高镍三元正极材料表面碱性物质研究进展

doi:10.19964/j.issn.1006-4990.2021-0046

摘要/Abstract

摘要：

高镍三元正极材料表面形成的碱性物质容易导致电池容量衰减加快、寿命缩短,因而调控三元材料表面碱性物质对于提高锂离子二次电池的功能和安全性至关重要。综述了高镍锂离子电池三元正极材料表面碱性物质的形成机理及处理手段,从不同角度阐述了环境中的水、二氧化碳对表面碱性物质形成的影响。探讨了表面碱性物质形成过程中,由于锂离子和过渡金属的迁移与固化引发的表面结构的相变现象,造成了三元正极材料的加工储存性能的恶化。还对降碱工艺中的洗涤、干燥、低温烧结等过程进行了重点说明,阐述了洗涤工艺对三元材料表面碱性物质降低及对材料性质的影响,指出需选择合适的洗涤、干燥条件,减小材料表面发生的变异。最后结合目前降碱工艺对后续研究方向提出了建议。

关键词: 高镍正极材料, 锂离子电池, 碳酸锂, 水洗

Abstract:

Alkaline substance is prone to form on the surface of nickel-rich ternary cathode materials,which accelerate the capacity fade and short the life of lithium-ion batteries.Therefore,it is vital to control the content of the lithium hydroxide and lithium carbonate on the surface of the nickel-rich cathode material for improving the performance and safety of batteries.The formation mechanism and the treatment of the lithium hydroxide and lithium carbonate on the surface of the Nickel-rich cathode materials were summarized.The effect of H₂O and CO₂ in the environment on the formation of the lithium hydroxide and lithium carbonate was discussed from different perspectives.The phase transformation of surface structure caused by the migration and solidification of Li⁺ and transition metals during the formation of alkaline materials on surface was discussed,wich led to the deterioration of the processing and storage properties of ternary cathode materials.Washing,drying,low tempera-ture sintering and the other “alkali-reducing” processes were also emphasized,it explained the effect of the washing process on the reduction of alkaline substances on the surface of the ternary material and the effect on the material properties.It was poin-ted out that it was necessary to choose appropriate washing and drying conditions to reduce the variation of the material surface.Finally,combined with the current alkali reduction process,suggestions on the follow-up research direction were put forward.

Key words: nickel-rich cathode material, lithium ion battery, lithium carbonate, washing

中图分类号:

TQ131.11

胡悦,徐乐乐,周彦方,徐哲,田守帅,廖凡,杨小俊. 高镍三元正极材料表面碱性物质研究进展[J]. 无机盐工业, 2021, 53(12): 74-79.

HU Yue,XU Lele,ZHOU Yanfang,XU Zhe,TIAN Shoushuai,LIAO Fan,YANG Xiaojun. Research progress on alkaline substance on surface of nickel-rich ternary cathode materials[J]. Inorganic Chemicals Industry, 2021, 53(12): 74-79.

图/表 4

参考文献 43

[1]	OHZUKU T, MAKIMURA Y. Layered lithium insertion matterial of LiCo_1/3Ni_1/3Mn_1/3O₂ for lithium-ion batterie[J]. Chemistry Letters, 2001, 30(7):642-643.
[2]	MANTHIRAM A, SONG B, LI W. A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries[J]. Energy Storage Materials, 2012, 6:125-139.
[3]	DING Y, MU D, WU B, et al. Recent progresses on nickel-rich layered oxide positive electrode materials used in lithium-ion batteries for electric vehicles[J]. Applied Energy, 2017, 195:586-599.
[4]	NOG H J, YOUN S, YOON C S, et al. Comparison of the structural and electrochemical properties of layered Li[Ni_xCo_yMn_z]O₂ (x=1/3,0.5, 0.6,0.7,0.8 and 0.85) cathode material for lithium-ion batteries[J]. Journal of Power Sources, 2013, 233:121-130.
[5]	LIU W, OH P, LIU X, et al. Nickel-rich layered lithium transition-me- tal oxide for high-energy lithium-ion batteries[J]. Angewandte Che- mie International Edition, 2015, 54(15):4440-4457.
[6]	ZHENG Jianming, KAN W H, MANTHIRAM A. Role of Mn content onthe electrochemical properties of nickel-rich layered LiNi_0.8-_xCo_0.1Mn_0.1+_xO₂(0.0≤x≤0.08) cathodes for lithium-ion ba- tteries[J]. ACS Applied Materials & Interfaces, 2015, 7(12):6926-6934.
[7]	BADOT J C, BIANCHI V, BAFFIER N, et al. Dielectric and conductivi- ty spectroscopy of Li_1-_xNi₁₊_xO₂ in the range of 10-10¹⁰ Hz：Polaron ho- pping[J]. Journal of Physics:Condensed Matter, 2002, 14(28):6917-6930.
[8]	ANDERSSON A M, ABRAHAM D P, HAASCH R, et al. Surface cha- racterization of electrodes from high power lithium-ion batteries[J]. Journal of the Electrochemical Society, 2002, 149(10A):1358-1369.
[9]	AURBACH D, GAMOLSKY K, MARKOVSKY B, et al. The study of surface phenomena related to electrochemical lithium intercalation into Li_xMO_y host materials(M=Ni,Mn)[J]. Journal of the Electro- chemical Society, 2000, 147(4):1322-1331.
[10]	BEYER H, MEINI S, TSIOUVARAS N, et al. Thermal and electro- chemical decomposition of lithium peroxide in non-catalyzed car- bon cathodes for Li-air batteries[J]. Physical Chemistry Chemical Physics, 2013, 15(26):11025-11037.
[11]	LIU H, YANG Y, ZHANG J. Investigation and improvement on the storage property of LiNi_0.8Co_0.2O₂ as a cathode material for lithium- ion batteries[J]. Journal of Power Sources, 2006, 162(1):644-650.
[12]	FAENZA N V, BRUCE L, LEBENS-HIGGINS Z W, et al. Editors′ choice-growth of ambient induced surface impurity species on la- yered positive electrode materials and impact on electrochemical performance[J]. Journal of the Electrochemical Society, 2017, 164(14):A3727-A3741.
[13]	MATSUMOTO K, KUZUO R, TAKEYA K, et al. Effects of CO₂ in air on Li deintercalation from LiNi₁-_x-_yCo_xAl_yO₂[J]. Journal of Power Sources, 1999, 81-82:558-561.
[14]	ZHANG X, JIANG W J, ZHU X P, et al. Aging of LiNi_1/3Mn_1/3Co_1/3O₂ cathode material upon exposure to H₂O[J]. Journal of Power Sour- ces, 2011, 196(11):5102-5108.
[15]	SICKLINGER J, METZGER M, BEYER H, et al. Ambient storage derived surface contamination of NCM811 and NCM111:Perfor- mance implications and mitigation strategies[J]. Journal of the El- ectrochemical Society, 2019, 166(12):A2322-A2335.
[16]	SHKROB I A, GILBERT J A, PHILLIPS P J, et al. Chemical wea- thering of layered Ni-rich oxide electrode materials:Evidence for cation exchange[J]. Journal of the Electrochemical Society, 2017, 164(7):A1489-A1498.
[17]	MOSHTEV R, ZLATILOVA P, VASILEV S, et al. Synjournal,XRD characterization and electrochemical performance of overlithiated LiNiO₂[J]. Journal of Power Sources, 1999, 81(81):434-441.
[18]	VAN DER VEN A, MORGAN D, MENG Y S, et al. Phase stability of nickel hydroxides and oxyhydroxides[J]. Journal of the Electroche- mical Society, 2006, 153(2):A210-A215.
[19]	LIU W, HU G, DU K, et al. Enhanced storage property of LiNi_0.8Co_0.15Al_0.05O₂ coated with LiCoO₂[J]. Journal of Power Sourc- es, 2013, 230:201-206.
[20]	LIU H S, ZHANG Z R, GONG Z L, et al. Origin of deterioration for LiNiO₂ cathode material during storage in air[J]. Electrochemical and Solid-State Letters, 2004, 7(7):A190-A193.
[21]	SHIZUKA K, KIYOHARA C, SHIMA K, et al. Effect of CO₂ on layered Li₁+_zNi₁-_x-yCo_xM_yO₂(M=Al,Mn) cathode materials for lithi- thium ion batteries[J]. Journal of Power Sources, 2007, 166(1):233-238.
[22]	LI J, DOWNIE L E, MA L, et al. Study of the failure mechanisms of LiNi_0.8Mn_0.1Co_0.1O₂ cathode material for lithium ion batteries[J]. Journal of the Electrochemical Society, 2015, 162(7):A1401-A1408.
[23]	GAUTHIER M, CARNEY T J, GRIMAUD A, et al. Electrodeelec- trolyte interface in li-ion batteries:Current understanding and new insights[J]. The Journal of Physical Chemistry Letters, 2015, 6(22):4653-4672.
[24]	GIORDANO L, KARAYAYLALIi P, YU Yang, et al. Chemical re- activity descriptor for the oxide-electrolyte interface in Li-ion ba- tteries[J]. The Journal of Physical Chemistry Letters, 2017, 8(16):3881-3887.
[25]	ZHUANG G V, CHEN G, SHIMV J, et al. Li₂CO₃ inLiNi_0.8Co_0.15Al_0.05O₂ cathodes and its effects on capacity and power[J]. Journal of Power Sources, 2004, 134(2):293-297.
[26]	BICHON M, SOTTA D, DUPRÉupré N, et al. Study of immersion of LiNi_0.5Mn_0.3Co_0.2O₂ material in water for aqueous processing of positive electrode for Li-ion batteries[J]. ACS Applied Materials & Interfaces, 2019, 11(20):18331-18341.
[27]	JUNG R, MORASCH R, KARAYAYLALI P, et al. Effect of ambient storage on the degradation of Ni-rich positive electrode materials (NMC811) for Li-ion batteries[J]. Journal of the Electrochemical Society, 2018, 165(2):A132-A141.
[28]	JUNG R, STROBL P, MAGLIA F, et al. Temperature dependence of oxygen release from LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) cathode materi- als for Li-ion batteries[J]. Journal of The Electrochemical Society, 2018, 165(11):A2869-A2879.
[29]	RENFREW S E, MCCLOSKEY B D. Quantification of surface oxy- gen depletion and solid carbonate evolution on the first cycle of LiNi_0.6Mn_0.2Co_0.2O₂ electrodes[J]. ACS Applied Energy Materials, 2019, 2(5):3762-3772.
[30]	HWANG S, CHANG W, KIM S M, et al. Investigation of changes in the surface structure of Li_xNi_0.8Co_0.15Al_0.05O₂ cathode materials indu- ced by the initial charge[J]. Chemistry of Materials, 2014, 26(2):1084-1092.
[31]	WANG L, MAXISCH T, CEDER G. A first-principles approach to studying the thermal stability of oxide cathode materials[J]. Che- mistry of Materials, 2007, 19(3):543-552.
[32]	JOHNSON C S, LI Naichao, LEFIEF C, et al. Synjournal,characte- rization and electrochemistry of lithium battery electrodes: XLi₂MnO₃·(1-x)LiMn_0.333Ni_0.333Co_0.333O₂(0≤x≤0.7)[J]. Chemistry of Materials, 2008, 20(19):6095-6106.
[33]	PAULSEN J, KIM J. High nickel cathode material having low soluble base content:EP, 2673823B1[P]. 2015-12-09.
[34]	PRITZL D, TEUFL T, FREIBERG A T S, et al. Editors′ choice-wa- shing of nickel-rich cathode materials for lithium-ion batteries:To- wards a mechanistic understanding[J]. Journal of the Electrochemi- cal Society, 2019, 166(16):A4056-A4066.
[35]	Loeffler N, KIM G T, MUELLER F, et al. In situ coating of Li[Ni_0.33Mn_0.33Co_0.33]O₂ particles to enable aqueous electrode pro- cessing[J]. ChemSusChem, 2016, 9(10):1112-1117.
[36]	HANG M N, GUNSOLUS I L, WAYLAND H, et al. Impact of nano- scale lithium nickel manganese cobalt oxide(NMC) on the bacte- rium shewanella oneidensis MR-1[J]. Chemistry of Materials, 2016, 28(4):1092-1100.
[37]	JEONG S, KIM J, MUN J. Self-generated coating of LiCoO₂ by wa- shing and heat treatment without coating precursors[J]. Journal of the Electrochemical Society, 2018, 166(3):A5038-A5044.
[38]	XIONG X, WANG Z, YUE P, et al. Washing effects on electroche- mical performance and storage characteristics of LiNi_0.8Co_0.1Mn_0.1O₂ as cathode material for lithium-ion batteries[J]. Journal of Power Sources, 2013, 222:318-325.
[39]	ZHENG X, LI X, WANG Z, et al. Investigation and improvement on the electrochemical performance and storage characteristics of LiNiO₂-based materials for lithium ion battery[J]. Electrochimica Acta, 2016, 191:832-840.
[40]	MARTINEZ A C, GRUGEON S, CAILLEU D, et al. High reactivity of the nickel-rich LiNi₁-_x-_yMn_xCo_yO₂ layered materials surface to- wards H₂O/CO₂ atmosphere and LiPF₆-based electrolyte[J]. Jour- nal of Power Sources, 2020, 468.Doi: 10.1016/j.jpowsour.2020.228204.
[41]	JO J H, JO C H, YASHIRO H, et al. Re-heating effect of Ni-rich cathode material on structure and electrochemical properties[J]. Journal of Power Sources, 2016, 313:1-8.
[42]	李萌, 刘雪东, 诸士春, 等. 锂离子电池正极材料超声强化水洗过程研究[J]. 化工进展, 2020, 39(2):635-642.
[43]	刘大亮, 孙国平, 刘亚飞, 等. 高镍三元正极材料后处理降碱工艺[J]. 电池, 2018, 48(1):41-44.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会