协同改性提升三元正极材料LiNi0.9Co0.05Mn0.05O2结构稳定性研究

doi:10.19964/j.issn.1006-4990.2024-0439

Abstract

Abstract:

Lithium-ion batteries（LIBs） play a crucial role in electric vehicles（EVs），high nickel layered metal oxides （LiNi _x Co _y Mn_1-_x_-_y O₂，NCM，x≥0.8） are one of the most important types of cathode materials for lithium-ion batteries.In order to improve the driving range of electric vehicles，increasing the nickel content in NCM cathode material can improve the actual specific discharge capacity of electric vehicles.However，high nickel content leads to structural instability of the cathode material and poor capacity retention ability.The strategy of doping exogenous elements can solve the above problems well.Using the method of solid phase sintering，a strategy of suppressing the volume shrinkage caused by lattice deformation by doping with high price W atoms was studied，while doping inactive Ti atoms to stabilize the rigid frame.This strategy significantly inhibited the concentration of stress，thereby stabilizing the structure，preventing the formation of micro-cracks，and improving electrochemical performance.Due to its unique structural characteristics，the initial capacity at 0.1C was 221.4 mA·h/g，the specific discharge capacity after 200 cycles at 0.5C was 162.9 mA·h/g，and the capacity retention rate was 74.6%.This study provided a new idea for the design of high performance layered cathode materials.

Key words: lithium-ion batteries, high nickel layer metal oxide, double doping, microcrack, discharge specific capacity

CLC Number:

TQ131.11

ZHANG Longhua, ZHANG Zhichao. Study on synergistic modification to improve structural stability of ternary cathode material LiNi_0.9Co_0.05Mn_0.05O₂[J]. Inorganic Chemicals Industry, 2025, 57(9): 82-87.

Figures/Tables 9

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References 20

[1]	刘娟，蒋庆来，张月异.4.6 V高电压钴酸锂正极材料Al-Zn共掺杂研究［J］.无机盐工业，2024，56（11）：59-64.
	LIU Juan， JIANG Qinglai， ZHANG Yueyi.Study on Al-Zn co-doping of 4.6 V high voltage lithium cobalt oxide cathode materials［J］.Inorganic Chemicals Industry，2024，56（11）：59-64.
[2]	况新亮，刘垂祥，熊朋.锂离子电池产业分析及市场展望［J］.无机盐工业，2022，54（8）：12-19，32.
	KUANG Xinliang， LIU Chuixiang， XIONG Peng.Industry analysis and market prospect of lithium ion battery［J］.Inorganic Chemicals Industry，2022，54（8）：12-19，32.
[3]	贲留斌，武怿达，朱永明，等.一代材料，一代电池：正极材料研究推动锂离子动力电池的升级换代［J］.物理，2022，51（6）：373-383.
	Liubin BEN， WU Yida， ZHU Yongming，et al.A generation of materials，a generation of batteries：Cathode materials can upgrade lithium-ion power batteries［J］.Physics，2022，51（6）：373-383.
[4]	ZHU Huawei， WANG Zhihong， CHEN Ling，et al.Strain engineering of Ni-rich cathode enables exceptional cyclability in pouch-type full cells［J］.Advanced Materials，2023，35（9）：2209357.
[5]	WANG Jian， HYUN H， SEO S，et al.A kinetic indicator of ultrafast nickel-rich layered oxide cathodes［J］.ACS Energy Letters，2023，8（7）：2986-2995.
[6]	KONG Defei， HU Jiangtao， CHEN Zhefeng，et al.Ti-gradient doping to stabilize layered surface structure for high performance high-Ni oxide cathode of Li-ion battery［J］.Advanced Energy Materials，2019，9（41）：1901756.
[7]	张德柳，张言，王海，等.镁掺杂协同氧化铝包覆优化锂离子电池高镍正极材料［J］.储能科学与技术，2023，12（2）：339- 348.
	ZHANG Deliu， ZHANG Yan， WANG Hai，et al.Optimization of high nickel cathode materials for lithium ion batteries by magnesium doped heterogeneous aluminum oxide coating［J］.Energy Storage Science and Technology，2023，12（2）：339-348.
[8]	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.
[9]	PARK K， HAM D J， PARK S Y，et al.High-Ni cathode material improved with Zr for stable cycling of Li-ion rechargeable batteri- es［J］.RSC Advances，2020，10（45）：26756-26764.
[10]	YANG Xing， TANG Yiwei， SHANG Guozhi，et al.Enhanced cyclability and high-rate capability of LiNi_0.88Co_0.095Mn_0.025O₂ cathodes by homogeneous Al³⁺ doping［J］.ACS Applied Materials & Interfaces，2019，11（35）：32015-32024.
[11]	冯准.B/Al/Zr协同策略改善高镍单晶正极材料高温稳定性［J］.无机盐工业，2023，55（8）：59-64，70.
	FENG Zhun.Improvement of high temperature stability of high nickel single crystal cathode materials by B/Al/Zr synergistic strategy［J］.Inorganic Chemicals Industry，2023，55（8）：59-64， 70.
[12]	沈华平，杨桃，吉盛，等.高镍多晶和高镍单晶混合正极材料对三元电池性能的影响［J］.机械设计与制造工程，2021，50（6）：81-84.
	SHEN Huaping， YANG Tao， JI Sheng，et al.Effect of high nickel polycrystalline and high nickel single crystalline mixed cathode materials on properties of ternary battery［J］.Machine Design and Manufacturing Engineering，2021，50（6）：81-84.
[13]	LI Wangda， ERICKSON E M， MANTHIRAM A.High-nickel layered oxide cathodes for lithium-based automotive batteries［J］.Nature Energy，2020，5（1）：26-34.
[14]	LI Wangda，ASL H Y，XIE Qiang，et al.Collapse of LiNi_1-x-yCo_xMn_yO₂ lattice at deep charge irrespective of nickel content in lithiumionbatteries［J］. Journal of the American Chemical Society，2019，141（13）：5097-5101.
[15]	HUA Weibo，SCHWARZ B，KNAPP M，et al.Lithiation mecha-nism of hierarchically layered LiNi_1/3Co_1/3Mn_1/3O₂ cathodes dur-ing high-voltage cycling［J］.Journal of the Electrochemical Soci-ety，2019，166（3）：A5025-A5032.
[16]	PARK N Y，KIM M C，HAN S M，et al.Mechanism behind the loss of fast charging capability in nickel-rich cathode materials［J］. Angewandte Chemie International Edition，2024，63（12）：e202319707.
[17]	LI Puliang，XUE Longlong，LI Yunjiao，et al.Modification of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material using nano TiO₂ to enhance the cycle stability in high-voltage ranges［J］.Materials Letters，2017，207：217-220.
[18]	SHEN Yabin，XUE Hongjin，WANG Shaohua，et al.A highly promising high-nickel low-cobalt lithium layered oxide cathode material for high-performance lithium-ion batteries［J］.Journal of Colloid and Interface Science，2021，597：334-344.
[19]	ZHAO Ruirui，YANG Zilian，LIANG Jiaxing，et al.Under-standing the role of Na-doping on Ni-rich layered oxide LiNi_0.5Co_0.2Mn_0.3O₂［J］.Journal of Alloys and Compounds，2016，689：318-325.
[20]	BI Yujing，TAO Jinhui，WU Yuqin，et al.Reversible planar glid-ing and microcracking in a single-crystalline Ni-rich cathode［J］.Science，2020，370（6522）：1313-1317.

样品	a/nm	c/nm	c/a	V/nm³	Ni/Li 混排值/%
NCM	0.288 6	1.419 8	4.920	0.102 5	4.86
0.25%（W，Ti）/NCM	0.287 5	1.417 5	4.930	0.102 5	4.75
0.50%（W，Ti）/NCM	0.286 4	1.420 3	4.959	0.102 4	4.58
0.75%（W，Ti）/NCM	0.288 4	1.418 6	4.919	0.102 5	4.67

样品	w（Ni）/%	w（Co）/%	w（Mn）/%	w（W）/%	w（Ti）/%
NCM	0.542	0.030 2	0.028	0	0
0.50%（W，Ti）/NCM	0.536	0.029 9	0.028	0.009	0.002

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on synergistic modification to improve structural stability of ternary cathode material LiNi_0.9Co_0.05Mn_0.05O₂

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Study on synergistic modification to improve structural stability of ternary cathode material LiNi0.9Co0.05Mn0.05O2