锂离子电池正极材料循环稳定性的基因规律

doi:10.19799/j.cnki.2095-4239.2020.0361

摘要/Abstract

摘要：

锂离子电池正极材料需要有较大的能量密度和稳定的循环寿命，循环寿命与其脱锂前后的结构变化有直接关系。但是，影响循环寿命的原子层次因素是什么，还没有明确的答案。探究和优化正极材料的核心工作就是要寻找微观结构与性能之间的关系，这里不仅需要用到大数据统计，也需要对比分析脱锂前后的结构变化特征参数。通过分子动力学方法计算得到了18种典型正极体系的体积和弹性模量的变化，分析发现不同正极材料体系都对应了一个反映收缩能力的压强值，它主要由体积变化率与弹性模量的乘积决定，体现了不同材料脱锂后的稳定性差异。对于含Co/Ni/Mn/Fe等过渡族金属的正极材料，这个参数与循环稳定性呈一定的线性关系，收缩压强大的体系有更优秀的循环性能。同时，电子结构层次中的电荷密度也是影响锂离子电池循环性能的本征因素之一。本研究探索也表明，大数据配合理论计算是寻找材料规律的有效方法，得到的基本规律对于优化和改善循环寿命有一定的理论指导意义。

关键词: 锂离子电池, 正极材料, 循环寿命, 大数据, 分子动力学, 电荷密度

Abstract:

The cathode material of lithium-ion batteries must have a large energy density and stable cycle life. Cycle life is directly related to structural changes before and after lithium loss. However, the atomic-level factor affecting the cycle life has not been clearly determined. The core work of exploring and optimizing cathode materials is finding the relationship between microstructures and performance, which requires big data statistics and comparing and analyzing the characteristic parameters of structural changes before and after lithium loss. The volume and elastic modulus of 18 typical positive materials were calculated using the molecular dynamics method. We found that different cathode materials corresponding to different pressures can reflect the shrinkage ability, mainly decided by the product of the volume change rate and elastic modulus. The pressure reflects the system's adaptability during contraction after lithium loss and the difference in the stability of different materials before and after lithium loss. For cathode materials containing transition metals such as Co, Ni, Mn, and Fe, this parameter has a certain linear relationship with the cycling stability; that is, the system with the higher pressure has the better cyclic performance. At the same time, the charge density in the electronic structure layer is also one of the intrinsic factors affecting the cycle performance of lithium-ion batteries. This research also shows that using big data combined with theoretical calculations is an effective method to find the laws of materials. The basic laws obtained have certain theoretical guiding significance for optimizing and improving the cycle life.

Key words: lithium-ion battery, cathode materials, cycle life, big data, molecular dynamics, charge density

中图分类号:

TM 912

杨民安, 陈宁, 王博, 张乾, 陈敬沛, 赵海雷, 李福燊. 锂离子电池正极材料循环稳定性的基因规律[J]. 储能科学与技术, 2021, 10(2): 462-469.

Min'an YANG, Ning CHEN, Bo WANG, Qian ZHANG, Jingpei CHEN, Hailei ZHAO, Fushen LI. Gene law about cycle stability of cathode material for lithium-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(2): 462-469.

图/表 5

图1

表1

图2

图3

图4

参考文献 55

1	王朔, 周格, 禹习谦, 等. 储能技术领域发表文章和专利概览综述[J]. 储能科学与技术, 2017, 6(4): 810-838.
	WANG Shuo, ZHOU Ge, YU Xiqian, et al. Overview of research papers and patents on energy storage technologies[J]. Energy Storage Science and Technology, 2017, 6(4): 810-838.
2	YANG Xiaoguang, WANG Chaoyang. Understanding the trilemma of fast charging, energy density and cycle life of lithium-ion batteries[J]. Journal of Power Sources, 2018, 402: 489-498.
3	BIRKL C R, ROBERTS M R, MCTURK E, et al. Degradation diagnostics for lithium ion cells[J]. Journal of Power Sources, 2017, 341: 373-386.
4	RAMADASS P, HARAN B, WHITE R, et al. Capacity fade of sony 18650 cells cycled at elevated temperatures (II:) Capacity fade analysis[J]. Journal of Power Sources, 2002, 112(2): 606-613.
5	FRIESEN A, MÖNNIGHOFF X, BÖRNER M, et al. Influence of temperature on the aging behavior of 18650-type lithium ion cells: A comprehensive approach combining electrochemical characterization and post-mortem analysis[J]. Journal of Power Sources, 2017, 342: 88-97.
6	ASAKURA K, SHIMOMURA M, SHODAI T. Study of life evaluation methods for Li-ion batteries for backup applications[J]. Journal of Power Sources, 2003, 119: 902-905.
7	范智伟, 乔丹, 崔海港. 锂离子电池充放电倍率对容量衰减影响研究[J]. 电源技术, 2020, 44(3): 325-329.
	FAN Zhiwei, QIAO Dan, CUI Haigang. Influence of charge and discharge rate on capacity fade of lithium ion battery[J]. Chinese Journal of Power Sources, 2020, 44(3): 325-329.
8	雷文, 何涌, 于江波. LiMn₂O₄锂离子电池正极材料结构稳定性的初步研究[J]. 材料导报, 2001(10): 62-64.
	LEI Wen, HE Yong, YU Jiangbo. Preliminary study of structural stability of cathode material LiMn₂O₄ for lithium batteries[J]. Materials Reports, 2001(10): 62-64.
9	WANG Wenhui, ZHANG Jiaolong, JIA Zheng, et al. Enhancement of the cycling performance of Li₃V₂(PO₄)₃/C by stabilizing the crystal structure through Zn²⁺ doping[J]. Physical Chemistry Chemical Physics, 2014, 16(27): 13858-13865.
10	唐致远, 阮艳莉. 锂离子电池容量衰减机理的研究进展[J]. 化学进展, 2005(1): 1-7.
	TANG Zhiyuan, RUAN Yanli. Progress in capacity fade mechanism of lithium ion battery[J]. Progress in Chemistry, 2005(1): 1-7.
11	AURBACH D, MARKOVSKY B, RODKIN A, et al. An analysis of rechargeable lithium-ion batteries after prolonged cycling[J]. Electrochimica Acta, 2003, 47(12): 1899-1911.
12	谢宗轩. 电动汽车用动力电池循环寿命的层析图像预测机理研究[D]. 广州: 华南理工大学, 2019.
	XIE Zongxuan. Research on prediction mechanism of cycle life of power battery for electric vehicle by tomography[D]. Guangzhou: South China University of Technology, 2019.
13	时玮. 动力锂离子电池组寿命影响因素及测试方法研究[D]. 北京: 北京交通大学, 2014.
	SHI Wei. Research on lifespan factors and test methods of traction lithium-ion batteries[D]. Beijing: Beijing Jiaotong University, 2014.
14	MURALIGANTH T, MANTHIRAM A. Understanding the shifts in the redox potentials of olivine LiM_1-yMyPO₄ (M = Fe, Mn, Co, and Mg) solid solution cathodes[J]. Journal of Physical Chemistry C, 2015, 114(36): 15530-15540.
15	CHEN Guimin, GENG Hailong, WANG Zhenwei, et al. On electrochemistry of Al₂O₃-coated LiCoO₂ composite cathode with improved cycle stability[J]. Ionics, 2015, 22(5): 629-636.
16	ZHANG Wei, CHI Zixiang, MAO Wenxin, et al. One-nanometer-precision control of Al₂O₃ nanoshells through a solution-based synthesis route[J]. Angewandte Chemie International Edition, 2014, 53(47): 12776-80.
17	CAO Hui, XIA Baojia, ZHANG Yao, et al. LiAlO-coated LiCoO as cathode material for lithium ion batteries[J]. Solid State Ionics, 2005, 176(9/10): 911-914.
18	KWON Sung Nam, SONG Myoung Youp, PARK Hye Ryoung. Electrochemical properties of LiNiO₂ substituted by Al or Ti for Ni via the combustion method[J]. Ceramics International, 2014, 40(9): 14141-14147.
19	SONG Myoung Youp, KWON IkHyun, SHIM Sungbo, et al. Electrochemical characterizations of Fe-substituted LiNiO₂ synthesized in air by the combustion method[J]. Ceramics International, 2010, 36(4): 1225-1231.
20	KWON Sung Nam, SONG Jihong, MUMM D R. Effects of cathode fabrication conditions and cycling on the electrochemical performance of LiNiO₂ synthesized by combustion and calcination[J]. Ceramics International, 2011, 37(5): 1543-1548.
21	PARK Hye Ryoung. Electrochemical properties of LiNiO₂ and LiNiO₂ substituted with Ga, Al and/or Ti[J]. Journal of Industrial and Engineering Chemistry, 2010, 16(5): 698-702.
22	YOSHIDA R, KODERA T, MYOUJIN K, et al. Synthesis and electrochemical properties of layered type LiMnO₂ powders by spray pyrolysis[J]. Transactions of the Materials Research Society of Japan, 2009, 34(1): 129-132.
23	JI Hongmei, MIAO Xiaowei, WANG Lu, et al. Effects of microwave-hydrothermal conditions on the purity and electrochemical performance of orthorhombic LiMnO₂[J]. ACS Sustainable Chemistry & Engineering, 2014, 2(3): 359-366.
24	HE Wen, CUI Jingjie, YUE Yuanzheng, et al. High-performance TiO₂ from Baker's yeast[J]. Journal of Colloid and Interface Science, 2011, 354(1): 109-15.
25	王雷, 唐致远, 阮艳莉, 等. 新型正极材料LiFePO₄的电化学性能的改进[J]. 电源技术, 2006, 30(7): 549-548.
	WANG Lei, TANG Zhiyuan, RUAN Yanli, et al. Improvement of electrochemical performance of LiFePO₄ as a novel cathode material[J]. Chinese Journal of Power Sources, 2006, 30(7): 549-548.
26	GUO Hui, ZHANG Xudong, HE Wen, et al. Fabricating three-dimensional mesoporous carbon network-coated LiFePO₄/Fe nanospheres using thermal conversion of alginate-biomass[J]. RSC Advances, 2016 6(21): 16933-16940.
27	XU Feifei, WANG Ruiqiong, ZHANG Ronglan, et al. Structure and electrochemical performance of LiFePO₄ modified with mononuclear and binuclear phthalocyanines as cathode materials[J]. Journal of Materials Research, 2017, 32(6): 1168-1176.
28	ORNEK, AHMET. The synthesis of novel LiNiPO₄ core and Co₃O₄/CoO shell materials by combining them with hard-template and solvothermal routes[J]. J Colloid Interface, 2017, 504: 468-478.
29	CHEN Houyong, CHEN Meng, DU Chunyu, et al. Synthesis and electrochemical performance of hierarchical nanocomposite of carbon coated LiCoPO₄ crosslinked by graphene[J]. Materials Chemistry & Physics, 2016, 171: 6-10.
30	EFTEKHARI A. Surface modification of thin-film based LiCoPO₄ 5 V cathode with metal oxide[J]. Journal of the Electrochemical Society, 2004, 151(9): A1456-A1460.
31	WANG Fei, YANG Jun, NULI Yanna, et al. Highly promoted electrochemical performance of 5 V LiCoPO₄ cathode material by addition of vanadium[J]. Journal of Power Sources, 2010, 195(19): 6884-6887.
32	KIM Jae-Kwang, SHIN Cho-Rong, AHN Jou-Hyeon, et al. Highly porous LiMnPO₄ in combination with an ionic liquid-based polymer gel electrolyte for lithium batteries[J]. Electrochemistry Communications, 2011, 13(10): 1105-1108.
33	MAEYOSHI Y, MIYAMOTO S, NODA Y, et al. Effect of organic additives on characteristics of carbon-coated LiCoPO₄ synthesized by hydrothermal method[J]. Journal of Power Sources, 2017, 337: 92-99.
34	SIVAKUMAR D, DURAISAMY N, RAMESH] S. Structural and electrochemical characterizations of LiMn_1-xAl_0.5xCu_0.5xPO₄ (x=0. 0, 0. 1, 0. 2) cathode materials for lithium ion batteries[J]. Materials Letters, 2016, 173: 131-135.
35	崔永丽, 徐坤, 袁铮, 等. 石墨烯/尖晶石LiMn₂O₄纳米复合材料制备及电化学性能[J]. 无机化学学报, 2013, 29(1): 50-56.
	CUI Yongli, XU Kun, YUAN Zheng, et al. Synthesis and electrochemical performance of graphene modified; nano-spinel LiMn₂O₄ cathode materials[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(1): 50-56.
36	王连邦, 唐伟杰, 苏利伟, 等. 纳米LiMn₂O₄的动态水热法制备及储锂性能[J]. 浙江工业大学学报, 2014, 42(5): 473-477.
	WANG Lianbang, TANG Weijie, SU Liwei, et al. Preparation and lithium storage performance of LiMn₂O₄ nanomaterials by dynamic hydrothermal synthesis[J]. Journal of Zhejiang University of Technology, 2014, 42(5): 473-477.
37	ZOU Xing, WU Peng, XIE Haichao. Effect of high levels of impurity calcium on the electrochemical performance of spinel LiMn₂O₄[C]//International Conference on Material Science & Engineering, 2016.
38	SHENOUDA A Y, SANAD M M S. Electrochemical performance optimization of Li₂NixFe_1-xSiO₄ cathode materials for lithium-ion batteries[J]. Journal of Electrochemical Energy Conversion & Storage, 2017, 14(2): 024501.
39	TAN Guiming, GUI D Y, XIONG Weijian, et al. Sol-gel synthesis of Li₂MnSiO₄/C nanocomposite with improved electrochemical performance for lithium-ion batteries [C]// 2015 16th International Conference on Electronic Packaging Technology (ICEPT), 2015.
40	吴婷婷, 刘婧雅, 李永虎, 等. B掺杂对Li₂MnSiO₄电化学性能的影响[J]. 电源技术, 2018, 42(3): 321-323.
	WU Tingting, LIU Jingya, LI Yonghu, et al. Effects of B doping on electrochemical performance of Li₂MnSiO₄[J]. Chinese Journal of Power Sources, 2018, 42(3): 321-323.
41	DONG Yongzhong, ZHAO Yanming, SHI Z D, et al. The structure and electrochemical performance of LiFeBO₃ as a novel Li-battery cathode material[J]. Electrochimica Acta, 2008, 53(5): 2339-2345.
42	CHEN Wei, ZHANG Hua, ZHANG Xiaoping, et al. Synthesis and electrochemical performance of carbon-coated LiMnBO₃ as cathode materials for lithium-ion batteries[J]. Ionics, 2018, 24: 73-81.
43	RAGUPATHI V, SRIMATHI K, PANIGRAHI P, et al. Electrochemical performance of sol-gel derived hexagonal LiMnBO₃ cathode material for lithium-ion batteries[J]. Nano Hybrids and Composites, 2017, 17: 106-112.
44	侯兴梅, 赵彦明, 董有忠. 新型锂离子电池正极材料LiMnBO₃的制备及其性能[J]. 电源技术, 2008, 32(9): 611-613.
	HOU Xingmei, ZhAO Yanming, DONG Youzhong. Preparation and characterization of new cathode material LiMnBO₃ for lithium ion battery[J]. Chinese Journal of Power Sources, 2008, 32(9): 611-613.
45	ZHANG Liqiang, WANG Xiuli, XIANG Jiayuan, et al. Synthesis and electrochemical performances of Li₃V₂(PO₄)₃/(Ag+C) composite cathode[J]. Journal of Power Sources, 2010, 195(15): 5057-5061.
46	LEE S N, KIM Hye Sook, AN J Y, et al. Preparation and characterization of chlorine doped Li₃V₂(PO₄)₃ as high rate cathode active material for lithium secondary batteries[J]. Journal of Nanoscience and Nanotechnology, 2014, 14(10): 7516-7520.
47	李万隆, 李月姣, 曹美玲, 等. 流变相法制备海藻酸基碳包覆Li₃V₂(PO₄)₃材料的电化学性能[J]. 物理化学学报, 2017, 33(11): 2261-2267.
	LI Wanlong, LI Yuejiao, CAO Meiling, et al. Synthesis and electrochemical performance of alginic acid-based carbon-coated Li₃V₂(PO₄)₃ composite by rheological phase method[J]. Acta Physico-Chimica Sinica, 2017, 33(11): 2261-2267.
48	LAI Chunyan, WEI Jiaojiao, WANG Zhen, et al. Li₃V₂(PO₄)₃/(SiO₂+C) composite with better stability and electrochemical properties for lithium-ion batteries[J]. Solid State Ionics, 2015, 272: 121-126.
49	XU Jiantie, CHOU Shulei, GU Qinfen, et al. Study on vanadium substitution to iron in Li₂FeP₂O₇ as cathode material for lithium-ion batteries[J]. Electrochimica Acta, 2014, 141: 195-202.
50	KERR T A. Highly reversible Li insertion at 4 V in ε-VOPO₄/α-LiVOPO₄ cathodes[J]. Electrochemical and Solid-State Letters, 1999, 3(10): 460.
51	SHEN Chao, ZHENG Junchao, ZHANG Bao, et al. Composite cathode material β-LiVOPO₄/LaPO₄ with enhanced electrochemical properties for lithium ion batteries[J]. RSC Advances, 2014, 4(77): 40912-40916.
52	HAMEED A S, NAGARATHINAM M, REDDY M V, et al. Synthesis and electrochemical studies of layer-structured metastable α-LiVOPO₄[J]. Journal of Materials Chemistry, 2012, 22(15): 7206-7213.
53	熊利芝, 何则强. 一种新的流变相法制备锂离子电池纳米LiVOPO₄正极材料[J]. 物理化学学报, 2010, 26(3): 573-577.
	XIONG Lizhi, HE Zeqiang. A new rheological phase route to synthesize nano-LiVOPO₄ cathode material for lithiumion batteries[J]. Acta Physico-Chimica Sinica, 2010, 26(3): 573-577.
54	REN Xiangzhong, HU Shengming, SHI Chuan, et al. Preparation and electrochemical properties of Zr-doped LiV₃O₈ cathode materials for lithium-ion batteries[J]. Journal of Solid State Electrochemistry, 2012, 16(6): 2135-2141.
55	REN Xiangzhong, HU Shengming, SHI Chuan, et al. Preparation of Ga-doped lithium trivanadates as cathode materials for lithium-ion batteries[J]. Electrochimica Acta, 2012, 63: 232-237.

体系	化学式	容量保持率/%	V₁/?³	V₂/?³	B₁/GPa	B₂/GPa	脱锂系数	p/GPa	参考文献
层状	LiCoO₂	90.64	240.01	180.04	154.08	205.62	0.5	14.96	[15-17]
	LiNiO₂	82.85	225.53	166.25	175.43	238.47	0.5	17.43	[18-21]
	LiMnO₂	79.14	167.95	134.50	158.68	198.64	0.5	13.32	[22-23]
橄榄石	LiFePO₄	91.95	366.38	321.03	300.34	58.73	1	17.72	[24-27]
	LiCoPO₄	9.40	253.87	239.93	103.89	258.15	0.75	0.83	[28-31]
	LiNiPO₄	30.00	320.77	317.45	394.61	96.36	0.75	9.88	[32]
	LiMnPO₄	48.19	217.56	210.61	296.86	359.57	0.75	13.11	[33-34]
尖晶石	LiMn₂O₄	78.78	251.95	238.13	266.86	255.57	0.75	15.96	[35-37]
硅酸盐	Li₂FeSiO₄	81.16	135.82	126.34	81.33	196.25	0.5	6.88	[38]
	Li₂MnSiO₄	17.61	367.10	288.23	55.70	108.39	0.5	4.45	[39-40]
	Li₂NiSiO₄	86.76	195.59	159.88	81.68	67.12	0.5	8.34	[38]
硼酸盐	LiFeBO₃	83.19	363.76	287.80	168.19	84.58	0.75	13.60	[41]
	LiMnBO₃	38.07	341.00	308.66	177.15	126.61	0.33	6.50	[42]
	LiCoBO₃	48.98	346.20	312.96	205.00	137.44	0.25	5.29	[43-44]
其他	Li₃V₂(PO₄)₃	69.70	322.00	292.21	188.04	162.17	0.667	2.24	[45-48]
	Li₂FeP₂O₇	78.38	785.47	772.58	162.50	155.07	0.5	5.20	[49]
	LiVOPO₄	93.19	242.10	228.20	165.67	127.69	0.75	2.58	[50-53]
	Li₄V₃O₈	77.74	327.57	320.94	48.11	157.41	0.75	3.90	[54-55]

[1]	李海涛, 孔令丽, 张欣, 余传军, 王纪威, 徐琳. N/P设计对高镍NCM/Gr电芯性能的影响[J]. 储能科学与技术, 2022, 11(7): 2040-2045.
[2]	陈龙, 夏权, 任羿, 曹高萍, 邱景义, 张浩. 多物理场耦合下锂离子电池组可靠性研究现状与展望[J]. 储能科学与技术, 2022, 11(7): 2316-2323.
[3]	易顺民, 谢林柏, 彭力. 基于VF-DW-DFN的锂离子电池剩余寿命预测[J]. 储能科学与技术, 2022, 11(7): 2305-2315.
[4]	祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331.
[5]	刘显茜, 孙安梁, 田川. 基于仿生翅脉流道冷板的锂离子电池组液冷散热[J]. 储能科学与技术, 2022, 11(7): 2266-2273.
[6]	徐雄文, 聂阳, 涂健, 许峥, 谢健, 赵新兵. 普鲁士蓝正极软包钠离子电池的滥用性能[J]. 储能科学与技术, 2022, 11(7): 2030-2039.
[7]	王宇作, 王瑨, 卢颖莉, 阮殿波. 孔结构对软碳负极储锂性能的影响[J]. 储能科学与技术, 2022, 11(7): 2023-2029.
[8]	霍思达, 薛文东, 李新丽, 李勇. 基于CiteSpace知识图谱的锂电池复合电解质可视化分析[J]. 储能科学与技术, 2022, 11(7): 2103-2113.
[9]	邓健想, 赵金良, 黄成德. 高能量锂离子电池硅基负极黏结剂研究进展[J]. 储能科学与技术, 2022, 11(7): 2092-2102.
[10]	孔为, 金劲涛, 陆西坡, 孙洋. 对称蛇形流道锂离子电池冷却性能[J]. 储能科学与技术, 2022, 11(7): 2258-2265.
[11]	申晓宇, 岑官骏, 乔荣涵, 朱璟, 季洪祥, 田孟羽, 金周, 闫勇, 武怿达, 詹元杰, 俞海龙, 贲留斌, 刘燕燕, 黄学杰. 锂电池百篇论文点评（2022.4.1—2022.5.31）[J]. 储能科学与技术, 2022, 11(7): 2007-2022.
[12]	周伟, 符冬菊, 刘伟峰, 陈建军, 胡照, 曾燮榕. 废旧磷酸铁锂动力电池回收利用研究进展[J]. 储能科学与技术, 2022, 11(6): 1854-1864.
[13]	张浩然, 车海英, 郭凯强, 申展, 张云龙, 陈航达, 周煌, 廖建平, 刘海梅, 马紫峰. Sn掺杂NaNi_1/3Fe_1/3Mn_1/3-_x Sn _x O₂ 正极材料制备及其电化学性能[J]. 储能科学与技术, 2022, 11(6): 1874-1882.
[14]	张言, 王海, 刘朝孟, 张德柳, 王佳东, 李建中, 高宣雯, 骆文彬. 锂离子电池富镍三元正极材料NCM的研究进展[J]. 储能科学与技术, 2022, 11(6): 1693-1705.
[15]	欧宇, 侯文会, 刘凯. 锂离子电池中的智能安全电解液研究进展[J]. 储能科学与技术, 2022, 11(6): 1772-1787.