锂/氟化碳电池电解液的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0903

摘要/Abstract

摘要：

锂/氟化碳(Li/CF _x )电池作为一种具有最高理论比容量(860 mAh/g)和能量密度(2180 Wh/kg)的一次电池，具有高安全性能、低自放电率、平稳的放电电压和环境友好等优点，广泛应用于医疗、军事、电子科技和航空航天等领域。电解液作为Li/CF _x 电池必不可缺的一部分，在正负极之间起到传递离子的作用，具有重要的研究意义。本文从Li/CF _x 电池的低温性能、倍率性能以及放电平台等方面综述了Li/CF _x 电池电解液的研究进展；重点阐述了电解液理化性质、界面浸润与相容、锂离子溶剂化结构、C—F键活化和LiF形成与溶解等因素对Li/CF _x 电池放电性能的影响；最后，对Li/CF _x 电池新型电解液的研究提出了思考与展望。

关键词: 电化学, 锂/氟化碳电池, 电解液, 低温性能, 倍率性能

Abstract:

Li/CF _x battery, a primary battery with the highest theoretical specific capacity and energy density, has the advantages of high safety performance, low self-discharge rate, stable discharge voltage, and eco-friendliness and is widely used in the medical, military, electronic technology, aerospace, and other fields. Electrolyte, an indispensable component of Li/CF _x battery, plays a pivotal role in transferring ions between the anode and cathode; it has important research significance. In this review, we summarize the research progress on electrolytes for Li/CF _x batteries, especially emphasizing the relationships between electrolyte factors, such as the physicochemical properties of electrolytes, interface wettability and compatibility, lithium-ion solvation structure, C—F bond activation, LiF formation, and dissolution, and the electrochemical performance of Li/CF _x batteries, such as low-temperature performance, high-rate performance, and discharge voltage platform. Finally, future research directions for Li/CF _x battery electrolytes are discussed.

Key words: electrochemistry, Li/CF _x battery, electrolytes, low temperature performance, high rate performance

中图分类号:

O 646.1

卢俊杰, 彭丹, 倪文静, 杨媛, 汪靖伦. 锂/氟化碳电池电解液的研究进展[J]. 储能科学与技术, 2024, 13(5): 1487-1495.

Junjie LU, Dan PENG, Wenjing NI, Yuan YANG, Jinglun WANG. Research progress on electrolyte for Li/CF _x battery[J]. Energy Storage Science and Technology, 2024, 13(5): 1487-1495.

图/表 7

表1

图1

图2

表2

图3

图4

图5

参考文献 51

1	国家发展和改革委员会, 国家能源局. "十四五"新型储能发展实施方案[R/OL]. [2023-01-05].https://www.gov.cn/zhengce/zhengceku/2022-03/22/5680417/files/41a50cec48e84cc4adfca855c3444f6b.pdf
2	WU F X, MAIER J, YU Y. Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries[J]. Chemical Society Reviews, 2020, 49(5): 1569-1614.
3	WANG H S, YU Z A, KONG X, et al. Liquid electrolyte: The nexus of practical lithium metal batteries[J]. Joule, 2022, 6(3): 588-616.
4	CAO W Z, LI Q, YU X Q, et al. Controlling Li deposition below the interface[J]. eScience, 2022, 2(1): 47-78.
5	LIM H D, PARK H, KIM H, et al. A new perspective on Li-SO₂ batteries for rechargeable systems[J]. Angewandte Chemie (International Ed in English), 2015, 54(33): 9663-9667.
6	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.
7	GAO M T, CAI D M, LUO S F, et al. Research progress in fluorinated carbon sources and the discharge mechanism for Li/CFx primary batteries[J]. Journal of Materials Chemistry A, 2023, 11(31): 16519-16538.
8	LEUNG K, SCHORR N B, MAYER M, et al. Edge-propagation discharge mechanism in CFx batteries—a first-principles and experimental study[J]. Chemistry of Materials, 2021, 33(5): 1760-1770.
9	汤才, 蒋江民, 王新峰, 等. Li/CFx一次电池研究进展[J]. 储能科学与技术, 2023, 12(4): 1093-1109.
	TANG C, JIANG J M, WANG X F, et al. Research progress of Li/CFx primary batteries[J]. Energy Storage Science and Technology, 2023, 12(4): 1093-1109.
10	XU K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. Chemical Reviews, 2004, 104(10): 4303-4417.
11	陈雨晴, 张洪章, 于滢, 等. 锂硫一次电池的研究现状及展望[J]. 储能科学与技术, 2017, 6(3): 529-533.
	CHEN Y Q, ZHANG H Z, YU Y, et al. The R & D status and prospects for primary lithium sulfur batteries[J]. Energy Storage Science and Technology, 2017, 6(3): 529-533.
12	CHEN X, ZHANG X Q, LI H R, et al. Cation-solvent, cation-anion, and solvent-solvent interactions with electrolyte solvation in Lithium batteries[J]. Batteries & Supercaps, 2019, 2(2): 114.
13	WHITACRE J F, WEST W C, SMART M C, et al. Enhanced low-temperature performance of Li-CFx batteries[J]. Electrochemical and Solid-State Letters, 2007, 10(7): A166.
14	ZHANG S S, XU K, JOW T R. Study of LiBF₄ as an electrolyte salt for a Li-ion battery[J]. Journal of the Electrochemical Society, 2002, 149(5): A586.
15	MA S, JIANG M D, TAO P, et al. Temperature effect and thermal impact in lithium-ion batteries: A review[J]. Progress in Natural Science: Materials International, 2018, 28(6): 653-666.
16	PIAO N, GAO X N, YANG H C, et al. Challenges and development of lithium-ion batteries for low temperature environments[J]. eTransportation, 2022, 11: 100145.
17	WATANABE N. Two types of graphite fluorides, (CF)n and (C₂F)n, and discharge characteristics and mechanisms of electrodes of (CF)n and (C₂F)n in lithium batteries[J]. Solid State Ionics, 1980, 1(1/2): 87-110.
18	NAKAJIMA T, KOH M, GUPTA V, et al. Electrochemical behavior of graphite highly fluorinated by high oxidation state complex fluorides and elemental fluorine[J]. Electrochimica Acta, 2000, 45(10): 1655-1661.
19	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.
20	BAN J, JIAO X X, FENG Y Y, et al. All-temperature, high-energy-density Li/CFx batteries enabled by a fluorinated ether as a cosolvent[J]. ACS Applied Energy Materials, 2021, 4(4): 3777-3784.
21	WATANABE N, NAKAJIMA T, HAGIWARA R. Discharge reaction and overpotential of the graphite fluoride cathode in a nonaqueous lithium cell[J]. Journal of Power Sources, 1987, 20(1/2): 87-92.
22	FANG Z, YANG Y, ZHENG T L, et al. An all-climate CFx/Li battery with mechanism-guided electrolyte[J]. Energy Storage Materials, 2021, 42: 477-483.
23	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.
24	HAN S S, YU T H, MERINOV B V, et al. Unraveling structural models of graphite fluorides by density functional theory calculations[J]. Chemistry of Materials, 2010, 22(6): 2142-2154.
25	PISCHEDDA V, RADESCU S, DUBOIS M, et al. Experimental and DFT high pressure study of fluorinated graphite (C₂F)N[J]. Carbon, 2017, 114: 690-699.
26	NAGASUBRAMANIAN G, SANCHEZ B. A new chemical approach to improving discharge capacity of Li/(CFx)n cells[J]. Journal of Power Sources, 2007, 165(2): 630-634.
27	LI Q, XUE W, SUN X, et al. Gaseous electrolyte additive BF3 for high-power Li/CFx primary batteries[J]. Energy Storage Materials, 2021, 38: 482-488.
28	DONG X L, WANG Y G, XIA Y Y. Promoting rechargeable batteries operated at low temperature[J]. Accounts of Chemical Research, 2021, 54(20): 3883-3894.
29	ZHANG N, DENG T, ZHANG S Q, et al. Critical review on low-temperature Li-ion/metal batteries[J]. Advanced Materials, 2022, 34(15): 2107899.
30	HUBBLE D, BROWN D E, ZHAO Y Z, et al. Liquid electrolyte development for low-temperature lithium-ion batteries[J]. Energy & Environmental Science, 2022, 15(2): 550-578.
31	KULOVA T L, SKUNDIN A M. A critical review of electrode materials and electrolytes for Low- Temperature Lithium-Ion Batteries[J]. International Journal of Electrochemical Science, 2020, 15(9): 8638-8661.
32	胡华坤, 薛文东, 霍思达, 等. 锂离子电池电解液SEI成膜添加剂的研究进展[J]. 化工学报, 2022, 73(4): 1436-1454.
	HU H K, XUE W D, HUO S D, et al. Review of SEI film forming additives for electrolyte of lithium ion battery[J]. CIESC Journal, 2022, 73(4): 1436-1454.
33	IGNATOVA A A, YARMOLENKO O V, TULIBAEVA G Z, et al. Influence of 15-crown-5 additive to a liquid electrolyte on the performance of Li/CFx-systems at temperatures up to-50 ℃[J]. Journal of Power Sources, 2016, 309: 116-121.
34	WANG N, LUO Z Y, ZHANG Q F, et al. Succinonitrile broadening the temperature range of Li/CFx primary batteries[J]. Journal of Central South University, 2023, 30(2): 443-453.
35	HOLOUBEK J, KIM K, YIN Y J, et al. Electrolyte design implications of ion-pairing in low-temperature Li metal batteries[J]. Energy & Environmental Science, 2022, 15(4): 1647-1658.
36	HOLOUBEK J, BASKIN A, LAWSON J W, et al. Predicting the ion desolvation pathway of lithium electrolytes and their dependence on chemistry and temperature[J]. The Journal of Physical Chemistry Letters, 2022, 13(20): 4426-4433.
37	ZHANG S S, FOSTER D, READ J. A low temperature electrolyte for primary Li/CFx batteries[J]. Journal of Power Sources, 2009, 188(2): 532-537.
38	LIANG H J, SU M Y, ZHAO X X, et al. Weakly-solvating electrolytes enable ultralow-temperature (-80 ℃) and high-power CFx/Li primary batteries[J]. Science China Chemistry, 2023, 66(7): 1982-1988.
39	XUE W R, QIN T, LI Q, et al. Exploiting the synergistic effects of multiple components with a uniform design method for developing low-temperature electrolytes[J]. Energy Storage Materials, 2022, 50: 598-605.
40	刘雯, 杨炜婧, 郭瑞, 等. 功率型锂/氟化碳一次电池的优化设计研究进展[J]. 化学通报, 2019, 82(6): 483-487.
	LIU W, YANG W J, GUO R, et al. Progress in optimization design of high-power lithium/carbon fluorides primary batteries[J]. Chemistry, 2019, 82(6): 483-487.
41	LI Y, FENG Y Y, FENG W. Deeply fluorinated multi-wall carbon nanotubes for high energy and power densities lithium/carbon fluorides battery[J]. Electrochimica Acta, 2013, 107: 343-349.
42	张懋慧. 有机电解液对氟化碳电极界面性能研究[D]. 昆明: 云南师范大学, 2014.
	ZHANG M H. Study on interfacial properties of organic electrolyte to fluorocarbon electrode[D]. Kunming: Yunnan Normal University, 2014.
43	ZHANG Y Q, JIANG J M, ZHANG L, et al. BF₃-based electrolyte additives promote electrochemical reactions to boost the energy density of Li/CFx primary batteries[J]. Electrochimica Acta, 2023, 470: 143311.
44	ZHOU X, PENG D, DENG K Q, et al. Synthesis and characterization of novel fluorinated nitriles as non-flammable and high-voltage electrolytes for lithium/lithium-ion batteries[J]. Journal of Power Sources, 2023, 557: 232557.
45	ZHOU X, KOZDRA M, RAN Q, et al. 3-(2, 2, 2-Trifluoroethoxy)propionitrile-based electrolytes for high energy density lithium metal batteries[J]. Nanoscale, 2022, 14(46): 17237-17246.
46	汪靖伦, 卢俊杰. 一种高比容量高倍率性能的锂-氟化碳电池电解液: CN116470080A[P]. 2023-07-21.
	WANG J L, LU J J. Lithium-carbon fluoride battery electrolyte with high specific capacity and high rate capability: CN116470080A[P]. 2023-07-21.
47	GUÉRIN K, YAZAMI R, HAMWI A. Hybrid-type graphite fluoride as cathode material in primary lithium batteries[J]. Electrochemical and Solid-State Letters, 2004, 7(6): A159.
48	PANG C K, DING F, SUN W B, et al. A novel dimethyl sulfoxide/1, 3-dioxolane based electrolyte for lithium/carbon fluorides batteries with a high discharge voltage plateau[J]. Electrochimica Acta, 2015, 174: 230-237.
49	FU A, XIAO Y K, JIAN J H, et al. Boosting the energy density of Li\|\|CFx primary batteries using a 1, 3-dimethyl-2-imidazolidinone-based electrolyte[J]. ACS Applied Materials & Interfaces, 2021, 13(48): 57470-57480.
50	XIAO Y K, JIAN J H, FU A, et al. Substantially promoted energy density of Li\|\|CFx primary battery enabled by Li⁺-DMP coordinated structure[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(19): 6217-6229.
51	KRISHNAMURTHY V, VISWANATHAN V. Beyond transition metal oxide cathodes for electric aviation: The case of rechargeable CFx[J]. ACS Energy Letters, 2020, 5(11): 3330-3335.

CF _x	Electrolyte	Temp./℃	E_1/2/V	Cut off voltage /V	Capacity /(mAh/g)	Discharge rate	Ref.
CF_0.65	0.5 mol/L LiBF₄-PC∶DME(2∶8, 体积比)+1.5%(体积分数)TTFEB	-60	~1.5	0.5	275	0.2C	[13]
CF _x	1 mol/L LiBF₄-GBL+2% (体积分数)15-crown-5	-45	1.5	0.25	140	—	[33]
CF _x	1mol/L LiPF₆-EC∶DMC∶EMC (1∶1∶3, 体积比)+2%(体积分数)15-crown-5	-50	1.3	0.25	110	—	[33]
CF _x	1 mol/L LiBF₄-PC∶DME (1∶1, 体积比)+10%(质量分数)SN	0	2.2	1.5	527	0.5C	[34]
CF_0.99~1.08	0.5 mol/L LiBF₄-AN∶BL (1∶1, 体积比)	-50	~1.8	1.5	~580	0.02C	[37]
CF_1.0	1 mol/L LiBF₄-Me₂O∶PC (6.5∶1, 体积比)	-60	~2.1	1.5	780	10 mA/g	[23]
CF_1.0	1 mol/L LiBF₄-PC∶MB (1∶2, 体积比)	-70	~1.0	0.5	240	0.1C	[22]
CF_1.0	0.78 mol/L LiBF₄+0.22 mol/L LiFSI-PC∶DME∶iBA (23∶69∶8, 体积比)	-60	~1.3	1.0	433	0.1C	[39]

CF _x	Electrolyte	Temp./℃	E_1/2/V	Cut off voltage/V	Capacity/(mAh/g)	Discharge rate	Ref.
CF_0.99~1.08	1 mol/L LiClO₄-TTE∶DME∶PC (2∶2∶1, 体积比)	25	~1.85	1.5	425	5000 mA/g	[20]
CF_1.0	1 mol/L LiBF₄-PC∶DME∶A(1∶1∶1, 体积比 )	50	2.16	1.5	758	2 C	[42]
CF_1.15	1 mol/L LiBF₄-EC∶DMC (1∶1, 体积比)+0.01 mol/L BF₃(g)	25	~1.8	1.5	416	15 C	[27]
CF_1.0	1 mol/L LiBF₄-PC∶DME (1∶1, 体积比)+1%(质量分数)PRZ	25	2.60	1.5	770	1000 mA/g	[43]
CF_1.11	1 mol/L LiBF₄-F5EON∶DME (1∶1, 体积比)	25	2.20	1.5	771	1000 mA/g	[46]

[1]	缪胤宝, 张文华, 刘伟昊, 王帅, 陈哲, 彭望, 曾杰. 富锂正极材料Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ 的制备及性能[J]. 储能科学与技术, 2024, 13(5): 1427-1434.
[2]	赵毅伟, 张福华, 颜顺, 丁坤, 蓝海枫, 刘辉. 普鲁士蓝类钠离子电池正极材料导电性研究进展[J]. 储能科学与技术, 2024, 13(5): 1474-1486.
[3]	石敏, 蒋鹏杰, 徐琛, 贺鑫, 梁宵. 抑制锂金属负极枝晶的电解液调控策略[J]. 储能科学与技术, 2024, 13(5): 1620-1634.
[4]	郭军丽. 电化学储能电站消防安全法律治理对策[J]. 储能科学与技术, 2024, 13(5): 1744-1747.
[5]	刘新, 毛喜玲, 闫欣雨, 王俊强, 李孟委. 三维孔道NiMn-MOF电极材料制备及电化学性能研究[J]. 储能科学与技术, 2024, 13(2): 361-369.
[6]	宋梦琼, 彭宇, 廖自强. 基于电化学热耦合模型的电池热管理研究[J]. 储能科学与技术, 2024, 13(2): 578-585.
[7]	周洋, 韩培玉, 牛迎春, 徐春明, 徐泉. 金属有机框架衍生的C-Bi/CC电极制备及其在铁铬液流电池中的电化学性能[J]. 储能科学与技术, 2024, 13(2): 381-389.
[8]	郭秀丽, 周小龙, 邹才能, 唐永炳. 水系双离子电池的研究进展与展望[J]. 储能科学与技术, 2024, 13(2): 462-479.
[9]	贾铭勋, 吴桐, 杨道通, 秦小茜, 刘景海, 段莉梅. 锂硫电池电解液多功能添加剂：作用机制及先进表征[J]. 储能科学与技术, 2024, 13(1): 36-47.
[10]	李顺, 黄建国, 何桂金. 木质素基碳/硫纳米球复合材料作为高性能锂硫电池正极材料[J]. 储能科学与技术, 2024, 13(1): 270-278.
[11]	梁宏毅, 陈锋, 甘友毅, 邵丹. 动力锂电池三元正极低温性能研究[J]. 储能科学与技术, 2024, 13(1): 293-298.
[12]	陈珊珊, 郑翔, 王若, 原铭蔓, 彭威, 鲁博明, 张光照, 王朝阳, 王军, 邓永红. 锂离子电池硅基负极电解液添加剂研究进展：挑战与展望[J]. 储能科学与技术, 2024, 13(1): 279-292.
[13]	肖也, 徐磊, 闫崇, 黄佳琦. 锂电池用参比电极的设计与应用[J]. 储能科学与技术, 2024, 13(1): 82-91.
[14]	曾坤, 郑晓妍, 龚慧玲, 邹博, 陈凯, 晏忠钠. 基于锂负极的液态金属电池研究进展[J]. 储能科学与技术, 2024, 13(1): 299-310.
[15]	闫苏, 钟芳芳, 刘俊伟, 丁美, 贾传坤. 高能量密度液流电池关键材料与先进表征[J]. 储能科学与技术, 2024, 13(1): 143-156.