高镍三元正极材料镍钴铝的掺杂改性研究进展

doi:10.19964/j.issn.1006-4990.2021-0533

Abstract

Abstract:

Due to the high energy density，high working voltage，low cost and environmental friendliness，high nickel ternary nickel-cobalt-aluminum（NCA） cathode material is likely to become one of the next generation widely used cathode materials for lithium ion batteries.However，increasing of nickel content，resulting in more unstable material structure，reduced cycle performance，and rate capability，limits its further development.The modification mechanism of ion doping at different positions from four aspects: lithium site，transition metal site，oxygen site doping and composite co-doping were summarized.A large number of research results showed that modification by composite co-doping could effectively improve the electrochemical performance of nickel-cobalt-aluminum cathode materials by combining the advantages of single ion doping.

Key words: NCA cathode material, ion doping modification, capacity decay mechanism, electrochemical performance

CLC Number:

TQ138.13

HOU Shunli,ZHAO Duan,ZHOU Geng,WEI Shishi,LI Jian,WANG Jiatai. Research progress on doping modification of high nickel ternary nickel-cobalt-aluminum cathode material[J]. Inorganic Chemicals Industry, 2022, 54(8): 40-46.

Figures/Tables 7

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References 40

1	倪闯将，刘亚飞，陈彦彬，等.镍钴锰三元材料的结构及改性研究进展[J].电源技术, 2021, 45(1): 123-126.
	NI Chuangjiang,LIU Yafei,CHEN Yanbin，et al.Research progress of structure and modification of Li（Ni _x Co _y Mn _z ）O₂ ternary materials[J].Chinese Journal of Power Sources, 2021, 45(1): 123-126.
2	张和，张梦诗，廖世军.富锂三元层状正极材料的研究进展[J].应用化学, 2018, 35(11): 1277-1288.
	ZHANG He,ZHANG Mengshi,LIAO Shijun.Recent progress in the lithium-rich ternary layered cathode materials[J].Chinese Journal of Applied Chemistry, 2018, 35(11): 1277-1288.
3	韩啸，张成锟，吴华龙，等.锂离子电池的工作原理与关键材料[J].金属功能材料, 2021, 28(2): 37-58.
	HAN Xiao,ZHANG Chengkun,WU Hualong，et al.Working mecha-
	nism and key materials of the lithium ion batteries[J].Metallic Functional Materials, 2021, 28(2): 37-58.
4	LIU Wen，OH P， LIU Xien，et al.Nickel-rich layered lithium tran-
	sition-metal oxide for high-energy lithium-ion batteries[J].Angewandte Chemie International Edition, 2015, 54(15): 4440-4457.
5	杨涛，刘文凤，马梦月，等.三元锂离子动力电池衰减机理[J].应用化学, 2020, 37(10): 1181-1186.
	YANG Tao,LIU Wenfeng,MA Mengyue，et al.Fade mechanism of ternary lithium ion power battery[J].Chinese Journal of Applied Chemistry, 2020, 37(10): 1181-1186.
6	TIAN Rongzheng,SU Jinran,MA Zhijie，et al.Influences of surface Al concentration on the structure and electrochemical performance of core-shell LiNi_0.8Co_0.15Al_0.05O₂ cathode material[J].Electrochimica Acta, 2020，337.Doi: 10.1016/j.electacta.2020.135769.
7	GAO Tianpeng,WONG K W,NG K M.High-quality LiNi_0.8Co_0.15Al_0.05O₂ cathode with excellent structural stability: Suppressed structural degradation and pore defects generation[J].Nano Energy, 2020，73.Doi: 10.1016/j.nanoen.2020.104798.
8	WANG Xiaodan,BAI Ying,WANG Xinran，et al.High-voltage layered ternary oxide cathode materials: Failure mechanisms and modification methods[J].Chinese Journal of Chemistry, 2020，
	38(12): 1847-1869.
9	MUKHERJEE P,FAENZA N V,PEREIRA N，et al.Surface structural and chemical evolution of layered LiNi_0.8Co_0.15Al_0.05O₂（NCA） under high voltage and elevated temperature conditions[J].Chemistry of Materials, 2018, 30(23): 8431-8445.
10	QIAN Ruicheng,LIU Yali,CHENG Tao，et al.Enhanced surface chemical and structural stability of Ni-rich cathode materials by synchronous lithium-ion conductor coating for lithium-ion batteries[J].ACS Applied Materials & Interfaces, 2020, 12(12): 13813-13823.
11	郭孝东，徐春柳，向伟，等.富镍三元正极材料的改性研究进展[J].工程科学与技术, 2020, 52(1): 9-17.
	GUO Xiaodong,XU Chunliu,XIANG Wei，et al.Research progress in the modification of nickel-rich cathode materials[J].Advanced Engineering Sciences, 2020, 52(1): 9-17.
12	SUN H H,RYU H H,KIM U H，et al.Beyond doping and coating: Prospective strategies for stable high-capacity layered Ni-rich cathodes[J].ACS Energy Letters, 2020, 5(4): 1136-1146.
13	HE Huihui,DONG Jian,ZHANG Dongyun，et al.Effect of Nb doping on the behavior of NCA cathode: Enhanced electrochemical performances from improved lattice stability towards 4.5 V application[J].Ceramics International, 2020, 46(15): 24564-24574.
14	WANG Ding,LIU Weihong,ZHANG Xuhong，et al.Review of modified nickel-cobalt lithium aluminate cathode materials for lithium-ion batteries[J].International Journal of Photoenergy, 2019.Doi: 10.1155/2019/2730849.
15	DONG Jian,XIAO Peng,ZHANG Dongyun，et al.Enhanced rate performance and cycle stability of LiNi_0.8Co_0.15Al_0.05O₂ via Rb doping[J].Journal of Materials Science: Materials in Electronics, 2018, 29(24): 21119-21129.
16	XIE Hongbin,DU Ke,HU Guorong，et al.The role of sodium in LiNi_0.8Co_0.15Al_0.05O₂ cathode material and its electrochemical behaviors[J].The Journal of Physical Chemistry C, 2016, 120(6): 3235-3241.
17	ZHAO Junkai,WANG Zhixing,WANG Jiexi，et al.Anchoring K⁺ in Li⁺ sites of LiNi_0.8Co_0.15Al_0.05O₂ cathode material to suppress its structural degradation during high-voltage cycling[J].Energy Technology, 2018, 6(12): 2358-2366.
18	WANG Yangyang,SUN Yanyun,LIU Sheng，et al.Na-doped LiNi_0.8Co_0.15Al_0.05O₂ with excellent stability of both capacity and potential as cathode materials for Li-ion batteries[J].ACS Applied Energy Materials, 2018, 1(8): 3881-3889.
19	LI Hongyang,LIU A,ZHANG Ning，et al.An unavoidable challenge for Ni-rich positive electrode materials for lithium-ion batteries[J].Chemistry of Materials, 2019, 31(18): 7574-7583.
20	QIU Qiqi,SHADIKE Z,WANG Qinchao，et al.Improving the electrochemical performance and structural stability of the LiNi_0.8Co_0.15Al_0.05O₂ cathode material at high-voltage charging through Ti substitution[J].ACS Applied Materials & Interfaces, 2019, 11(26): 23213-23221.
21	BAI Xue,WEI Aijia,HE Rui，et al.The structural and electrochemical performance of Mg-doped LiNi_0.85Co_0.10Al_0.05O₂ prepared by a solid state method[J].Journal of Electroanalytical Chemistry, 2020，858.Doi: 10.1016/j.jelechem.2019.113771.
22	LIU Shuaiwei,LI Yunjiao,WANG Shilei，et al.Towards superior cyclability of LiNi_0.8Co_0.15Al_0.05O₂ cathode material for lithium ion batteries via yttrium modification[J].Journal of Alloys and Compounds, 2021，874.Doi: 10.1016/j.jallcom.2021.159713.
23	CHE Wen,WAN Xiaowen,ZHANG Dongyun，et al.Stabilized performance of LiNi₀₉₀Co0.07Al_0.03O₂ cathodes via Zr4+ doping upon 4.5 V application due to the suppression of H2-H3 phase transitions.[J].ACS Sustainable Chemistry & Engineering, 2021, 9(16): 5536-5545.
24	JANG B C,SON J T.Structural analysis of iron-doped LiNi₀₈₅Co0.10Al_0.05O₂ cathode materials for lithium-ion batteries.[J].Journal of Nanoscience and Nanotechnology, 2016, 16(10): 10649-10653.
25	DU Fanghui,CHEN Ruofan,ZHUANG Yan，et al.Effect of substitution of cobalt with iron on electrochemical behavior and solid electrolyte interface of LiNi_0.8Co_0.15Al_0.05O₂ [J].Applied Surface Science, 2019, 484: 374-382.
26	XIONG Yike,CAO Guolin,LI Yunjiao，et al.The synergistic effect of Gd modification on improving the electrochemical performance of LiNi_0.88Co_0.09Al_0.03O₂ cathode materials[J].Journal of the Electrochemical Society, 2021, 168(3）.Doi: 10.1149/1945-7111/abe28c.
27	ZHANG Shu,MA Jun,HU Zhenglin，et al.Identifying and addressing critical challenges of high-voltage layered ternary oxide cathode materials[J].Chemistry of Materials, 2019, 31(16): 6033-6065.
28	HE Shiyu,WEI Aijia,LI Wen，et al.An in-depth analysis detailing the structural and electrochemical properties within Br-modified LiNi_0.815Co_0.15Al_0.035O₂（NCA） cathode material[J].Electrochimica Acta, 2019, 318: 362-373.
29	LI Xiang,XIE Zhengwei,LIU Wenjing，et al.Effects of fluorine doping on structure，surface chemistry，and electrochemical performance of LiNi_0.8Co_0.15Al_0.05O₂ [J].Electrochimica Acta, 2015, 174: 1122-1130.
30	XIE Zhicheng,ZHANG Yingying,MIN Xiuqin，et al.One-step bulk and surface co-modification of LiNi_0.8Co_0.15Al_0.05O₂ cathode material towards excellent long-term cyclability[J].Electrochimica Acta, 2021，379.Doi: 10.1016/j.electacta.2021.138124.
31	CHEN Tao,LI Xiang,WANG Hao，et al.The effect of gradient boracic polyanion-doping on structure，morphology，and cycling performance of Ni-rich LiNi_0.8Co_0.15Al_0.05O₂ cathode material[J].Journal of Power Sources, 2018, 374: 1-11.
32	QIU Zhenping,LIU Zheng,FU Xingjie，et al.Improving the cycling performance of LiNi_0.8Co_0.15Al_0.05O₂ cathode materials via zirconium and fluorine co-substitution[J].Journal of Alloys and Compounds, 2019, 806: 136-145.
33	HE Huihui,LIU Sanchao,ZHANG Dongyun，et al.Na and Nb co-doped LiNi_0.85Co_0.15Al_0.05O₂ cathode materials for enhanced electrochemical performance upon 4.5 V application[J].Ceramics International, 2021, 47(11): 15260-15266.
34	YANG Bin,ZHOU Lang,HU Xuebu，et al.Enhancing the electrochemical performances of LiNi_0.8Co_0.15Al_0.05O₂ cathode material by anion/cation co-doping[J].Ionics, 2021, 27(4): 1491-1499.
35	SEO J H,KIM U H,SUN Y K，et al.Multi-doped（Ga，B） Li［Ni_0.885Co_0.100Al_0.015］O₂ cathode[J].Journal of the Electrochemical Society, 2020, 167(10）.Doi: 10.1149/1945-7111/ab9e82.
36	QIU Zhenping,ZHANG Yelong,LIU Zheng，et al.Stabilizing Ni-rich LiNi_0.92Co_0.06Al_0.02O₂ cathodes by boracic polyanion and tungsten cation co-doping for high-energy lithium-ion batteri- es[J].ChemElectroChem, 2020, 7(18): 3811-3817.
37	QIU Lang,XIANG Wei,TIAN Wen，et al.Polyanion and cation co-doping stabilized Ni-rich Ni-Co-Al material as cathode with enhanced electrochemical performance for Li-ion battery[J].Nano Energy, 2019，63.Doi: 10.1016/j.nanoen.2019.06.014.
38	陈良丹.高镍三元正极材料的掺杂改性及其储锂性能研究［D］.武汉: 武汉理工大学，2020.
	CHEN Liangdan.Research on doping modification and lithium storage properties of nickel rich cathode materials［D］.Wuhan: Wuhan University of Technology，2020.
39	HUANG Zhenjun,WANG Zhixing,ZHENG Xiaobo，et al.Effect of Mg doping on the structural and electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials[J].Electrochimica Acta, 2015, 182: 795-802.
40	KIM S B,KIM H,PARK D H，et al.Li-ion diffusivity and electrochemical performance of Ni-rich cathode material doped with fluoride ions[J].Journal of Power Sources, 2021，506.Doi: 10.1016/j.jpowsour.2021.230219.

掺杂分类	取代位置	掺杂离子	化合价	离子半径/nm	放电速率	循环次数	容量保持率/%
单离子掺杂	Li位	Na^+［16］	+1	0.102	1.0C	200	90.71
	Li位	K^+［17］	+1	0.138	1.0C	150	87.4
	M位	Ti^4+［20］	+4	0.060 5	0.1C	100	86.9
	M位	Mg^2+［21］	+3	0.072	0.5C	100	84.9
	O位	Br^-［28］	-1	0.196	0.5C	100	73.7
	O位	S^2-［30］	-2	0.184	1.0C	1 100	70.4
复合共掺杂	Li位 O位	Na^+［33］ Nb^5+［33］	+1 +5	0.102 0.069	0.5C	100	94.3
复合共掺杂	Li位 O位	Na^+［34］ Br^-［34］	+1 -1	0.102 0.196	2.0C	100	91.5

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Research progress on doping modification of high nickel ternary nickel-cobalt-aluminum cathode material

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