Hierarchical hollow microcuboid LiNi0.5Mn1.5O4 as cathode material with excellent rate and cycling performance for lithium-ion batteries

  • Tao PengEmail author
  • Wei Guo
  • Chang Liu
  • Yingge Zhang
  • Yangbo Wang
  • Yan Guo
  • Deyang Zhang
  • Hailong Yan
  • Yang Lu
  • Yongsong LuoEmail author
Original Paper


The rational design of the structure is the key to engineering spinel LiNi0.5Mn1.5O4 cathode material to enhance Li+/electron transport and relieve the structural damage during the reduplicative Li+ intercalation/deintercalation, which is closely to the rate and cycling performance. Here, we report hollow microcuboid LiNi0.5Mn1.5O4 composed of interconnected nanoparticles which can simultaneously achieve the easy Li+ diffusion and high structure robustness. The hollow microcuboid has been fabricated by a facile solvothermal reaction followed by a lithiation process. It is found that the morphology and the size can be easily controlled, which depends on the initial nucleation process. The obtained hollow microcuboid LiNi0.5Mn1.5O4 presents excellent rate and cycling performance. It delivers a capacity of 125 mAh g−1 at the discharge rate of 1 C. Even at a high discharge rate of 30 C, the capacity of 109 mAh g−1 and a discharge capacity retention of 94.4% after 900 cycles can be achieved. The excellent performance should be ascribed to its intrinsic hierarchical hollow structure, which not only benefits the diffusion of Li+ but also provides pore spaces to relieve the volume expansion during the high rate charge/discharge process. The result suggests the potential application of hollow microcuboid LiNi0.5Mn1.5O4 cathode material for high-rate and long-life Li ion batteries.


Lithium-ion batteries Cathode LiNi0.5Mn1.5O4 Hollow microcuboid 


Funding information

This work was supported by the National Natural Science Foundation of China (No. 61704146, 51502257, 61874093, and 61574122), and Zhongyuan Thousand Talents Plan -Science & Technology Innovation Leading Talents Project (No. 194200510009). This work was also supported by the Nanhu Scholars Program for Young Scholars of Xinyang Normal University.

Supplementary material

10008_2019_4396_MOESM1_ESM.doc (8.6 mb)
ESM 1 (DOC 8805 kb)


  1. 1.
    Han X, Gui X, Yi T-F, Li Y, Yue C (2018) Recent progress of NiCo2O4-based anodes for high-performance lithium-ion batteries. Curr Opin Solid State Mater Sci 22(4):109–126CrossRefGoogle Scholar
  2. 2.
    Yi T-F, Zhu Y-R, Tao W, Luo S, Xie Y, Li X-F (2018) Recent advances in the research of MLi2Ti6O14 (M=2Na, Sr, Ba, Pb) anode materials for Li-ion batteries. J Power Sources 399:26–41CrossRefGoogle Scholar
  3. 3.
    Luo YS, Luo RJ, Jiang J, Zhou WW, Yang HP, Qi XY, Zhang H, Fan HJ, Denis YWY, Li CM (2012) Seed-assisted synthesis of highly ordered TiO2@α-Fe2O3 core/shell arrays on carbon textiles for lithium-ion battery applications. Energy Environ Sci 5(4):6559–6566CrossRefGoogle Scholar
  4. 4.
    Sun WW, Li YJ, Liu YM, Guo QP, Luo SQ, Yang JG, Zheng CM, Xie K (2018) Hierarchical waxberry-like LiNi0.5Mn1.5O4 as an advanced cathode material for lithium-ion batteries with a superior rate capability and long-term cyclability. J Mater Chem A 6(29):14155–14161CrossRefGoogle Scholar
  5. 5.
    Peng T, Liu C, Hou XY, Zhang ZW, Wang CL, Yan HL, Lu Y, Liu XM, Luo YS (2017) Control growth of mesoporous nickel tungstate nanofiber and its application as anode material for lithium-ion batteries. Electrochim Acta 224:460–467CrossRefGoogle Scholar
  6. 6.
    Zhang Q, Sun C, Fan L, Zhang N, Sun K (2019) Iron fluoride vertical nanosheets array modified with graphene quantum dots as long-life cathode for lithium ion batteries. Chem Eng J 371:245–251CrossRefGoogle Scholar
  7. 7.
    Peng T, Guo W, Zhang Q, Zhang YG, Chen M, Wang YH, Yan HL, Lu Y, Luo YS (2018) Uniform coaxial CNT@Li2MnSiO4@C as advanced cathode material for lithium-ion battery. Electrochim Acta 291:1–8CrossRefGoogle Scholar
  8. 8.
    Ma Y, Wang L, Zuo X, Nan J (2018) Co-precipitation spray-drying synthesis and electrochemical performance of stabilized Li Ni0.5Mn1.5O4 cathode materials. J Solid State Electrochem 22(7):1963–1969CrossRefGoogle Scholar
  9. 9.
    Mou J, Wu H, Deng Y, Zhou L, Zheng Q, Liao J, Lin D (2017) BiFeO3-coated spinel LiNi0.5Mn1.5O4 with improved electrochemical performance as cathode materials for lithium-ion batteries. J Solid State Electrochem 21(10):2849–2858CrossRefGoogle Scholar
  10. 10.
    Xu R, Zhang XF, Chamoun R, Shui JL, .Li JCM, Lu J, Amine K, Belharouak L (2015) Enhanced rate performance of LiNi0.5Mn1.5O4 fibers synthesized by electrospinning. Nano Energy 15:616–624CrossRefGoogle Scholar
  11. 11.
    Deng M-M, Zou B-K, Shao Y, Tang Z-F, Chen C-H (2017) Comparative study of the electrochemical properties of LiNi0.5Mn1.5O4 doped by bivalent ions (Cu2+, Mg2+, and Zn2+). J Solid State Electrochem 21(6):1733–1742CrossRefGoogle Scholar
  12. 12.
    Jiao C, Meng T, Lu H, Zuo Y, Zhi X, Liang G (2017) Improvement of the electrochemical properties of a LiNi0.5Mn1.5O4 cathode material formed by a new solid-state synthesis method. J Solid State Electrochem 21(2):495–501CrossRefGoogle Scholar
  13. 13.
    Ma G, Zhang Y, Lin J, Chen Z, Zhao R, Tong P, Zou L, Chen H (2015) Synthesis of high-voltage spinel LiNi0.5Mn1.5O4 material for lithium-ion batteries by a metal-cholate supramolecular hydrogel as precursor. J Solid State Electrochem 19(11):3365–3372CrossRefGoogle Scholar
  14. 14.
    Myung ST, Komaba S, Kumagai N, Yashiro H, Chung HT, Cho TH (2002) Nano-crystalline LiNi0.5Mn1.5O4 synthesized by emulsion drying method. Electrochim Acta 47(15):2543–2549CrossRefGoogle Scholar
  15. 15.
    Xiao BW, Liu HS, Liu J, Sun Q, Wang BQ, Kaliyappan K, Zhao Y, Banis MN, Liu YL, Li RY, Sham TK, Botton GA, Cai M, Sun XL (2017) Nanoscale manipulation of spinel lithium nickel manganese oxide surface by multisite Ti occupation as high-performance cathode. Adv Mater 29(47):1703764CrossRefGoogle Scholar
  16. 16.
    Tang LK, He YB, Wang C, Wang S, Wagemaker M, Li BH, Yang QH, Kang FY (2017) High-density microporous Li4Ti5O12 microbars with superior rate performance for lithium-ion batteries. Adv Sci 4:1600311CrossRefGoogle Scholar
  17. 17.
    Fan L, Wu H, Wu X, Wang M, Cheng J, Zhang N, Feng Y, Sun K (2019) Fe-MOF derived jujube pit like Fe3O4/C composite as sulfur host for lithium-sulfur battery. Electrochim Acta 295:444–451CrossRefGoogle Scholar
  18. 18.
    Zhang Y, Wang P, Yin Y, Zhang X, Fan L, Zhang N, Sun K (2019) Heterostructured SnS-ZnS@C hollow nanoboxed embedded in graphene for high performance lithium and sodium ion batteries. Chem Eng J 356:1042–1051CrossRefGoogle Scholar
  19. 19.
    Zhang KL, Li XN, Liang JW, Zhu YC, Hu L, Cheng QS, Guo C, Lin N, Qian YT (2015) Nitrogen-doped porous interconnected double-shelled hollow carbon spheres with high capacity for lithium ion batteries and sodium ion batteries. Electrochim Acta 155:174–182CrossRefGoogle Scholar
  20. 20.
    Cho JS, Hong YJ, Lee JH, Kang YC (2015) Design and synthesis of micron-sized spherical aggregates composed of hollow Fe2O3 nanospheres for use in lithium-ion batteries. Nanoscale 7(18):8361–8367CrossRefGoogle Scholar
  21. 21.
    Park DG, Kim JH, Kang YC (2018) Lithium-ion storage performances of sunflower-like and nano-sized hollow SnO2 spheres by spray pyrolysis and the nanoscale Kirkendall effect. Nanoscale 10(28):13531–13538CrossRefGoogle Scholar
  22. 22.
    Wang L, Liu GJ, Wu W, Chen D, Liang GC (2015) Synthesis of porous peanut-like LiNi0.5Mn1.5O4 cathode materials through an ethylene glycol-assisted hydrothermal method using urea as a precipitant. J Mater Chem A 3(38):19497–19506CrossRefGoogle Scholar
  23. 23.
    Kim JH, Myung ST, Yoon SC, Kang SG, Sun YK (2004) Comparative study of LiNi0.5Mn1.5O4-δ and LiNi0.5Mn1.5O4 cathodes having two crystallographic structures: Fd3̄m and P4332. Chem Mater 16(5):906–914CrossRefGoogle Scholar
  24. 24.
    Liu HD, Wang J, Zhang XF, Zhou D, Qi X, Qiu B, Fang JH, Kloepsch R, Schumacher G, Liu ZP, Li J (2016) Morphological evolution of high-voltage spinel LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries: the critical effects of surface orientations and particle size. ACS Appl Mater Interfaces 8(7):4661–4675CrossRefGoogle Scholar
  25. 25.
    Yang SF, Chen J, Liu YJ, Yi BL (2014) Preparing LiNi0.5Mn1.5O4 nanoplates with superior properties in lithium-ion batteries using bimetal–organic coordination-polymers as precursors. J Mater Chem A 2(24):9322–9330CrossRefGoogle Scholar
  26. 26.
    Hao XG, Austin MH, Bartlett MB (2012) Two-step hydrothermal synthesis of submicron Li1+xNi0.5Mn1.5O4−δ for lithium-ion battery cathodes (x = 0.02, δ = 0.12). Dalton Trans 41(26):8067–8076CrossRefGoogle Scholar
  27. 27.
    Li L, Sui JS, Chen J, Lu YC (2019) LiNi0.5Mn1.5O4 microrod with ultrahigh Mn3+ content: a high performance cathode material for lithium ion battery. Electrochim Acta 305:433–442CrossRefGoogle Scholar
  28. 28.
    Wang HL, Tan TA, Yang P, Lai MO, Lu L (2011) High-rate performances of the Ru-doped spinel LiNi0.5Mn1.5O4: effects of doping and particle size. J Phys Chem C 115(13):6102–6110CrossRefGoogle Scholar
  29. 29.
    Chong J, Xun SD, Song XY, Liu G, Battaglia VS (2013) Surface stabilized LiNi0.5Mn1.5O4 cathode materials with high-rate capability and long cycle life for lithium ion batteries. Nano Energy 2(2):283–293CrossRefGoogle Scholar
  30. 30.
    Li L, Zhao R, Xu TH, Wang DD, Pan D, Lu X, He GJ, Zhang K, Yu CY, Bai Y (2019) Stabilizing a high-voltage LiNi0.5Mn1.5O4 cathode towards all solid state batteries: a Li–Al–Ti–P–O solid electrolyte nano-shell with a host material. Nanoscale 11(18):8967–8977CrossRefGoogle Scholar
  31. 31.
    Yin CJ, Zhou HM, Yang ZH, Li J (2018) Synthesis and electrochemical properties of LiNi0.5Mn1.5O4 for Li-ion batteries by the metal–organic framework method. ACS Appl Mater Interfaces 10(16):13625–13634CrossRefGoogle Scholar
  32. 32.
    Liu SK, Xu J, Li DZ, Hu Y, Liu X, Xie K (2013) High capacity Li2MnSiO4/C nanocomposite prepared by sol–gel method for lithium-ion batteries. J Power Sources 232:258–263CrossRefGoogle Scholar
  33. 33.
    Liu GY, Kong X, Sun HY, Wang BS, Yi ZZ, Wang QB (2014) A facile template method to synthesize significantly improved LiNi0.5Mn1.5O4 using corn stalk as a bio-template. Electrochim Acta 141:141–148CrossRefGoogle Scholar
  34. 34.
    Zhang XL, Cheng FY, Yang JG, Chen J (2013) LiNi0.5Mn1.5O4 porous nanorods as high-rate and long-life cathodes for Li-ion batteries. Nano Lett 13(6):2822–2825CrossRefGoogle Scholar
  35. 35.
    Xue Y, Wang ZB, Yu FD, Zhang Y, Yin GP (2014) Ethanol-assisted hydrothermal synthesis of LiNi0.5Mn1.5O4 with excellent long-term cyclability at high rate for lithium-ion batteries. J Mater Chem A 2(12):4185–4191CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Physics and Electronic EngineeringXinyang Normal UniversityXinyangPeople’s Republic of China
  2. 2.Key Laboratory of Microelectronics and Energy of Henan Province, Henan Joint International Research Laboratory of New Energy Storage TechnologyXinyang Normal UniversityXinyangPeople’s Republic of China
  3. 3.School of Physics and ElectronicsHunan UniversityChangshaPeople’s Republic of China

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