Comparative study on self-discharge rate of new CFx lithium primary batteries and recommendations for their use

doi:10.19799/j.cnki.2095-4239.2024.0922

Abstract

Abstract:

The emergence of new high specific energy fluorinated carbon (CFx) materials has continuously improved the specific energy/specific power characteristics of Li/CFx primary batteries, especially the power type Li/CFx batteries have begun to be used in small commercial power systems and may become the power type lithium primary batteries with the highest specific energy. However, there is a lack of comparative study on the self-discharge of Li/CFx lithium primary batteries prepared from different types of CFx materials. This article selects four typical novel CFx materials that are divided into energy type and power type materials according to their applications, among which two energy type CFx materials have F/C ratios close to 1 and more stable and saturated C-F chemical bonds, while two power type CFx materials have lower F/C ratios and more ionic C-F bonds, resulting in better conductivity and rate performance. After being stored at a high temperature of 55 ℃, the self-discharge rate of the industrially prepared BR18650 Li/CFx battery, regardless of whether it has been discharged or not, is almost zero, making it suitable for long-life shelf storage. However, for power batteries stored at 55 ℃, the higher the depth of discharge (DOD), the greater the internal resistance and self-discharge rate of the battery. The pre-discharge treatment that is commonly used in lithium primary battery industry can lead to an increase in the self-discharge rate of power type batteries, which means that power type batteries should be put into use immediately after pre-discharge activation. Intermittent use of power type batteries can lead to an increase in their self-discharge rate and internal resistance, which may be due to the damage of the loose LiF protective film causing the fresh CFx interface to be exposed to the electrolyte and continuous reaction, but the energy type CFx material has less impact due to its more stable saturated C-F covalent bonds.

Key words: lithium/carbon fluoride battery, primary battery, self-discharge rate

CLC Number:

TM911

Wei YANG, Zhiguo LI, Caiting LAI, Ruirui ZHAO, Yu LI, Yingke ZHOU, Yiling HUANG, Licai ZHU, Wei FENG, Wenlong WANG, Zhongzhi YUAN. Comparative study on self-discharge rate of new CFx lithium primary batteries and recommendations for their use[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2024.0922.

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材料	F/C	粒径/μm				杂质元素含量/ppm							振实密度 g/cm³	克容量 mAh/g
材料	F/C	D10	D50	D90	Dmax	Fe	Cu	Ni	Zn	Na	Mg	Cr	振实密度 g/cm³	克容量 mAh/g
CF01	0.98	3.000	8.250	17.470	35.566	4.43	ND	6.068	ND	1.41	0.03	2.41	0.9517	849.66
CF02	0.94	2.265	5.946	12.735	25.178	80.81	0.217	84.69	ND	14.87	ND	9.313	0.9616	814.42
CF03	0.88	2.919	5.804	10.626	17.825	20.09	1.784	20.78	3.149	ND	0.263	4.611	0.7926	756.13
CF04	0.87	1.984	10.515	22.657	39.905	19.34	0.678	15.65	2.11	ND	0.225	1.694	1.0045	750.28

CFx样品	比表面积m²/g	孔体积cm³/g
CF01	226.04	0.1178
CF02	312.32	0.1693
CF03	440.67	0.3170
CF04	283.84	0.1612

谱图		C1s				表面元素含量/%
峰位置/eV	284.73	287.17	289.10	290.00	291.92	C	F
键类型	C1(C=C<)	C2(CF-C <)	C3(FC(C3))-Semi-ionic	C3(FC(C3))-Covalent	C4(F2C(CF)2)	C	F
CF01	8.03	3.05	1.92	75.50	11.50	45.24	54.76
CF02	6.82	9.00	2.27	64.71	17.00	45.00	55.00
CF03	10.20	20.68	3.70	50.89	14.53	46.79	53.21
CF04	6.81	16.67	2.70	55.00	18.82	50.10	49.90

电池	55℃存储/d	放电倍率/C	放电截止2V的容量保持率/%
电池	55℃存储/d	放电倍率/C	0%DOD	10%DOD	30%DOD	50%DOD
Li/CF01	30d	0.01C	99.59	99.72	101.17	100.42
	60d		99.55	99.88	101.36	100.14
	90d		99.64	99.94	100.71	100.40
Li/CF02	30d	0.01C	99.41	100.10	100.21	100.78
	60d		99.44	99.59	99.47	99.35
	90d		99.52	99.62	99.83	99.27
Li/CF03	30d	0.5C	96.76	99.20	99.42	76.20
	60d		96.20	97.30	95.60	75.63
	90d		95.50	92.59	89.91	66.73
Li/CF04	30d	0.5C	98.63	98.47	97.86	98.23
	60d		98.67	98.18	97.02	97.92
	90d		98.35	96.95	96.65	94.71

方案	存储时间/d	截止2V材料发挥率/%	截止2V容量保持率/%	自放电率/%
CF03(-)	0d	77.09
CF03(-)	30d	76.19	99.43	0.57
CF03(+)	0d	72.94
CF03(+)	30d	70.33	96.76	3.42