Thermal behavior of lithium titanate based Li ion batteries under slight over-discharging condition

doi:10.19799/j.cnki.2095-4239.2021.0534

Abstract

Abstract:

Lithium titanate (LTO) batteries are well-known for their long cycle life, good rate performance, and thermal safety. However, few studies reported the effects of electric and thermal abuse on the electrochemical performance and thermal safety of LTO batteries. In this study, the electrical and thermal safety properties, as well as the microstructure of electrode materials of certain types of commercial cylindrical 18650 LTO batteries were studied under a series of slight over-discharging conditions at various current rates (0.5 C, 1 C, 2 C, 5 C, and 1 C 100 cycles) with the aid of an electrochemical workstation and accelerating rate calorimeter. Moreover, we then adopted a "top-down" strategy to disassemble the LTO batteries to obtain their anode and cathode materials. We also examined the structure of such electrode materials via an X-ray diffractometer and scanning electron microscope from a microscopic point of view. Related results have illustrated that (1) the internal resistances of LTO batteries changed little after the first cycle of over-discharging with current rates of no more than 5 C. While manifold cycles of over-discharging dramatically accelerated the aging of LTO batteries, reflected by the quick drop in their energy retention rate and the rise in internal resistance. However, the thermal safety character of the batteries with manifold cycles of over-discharging has shown no significant change. (2) The thermal safety of LTO batteries can be significantly reduced after over-discharging treatment at a large current rate (5 C), with the onset temperature of self-heating (T₁) decreasing and the maximum temperature (T₃) in the thermal runaway process rising simultaneously. The partial cracking and pulverizing of LTO particles and the uneven SEI generated on the anode material are the leading causes for the deterioration of the thermal safety character of LTO batteries under over-discharging conditions. This research has illustrated the potential risk of over-discharging on the electrochemical performance and thermal safety of LTO batteries. We hope this work could bring attention to the safe application of LTO batteries.

Key words: lithium titanate (LTO) batteries, over-discharge, thermal safety, anode material

CLC Number:

TM 911.3

Honghui WANG, Zeqin WU, Deren CHU. Thermal behavior of lithium titanate based Li ion batteries under slight over-discharging condition[J]. Energy Storage Science and Technology, 2022, 11(5): 1305-1313.

Figures/Tables 11

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电池样品	R_o/mΩ	R_SEI/mΩ	R_ct/mΩ
LTO-Fresh	42.51	—	4.978
LTO-0.5 C	40.75	—	3.947
LTO-1 C	46.57	—	7.122
LTO-2 C	43.75	—	3.512
LTO-5 C	40.94	—	5.217
LTO-100CYC	44.91	10.00	6.741

电池样品	T₁/℃	T_vent/℃	T₂/℃	T₃/℃
LTO-Fresh	72.0	138.2	235.4	308.8
LTO-2 C	97.3	137.6	235.7	305.3
LTO-5 C	63.1	140.0	238.1	323.8
LTO-0 V	96.8	135.6	—	305.0
NCM-Fresh	62.5	127.9	183.6	617.2
NCM-0 V	92.7	120.1	—	305.0

电池样品	A/s^-1	E_a/(kJ/mol)	R²
LTO-Fresh	3.166×10²⁰	203.87	0.9985
LTO-2 C	6.394×10²⁰	206.89	0.9986
LTO-5 C	1.293×10²¹	211.06	0.9883
NCM-Fresh	4.409×10¹³	125.41	0.9977

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