Comparative study on self-discharge rate of new CF x 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 (CF _x ) materials has continuously improved the specific energy/specific power characteristics of Li/CF _x primary batteries, especially the power type Li/CF _x 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/CF _x lithium primary batteries prepared from different types of CF _x materials. This article selects four typical novel CF _x materials that are divided into energy type and power type materials according to their applications, among which two energy type CF _x materials have F/C ratios close to 1 and more stable and saturated C－F chemical bonds, while two power type CF _x 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/CF _x 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 CF _x interface to be exposed to the electrolyte and continuous reaction, but the energy type CF _x 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:

TM 911

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 CF _x lithium primary batteries and recommendations for their use[J]. Energy Storage Science and Technology, 2024, 13(11): 3742-3753.

Figures/Tables 14

Table 1

Fig.1

Fig.2

Fig.3

Table 2

Fig.4

Table 3

Fig.5

Table 4

Fig.6

Table 5

Fig.7

Fig.8

Table 6

References 29

1	ZHANG S X, KONG L C, LI Y, et al. Fundamentals of Li/CFx battery design and application[J]. Energy & Environmental Science, 2023, 16(5): 1907-1942. DOI: 10.1039/D2EE04179K.
2	ZHU H J, GAVRIL M, FENG L, et al. Li/CFx medical battery development[J]. ECS Transactions, 2008, 11(32): 11-17. DOI: 10.1149/1.2992489.
3	YANG W J, DAI Y, CAI S D, et al. Graphene/Au composite paper as flexible current collector to improve electrochemical performances of CFx cathode[J]. Journal of Power Sources, 2014, 255: 37-42. DOI: 10.1016/j.jpowsour.2013.12.122.
4	YAN K, ZOU Y, BAO L X, et al. Fluorinated N,P co-doped biomass carbon with high-rate performance as cathode material for lithium/fluorinated carbon battery[J]. Rare Metals, 2024. DOI: 10.1007/s12598-024-02894-4.
5	ZHANG Q, D'ASTORG S, XIAO P, et al. Carbon-coated fluorinated graphite for high energy and high power densities primary lithium batteries[J]. Journal of Power Sources, 2010, 195(9): 2914-2917. DOI: 10.1016/j.jpowsour.2009.10.096.
6	LUO Z Y, LUO S, YANG M, et al. Revealing the mechano-electrochemical coupling behavior and discharge mechanism of fluorinated carbon cathodes toward high-power lithium primary batteries[J]. Small, 2024, 20(7): 2305980. DOI: 10.1002/smll.202305980.
7	GUÉRIN K, DUBOIS M, HOUDAYER A, et al. Applicative performances of fluorinated carbons through fluorination routes: A review[J]. Journal of Fluorine Chemistry, 2012, 134: 11-17. DOI: 10.1016/j.jfluchem.2011.06.013.
8	JIANG S B, HUANG P, LU J C, et al. The electrochemical performance of fluorinated ketjenblack as a cathode for lithium/fluorinated carbon batteries[J]. RSC Advances, 2021, 11(41): 25461-25470. DOI: 10.1039/d1ra03873g.
9	PENG C, LI Y, YAO F N, et al. Ultrahigh-energy-density fluorinated calcinated macadamia nut shell cathodes for lithium/fluorinated carbon batteries[J]. Carbon, 2019, 153: 783-791. DOI: 10.1016/j.carbon.2019.07.065.
10	KONG L C, LI Y, PENG C, et al. Defective nano-structure regulating C－F bond for lithium/fluorinated carbon batteries with dual high-performance[J]. Nano Energy, 2022, 104: 107905. DOI: 10.1016/j.nanoen.2022.107905.
11	LAM P, YAZAMI R. Physical characteristics and rate performance of (CFx)n (0.33<x<0.66) in lithium batteries[J]. Journal of Power Sources, 2006, 153(2): 354-359. DOI: 10.1016/j.jpowsour. 2005.05.022.
12	MA J, LIU Y F, PENG Y, et al. UV-radiation inducing strategy to tune fluorinated carbon bonds delivering the high-rate Li/CFx primary batteries[J]. Composites Part B: Engineering, 2022, 230: 109494. DOI: 10.1016/j.compositesb.2021.109494.
13	DAI Y, FANG Y, CAI S D, et al. Surface modified pinecone shaped hierarchical structure fluorinated mesocarbon microbeads for ultrafast discharge and improved electrochemical performances[J]. Journal of the Electrochemical Society, 2016, 164(2): A1-A7. DOI: 10.1149/2.0451614jes.
14	DAI Y, CAI S D, WU L J, et al. Surface modified CFx cathode material for ultrafast discharge and high energy density[J]. Journal of Materials Chemistry A, 2014, 2(48): 20896-20901. DOI: 10.1039/C4TA05492J.
15	YIN Y J, HOLOUBEK J, LIU A, et al. Ultralow-temperature Li/CFx batteries enabled by fast-transport and anion-pairing liquefied gas electrolytes[J]. Advanced Materials, 2023, 35(3): e2207932. DOI: 10.1002/adma.202207932.
16	WANG X X, SONG Z Y, WU H, et al. Anion donicity of liquid electrolytes for lithium carbon fluoride batteries[J]. Angewandte Chemie International Edition, 2022, 61(47): e202211623. DOI: 10.1002/anie.202211623.
17	YU J, WANG D, WANG G, et al. Breaking the electronic conductivity bottleneck of manganese oxide family for high-power fluorinated graphite composite cathode by ligand-field high-dimensional constraining strategy[J]. Advanced Materials, 2023, 35(8): 2209210.
18	LI L Y, WU R Z, MA H C, et al. Toward the high-performance lithium primary batteries by chemically modified fluorinate carbon with δ-MnO₂[J]. Small, 2023, 19(26): 2300762. DOI: 10.1002/smll.202300762.
19	LI Y Y, WU X Z, LIU C, et al. Fluorinated multi-walled carbon nanotubes as cathode materials of lithium and sodium primary batteries: Effect of graphitization of carbon nanotubes[J]. Journal of Materials Chemistry A, 2019, 7(12): 7128-7137. DOI: 10.1039/c8ta12074a.
20	阳晓霞, 段征, 金晶龙, 等. 高比能氟化碳材料及Li/CFx电池的特性研究[J]. 电源技术, 2018, 42(8): 1161-1162, 1170. DOI: 10.3969/j.issn.1002-087X.2018.08.021.
	YANG X X, DUAN Z, JIN J L, et al. Performance research of polycarbon mono-fluoride and Li/CFx cell[J]. Chinese Journal of Power Sources, 2018, 42(8): 1161-1162, 1170. DOI: 10.3969/j.issn.1002-087X.2018.08.021.
21	卢立丽, 王松蕊. 锂氟化碳电池放电热效应的模拟研究[J]. 电源技术, 2016, 40(5): 1098-1102. DOI: 10.3969/j.issn.1002-087X.2016.05.048.
	LU L L, WANG S R. Studies on thermal effects during discharging of lithium carbon fluoride cells by simulation[J]. Chinese Journal of Power Sources, 2016, 40(5): 1098-1102. DOI: 10.3969/j.issn.1002-087X.2016.05.048.
22	LIU W, YAN T F, GUO R, et al. Analysis of electrochemical performance of lithium carbon fluorides primary batteries after storage[J]. Journal of Materiomics, 2021, 7(6): 1225-1232. DOI: 10.1016/j.jmat.2021.02.010.
23	ZHOU R X, LI Y, FENG Y Y, et al. The electrochemical performances of fluorinated hard carbon as the cathode of lithium primary batteries[J]. Composites Communications, 2020, 21: 100396. DOI: 10.1016/j.coco.2020.100396.
24	GONG P W, WANG Z F, WANG J Q, et al. One-pot sonochemical preparation of fluorographene and selective tuning of its fluorine coverage[J]. Journal of Materials Chemistry, 2012, 22(33): 16950-16956. DOI: 10.1039/C2JM32294C.
25	张红梅, 甘潦, 王开琼, 等. 纳米Ag改性方式对锂氟化碳电池性能的影响[J]. 电源技术, 2023, 47(9): 1164-1168. DOI: 10.3969/j.issn.1002-087X.2023.09.013.
	ZHANG H M, GAN L, WANG K Q, et al. Effect of nano-Ag modification methods on performance of lithium fluoride carbon batteries[J]. Chinese Journal of Power Sources, 2023, 47(9): 1164-1168. DOI: 10.3969/j.issn.1002-087X.2023.09.013.
26	LIU W, MA S, LI Y, et al. Electrochemical impedance spectroscopy analysis for lithium carbon fluorides primary battery[J]. Journal of Energy Storage, 2023, 68: 107699. DOI: 10.1016/j.est.2023.107699.
27	ZHONG G M, CHEN H X, CHENG Y, et al. Insights into the lithiation mechanism of CFx by a joint high-resolution ¹⁹F NMR, in situ TEM and ⁷Li NMR approach[J]. Journal of Materials Chemistry A, 2019, 7(34): 19793-19799. DOI: 10.1039/C9TA06800G.
28	LI Q, XUE W R, SUN X R, et al. Gaseous electrolyte additive BF₃ for high-power Li/CFx primary batteries[J]. Energy Storage Materials, 2021, 38: 482-488. DOI: 10.1016/j.ensm.2021.03.024.
29	SROUT M, CARBONI M, GONZALEZ J A, et al. Insights into the importance of native passivation layer and interface reactivity of metallic lithium by electrochemical impedance spectroscopy[J]. Small, 2023, 19(7): 2206252. DOI: 10.1002/smll.202206252.

材料	F/C	粒径/μm				杂质元素含量/ppm							振实密度/(g/cm³)	比容量/(mAh/g)
材料	F/C	D₁₀	D₅₀	D₉₀	D_max	Fe	Cu	Ni	Zn	Na	Mg	Cr	振实密度/(g/cm³)	比容量/(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

CF _x 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

	C 1s/eV					表面元素含量/%
样本	284.73	287.17	289.10	290.00	291.92	C	F
	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	放电倍率	放电截止2 V的容量保持率/%
电池	55℃存储	放电倍率	0% DOD	10% DOD	30% DOD	50% DOD
Li/CF01	30 d	0.01C	99.59	99.72	101.17	100.42
	60 d		99.55	99.88	101.36	100.14
	90 d		99.64	99.94	100.71	100.40

Li/CF02	30 d	0.01C	99.41	100.10	100.21	100.78
	60 d		99.44	99.59	99.47	99.35
	90 d		99.52	99.62	99.83	99.27

Li/CF03	30 d	0.5C	96.76	99.20	99.42	76.20
	60 d		96.20	97.30	95.60	75.63
	90 d		95.50	92.59	89.91	66.73

Li/CF04	30 d	0.5C	98.63	98.47	97.86	98.23
	60 d		98.67	98.18	97.02	97.92
	90 d		98.35	96.95	96.65	94.71

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

CF03(+)	0 d	72.94
CF03(+)	30 d	70.33	96.76	3.42