氟化科琴黑/石墨烯复合材料及电化学性能研究

doi:10.19799/j.cnki.2095-4239.2024.1038

摘要/Abstract

摘要：

锂氟化碳(Li/CF _x )电池在目前已知锂原电池中具有最高的比能量，然而这种电池在放电过程中存在电压平台较低、实际比能量低、倍率性能较差等问题。本文以科琴黑作为碳源，采用固相直接氟化法制备氟化科琴黑(fluorinated Keqin black, FKB)，通过溶液-热还原法制备氟化科琴黑/石墨烯复合材料(FKB/RGO)，提高了材料的导电性，增大了电极材料与电解液的活性接触面积，缩短了锂离子的扩散路径，实现了FKB/RGO在0.1 C倍率下放电比容量为858.4 mAh/g，10 C放电容量达到550.6 mAh/g，表现出优异的能量密度和倍率性能。本研究有助于推动FKB/RGO材料在锂氟化碳电池中的工程化应用。

关键词: 氟化科琴黑, 石墨烯, 能量密度, 锂氟化碳电池

Abstract:

Lithium fluoride carbon (Li/CF _x ) batteries are known for their exceptionally high specific energy among lithium primary batteries. However, they face challenges such as low voltage plateau, low actual specific energy, and poor rate performance during discharge. This article uses commercial Keqin black as a carbon source and uses a solid-phase direct fluorination method to prepare fluorinated Keqin black (FKB). To enhance material properties, the FKB/RGO composite is prepared via a solution thermal reduction method. This approach improves material conductivity, increases the active contact area between the electrode material and the electrolyte, and shortens the lithium-ion diffusion pathway. The resulting FKB/RGO material achieves a discharge specific capacity of 858.4 mAh/g at 0.1 C and a discharge capacity of 550.6 mAh/g at 10 C, demonstrating excellent energy density and rate performance. This work contributes to promoting the engineering application of FKB/RGO materials in high-performance battery systems.

Key words: fluorinated Keqin black, graphene, energy density, lithium fluoride carbon batteries

中图分类号:

TM 912.9

张亮, 周雄, 滕久康, 杨文静, 黎学明. 氟化科琴黑/石墨烯复合材料及电化学性能研究[J]. 储能科学与技术, 2025, 14(5): 1841-1849.

Liang ZHANG, Xiong ZHOU, Jiukang TENG, Wenjing YANG, Xueming LI. Electrochemical properties of fluorinated Keqin black/graphene composite materials[J]. Energy Storage Science and Technology, 2025, 14(5): 1841-1849.

图/表 12

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

参考文献 26

1	HAMWI A, GUÉRIN K, DUBOIS M. Fluorine-intercalated graphite for lithium batteries[M]//Fluorinated Materials for Energy Conversion. Amsterdam: Elsevier, 2005: 369-395. DOI: 10.1016/b978-008044472-7/50045-x.
2	GIRAUDET J, DELABARRE C, GUÉRIN K, et al. Comparative performances for primary lithium batteries of some covalent and semi-covalent graphite fluorides[J]. Journal of Power Sources, 2006, 158(2): 1365-1372. DOI: 10.1016/j.jpowsour.2005.10.020.
3	CHEN X Y, FAN K, LIU Y, et al. Recent advances in fluorinated graphene from synthesis to applications: Critical review on functional chemistry and structure engineering[J]. Advanced Materials, 2022, 34(1): 2101665. DOI: 10.1002/adma.202101665.
4	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.
5	LI X T, ZHANG H C, LIU C, et al. A MOF-derived multifunctional nano-porous fluorinated carbon for high performance lithium/fluorinated carbon primary batteries[J]. Microporous and Mesoporous Materials, 2021, 310: 110650. DOI: 10.1016/j.micromeso. 2020. 110650.
6	HIGHTOWER A, DAROLLES I, YAZAMI R. Surface species on Ag modified carbon fluoride (CFx) rechargeable battery electrodes measured by XPS[J]. ECS Meeting Abstracts, 2010, MA2010-03(1): 518. DOI: 10.1149/ma2010-03/1/518.
7	ZHANG H M, XIAO P, SHI J Y, et al. Silver-modified carbon fluoride as the cathode material for pouch-type primary lithium batteries[J]. Journal of Electronic Materials, 2021, 50(7): 4075-4082. DOI: 10.1007/s11664-021-08936-2.
8	SIDERIS P J, YEW R, NIEVES I, et al. Charge transfer in Li/CFx-silver vanadium oxide hybrid cathode batteries revealed by solid state 7Li and 19F nuclear magnetic resonance spectroscopy[J]. Journal of Power Sources, 2014, 254: 293-297. DOI: 10.1016/j.jpowsour.2013.12.108.
9	MEDURI P, CHEN H H, CHEN X L, et al. Hybrid CFx-Ag₂V₄O₁₁ as a high-energy, power density cathode for application in an underwater acoustic microtransmitter[J]. Electrochemistry Communications, 2011, 13(12): 1344-1348. DOI: 10.1016/j.elecom.2011.08.006.
10	JONES J P, JONES S C, KRAUSE F C, et al. Additive effects on Li‖CFx and Li‖CFx-MnO₂ primary cells at low temperature[J]. Journal of the Electrochemical Society, 2017, 164(13): A3109-A3116. DOI: 10.1149/2.0831713jes.
11	NAGATA M, YI J, TOMCSI M, et al. Performance of lithium primary cell using a hybrid positive electrode of LiV₃O₈ and CFx[J]. ECS Transactions, 2011, 33(39): 223-237. DOI: 10.1149/1. 3589931.
12	YIN X D, LI Y, FENG Y Y, et al. Polythiophene/graphite fluoride composites cathode for high power and energy densities lithium primary batteries[J]. Synthetic Metals, 2016, 220: 560-566. DOI: 10.1016/j.synthmet.2016.07.032.
13	LI L, ZHU L, PAN Y, et al. Integrated polyaniline-coated CFx cathode materials with enhanced electrochemical capabilities for Li/CFx primary battery[J]. International Journal of Electrochemical Science, 2016, 11(8): 6838-6847. DOI: 10.20964/2016.08.41.
14	ZHANG S S, FOSTER D, READ J. Enhancement of discharge performance of Li/CFx cell by thermal treatment of CFx cathode material[J]. Journal of Power Sources, 2009, 188(2): 601-605. DOI: 10.1016/j.jpowsour.2008.12.007.
15	ZHANG S S, FOSTER D, READ J. Carbothermal treatment for the improved discharge performance of primary Li/CFx battery[J]. Journal of Power Sources, 2009, 191(2): 648-652. DOI: 10.1016/j.jpowsour.2009.02.007.
16	ZHU L, PAN Y, LI L, et al. Preparation of CFx@C microcapsules as a high-rate capability cathode of lithium primary battery[J]. International Journal of Electrochemical Science, 2016, 11(1): 14-22. DOI: 10.1016/S1452-3981(23)15822-6.
17	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.
18	JIANG C, WANG B J, WU Z R, et al. Electrolyte-assisted dissolution-recrystallization mechanism towards high energy density and power density CF cathodes in potassium cell[J]. Nano Energy, 2020, 70: 104552. DOI: 10.1016/j.nanoen. 2020. 104552.
19	ZHONG G M, CHEN H X, HUANG X K, et al. High-power-density, high-energy-density fluorinated graphene for primary lithium batteries[J]. Frontiers in Chemistry, 2018, 6: 50. DOI: 10. 3389/fchem.2018.00050.
20	ROOT M J, DUMAS R, YAZAMI R, et al. The effect of carbon starting material on carbon fluoride synthesized at room temperature: Characterization and electrochemistry[J]. Journal of the Electrochemical Society, 2001, 148(4): A339. DOI: 10.1149/1. 1354612.
21	GROULT H, JULIEN C M, BAHLOUL A, et al. Improvements of the electrochemical features of graphite fluorides in primary lithium battery by electrodeposition of polypyrrole[J]. Electrochemistry Communications, 2011, 13(10): 1074-1076. DOI: 10.1016/j.elecom.2011.06.038.
22	JIANG C M, LI X J, YING Y B, et al. Fluorinated graphene-enabled durable triboelectric coating for water energy harvesting[J]. Small, 2021, 17(8): 2007805. DOI: 10.1002/smll.202007805.
23	AHMAD Y, DUBOIS M, GUÉRIN K, et al. Pushing the theoretical limit of Li-CFx batteries using fluorinated nanostructured carbon nanodiscs[J]. Carbon, 2015, 94: 1061-1070. DOI: 10.1016/j.carbon.2015.07.073.
24	WANG J L, SUN M H, LIU Y, et al. Unraveling nanoscale electrochemical dynamics of graphite fluoride by in situ electron microscopy: Key difference between lithiation and sodiation[J]. Journal of Materials Chemistry A, 2020, 8(12): 6105-6111. DOI: 10.1039/D0TA00093K.
25	AMATUCCI G G, PEREIRA N. Fluoride based electrode materials for advanced energy storage devices[J]. Journal of Fluorine Chemistry, 2007, 128(4): 243-262. DOI: 10.1016/j.jfluchem.2006.11.016.
26	LUO Z Y, WANG X, CHEN D W, et al. Ultrafast Li/fluorinated graphene primary batteries with high energy density and power density[J]. ACS Applied Materials & Interfaces, 2021, 13(16): 18809-18820. DOI: 10.1021/acsami.1c02064.

[1]	许陈程, 王湛, 李爽, 蒋江民, 鞠治成. 锂离子电池预锂化技术研究进展及工程化应用展望[J]. 储能科学与技术, 2025, 14(3): 930-946.
[2]	刘通, 杨瑰婷, 毕辉, 梅悦旎, 刘硕, 宫勇吉, 罗文雷. 高能量密度与高功率密度兼顾型锂离子电池研究现状与展望[J]. 储能科学与技术, 2025, 14(1): 54-76.
[3]	梅悦旎, 屈雯洁, 程广玉, 向永贵, 陆海燕, 邵晓丹, 张益明, 王可. 锂离子电池正极补锂技术研究进展[J]. 储能科学与技术, 2025, 14(1): 77-89.
[4]	冯仁超, 董宇, 朱新宇, 刘偲, 陈胜, 李达, 郭若禹, 王斌, 王炯辉, 李宁, 苏岳锋, 吴锋. 钠离子电池氧化石墨基负极研究进展[J]. 储能科学与技术, 2024, 13(6): 1835-1848.
[5]	杨建航, 冯文婷, 韩俊伟, 魏欣茹, 马晨宇, 毛常明, 智林杰, 孔德斌. 锂/钠-氯二次电池的最新进展——从材料构建到性能评估[J]. 储能科学与技术, 2024, 13(6): 1824-1834.
[6]	姜媛媛, 屠芳芳, 张芳平, 王盈来, 蔡佳文, 杨东辉, 李艳红, 相佳媛, 夏新辉, 傅继澎. 高性能磷酸铁锂电池补锂技术及机制[J]. 储能科学与技术, 2024, 13(5): 1435-1442.
[7]	李召阳, 刘定宏, 赵岩岩, 陈满, 雷旗开, 彭鹏, 刘磊. 高比能量锂离子软包电池针刺测试的影响因素研究[J]. 储能科学与技术, 2024, 13(1): 57-71.
[8]	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.
[9]	李悦, 王博, 吴楠. 石墨烯/Si/SiO _x 纳米复合材料的制备及储锂性能研究[J]. 储能科学与技术, 2023, 12(9): 2752-2759.
[10]	江婉薇, 梁呈景, 钱历, 刘梅城, 朱孟想, 马骏. 锡基三维石墨烯泡沫调控及其锂电池负极性能[J]. 储能科学与技术, 2023, 12(9): 2746-2751.
[11]	李淼, 于永利, 吴剑扬, 雷敏, 周恒辉. 高能量密度磷酸铁锂正极设计[J]. 储能科学与技术, 2023, 12(7): 2045-2058.
[12]	冯准. 基于石墨烯电极的埃洛石/聚苯胺超高柔性复合电极[J]. 储能科学与技术, 2023, 12(6): 1794-1803.
[13]	谭超, 王超. 功能化氧化石墨烯作为锂硫电池正极硫载体的性能研究[J]. 储能科学与技术, 2023, 12(4): 1025-1033.
[14]	曹潘磊, 隋林秀, 冯靖芸, 张维福, 罗城城, 袁小亚. Fe³⁺ 交联的预包覆Fe₃O₄ 纳米粒子改性rGO自支撑膜的储锂性能[J]. 储能科学与技术, 2023, 12(3): 710-720.
[15]	何凤荣, 张啟文, 郭德超, 郭义敏, 郭孝东. 电极结构对（NCM+AC）/HC混合型电容器电性能的影响[J]. 储能科学与技术, 2022, 11(7): 2051-2058.