1 College of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China 2 Research Center of Metallurgical Electrode Materials Engineering Technology,Kunming 650106, China 3 Kunming Hendera Science and Technology Co., Ltd., Kunming 650106, China
Abstract: Lithium-ion batteries have the advantages of high energy density, long cycle life, low self-discharge rate, and low environmental pollution, which have become the typical electrochemical energy storage batteries with the largest proportion of energy equipment. As the main supp-lier of Li+ in lithium-ion batteries, the research and development of cathode materials has always attracted widespread attention of scientific and technological workers. Lithium-rich manganese-based cathode materials possess the merits of high specific capacity, high voltage, and excellent high-temperature performance, and are considered to be potential cathode materials. However, lithium-rich manganese-based cathode materials commonly suffer from the stability problems. For example, the lithium-nickel mixing during the charge and discharge cycle of the lithium-manganese-rich materials leads to the collapse of the layered structure and affects the mate-rial performance, further obstructing the application of such cathode materials. Therefore, a large number of modification approaches have been performed on lithium-rich manganese-based cathode materials in recent years, and excellent results have been achieved. In all modification met-hods, the ion doping modification has been regarded an excellent choice in the modification methods. Commonly, the ion doping approaches mainly contain cation doping, anion doping, polyanion doping and co-doping. Cation doping is the most common doping option at this stage. It is mainly doped at the transition metal position, and a small part is doped with Li site. Cation doping can inhibit the migration of excessive metal ions to the lithium layer, slow the spinel phase formation, and increase the structural stability of lithium manganese-based cathode materials. Anion doping mainly compensates and replaces the oxygen vacancies formed during the charging process. This method can suppress the formation of oxygen vacancies, improve the safety and the coulomb efficiency of the cathode electrode material. Polyanion doping is similar to anion doping, and is also doped at the oxygen position of the cathode electrode material. As the strong binding energy of the polyanion and the transition metals, the migration of the transition metals is suppressed, resulting into the stable layered structure and significantly improved electrochemical performances. Co-doping is the simultaneous doping of cations and anions into the cathode electrode material. This method combines the synergistic effect of the cations and cations simultaneously, which can stabilize the layered structure, significantly improve its stability, and improve the cycling ability of the battery. This article summarizes the structural composition, reaction mechanism, and intrinsic defects of lithium-rich manganese-based cathode mate-rials. We emphatically focus on the doping methods of cation doping, anion doping, polyanion doping, and co-doping and analyze their effects on the material properties. Besides, the existing problems of the doping modification at this stage are also elaborated, and future research directions are prospected in order to provide a reference for the preparation of stable and high-performance lithium-manganese-based cathode materials.
1 Goodenough J B, Kim Y, et al. Chemistry of Materials, 2009, 22(3), 587. 2 Qiu B, Zhang M, Wu L, et al. Nature Communications, 2016, 7, 12108. 3 Gao X P, Yang H X. Energy & Environmental Science, 2010, 3(2), 174. 4 Goodenough J B, Park K S. Journal of the American Chemical Society, 2013, 135(4), 1167. 5 Su L, Jing Y, Zhou Z,et al. Nanoscale, 2011, 3(10), 3967. 6 Hu L, Freeland J W, Cabana J,et al. ACS Applied Energy Materials, 2019, 2(3), 2149. 7 Yang H, Yang J, Savory C N, et al. The Journal of Physical Chemistry Letters, 2019, 10(18), 5552. 8 Wu X, Li Y, Li C, et al. Journal of Power Sources, 2015, 300, 453. 9 Liu S, Fang H, Dai E, et al. Electrochimica Acta, 2014, 116, 97. 10 Thackeray M M, Kang S H, Johnson C S, et al. Journal of Materials Chemistry, 2007, 17(30), 3112. 11 Kang S H, Kempgens P, Greenbaum S, et al. Journal of Materials Chemistry, 2007, 17(20), 2069. 12 Jarvis K A, Deng Z, Allard L F, et al. Chemistry of Materials, 2011, 23(16), 3614. 13 Yu H, Ishikawa R, So Y G, et al. Angewandte Chemie International Edition, 2013, 52(23), 5969. 14 Zheng J, Myeong S, Cho W, et al. Advanced Energy Materials, 2017, 7(6), 1601284. 15 Luo D, Li G, Fu C, et al. Advanced Energy Materials, 2014, 4(11), 1400062. 16 Gu M, Belharouak I, Zheng J, et al. ACS Nano, 2012, 7(1), 760. 17 Sathiya M, Abakumov A M, Foix D, et al. Nature Materials, 2015, 14,230. 18 Zhou L Z,Xu J J,Tang W P,et al.Journal of Electrochemistry, 2015, 21(2), 138. 周罗增, 徐群杰, 汤卫平.电化学, 2015, 21(2), 138. 19 Dogan F, Long B R, Croy J R, et al. Journal of the American Chemical Society, 2015, 137(6), 2328. 20 Pechen L S, Makhonina E V, Rumyantsev A M, et al. Russian Chemical Bulletin, 2019, 68(2), 293. 21 Mohanty D, Kalnaus S, Meisner R A, et al. Journal of Power Sources, 2013, 229,239. 22 Liu Y, Ning D, Zheng L, et al. Journal of Power Sources, 2018, 375,1. 23 Xie D, Zhou W, Lin K, et al. Materials Letters, 2019, 253, 82. 24 Zhang X, Xiong Y, Dong M, et al. Journal of the Electrochemical Society, 2019, 166(13), A2960. 25 Cho S W, Kim G O, Ryu K S, et al. Solid State Ionics, 2012, 206, 84. 26 Choi A, Lim J, Kim H J, et al. Advanced Energy Materials, 2018, 8(11), 1702514. 27 Xu X X, Yang J, Wang Y Q, et al. Journal of Power Sources, 2007, 174(2), 1113. 28 Qin M, Cao K, Wang X, et al. Ionics, 2013, 19(12),1891. 29 Zhou Z X, Ma Y L, Wang L, et al. Electrochimica Acta, 2016, 216, 44. 30 Bao L, Yang Z, Chen L, et al. ChemSusChem, 2019, 12(10), 2294. 31 Li W. Preparation and doping modification of LiNi1/3Co1/3Mn1/3O2 cat-hode materials for Li-ion batteries. Master's Thesis, Inner Mongolia University of Technology, China, 2015(in Chinese). 李伟. 锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的制备及掺杂改性研究. 硕士学位论文, 内蒙古工业大学,2015. 32 Konishi H, Gunji A, Feng X, et al. Journal of Solid State Chemistry, 2017, 249,80. 33 Hu X, Guo H, Peng W, et al. Journal of Electroanalytical Chemistry, 2018, 822, 57. 34 Zhao L, Wu Q, Wu J, et al. Journal of Solid State Electrochemistry, 2018, 22(7), 2141. 35 Zhao J, Wang Z, Guo H, et al. Ceramics International, 2015, 41(9), 11396. 36 Choi A, Lim J, Kim H, et al. ACS Applied Energy Materials, 2019, 2(5), 3427. 37 Yu R, Wang G, Liu M, et al. Journal of Power Sources, 2016, 335, 65. 38 Pan L, Xia Y, Qiu B, et al. Journal of Power Sources, 2016, 327, 273. 39 Sun Z, Xu L, Dong C, et al. Journal of Materials Chemistry A, 2019, 7(7), 3375. 40 Li N, An R, Su Y, et al. Journal of Materials Chemistry A, 2013, 1(34), 9760. 41 Yi T F, Xie Y, Ye M F, et al. Ionics, 2011, 17(5), 383. 42 Song J H, Kapylou A, Choi H S, et al. Journal of Power Sources, 2016, 313, 65. 43 Li L, Song B H, Chang Y L, et al. Journal of Power Sources, 2015, 283, 162. 44 Liu T, Zhao S X, Gou L L, et al. Rare Metals, 2019, 38(3), 189. 45 Kapylou A, Song J H, Missiul A, et al. ChemPhysChem, 2018, 19(1), 116. 46 Sun Y K, Oh S W, Yoon C S, et al. Journal of Power Sources, 2006, 161(1), 19. 47 An J, Shi L, Chen G, et al. Journal of Materials Chemistry A, 2017, 5(37), 19738. 48 Gong Z, Yang Y, et al. Energy & Environmental Science, 2011, 4(9), 3223. 49 Zhang H Z, Qiao Q Q, Li G R, et al. Journal of Materials Chemistry A, 2014, 2(20), 7454. 50 Liu J, Wang S, Ding Z, et al. ACS Applied Materials & Interfaces, 2016, 8(28), 18008. 51 Ma L, Mao L, Zhao X, et al. ChemElectroChem, 2017, 4(12), 3068. 52 Li B,Yan H,Ma J,Yu P,Xia D,Huang W, et al. Advanced Functional Materials,2014,24( 32), 5112. 53 Choi J, Manthiram A, et al. Journal of The Electrochemical Society, 2005, 152(9), A1714. 54 Cong L, Zhao Q, Wang Z, et al. Electrochimica Acta, 2016, 201, 8. 55 Zhang H Z, Li F, Pan G L, et al. Journal of The Electrochemical Society, 2015, 162(9), A1899. 56 Cao H, Xia B, Xu N, et al. Journal of Alloys and Compounds, 2004, 376(1-2), 282. 57 Ming L, Zhang B, Cao Y, et al. Frontiers in Chemistry, 2018, 6, 76. 58 Xie D, Li G, Li Q, et al. Electrochimica Acta, 2016, 196, 505. 59 Lim S N, Seo J Y, Jung D S, et al. Journal of Electroanalytical Chemistry, 2015, 740, 88. 60 Liao L, Wang X, Luo X, et al. Journal of Power Sources, 2006, 160(1), 657.