Exploration of the cause of hydrogen generation in NCM lithium-ion batteries

doi:10.19799/j.cnki.2095-4239.2020.0222

Abstract

Abstract:

In this work, gas chromatography (GC) and rechargeable symmetrical lithium-ion batteries were used to explore the causes of H₂ generation in NCM lithium-ion batteries (LIBs). In addition to determining whether H₂ is produced by the reduction of trace water in the battery, this paper explores whether the H₂ generation mechanisms for NCM LIBs are best described as arising from the proton electrolyte oxide (R-H⁺) or carbonate dissociation into H^?. Considering that R-H⁺ deposited on the negative electrode is the related product between the positive and negative electrodes, the graphite/graphite negative symmetrical cell (NSC), the NCM/NCM (LiNi_0.6Co_0.2Mn_0.2O₂ is defined as NCM) positive symmetrical cell (PSC), and graphite/NCM pouch cell (PC) with charge and discharge capacity were prepared. After a room temperature cycling test and an overcharge test, the GC results indicated that H₂ was produced in the soft package full cell and the negative symmetrical battery, but not in the positive symmetrical battery. This result supports the R-H⁺ mechanism, where H2 is produced by the reduction of the R-H⁺ deposited on the negative electrode, so in the positive symmetrical cell, no H₂ is produced. In order to eliminate any interfering signal of H₂ produced by the reduction of trace water in the battery, the positive symmetrical battery without H₂ generation after cycles was selected. After adding trace water to the system, H₂ was indeed detected in the GC results. Therefore, H₂ production from trace moisture in the original cells can be ignored. Finally, the mechanism of H₂ production by the dissociation of carbonate to H^? was tested using the positive symmetric cell. The influence of R-H⁺ and water on the final H₂ production can be ignored according to the previous experimental results. After a high temperature storage and a high temperature overcharge test, no H₂ was detected in the cathode symmetry battery after cycling, so the mechanism of H₂ production by dissociation of carbonate to H^? is not the active mechanism.

Key words: gas chromatography, symmetric cells, H₂, R-H⁺, $H ?$

CLC Number:

TM 911

Xueqin YUAN, Lei YANG. Exploration of the cause of hydrogen generation in NCM lithium-ion batteries[J]. Energy Storage Science and Technology, 2021, 10(1): 150-155.

Figures/Tables 10

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样品	PC1	PC2	NSC1	NSC2	PSC1	PSC2
H₂	56.10	72.72	18.32	26.81	0.00	0.00
O₂	0.00	0.00	0.00	0.00	0.00	0.00
CO	4.63	3.36	55.90	0.00	0.00	0.00
CH₄	14.32	3.29	12.84	3.40	0.00	0.00
CO₂	2.72	2.74	5.90	64.82	100.00	100.00
C₂H₄	21.19	17.33	4.09	2.96	0.00	0.00
C₂H₆	1.04	0.56	2.96	0.48	0.00	0.00
C₃H₆	0.00	0.00	0.00	1.53	0.00	0.00
C₃H₈	0.00	0.00	0.00	0.00	0.00	0.00

样品	R_s/Ω	R_f/Ω	R_ct/Ω
全电池	0.59	1.10	1.98
负极对称电池	1.15	1.09	1.92
正极对称电池	0.58	0.42	0.86

气体	PC1	PC2	NSC1	NSC2	PSC1	PSC2
H₂	42.64	54.41	46.45	63.96	0.00	0.00
O₂	0.00	0.00	0.00	0.00	0.00	0.00
CO	8.96	2.40	13.26	0.00	12.87	20.57
CH₄	7.71	9.81	2.29	7.81	0.00	0.00
CO₂	34.53	29.29	26.56	23.70	84.98	77.29
C₂H₄	1.81	0.13	10.97	2.39	2.15	2.14
C₂H₆	3.38	3.95	0.38	2.13	0.00	0.00
C₃H₆	0.89	0.00	0.10	0.00	0.00	0.00
C₃H₈	0.09	0.00	0.00	0.00	0.00	0.00