zn-Co-S na-nowires as advanced electrodes for all solid state asymmetric supercapacitors. Adv Energy Mater, 2018, 8: 1702014
Dresselhaus MS, Thomas IL. Alternative energy technologies. Nature, 2001, 414: 332–337
El-Kady MF, Strong V, Dubin S, et al. Laser scribing of highperformance and flexible graphene-based electrochemical capacitors. Science, 2012, 335: 1326–1330
Wen L, Li F, Cheng HM. Carbon nanotubes and graphene for flexible electrochemical energy storage: from materials to devices. Adv Mater, 2016, 28: 4306–4337
Guo K, Ma Y, Li H, et al. Flexible wire-shaped supercapacitors in parallel double helix configuration with stable electrochemical properties under static/dynamic bending. Small, 2016, 12: 1024–1033
Hu W, Chen R, Xie W, et al. CoNi2S4 nanosheet arrays supported on nickel foams with ultrahigh capacitance for aqueous asymmetric supercapacitor applications. ACS Appl Mater Interfaces, 2014, 6: 19318–19326
Wen Y, Liu Y, Dang S, et al. High mass loading Ni-decorated Co9S8 with enhanced electrochemical performance for flexible quasi-solid-state asymmetric supercapacitors. J Power Sources, 2019, 423: 106–114
Han X, Tao K, Wang D, et al. Design of a porous cobalt sulfide nanosheet array on Ni foam from zeolitic imidazolate frameworks as an advanced electrode for supercapacitors. Nanoscale, 2018, 10: 2735–2741
Huang Y, Quan L, Liu T, et al. Construction of MOF-derived hollow Ni-Zn-Co-S nanosword arrays as binder-free electrodes for asymmetric supercapacitors with high energy density. Na-noscale, 2018, 10: 14171–14181
Wang Q, Gao F, Xu B, et al. ZIF-67 derived amorphous CoNi2S4 nanocages with nanosheet arrays on the shell for a high-performance asymmetric supercapacitor. Chem Eng J, 2017, 327: 387–396
Yilmaz G, Yam KM, Zhang C, et al. In situ transformation of MOFs into layered double hydroxide embedded metal sulfides for improved electrocatalytic and supercapacitive performance. Adv Mater, 2017, 29: 1606814–1606822
Yu XY, Yu L, Lou XWD. Metal sulfide hollow nanostructures for electrochemical energy storage. Adv Energy Mater, 2016, 6: 1501333–1501347
Jia R, Li L, Ai Y, et al. Self-healable wire-shaped supercapacitors with two twisted NiCo2O4 coated polyvinyl alcohol hydrogel fibers. Sci China Mater, 2018, 61: 254–262
Zhao J, Li Z, Zhang M, et al. Vertically cross-linked and porous CoNi2S4 nanosheets-decorated SiC nanowires with exceptional capacitive performance as a free-standing electrode for asymmetric supercapacitors. J Power Sources, 2016, 332: 355–365
Ji Y, Liu X, Liu W, et al. A facile template-free approach for the solid-phase synthesis of CoS2 nanocrystals and their enhanced storage energy in supercapacitors. RSC Adv, 2014, 4: 50220–50225
Mi L, Wei W, Zheng Z, et al. Tunable properties induced by ion exchange in multilayer intertwined CuS microflowers with hier-archal structures. Nanoscale, 2013, 5: 6589–6598
Wei W, Mi L, Gao Y, et al. Partial ion-exchange of nickel-sulfide-derived electrodes for high performance supercapacitors. Chem Mater, 2014, 26: 3418–3426
Xiao J, Wan L, Yang S, et al. Design hierarchical electrodes with highly conductive NiCo2S4 nanotube arrays grown on carbon fiber paper for high-performance pseudocapacitors. Nano Lett, 2014, 14: 831–838
Ma L, Hu Y, Chen R, et al. Self-assembled ultrathin NiCo2S4 na-noflakes grown on Ni foam as high-performance flexible electrodes for hydrogen evolution reaction in alkaline solution. Nano Energy, 2016, 24: 139–147
Fu W, Zhao C, Han W, et al. Cobalt sulfide nanosheets coated on NiCo2S4 nanotube arrays as electrode materials for high-performance supercapacitors. J Mater Chem A, 2015, 3: 10492–10497
Bai D, Wang F, Lv J, et al. Triple-confined well-dispersed biactive NiCo2S4/Ni0.96S on graphene aerogel for high-efficiency lithium storage. ACS Appl Mater Interfaces, 2016, 8: 32853–32861
Shen J, Wu J, Pei L, et al. CoNi2S4-graphene-2D-MoSe2 as an advanced electrode material for supercapacitors. Adv Energy Mater, 2016, 6: 1600341–1600349
Xiong T, Yu ZG, Wu H, et al. Defect engineering of oxygen-deficient manganese oxide to achieve high-performing aqueous zinc ion battery. Adv Energy Mater, 2019, 9: 1803815
Li Z, Zhao D, Xu C, et al. Reduced CoNi2S4 nanosheets with enhanced conductivity for high-performance supercapacitors. Electrochim Acta, 2018, 278: 33–41
Wen Y, Peng S, Wang Z, et al. Facile synthesis of ultrathin NiCo2S4 nano-petals inspired by blooming buds for high-performance supercapacitors. J Mater Chem A, 2017, 5: 7144–7152
Qin T, Dang S, Hao J, et al. Carbon fabric supported 3D cobalt oxides/hydroxide nanosheet network as cathode for flexible all-solid-state asymmetric supercapacitor. Dalton Trans, 2018, 47: 11503–11511
Wen Y, Qin T, Wang Z, et al. Self-supported binder-free carbon fibers/MnO2 electrodes derived from disposable bamboo chopsticks for high-performance supercapacitors. J Alloys Compd, 2017, 699: 126–135
Nguyen VH, Shim JJ. In situ growth of hierarchical mesoporous NiCo2S4@MnO2 arrays on nickel foam for high-performance supercapacitors. Electrochim Acta, 2015, 166: 302–309
Hao J, Peng S, Qin T, et al. Fabrication of hybrid Co3O4/NiCo2O4 nanosheets sandwiched by nanoneedles for high-performance supercapacitors using a novel electrochemical ion exchange. Sci China Mater, 2017, 60: 1168–1178
Gao Z, Chen C, Chang J, et al. Enhanced cycleability of Faradic CoNi2S4 electrode by reduced graphene oxide coating for efficient asymmetric supercapacitor. Electrochim Acta, 2018, 281: 394–404
He W, Wang C, Li H, et al. Ultrathin and porous Ni3S2/CoNi2S4 3D-network structure for superhigh energy density asymmetric supercapacitors. Adv Energy Mater, 2017, 7: 1700983
Patil SJ, Kim JH, Lee DW. Self-assembled Ni3S2//CoNi2S4 na-noarrays for ultra high-performance supercapacitor. Chem Eng J, 2017, 322: 498–509
Marini C, Perucchi A, Chermisi D, et al. Combined Raman and infrared investigation of the insulator-to-metal transition in NiS2-x,Sex compounds. Phys Rev B, 2011, 84: 235134–235136
Lu F, Zhou M, Li W, et al. Engineering sulfur vacancies and impurities in NiCo2S4 nanostructures toward optimal supercapacitive performance. Nano Energy, 2016, 26: 313–323
Tingting Y, Ruiyi L, Zaijun L, et al. Hybrid of NiCo2S4 and nitrogen and sulphur-functionalized multiple graphene aerogel for application in supercapacitors and oxygen reduction with significant electrochemical synergy. Electrochim Acta, 2016, 211: 59–70
Wang H, Wang C, Qing C, et al. Construction of carbon-nickel cobalt sulphide hetero-structured arrays on nickel foam for high performance asymmetric supercapacitors. Electrochim Acta, 2015, 174: 1104–1112
Yu L, Zhang L, Wu HB, et al. Formation of NixCo3-xS4 hollow nanoprisms with enhanced pseudocapacitive properties. Angew Chem Int Ed, 2014, 53: 3711–3714
Sivanantham A, Ganesan P, Shanmugam S. Hierarchical NiCo2S4 nanowire arrays supported on Ni foam: an efficient and durable bifunctional electrocatalyst for oxygen and hydrogen evolution reactions. Adv Funct Mater, 2016, 26: 4661–4672
Xu J, Sun Y, Lu M, et al. One-step electrodeposition fabrication of Ni3S2 nanosheet arrays on Ni foam as an advanced electrode for asymmetric supercapacitors. Sci China Mater, 2018, 62: 699–710
Wen J, Li S, Li B, et al. Synthesis of three dimensional Co9S8 nanorod@Ni(OH)2 nanosheet core-shell structure for high performance supercapacitor application. J Power Sources, 2015, 284: 279–286
Wang F, Li G, Zheng J, et al. Microwave synthesis of three-dimensional nickel cobalt sulfide nanosheets grown on nickel foam for high-performance asymmetric supercapacitors. J Colloid Interface Sci, 2018, 516: 48–56
Xie J, Qu H, Xin J, et al. Defect-rich MoS2 nanowall catalyst for efficient hydrogen evolution reaction. Nano Res, 2017, 10: 1178–1188
Andersson K, Nyberg M, Ogasawara H, et al. Experimental and theoretical characterization of the structure of defects at the pyrite FeS2 (100) surface. Phys Rev B, 2004, 70: 195404
Wang J, Shen Y, Wei G, et al. Synthesis of ultrathin Co2AlO4 nanosheets with oxygen vacancies for enhanced electrocatalytic oxygen evolution. Sci China Mater, 2019, 63: 91–99
Wen J, Li S, Chen T, et al. Three-dimensional hierarchical NiCo hydroxide@Ni3S2 nanorod hybrid structure as high performance positive material for asymmetric supercapacitor. Electrochim Acta, 2016, 222: 965–975
Wang R, Luo Y, Chen Z, et al. The effect of loading density of nickel-cobalt sulfide arrays on their cyclic stability and rate performance for supercapacitors. Sci China Mater, 2016, 59: 629–638
Shen L, Yu L, Yu XY, et al. Self-templated formation of uniform NiCo2O4 hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors. Angew Chem Int Ed, 2015, 54: 1868–1872
Du W, Wang Z, Zhu Z, et al. Facile synthesis and superior electrochemical performances of CoNi2S4/graphene nanocomposite suitable for supercapacitor electrodes. J Mater Chem A, 2014, 2: 9613–9619
Puthusseri D, Aravindan V, Madhavi S, et al. 3D micro-porous conducting carbon beehive by single step polymer carbonization for high performance supercapacitors: the magic ofin situ porogen formation. Energy Environ Sci, 2014, 7: 728–735
Wei XP, Luo YL, Xu F, et al. In-situ non-covalent dressing of multi-walled carbon nanotubes@titanium dioxides with carbox-ymethyl chitosan nanocomposite electrochemical sensors for detection of pesticide residues. Mater Des, 2016, 111: 445–452
Xuan X, Qian M, Han L, et al. In-situ growth of hollow NiCo layered double hydroxide on carbon substrate for flexible super-capacitor. Electrochim Acta, 2019, 321: 134710
Dubal DP, Gund GS, Lokhande CD, et al. Controlled growth of CoSx nanostrip arrays (CoSx-NSA) on nickel foam for asymmetric supercapacitors. Energy Tech, 2014, 2: 401–408
Zhu G, He Z, Chen J, et al. Highly conductive three-dimensional MnO2-carbon nanotube-graphene-Ni hybrid foam as a binder-free supercapacitor electrode. Nanoscale, 2014, 6: 1079–1085
Zhou K, Zhou W, Yang L, et al. Ultrahigh-performance pseudo-capacitor electrodes based on transition metal phosphide na-nosheets array via phosphorization: a general and effective approach. Adv Funct Mater, 2015, 25: 7530–7538
Zhu Y, Wu Z, Jing M, et al. Mesoporous NiCo2S4 nanoparticles as high-performance electrode materials for supercapacitors. J Power Sources, 2015, 273: 584–590
Li Y, Cao L, Qiao L, et al. Ni-Co sulfide nanowires on nickel foam with ultrahigh capacitance for asymmetric supercapacitors. J Mater Chem A, 2014, 2: 6540–6548
Acknowledgements
This work was supported by the National Natural Science Foundation of China (61376011 and 51402141), Gansu Provincial Natural Science Foundation (17JR5RA198), the Fundamental Research Funds for the Central Universities (lzujbky-2018-119 and lzujbky-2018-ct08), and Shenzhen Science and Technology Innovation Committee (JCYJ20170818155813437).
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Liu Y, Wen Y and Li H designed and engineered the samples; Liu Y, Wen Y conceived the post-fabrication tuning of random modes; Liu Y and Zhang Y performed the experiments; Liu Y, Wen Y and Zhang Y performed the data analysis; Liu Y wrote the paper with support from Wen Y; Liu Y, Wen Y, Huang J and Peng S contributed to the theoretical analysis. All authors contributed to the general discussion.
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The authors declare that they have no conflict of interest.
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Supporting data are available in the online version of the paper.
Yanpeng Liu was awarded a BSc degree by Harbin Institute of Technology in 2018. He is currently a graduate student in the School of Materials Science and Engineering at Lanzhou University. His main research interests are nanostructure design of NiCoS supercapacitors and aqueous zinc ion batteries.
Shanglong Peng is a professor of Lanzhou University. From 2010 to 2016, he worked at the University of Washington, Seoul National University and the Hong Kong University of Science and Technology. Currently, he is mainly engaged in the design of nanomaterials, interface regulation and their applications in energy conversion and storage, including supercapacitors, solar cells and flexible wearable integrated energy conversion and storage integrated devices.
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Reduced CoNi2S4 Nanosheets Decorated by Sulfur Vacancies with Enhanced Electrochemical Performance for Asymmetric Supercapacitors
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Liu, Y., Wen, Y., Zhang, Y. et al. Reduced CoNi2S4 nanosheets decorated by sulfur vacancies with enhanced electrochemical performance for asymmetric supercapacitors. Sci. China Mater. 63, 1216–1226 (2020). https://doi.org/10.1007/s40843-020-1302-6
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DOI: https://doi.org/10.1007/s40843-020-1302-6