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In situ preparation of flaky attached CuCo2S4 microspheres for high-performance asymmetric supercapacitors

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Abstract

Bimetallic sulfides are appealing great interest for renewable accumulated energy and conversion devices because of the multiple merits. Herein, flaky attached CuCo2S4 microspheres are reported via a simple solvothermal strategy and serve as an electrode to evaluate the supercapacitors characteristics. It should be noted that such electrode presents a high specific capacitance of 752 F·g−1 at 1 A·g−1 and excellent cycling stability over 4500 cycles. In addition, an asymmetric device is assembled by using CuCo2S4 and AC as the positive electrode and negative electrode, respectively, which achieves a high-energy density (46.2 Wh·kg−1 at 0.796 kW·kg−1) and retains a long cycling life over 8000 cycles. Such performance demonstrates that CuCo2S4 with the unique structure might be great potential for energy storage.

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References

  1. Wang P, Zhang Y, Yin Y, Fan L, Zhang N, Sun K (2018) In situ synthesis of CuCo2S4@N/S-doped graphene composites with pseudocapacitive properties for high-performance lithium-ion batteries. ACS Appl Mater Interfaces 10(14):11708–11714. https://doi.org/10.1021/acsami.8b00632

    Article  CAS  PubMed  Google Scholar 

  2. Sial MAZG, Din MAU, Wang X (2018) Multimetallic nanosheets: synthesis and applications in fuel cells. Chem Soc Rev 47(16):6175–6200. https://doi.org/10.1039/c8cs00113h

    Article  CAS  Google Scholar 

  3. Tang J, Ge Y, Shen J, Ye M (2016) Facile synthesis of CuCo2S4 as a novel electrode material for ultrahigh supercapacitor performance. Chem Commun 52(7):1509–1512. https://doi.org/10.1039/C5CC09402J

    Article  CAS  Google Scholar 

  4. Wang Y, Song Y, Xia Y (2016) Electrochemical capacitors: mechanism, materials, systems, characterization and applications. Chem Soc Rev 45(21):5925–5950. https://doi.org/10.1039/c5cs00580a

    Article  CAS  PubMed  Google Scholar 

  5. Salanne M, Rotenberg B, Naoi K, Kaneko K, Taberna PL, Grey CP, Dunn B, Simon P (2016) Efficient storage mechanisms for building better supercapacitors. Nat Energy 1(6):16070. https://doi.org/10.1038/nenergy.2016.70

    Article  CAS  Google Scholar 

  6. Simon P, Gogotsi Y, Dunn B (2014) Where do batteries end and supercapacitors begin? Science 343(6176):1210–1211. https://doi.org/10.1126/science.1249625

    Article  CAS  PubMed  Google Scholar 

  7. Wang G, Zhang L, Zhang J (2012) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41(2):797–828. https://doi.org/10.1039/c1cs15060j

    Article  CAS  PubMed  Google Scholar 

  8. Merabet L, Rida K, Boukmouche N (2018) Sol-gel synthesis, characterization, and supercapacitor applications of MCo2O4 (M = Ni, Mn, Cu, Zn) cobaltite spinels. Ceram Int 44(10):11265–11273. https://doi.org/10.1016/j.ceramint.2018.03.171

    Article  CAS  Google Scholar 

  9. Liu L, Niu Z, Chen J (2016) Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations. Chem Soc Rev 45(15):4340–4363. https://doi.org/10.1039/c6cs00041j

    Article  CAS  PubMed  Google Scholar 

  10. Wei J, Li X, Xue H, Shao J, Zhu R, Pang H (2018) Hollow structural transition metal oxide for advanced supercapacitors. Adv Mater Interfaces 5(9):1701509. https://doi.org/10.1002/admi.201701509

    Article  CAS  Google Scholar 

  11. Liu W, Niu H, Yang J, Cheng K, Ye K, Zhu K, Wang G, Cao D, Yan J (2018) Ternary transition metal sulfides embedded in graphene nanosheets as both the anode and cathode for high-performance asymmetric supercapacitors. Chem Mater 30(3):1055–1068. https://doi.org/10.1021/acs.chemmater.7b04976

    Article  CAS  Google Scholar 

  12. Liu T, Zhang L, Cheng B, You W, Yu J (2018) Fabrication of a hierarchical NiO/C hollow sphere composite and its enhanced supercapacitor performance. Chem Commun 54(30):3731–3734. https://doi.org/10.1039/c8cc00991k

    Article  CAS  Google Scholar 

  13. Xing L, Dong Y, Hu F, Wu X, Umar A (2018) Co3O4 nanowire@NiO nanosheet arrays for high performance asymmetric supercapacitors. Dalton Trans 47(16):5687–5694. https://doi.org/10.1039/c8dt00750k

    Article  CAS  PubMed  Google Scholar 

  14. Sun J, Guo L, Sun X, Zhang J, Hou L, Li L, Yang S, Yuan C (2019) One-dimensional nanostructured pseudocapacitive materials: design, synthesis and applications in supercapacitors. Batteries Supercaps 2(10):820–841. https://doi.org/10.1002/batt.201900021

  15. Sun J, Wu C, Sun X, Hu H, Zhi C, Hou L, Yuan C (2017) Recent progresses in high-energy-density all pseudocapacitive-electrode-materials-based asymmetric supercapacitors. J Mater Chem A 5(20):9443–9464. https://doi.org/10.1039/c7ta00932a

    Article  CAS  Google Scholar 

  16. Saleki F, Mohammadi A, Moosavifard SE, Hafizi A, Rahimpour MR (2019) MOF assistance synthesis of nanoporous double-shelled CuCo2O4 hollow spheres for hybrid supercapacitors. J Colloid Interface Sci 556:83–91. https://doi.org/10.1016/j.jcis.2019.08.044

    Article  CAS  PubMed  Google Scholar 

  17. He W, Wang C, Li H, Deng X, Xu X, Zhai T (2017) Ultrathin and porous Ni3S2/CoNi2S4 3D-network structure for super high energy density asymmetric supercapacitors. Adv Energy Mater 7(21):1700983. https://doi.org/10.1002/aenm.201700983

    Article  CAS  Google Scholar 

  18. Tao K, Han X, Cheng Q, Yang Y, Yang Z, Ma Q, Han L (2018) A zinc cobalt sulfide nanosheet array derived from a 2D bimetallic metal-organic frameworks for high-performance supercapacitors. Chem Eur J 24(48):12584–12591. https://doi.org/10.1002/chem.201800960

    Article  CAS  PubMed  Google Scholar 

  19. Guo M, Balamurugan J, Tran TD, Kim NH, Lee JH (2016) Facile fabrication of Co2CuS4 nanoparticle anchored N-doped graphene for high-performance asymmetric supercapacitors. J Mater Chem A 4(44):17560–17571. https://doi.org/10.1039/C6TA07400F

    Article  CAS  Google Scholar 

  20. Zhang P, Guan B, Yu L, Lou XD (2017) Formation of double-shelled zinc-cobalt sulfide dodecahedral cages from bimetallic zeolitic imidazolate frameworks for hybrid supercapacitors. Angew Chem 56(25):7141–7145. https://doi.org/10.1002/anie.201702649

    Article  CAS  Google Scholar 

  21. Chen Q, Chen W, Ye J, Wang Z, Lee JY (2015) L-cysteine-assisted hydrothermal synthesis of nickel disulfide/graphene composite with enhanced electrochemical performance for reversible lithium storage. J Power Sources 294:51–58. https://doi.org/10.1016/j.jpowsour.2015.06.071

    Article  CAS  Google Scholar 

  22. Wan H, Ji X, Jiang J, Yu J, Miao L, Zhang L, Bie S, Chen H, Ruan Y (2013) Hydrothermal synthesis of cobalt sulfide nanotubes: the size control and its application in supercapacitors. J Power Sources 243:396–402. https://doi.org/10.1016/j.jpowsour.2013.06.027

    Article  CAS  Google Scholar 

  23. Kalimuldina G, Taniguchi I (2016) Synthesis and electrochemical characterization of stoichiometric Cu2S as cathode material with high rate capability for rechargeable lithium batteries. J Power Sources 331:258–266. https://doi.org/10.1016/j.jpowsour.2016.09.047

    Article  CAS  Google Scholar 

  24. Podili S, Geetha D, Ramesh PS (2017) One-pot synthesis of CTAB stabilized mesoporous cobalt doped CuS nano flower with enhanced pseudocapacitive behavior. J Mater Sci Mater Electron 28(20):15387–15397. https://doi.org/10.1007/s10854-017-7424-2

    Article  CAS  Google Scholar 

  25. Pujari RB, Lokhande AC, Kim JH, Lokhande CD (2016) Bath temperature controlled phase stability of hierarchical nanoflakes CoS2 thin films for supercapacitor application. RSC Adv 6(46):40593–40601. https://doi.org/10.1039/c6ra06442f

    Article  CAS  Google Scholar 

  26. Li M, Liang J, Chai Y, Li D, Lu J, Li L (2017) One-step synthesis of alpha-MnS nanosheets for supercapacitor electrode materials. Micro Nano Lett 12(10):735–737. https://doi.org/10.1049/mnl.2017.0157

  27. Xu B, Pan L, Zhu Q (2016) Synthesis of Co3S4 nanosheets and their superior supercapacitor property. J Mater Eng Perform 25(3):1117–1121. https://doi.org/10.1007/s11665-016-1955-1

    Article  CAS  Google Scholar 

  28. Ma G, Peng H, Mu J, Huang H, Zhou X, Lei Z (2013) In situ intercalative polymerization of pyrrole in graphene analogue of MoS2 as advanced electrode material in supercapacitor. J Power Sources 229:72–78. https://doi.org/10.1016/j.jpowsour.2012.11.088

    Article  CAS  Google Scholar 

  29. Peng S, Li L, Li C, Tan H, Cai R, Yu H, Mhaisalkar S, Srinivasan M, Ramakrishna S, Yan Q (2013) In situ growth of NiCo2S4 nanosheets on graphene for high-performance supercapacitors. Chem Commun 49(86):10178–10180. https://doi.org/10.1039/c3cc46034g

    Article  CAS  Google Scholar 

  30. Hou L, Shi Y, Wu C, Zhang Y, Ma Y, Sun X, Sun J, Zhang X, Yuan C (2018) Monodisperse metallic NiCoSe2 hollow sub-microspheres: formation process, intrinsic charge-storage mechanism, and appealing pseudocapacitance as highly conductive electrode for electrochemical supercapacitors. Adv Funct Mater 28(13):1705921. https://doi.org/10.1002/adfm.201705921

    Article  CAS  Google Scholar 

  31. Hou L, Shi Y, Zhu S, Rehan M, Pang G, Zhang X, Yuan C (2017) Hollow mesoporous hetero-NiCo2S4/Co9S8 submicro-spindles: unusual formation and excellent pseudocapacitance towards hybrid supercapacitors. J Mater Chem A 5(1):133–144. https://doi.org/10.1039/c6ta05788h

    Article  CAS  Google Scholar 

  32. Yu F, Chang Z, Yuan X, Wang F, Zhu Y, Fu L, Chen Y, Wang H, Wu Y, Li W (2018) Ultrathin NiCo2S4@graphene with a core–shell structure as a high performance positive electrode for hybrid supercapacitors. J Mater Chem A 6(14):5856–5861. https://doi.org/10.1039/c8ta00835c

    Article  CAS  Google Scholar 

  33. Pramanik A, Maiti S, Dhawa T, Sreemany M, Mahanty S (2018) High faradaic charge storage in ZnCo2S4 film on Ni-foam with a hetero-dimensional microstructure for hybrid supercapacitor. Mater Today Energy 9:416–427. https://doi.org/10.1016/j.mtener.2018.07.007

  34. Xu X, Song Y, Xue R, Zhou J, Gao J, Xing F (2016) Amorphous CoMoS4 for a valuable energy storage material candidate. Chem Eng J 301:266–275. https://doi.org/10.1016/j.cej.2016.05.033

    Article  CAS  Google Scholar 

  35. You H, Zhang L, Jiang Y, Shao T, Li M, Gong J (2018) Bubble-supported engineering of hierarchical CuCo2S4 hollow spheres for enhanced electrochemical performance. J Mater Chem A 6(13):5265–5270. https://doi.org/10.1039/c7ta07890k

    Article  CAS  Google Scholar 

  36. Zhu Y, Chen X, Zhou W, Xiang K, Hu W, Chen H (2017) Controllable preparation of highly uniform CuCo2S4 materials as battery electrode for energy storage with enhanced electrochemical performances. Electrochim Acta 249:64–71. https://doi.org/10.1016/j.electacta.2017.08.003

    Article  CAS  Google Scholar 

  37. Xu W, Lu J, Huo W, Li J, Wang X, Zhang C, Gu X, Hu C (2018) Direct growth of CuCo2S4 nanosheets on carbon fiber textile with enhanced electrochemical pseudocapacitive properties and electrocatalytic properties towards glucose oxidation. Nanoscale 10(29):14304–14313. https://doi.org/10.1039/c8nr04519d

    Article  CAS  PubMed  Google Scholar 

  38. Xie T, Gai Y, Shang Y, Ma C, Su L, Liu J, Gong L (2018) Self-supporting CuCo2S4 microspheres for high-performance flexible asymmetric solid-state supercapacitors. Eur J Inorg Chem 2018(43):4711–4719. https://doi.org/10.1002/ejic.201800676

    Article  CAS  Google Scholar 

  39. Li Y, Yin J, An L, Lu M, Sun K, Zhao Y, Cheng F, Xi P (2018) Metallic CuCo2S4 nanosheets of atomic thickness as efficient bifunctional electrocatalysts for portable, flexible Zn-air batteries. Nanoscale 10(14):6581–6588. https://doi.org/10.1039/C8NR01381K

    Article  CAS  PubMed  Google Scholar 

  40. Mohammadi A, Moosavifard SE, Goljanian Tabrizi A, Abdi MM, Karimi G (2018) Nanoporous CuCo2S4 microspheres: a novel positive electrode for high-performance hybrid energy storage devices. ACS Appl Energy Mater 2(1):627–635. https://doi.org/10.1021/acsaem.8b01651

    Article  CAS  Google Scholar 

  41. Jia H, Cai Y, Wang Z, Zheng X, Li C, Liang H, Qi J, Cao J, Feng J, Fei W (2019) Sea urchin-like CuCo2S4 microspheres with a controllable interior structure as advanced electrode materials for high-performance supercapacitors. Inorg Chem Front. https://doi.org/10.1039/C9QI01269A

  42. Wiltrout AM, Read CG, Spencer EM, Schaak RE (2016) Solution synthesis of thiospinel CuCo2S4 nanoparticles. Inorg Chem 55(1):221–226. https://doi.org/10.1021/acs.inorgchem.5b02158

    Article  CAS  PubMed  Google Scholar 

  43. Xu J, Hou K, Ju Z, Ma C, Wang W, Wang C, Cao J, Chen Z (2017) Synthesis and electrochemical properties of carbon dots/manganese dioxide (CQDs/MnO2) nanoflowers for supercapacitor applications. J Electrochem Soc 164(2):A430–A437. https://doi.org/10.1149/2.1241702jes

    Article  CAS  Google Scholar 

  44. Wei T, Chen C, Chien H, Lu S, Hu C (2010) A cost-effective supercapacitor material of ultrahigh specific capacitances: spinel nickel cobaltite aerogels from an epoxide-driven sol-gel process. Adv Mater 22(3):347–351. https://doi.org/10.1002/adma.200902175

    Article  CAS  PubMed  Google Scholar 

  45. Wei C, Huang Y, Xue S, Zhang X, Chen X, Yan J, Yao W (2017) One-step hydrothermal synthesis of flaky attached hollow-sphere structure NiCo2S4 for electrochemical capacitor application. Chem Eng J 317:873–881. https://doi.org/10.1016/j.cej.2017.02.130

    Article  CAS  Google Scholar 

  46. Guo SH, Yuan PW, Wang J, Chen WQ, Ma KY, Liu F, Cheng JP (2017) One-step synthesis of copper-cobalt carbonate hydroxide microsphere for electrochemical capacitors with superior stability. J Electroanal Chem 807:10–18. https://doi.org/10.1016/j.jelechem.2017.11.009

    Article  CAS  Google Scholar 

  47. Yang L, Xie L, Ren X, Wang Z, Liu Z, Du G, Asiri AM, Yao Y, Sun X (2018) Hierarchical CuCo2S4 nanoarrays for high-efficient and durable water oxidation electrocatalysis. Chem Commun 54(1):78–81. https://doi.org/10.1039/C7CC07259G

    Article  CAS  Google Scholar 

  48. Cheng S, Shi T, Chen C, Zhong Y, Huang Y, Tao X, Li J, Liao G, Tang Z (2017) Construction of porous CuCo2S4 nanorod arrays via anion exchange for high-performance asymmetric supercapacitor. Sci Rep 7(1):6681. https://doi.org/10.1038/s41598-017-07102-1

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  49. Yuan X, Tang B, Sui Y, Huang S, Qi J, Pu Y, Wei F, He Y, Meng Q, Cao P (2018) CuCo2S4 nanotubes on carbon fiber papers for high-performance all-solid-state asymmetric supercapacitors. J Mater Sci Mater Electron 29(10):8636–8648. https://doi.org/10.1007/s10854-018-8878-6

    Article  CAS  Google Scholar 

  50. Tang N, You H, Li M, Chen GZ, Zhang L (2018) Cross-linked Ni(OH)2/CuCo2S4/Ni networks as binder-free electrodes for high performance supercapatteries. Nanoscale 10(44):20526–20532. https://doi.org/10.1039/c8nr05662e

    Article  CAS  PubMed  Google Scholar 

  51. Li H, Li Z, Wu Z, Sun M, Han S, Cai C, Shen W, Liu X, Fu Y (2019) Enhanced electrochemical performance of CuCo2S4/carbon nanotubes composite as electrode material for supercapacitors. J Colloid Interface Sci 549:105–113. https://doi.org/10.1016/j.jcis.2019.04.056

    Article  CAS  PubMed  Google Scholar 

  52. Zhu J, Tang S, Wu J, Shi X, Zhu B, Meng X (2017) Wearable high-performance supercapacitors based on silver-sputtered textiles with FeCo2S4–NiCo2S4 composite nanotube-built multitripod architectures as advanced flexible electrodes. Adv Energy Mater 7(2):1601234. https://doi.org/10.1002/aenm.201601234

    Article  CAS  Google Scholar 

  53. Gao S, Liao F, Ma S, Zhu L, Shao M (2015) Network-like mesoporous NiCo2O4 grown on carbon cloth for high-performance pseudocapacitors. J Mater Chem A 3(32):16520–16527. https://doi.org/10.1039/c5ta02876k

    Article  CAS  Google Scholar 

  54. Moosavifard SE, Fani S, Rahmanian M (2016) Hierarchical CuCo2S4 hollow nanoneedle arrays as novel binder-free electrodes for high-performance asymmetric supercapacitors. Chem Commun 52(24):4517–4520. https://doi.org/10.1039/C6CC00215C

    Article  CAS  Google Scholar 

  55. Kong W, Lu C, Zhang W, Pu J, Wang Z (2015) Homogeneous core–shell NiCo2S4 nanostructures supported on nickel foam for supercapacitors. J Mater Chem A 3(23):12452–12460. https://doi.org/10.1039/C5TA02432C

    Article  CAS  Google Scholar 

  56. Zhu Y, Wu Z, Jing M, Yang X, Song W, Ji X (2015) Mesoporous NiCo2S4 nanoparticles as high-performance electrode materials for supercapacitors. J Power Sources 273:584–590. https://doi.org/10.1016/j.jpowsour.2014.09.144

    Article  CAS  Google Scholar 

  57. Wang Y, Yang D, Zhou T, Pan J, Wei T, Sun Y (2017) Oriented CuCo2S4 nanograss arrays/Ni foam as an electrode for a high-performance all-solid-state supercapacitor. Nanotechnology 28(46):465402. https://doi.org/10.1088/1361-6528/aa8d85

    Article  CAS  PubMed  Google Scholar 

  58. Kaverlavani SK, Moosavifard SE, Bakouei A (2017) Self-templated synthesis of uniform nanoporous CuCo2O4 double-shelled hollow microspheres for high-performance asymmetric supercapacitors. Chem Commun 53(6):1052–1055. https://doi.org/10.1039/C6CC08888K

    Article  CAS  Google Scholar 

  59. Jin C, Cui Y, Zhang G, Luo W, Liu Y, Sun Y, Tian Z, Zheng W (2018) Synthesis of copper-cobalt hybrid oxide microflowers as electrode material for supercapacitors. Chem Eng J 343:331–339. https://doi.org/10.1016/j.cej.2018.02.117

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the Natural Science Foundation of Shandong Province (ZR2017LB031).

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  1. College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, 266109, People’s Republic of China

    Tian Xie, Jinxiao Xu, Jie Wang, Chuangli Ma, Linghao Su, Fengying Dong & Liangyu Gong

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  1. Tian Xie
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Xie, T., Xu, J., Wang, J. et al. In situ preparation of flaky attached CuCo2S4 microspheres for high-performance asymmetric supercapacitors. Ionics 26, 3555–3563 (2020). https://doi.org/10.1007/s11581-020-03453-4

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