Study on the cyclic aging mechanism of nickel-rich silicon-graphite lithium-ion cells

doi:10.19799/j.cnki.2095-4239.2024.0272

Abstract

Abstract:

High nickel lithium-ion batteries offer high energy density and power density, making them widely used today. However, capacity loss due to aging remains a challenge for their efficient utilization. This study investigates the aging mechanism of high-nickel lithium-ion batteries, conducting cyclic aging experiments on high-nickel/silicon carbon-based lithium batteries. The aging modes at different life stages of high-nickel ternary lithium-ion batteries are comprehensively analyzed and verified using both nondestructive and destructive tests. The results indicate that the capacity of Li-ion batteries decreases in two distinct stages. In the first stage, the capacity loss is linear, primarily due to the loss of lithium ions, with the main aging mechanisms being the growth of the SEI and the degradation of anode materials. In the second stage, the capacity decreases abruptly, driven by both the loss of lithium ions and a decline in electrical conductivity. The primary aging mechanisms during this stage include the dissolution of cathode materials, irreversible changes in cathode crystal structures, and the degradation of the battery separator. The main aging mechanisms include the dissolution of anode material, irreversible changes in anode crystal structure, and blockage of the battery separator. Computed tomography analysis of the overall morphology of lithium-ion batteries at different life stages reveals that the initial battery production process significantly impacts the areas where aging occurs. XPS test results indicate that the passivation layer on the surfaces of both the anode and cathode continues to thicken throughout the battery's cycling experiments. Additionally, the deposition of transition metal Ni on the surface of the cathode material is observed, which significantly affects the battery's energy storage capacity. This paper reveals the aging characteristics and mechanism of high-nickel lithium battery, offering valuable theoretical insights for the graded utilization of these batteries.

Key words: high-nickel ternary lithium battery, aging characteristics battery capacity loss, electrochemical characteristics, morphological characteristics, aging mechanism

CLC Number:

TM 912

Wenhao HU, Chenxi ZHAO, Zhuo'er SUN, Pei ZHANG, Xuehui WANG, Jian WANG. Study on the cyclic aging mechanism of nickel-rich silicon-graphite lithium-ion cells[J]. Energy Storage Science and Technology, 2024, 13(10): 3504-3514.

Figures/Tables 13

Fig. 1

Fig. 2

Table 1

Lithium battery impedance table"

健康度	$R Ω / m Ω$	$I C L$	$R c t + R s e i / m Ω$	$I L L I$	$W / m Ω - 1$	$I L A M$
100%SOH	33.19	0	8.211	0	242.2	0
80%SOH	36.62	0.103	31.008	2.776	184.7	0.31
40%SOH	59.68	0.798	59.96	6.302	109.6	1.22

Table 1

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

Fig. 8

Fig. 9

Fig. 10

Fig. 11

Fig. 12

References 32

1	DIOUF B, PODE R. Potential of lithium-ion batteries in renewable energy[J]. Renewable Energy, 2015, 76: 375-380. DOI: 10.1016/j.renene.2014.11.058.
2	ARMAND M, TARASCON J M. Building better batteries[J]. Nature, 2008, 451(7179): 652-657. DOI: 10.1038/451652a.
3	JUNG R, METZGER M, MAGLIA F, et al. Oxygen release and its effect on the cycling stability of LiNixMnyCozO₂(NMC) cathode materials for Li-ion batteries[J]. Journal of the Electrochemical Society, 2017, 164(7): A1361-A1377. DOI: 10.1149/2.0021707jes.
4	BELHAROUAK I, SUN Y K, LIU J, et al. Li(Ni_1/3Co_1/3Mn_1/3)O₂ as a suitable cathode for high power applications[J]. Journal of Power Sources, 2003, 123(2): 247-252. DOI: 10.1016/S0378-7753(03)00529-9.
5	WHITTINGHAM M S. Lithium batteries and cathode materials[J]. Chemical Reviews, 2004, 104(10): 4271-4302. DOI: 10.1021/cr020731c.
6	YABUUCHI N, MAKIMURA Y, OHZUKU T. Solid-state chemistry and electrochemistry of LiCo_1∕3Ni_1∕3Mn_1∕3O₂ for advanced lithium-ion batteries[J]. Journal of the Electrochemical Society, 2007, 154(4): A314. DOI: 10.1149/1.2455585.
7	KIM M G, SHIN H J, KIM J H, et al. XAS investigation of inhomogeneous metal-oxygen bond covalency in bulk and surface for charge compensation in Li-ion battery cathode Li[Ni_1∕3Co_1∕3Mn_1∕3]O₂ material[J]. Journal of the Electrochemical Society, 2005, 152(7): A1320. DOI: 10.1149/1.1926647.
8	NOH H J, YOUN S, YOON C S, et al. Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]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. DOI: 10.1016/j.jpowsour.2013.01.063.
9	LUO Z J, FAN D D, LIU X L, et al. High performance silicon carbon composite anode materials for lithium ion batteries[J]. Journal of Power Sources, 2009, 189(1): 16-21. DOI: 10.1016/j.jpowsour.2008.12.068.
10	LIANG T, KNAPPETT J A. Centrifuge modelling of the influence of slope height on the seismic performance of rooted slopes[J]. Géotechnique, 2017, 67(10): 855-869. DOI: 10.1680/jgeot.16.p.072.
11	FUCHSBICHLER B, STANGL C, KREN H, et al. High capacity graphite-silicon composite anode material for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(5): 2889-2892. DOI: 10.1016/j.jpowsour.2010.10.081.
12	杨阳. 退役锂电池梯级利用、容量衰减及回收流程研究[D]. 长沙: 湖南大学, 2019. DOI: 10.27135/d.cnki.ghudu.2019.003985.
	YANG Y. Study on cascade utilization, capacity attenuation and recovery process of retired lithium batteries[D]. Changsha: Hunan University, 2019. DOI: 10.27135/d.cnki.ghudu.2019.003985.
13	CHAN C K, PENG H L, LIU G, et al. High-performance lithium battery anodes using silicon nanowires[J]. Nature Nanotechnology, 2008, 3(1): 31-35. DOI: 10.1038/nnano.2007.411.
14	葛昊, 李哲, 张剑波. 锂离子电池开路电压曲线形状与多阶段容量损失[J]. 储能科学与技术, 2019, 8(6): 1089-1095. DOI: 10.12028/j.issn.2095-4239.2019.0098.
	GE H, LI Z, ZHANG J B. Multi-stage capacity loss of lithium-ion batteries originating from the multi-slope nature of open circuit voltage curves[J]. Energy Storage Science and Technology, 2019, 8(6): 1089-1095. DOI: 10.12028/j.issn.2095-4239.2019.0098.
15	潘伟民. 高温下镍钴铝/石墨锂电池全生命周期老化机理研究[J]. 农业装备与车辆工程, 2024, 62(3): 116-120.
	PAN W M. Research on aging mechanism of NCA/Graphite lithium battery at high temperature on full cycle life[J]. Agricultural Equipment & Vehicle Engineering, 2024, 62(3): 116-120.
16	李浩强, 范茂松, 周自强, 等. 三元锂离子电池的容量跳水机理研究[J]. 电源技术, 2021, 45(2): 153-157, 162. DOI: 10.3969/j.issn.1002-087X.2021.02.004.
	LI H Q, FAN M S, ZHOU Z Q, et al. Research on capacity diving mechanism of ternary lithium-ion batteries[J]. Chinese Journal of Power Sources, 2021, 45(2): 153-157, 162. DOI: 10.3969/j.issn.1002-087X.2021.02.004.
17	KRAUSE F C, RUIZ J P, JONES S C, et al. Performance of commercial Li-ion cells for future NASA missions and aerospace applications[J]. Journal of the Electrochemical Society, 2021, 168(4): 040504. DOI: 10.1149/1945-7111/abf05f.
18	HEENAN T M M, JNAWALI A, KOK M D R, et al. An advanced microstructural and electrochemical datasheet on 18650 Li-ion batteries with nickel-rich NMC811 cathodes and graphite-silicon anodes[J]. Journal of the Electrochemical Society, 2020, 167(14): 140530. DOI: 10.1149/1945-7111/abc4c1.
19	CHOI W, SHIN H C, KIM J M, et al. Modeling and applications of electrochemical impedance spectroscopy (EIS) for lithium-ion batteries[J]. Journal of Electrochemical Science and Technology, 2020, 11(1): 1-13. DOI: 10.33961/jecst.2019.00528.
20	陈芬放. 高能量密度NCA正极锂离子电池老化过程产热特性研究[D]. 杭州: 浙江大学, 2021. DOI: 10.27461/d.cnki.gzjdx.2021.002479.
	CHEN F F. Study on heat generation characteristics of high energy density NCA cathode lithium ion battery during aging[D]. Hangzhou: Zhejiang University, 2021. DOI: 10.27461/d.cnki.gzjdx.2021.002479.
21	杨小龙, 罗卫, 樵燊, 等. 镍钴铝三元锂电池容量"跳水" 机理研究[J]. 湖南大学学报(自然科学版), 2023, 50(6): 171-179. DOI: 10.16339/j.cnki.hdxbzkb.2023305.
	YANG X L, LUO W, QIAO S, et al. Research on capacity plunge mechanisms of NCA/graphite lithium-ion batteries[J]. Journal of Hunan University (Natural Sciences), 2023, 50(6): 171-179. DOI: 10.16339/j.cnki.hdxbzkb.2023305.
22	ANSEÁN D, DUBARRY M, DEVIE A, et al. Fast charging technique for high power LiFePO₄ batteries: A mechanistic analysis of aging[J]. Journal of Power Sources, 2016, 321: 201-209. DOI: 10.1016/j.jpowsour.2016.04.140.
23	XIE W L, HE R, GAO X L, et al. Degradation identification of LiNi_0.8Co_0.1Mn_0.1O₂/graphite lithium-ion batteries under fast charging conditions[J]. Electrochimica Acta, 2021, 392: 138979. DOI: 10. 1016/j.electacta.2021.138979.
24	OHZUKU T, IWAKOSHI Y, SAWAI K. Formation of lithium-graphite intercalation compounds in nonaqueous electrolytes and their application as a negative electrode for a lithium ion (shuttlecock) cell[J]. Journal of the Electrochemical Society, 1993, 140(9): 2490-2498. DOI: 10.1149/1.2220849.
25	ZILBERMAN I, STURM J, JOSSEN A. Reversible self-discharge and calendar aging of 18650 nickel-rich, silicon-graphite lithium-ion cells[J]. Journal of Power Sources, 2019, 425: 217-226. DOI: 10.1016/j.jpowsour.2019.03.109.
26	ZILBERMAN I, LUDWIG S, JOSSEN A. Cell-to-cell variation of calendar aging and reversible self-discharge in 18650 nickel-rich, silicon–graphite lithium-ion cells[J]. Journal of Energy Storage, 2019, 26: 100900. DOI: 10.1016/j.est.2019.100900.
27	LI T Y, YUAN X Z, ZHANG L, et al. Degradation mechanisms and mitigation strategies of nickel-rich NMC-based lithium-ion batteries[J]. Electrochemical Energy Reviews, 2020, 3(1): 43-80. DOI: 10.1007/s41918-019-00053-3.
28	马天翼, 苏素, 张宗, 等. 计算机断层扫描技术在锂离子电池检测中的应用研究[J]. 重庆理工大学学报(自然科学), 2020, 34(2): 133-139. DOI: 10.3969/j.issn.1674-8425(z).2020.02.019.
	MA T Y, SU S, ZHANG Z, et al. Application of computed tomography in lithium-ion battery detection[J]. Journal of Chongqing University of Technology (Natural Science), 2020, 34(2): 133-139. DOI: 10.3969/j.issn.1674-8425(z).2020.02.019.
29	LIU Y J, XIA Y, ZHOU Q. Effect of low-temperature aging on the safety performance of lithium-ion pouch cells under mechanical abuse condition: A comprehensive experimental investigation[J]. Energy Storage Materials, 2021, 40: 268-281. DOI: 10.1016/j.ensm.2021.05.022.
30	LI Z, HUANG J, YANN LIAW B, et al. A review of lithium deposition in lithium-ion and lithium metal secondary batteries[J]. Journal of Power Sources, 2014, 254: 168-182. DOI: 10.1016/j.jpowsour.2013.12.099.
31	李胡. 镍钴锰三元锂离子电池老化机理的研究[D]. 厦门: 厦门大学, 2019. DOI: 10.27424/d.cnki.gxmdu.2019.001079.
	LI H. Study on aging mechanism of Ni-Co-Mn ternary lithium ion battery[D]. Xiamen: Xiamen University, 2019. DOI: 10.27424/d.cnki.gxmdu.2019.001079.
32	FLEISCHHAMMER M, WALDMANN T, BISLE G, et al. Interaction of cyclic ageing at high-rate and low temperatures and safety in lithium-ion batteries[J]. Journal of Power Sources, 2015, 274: 432-439. DOI: 10.1016/j.jpowsour.2014.08.135.