新型CFx锂原电池自放电率的比较研究及其应用建议

doi:10.19799/j.cnki.2095-4239.2024.0922

摘要/Abstract

摘要：

新型高比能氟化碳(CFx)材料不断涌现，使Li/CFx原电池的比能量/比功率特性不断提升，特别是功率型Li/CFx电池已开始用于小型商业化动力系统中，可能成为比能量最高的动力型锂原电池。但不同类型CFx材料制备的Li/CFx锂原电池的自放电情况尚缺乏比较研究。本文选择4种典型的新型CFx材料，根据其应用目标分为能量型和功率型材料，其中2种能量型CFx的F/C比接近1，具有更稳定而饱和的C-F化学键，而2种功率型CFx材料F/C比略低，离子型C-F键更多，具有更好的导电性和更好的倍率性能。通过工业化设备工艺制备成的BR18650型Li/CFx原电池经55℃高温储存后，无论是否放电过的能量型电池的自放电率几乎为0，具有长寿命货架储存特性；而功率型电池55℃储存后，放电深度(DOD)越高的电池的内阻越大、自放电率也越大，锂原电池常用的预放电处理工艺会导致功率型电池的自放电率上升，意味着功率型电池一旦预放电激活后就应立即投入使用。功率型电池间歇式使用会导致其自放电率增大和内阻增加，原因可能是松散LiF保护膜的破坏造成新鲜CFx界面暴露于电解液中继续反应，但能量型CFx材料因其具有更多稳定的饱和C-F共价键而影响较小。

关键词: 锂/氟化碳电池, 原电池, 自放电率

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

中图分类号:

TM911

杨微, 李治国, 赖彩婷, 赵瑞瑞, 李瑀, 周盈科, 黄依玲, 朱立才, 封伟, 王文龙, 袁中直. 新型CFx锂原电池自放电率的比较研究及其应用建议[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2024.0922.

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