Abstract：Lithium-rich manganese-based materials have attracted much attention because of their high charge-discharge capacity. In order to solve the problems of low coulombic efficiency, poor cycling performance and poor rate capability, lithium-ion conductor Li2ZrO3 with three-dimensional Li+ channel was employed to coat lithium-rich manganese-based cathode material Li[Li0.2Ni0.2Mn0.6]O2. According to the structure and morphological analysis, different amounts of Li2ZrO3 were successfully coated on the surface of the sample. When the thickness of the coating layer is 3 nm (1% coating amount, mass fraction), the electrochemical performance of the composite material is significantly improved. The first discharge specific capacity is 271.5 mAh·g-1 and the first coulombic efficiency is 72.4%. The first irreversible capacity loss is obviously reduced. The discharge specific capacity at 0.5 C is 191.5 mAh·g-1 and the capacity retention is 89.5%. The specific capacity at 5 C is 75 mAh·g-1 and the rate performance is improved. The results show that a uniform thickness of Li2ZrO3 coating layer can form a core-shell structure on the surface of the sample to make the sample more stable. It can reduce surface side reactions and prevent the formation of thicker SEI films. All of these results benefit from the high conductivity, high electrochemical stability and good lithium ion conductivity of Li2ZrO3 coating layer.
蔺佳明, 赵桃林, 王育华. Li2ZrO3包覆锂离子电池正极材料Li[Li0.2Ni0.2Mn0.6]O2的制备及其电化学性能[J]. 材料工程, 2020, 48(3): 112-120.
LIN Jia-ming, ZHAO Tao-lin, WANG Yu-hua. Fabrication and electrochemical performance of Li[Li0.2Ni0.2Mn0.6]O2 coated with Li2ZrO3 as cathode material for lithium-ion batteries. Journal of Materials Engineering, 2020, 48(3): 112-120.
 CHIANG Y M. Building a better battery[J]. Science, 2010, 330(6010):1485-1486.
 YOSHINO A. The birth of the lithium-ion battery[J]. Angewandte Chemie International Edition,2012, 51:5798-5800.
 THACKERAY M M, WOLVERTON C, ISAACS E D. Electrical energy storage for transportation-approaching the limits of, and going beyond, lithium-ion batteries[J]. Energy & Environmental Science,2012, 5(7):7854-7863.
 KALLURI S, YOON M, JO M, et al. Surface engineering strategies of layered LiCoO2 cathode material to realize high-energy and high-voltage Li-ion cells[J]. Advanced Energy Materials,2016,7(1):1601507.
 SHAJU K M, BRUCE P G. A stoichiometric nano-LiMn2O4 spinel electrode exhibiting high power and stable cycling[J]. Chemistry Materials,2008, 20(17):5557-5562.
 DELMAS C, MACCARIO M, CROGUENNEC L, et al. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model[J]. Nature Materials,2008, 7(8):665-671.
 WU Y, CAO C, ZHU Y, et al. Cube-shaped hierarchical LiNi1/3Co1/3Mn1/3O2 with enhanced growth of nanocrystal planes as high-performance cathode materials for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2015, 3:15523-15528.
 XIE Y, SAUBANERE M, DOUBLET M L. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries[J]. Energy & Environmental Science,2017, 10(1):266-274.
 MANTHIRAM A, KNIGHT J C, et al. Nickel-rich and lithium-rich layered oxide cathodes:progress and perspectives[J]. Advanced Energy Materials,2015,6(1):1501010.
 ZHENG J, MYEONG S, CHO W, et al. Li-and Mn-rich cathode materials:challenges to commercialization[J]. Advanced Energy Materials,2016,7(6):1601284.
 YAN J, LIU X, LI B. Recent progress in Li-rich layered oxides as cathode materials for Li-ion batteries[J]. RSC Advanced, 2014, 4(108):63268-63284.
 ARMSTRONG A R, HOLZAPFEL M, NOVAK P, et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2[J]. Journal of the American Chemical Society,2006, 128(26):8694-8698.
 SATHIYA M, ABAKUMOV A M, FOIX D, et al. Origin of voltage decay in high-capacity layered oxide electrodes[J]. Nature Materials,2015, 14(2):230-238.
 ZHANG J, ZHANG H, GAO R, et al. New insights into the modification mechanism of Li-rich Li1.2Mn0.6Ni0.2O2 coated by Li2ZrO3[J]. Physical Chemistry Chemical Physics, 2016, 18(19):13322.
 SONG L, JIAO L, XIAO Z, et al. Thermoeletrochemical study on LiNi0.8Co0.1Mn0.1O2 with in situ modification of Li2ZrO3[J]. Ionics, 2018(1):1-11.
 HU G, ZHANG M, WU L, et al. Enhanced electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathodes produced via nanoscale coating of Li+-conductive Li2SnO3[J]. Electrochimica Acta, 2016, 213:547-556.
 MO Y, HOU B, LI D, et al. Enhanced high-rate capability and high voltage cycleability of Li2TiO3-coated LiNi0.5Co0.2Mn0.3O2 cathode materials[J]. RSC Advanced, 2016,6(91):88713-88718.
 KANG S H, THACKERAY M M. Enhancing the rate capability of high capacity xLi2MnO3·(1-x)LiMO2(M=Mn, Ni, Co) electrodes by Li-Ni-PO4 treatment[J]. Electrochemistry Communications,2009, 11(14):748-751.
 QIAO Q Q, ZHANG H Z, LI G R, et al. Surface modification of Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide with Li-Mn-PO4 as the cathode for lithium-ion batteries[J]. Journal of Materials Chemistry:A,2013, 1(17):5262-5268.
 苏银利,王丹,陈丽,等. ZrO2包覆富锂正极材料Li[Li0.2Ni0.2Mn0.6]O2[J]. 化学工业与工程, 2015, 32(4):30-33. SU Y L, WANG D, CHEN L, et al. ZrO2 coated Li rich cathode material Li[Li0.2Ni0.2Mn0.6]O2[J].Chemical Industry and Engineering, 2015, 32(4):30-33.
 SUN Y K, LEE M J, YOON C S, et al.The role of AlF3 coatings in improving electrochemical cycling of Li-enriched nickel-manganese oxide electrodes for Li-ion batteries[J]. Advanced Materials, 2012, 24(9):1192-1196.
 岳鹏. 锂离子电池用富锂锰基正极材料的研究进展[J]. 山东化工, 2016, 45(18):35-37. YUE P. Research progress of lithium rich manganese based cathode materials for lithium ion batteries[J]. Shandong Chemical Industry, 2016, 45(18):35-37.
 LIANG H, WANG Z, GUO H, et al. Improvement in the electrochemical performance of LiNi0.8Co0.1Mn0.1O2 cathode material by Li2ZrO3 coating[J]. Applied Surface Science, 2017, 423:1045-1053.
 ZHANG S, GU H, TIAN T, et al. Insight into the synergistic effect mechanism between the Li2MO3 phase and the LiMO2 phase (M=Ni, Co, and Mn) in Li- and Mn-rich layered oxide cathode materials[J]. Electrochimica Acta, 2018, 266:66-77.