LiNi0.8Co0.15Al0.05O2/石墨锂离子电池高荷电存储老化机理研究

doi:10.15541/jim20200012

无机材料学报 ›› 2021, Vol. 36 ›› Issue (2): 175-180.DOI: 10.15541/jim20200012 CSTR: 32189.14.10.15541/jim20200012

所属专题：能源材料论文精选(2021)

LiNi_0.8Co_0.15Al_0.05O₂/石墨锂离子电池高荷电存储老化机理研究

刘勇¹, 白海军¹, 赵奇志¹, 杨金戈¹, 李宇杰²(), 郑春满²(), 谢凯²

1.中国人民解放军61699部队, 枝江 443200
2.国防科技大学空天科学学院, 长沙 410073

收稿日期:2020-01-08 修回日期:2020-03-27 出版日期:2021-02-20 网络出版日期:2020-04-05
通讯作者: 李宇杰, 副教授. E-mail: powerlyj@hotmail.com;
作者简介:刘勇(1989-), 男, 博士, 工程师. E-mail: liuzi244@sina.com
基金资助:
装备预研领域基金(JZX5Y20190261003101)

Storage Aging Mechanism of LiNi_0.8Co_0.15Al_0.05O₂/Graphite Li-ion Batteries at High State of Charge

LIU Yong¹, BAI Haijun¹, ZHAO Qizhi¹, YANG Jinge¹, LI Yujie²(), ZHENG Chunman²(), XIE Kai²

1. 61699 Unit of People’s Liberation Army of China, Zhijiang 443200, China
2. College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Received:2020-01-08 Revised:2020-03-27 Published:2021-02-20 Online:2020-04-05
About author:LIU Yong(1989-), male, PhD, engineer. E-mail: liuzi244@sina.com
Supported by:
Equipment Pre Research Fund(JZX5Y20190261003101)

摘要/Abstract

摘要：

高荷电存储寿命对锂离子电池的使用性能具有重要影响, 但是相关研究却较为缺乏。本研究通过高温加速实验, 研究了LiNi_0.8Co_0.15Al_0.05O₂(NCA)/石墨锂离子电池在55 ℃下的存储寿命, 分析了正负极材料在电池寿命终点时的电化学性能和界面变化。研究结果表明, 在55 ℃、高荷电状态下NCA/石墨锂离子电池的存储寿命约为90 d。在寿命终点时, 正负极活性材料的容量有一定下降, 但不是电池容量衰减的主要原因。界面分析表明, 存储后负极表面固体电解质界面(SEI)膜增长明显, 而正极表面固体电解质界面(PEI)膜无明显变化。SEI膜的增长主要是由于电解液溶剂和锂反应, 造成石墨内锂损失, 使电池内可循环锂减少, 这是NCA/石墨电池在存储过程中容量损失的主要原因。

关键词: 锂离子电池, NCA/石墨, 存储老化, 容量损失, 固体电解质界面膜

Abstract:

Storage life at high state of charge is a key factor affecting the application of Li ion battery, but the related mechanism research is insufficient. In this study, the storage life of LiNi_0.8Co_0.15Al_0.05O₂ (NCA)/graphite battery was evaluated via accelerating experiment at elevated temperature, and the electrochemistry performances and interface properties of fresh and aged active materials were analyzed. Storage experiment shows that the storage life of NCA/graphite battery at high state of charge under 55 ℃ is about 90 d. Electrochemical test shows that the capacities of NCA and graphite decrease when the batteries reach the end of life, but that is not the main cause inducing capacity degradation. Interface analysis illustrates that the solid electrolyte interface (SEI) film on graphite anode significantly grows when batteries reach the end of life, while the positive solid electrolyte interface (PEI) film on NCA cathode keeps basically unchanged. The growth of SEI film on graphite owing to the decomposition of carbonates in electrolyte results in Li loss in anode, which contributes to the capacity loss of NCA/graphite battery during the storage aging at high state of charge.

Key words: Li ion battery, NCA/graphite, storage aging, capacity fading, solid electrolyte interface (SEI)

中图分类号:

TM911

刘勇, 白海军, 赵奇志, 杨金戈, 李宇杰, 郑春满, 谢凯. LiNi_0.8Co_0.15Al_0.05O₂/石墨锂离子电池高荷电存储老化机理研究[J]. 无机材料学报, 2021, 36(2): 175-180.

LIU Yong, BAI Haijun, ZHAO Qizhi, YANG Jinge, LI Yujie, ZHENG Chunman, XIE Kai. Storage Aging Mechanism of LiNi_0.8Co_0.15Al_0.05O₂/Graphite Li-ion Batteries at High State of Charge[J]. Journal of Inorganic Materials, 2021, 36(2): 175-180.

图/表 7

图1 55 ℃下存储不同时间的电池在循环活化后的放电曲线

Fig. 1 Discharge curves of NCA/C batteries after stored at 55 ℃ for different time

图2 电池存储前后(a, b)正极以及(c, d)负极的(a, c) CV曲线和(b, d)放电曲线

Fig. 2 (a, c) CV and (b, d) discharge curves of (a, b) cathode and (c, d) anode before and after storage aging

图3 NCA(a, b)原料以及存储(c)前(d)后的SEM照片

Fig. 3 SEM images of NCA (a, b) pristine, (c) before and (d) after storage aging

图4 NCA(a)原料以及存储(b)前(c)后的TEM照片

Fig. 4 TEM images of NCA (a) pristine, (b) before and (c) after storage aging

图5 石墨负极(a)原料以及存储(b)前(c)后的SEM照片

Fig. 5 SEM images of graphite anode (a) pristine, (b) before and (c) after storage aging

图6 (a)石墨负极原材料TEM照片; 存储前石墨负极的(b)TEM和(c)STEM照片; 存储后石墨负极的(d)TEM和(e) STEM照片及(f)图6(e)方框区域的元素能谱图

Fig. 6 (a) TEM image of pristine graphite anode; (b) TEM and (c) STEM images of graphite anode before storage aging; (d) TEM, (e) STEM images of graphite anode after storage aging and (f) corresponding EDS mappings results in selected square area in Fig. 6(e)

图7 电解液溶剂的典型分解机理(EC为例)[26]

Fig. 7 Typical decomposition mechanism of electrolyte solvent (EC as example)[26]

参考文献 26

[1]	NITTA N, WU F, LEE J T, et al. Li-ion battery materials: present and future. Materials Today, 2015,18(5):252-264.
[2]	Battery Calendar Life Estimator Manual Modeling and Simulation, INL/EXT- 08015136,2012.
[3]	XU K. Electrolytes and interfaces in Li-ion batteries and beyond. Chemical Reviews, 2014,114(23):11503-11618.
[4]	BRYNGELSSON H, STJERNDAHL M, GUSTAFSSON T, et al. How dynamic is the SEI? Journal of Power Sources, 2007,174(2):970-975.
[5]	LIU R R, DENG X, LIU X R, et al. Facet dependent SEI formation on LiNi_0.5Mn_1.5O₄ cathode identified by in-situ single particle atomic force microscopy. Chemical Communications, 2014,50(99):15756-15759.
[6]	EDSTR M K, GUSTAFSSON T, THOMAS J O. The cathode- electrolyte interface in the Li-ion battery. Electrochimica Acta, 2004,50(2/3):397-403.
[7]	PALAC N M R, DE G A. Why do batteries fail? Science, 2016,351(6273):1253292.
[8]	EDDAHECH A, BRIAT O, VINASSA J M. Performance comparison of four lithium-ion battery technologies under calendar aging. Energy, 2015,84:542-550.
[9]	HAN X, LU L, ZHENG Y, et al. A review on the key issues of the lithium ion battery degradation among the whole life cycle. eTransportation, 2019,1:100005.
[10]	WATANABE S, KINOSHITA M, NAKURA K. Capacity fade of LiA_ylNi_1-_x_-_yCo_xO₂ cathode for lithium-ion batteries during accelerated calendar and cycle life test. I. Comparison analysis between LiA_ylNi_1-_x_-_yCo_xO₂and LiCoO₂ cathodes in cylindrical lithium-ion cell. Journal of Power Sources, 2014,247(2):412-422.
[11]	KASSEM M, BERNARD J, REVEL R, et al. Calendar aging of a graphite/LiFePO₄ cell. Journal of Power Sources, 2012,208(2):296-305.
[12]	GROLLEAU S, DELAILLE A, GUALOUS H, et al. Calendar aging of commercial graphite/LiFePO₄ cell-predicting capacity fade under time dependent storage conditions. Journal of Power Sources, 2014,255(6):450-458.
[13]	THOMAS E V, BLOOM I, CHRISTOPHERSEN J P, et al. Rate-based degradation modeling of lithium-ion cells. Journal of Power Sources, 2012,206(206):378-382.
[14]	LEKGOATHI M D S, VILAKAZI B M, WAGENER J B, et al. Decomposition kinetics of anhydrous and moisture exposed LiPF₆ salts by thermogravimetry. Journal of Fluorine Chemistry, 2013,149(2):53-56.
[15]	KAWAMURA T, OKADA S, YAMAKI J I. Decomposition reaction of LiPF₆-based electrolytes for lithium ion cells. Journal of Power Sources, 2006,156(2):547-554.
[16]	PINSON M B, BAZANT M Z. Theory of SEI formation in rechargeable batteries: capacity fade, accelerated aging and lifetime prediction. Journal of the Electrochemical Society, 2012,160(2):A243-A250.
[17]	CHUNG K Y, YOON W S, KIM K B, et al. Formation of an SEI on a LiMn₂O₄ cathode during room temperature charge-discharge cycling studied by soft X-ray absorption spectroscopy at the fluorine k-edge. Journal of Applied Electrochemistry, 2011,41(11):1295-1299.
[18]	ABRAHAM D P, TWESTEN R D, BALASUBRAMANIAN M, et al. Microscopy and spectroscopy of lithium nickel oxide-based particles used in high power lithium-ion cells. Journal of the Electrochemical Society, 2003,150(150):A1450-A1456.
[19]	ABRAHAM D P, TWESTEN R D, BALASUBRAMANIAN M, et al. Surface changes on LiNi_0.8Co_0.2O₂ particles during testing of high-power lithium-ion cells. Electrochemistry Communications, 2002,4(8):620-625.
[20]	NIE M, CHALASANI D, ABRAHAM D P, et al. Lithium ion battery graphite solid electrolyte interface revealed by microscopy and spectroscopy. Journal of Physical Chemistry C, 2013,117(3):1257-1267.
[21]	PELED E, MENKIN S. Review—SEI: past, present and future. Journal of the Electrochemical Society, 2017,164(7):A1703-A1719.
[22]	GAUTHIER M, CARNEY T J, GRIMAUD A, et al. Electrode- electrolyte interface in Li-ion batteries: current understanding and new insights. The Journal of Physical Chemistry Letters, 2015,6(22):4653-4672.
[23]	VERMA P, MAIRE P, NOV K P. A review of the features and analyses of the solid electrolyte interface in Li-ion batteries. Electrochimica Acta, 2010,55(22):6332-6341.
[24]	NANDA J, YANG G, HOU T, et al. Unraveling the nanoscale heterogeneity of solid electrolyte interface using tip-enhanced Raman spectroscopy. Joule, 2019,3(8):2001-2019.
[25]	AGUBRA V A, FERGUS J W. The formation and stability of the solid electrolyte interface on the graphite anode. Journal of Power Sources, 2014,268(268):153-162.
[26]	HEISKANEN S K, KIM J, LUCHT B L. Generation and evolution of the solid electrolyte interface of lithium-ion batteries. Joule, 2019,3(10):2322-2333.

LiNi_0.8Co_0.15Al_0.05O₂/石墨锂离子电池高荷电存储老化机理研究

Storage Aging Mechanism of LiNi_0.8Co_0.15Al_0.05O₂/Graphite Li-ion Batteries at High State of Charge

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