Li/Cr8O21 电池宽温电解液的设计与应用

doi:10.19799/j.cnki.2095-4239.2024.0965

摘要/Abstract

摘要：

铬氧化物(Cr₈O₂₁)凭借其高的电压平台与理论比容量，成为当下锂电池正极材料的研究热点。然而，设计与之相匹配的新型电解液，以满足其在不同场景中的应用也至关重要。本工作一方面通过理论计算与实验相结合，设计了一种新型双盐电解液(FB55-10%)。其中四氟硼酸锂(LiBF₄)用以提升电池在低温下的放电性能，双氟磺酰亚胺锂(LiFSI)具有良好的稳定性，也能弥补常温下LiBF₄离子电导率较低的不足。同时，选用低熔点与低黏度的丁酸甲酯(MB)与碳酸丙烯酯(PC)组成共溶剂，以拓宽电解液的熔沸点区间，从而满足Li/Cr₈O₂₁电池在宽温条件下(-45～65 ℃)的应用。另一方面，通过构筑固态电解质Li_1.3Al_0.3Ti_0.7(PO₄)₃(LATP)与正极的复合材料，使其在低温(-45 ℃)下性能再次提升。最终测得Li/Cr₈O₂₁电池在电流为0.02C时，常温(25 ℃)、高温(65 ℃)和低温(-45 ℃)条件下的放电比容量分别为404 mAh/g、410 mAh/g与223 mAh/g。此外，设计了适配此电解液体系的3 Ah软包电池并进行测试，结果依然能表现出较好的性能，证明该电解液体系具有良好的宽温适用性。

关键词: 铬氧化物, 宽温电解液, 固态电解质, 锂电池

Abstract:

Chromium oxides (Cr₈O₂₁) have been extensively studied as cathode materials for lithium primary batteries due to their high specific capacity and stable voltage plateau. However, designing state-of-the-art electrolytes for Li/Cr₈O₂₁ is crucial to ensure applicability under various conditions. In this study, a novel dual-salt electrolyte (FB55-10%) was developed through theoretical calculations and experimental validation. LiBF₄ enhances the low-temperature performance of Li/Cr₈O₂₁, while LiFSI, with its superior stability, compensates for the low ionic conductivity of LiBF₄ at normal temperatures. In addition, methyl butyrate (MB), characterized by low viscosity and a low melting point, was selected as a co-solvent with propylene carbonate (PC) to extend the operating temperature range from the melting point to the boiling point, thereby enabling Li/Cr₈O₂₁applications across a wide temperature range (-45—65 ℃). Furthermore, the low-temperature (-45 ℃) performance of Li/Cr₈O₂₁was further improved by incorporating a solid-state electrolyte, Li_1.3Al_0.3Ti_0.7(PO₄)₃(LATP), into Cr₈O₂₁ composite materials. As a result, the Li/Cr₈O₂₁ coin cell achieved specific capacities of 404 mAh/g, 410 mAh/g, and 223 mAh/g at 25 ℃, 65 ℃, and -45 ℃, respectively, at a current density of 0.02C. In addition, a 3 Ah pouch cell incorporating this novel electrolyte demonstrated excellent electrochemical performance, confirming the superior wide-temperature adaptability of this electrolyte system.

Key words: chromium oxide, wide-temperature electrolyte, solid-state-electrolyte, lithium primary battery

中图分类号:

TQ 152

金成龙, 孙梦婷, 孟庆飞, 张姝玮, 周舟, 齐宇阳. Li/Cr₈O₂₁ 电池宽温电解液的设计与应用[J]. 储能科学与技术, 2025, 14(4): 1369-1376.

Chenglong JIN, Mengting SUN, Qingfei MENG, Shuwei ZHANG, Zhou ZHOU, Yuyang QI. Design and application of wide-temperature electrolytes for Li/Cr₈O₂₁ batteries[J]. Energy Storage Science and Technology, 2025, 14(4): 1369-1376.

图/表 10

表1

表2

图1

图2

图3

图4

图5

图6

图7

图8

参考文献 21

1	YAMAMOTO O, TAKEDA Y, KANNO R, et al. Amorphous chromium oxide; A new lithium battery cathode[J]. Journal of Power Sources, 1987, 20(1/2): 151-156. DOI: 10.1016/0378-7753(87)80105-2.
2	滕久康, 王庆杰, 张亮, 等. 热处理时间对锂电池正极材料Cr₈O₂₁的影响[J]. 电化学, 2021, 27(6): 689-697. DOI: 10.13208/j.electrochem.210121.
	TENG J K, WANG Q J, ZHANG L, et al. Influence of heat treatment time on cathode material Cr₈O₂₁ for lithium battery[J]. Journal of Electrochemistry, 2021, 27(6): 689-697. DOI: 10.13208/j.electrochem.210121.
3	LIU J Y, WANG Z X, LI H, et al. Synthesis and characterization of Cr₈O₂₁ as cathode material for rechargeable lithium batteries[J]. Solid State Ionics, 2006, 177(26/27/28/29/30/31/32): 2675-2678. DOI: 10.1016/j.ssi.2006.05.017.
4	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. DOI: 10.1021/acssuschemeng.1c08707.
5	杨睿, 李惠, 孟庆飞, 等. PC基电解液对Li/CrOx一次电池高倍率性能的影响[J]. 物理化学学报, 2024, 40(9): 68-74.
	YANG R, LI H, MENG Q F, et al. Influence of PC-based electrolyte on high-rate performance in Li/CrOx primary battery[J]. Acta Physico-Chimica Sinica, 2024, 40(9): 68-74.
6	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. DOI: 10.1016/j.ensm.2021.08.002.
7	CHANG Y L, WANG M, WANG S P, et al. Ultralong storage life of Li/MnO₂ primary batteries using MnO₂-(CFx)n with C—F semi-ionic bond as cathode materials[J]. Electrochimica Acta, 2019, 320: 134618. DOI: 10.1016/j.electacta.2019.134618.
8	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. DOI: 10.1016/j.jpowsour.2016.01.075.
9	YAAKOV D, GOFER Y, AURBACH D, et al. On the study of electrolyte solutions for Li-ion batteries that can work over a wide temperature range[J]. Journal of the Electrochemical Society, 2010, 157(12): A1383. DOI: 10.1149/1.3507259.
10	YANG C C, JIANG J R, KARUPPIAH C, et al. LATP ionic conductor and in situ graphene hybrid-layer coating on LiFePO₄ cathode material at different temperatures[J]. Journal of Alloys and Compounds, 2018, 765: 800-811. DOI: 10.1016/j.jallcom.2018.06.289.
11	NIE Y, XIAO W, MIAO C, et al. Boosting the electrochemical performance of LiNi_0.8Co_0.15Al_0.05O₂ cathode materials in situ modified with Li_1.3Al_0.3Ti_1.7(PO₄)₃ fast ion conductor for lithium-ion batteries[J]. Electrochimica Acta, 2020, 353: 136477. DOI: 10.1016/j.electacta.2020.136477.
12	YANG Y, YANG W H, YANG H J, et al. Electrolyte design principles for low-temperature lithium-ion batteries[J]. eScience, 2023, 3(6): 100170. DOI: 10.1016/j.esci.2023.100170.
13	BI K, ZHAO S X, HUANG C, et al. Improving low-temperature performance of spinel LiNi_0.5Mn_1.5O₄ electrode and LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ full-cell by coating solid-state electrolyte Li-Al-Ti-P-O[J]. Journal of Power Sources, 2018, 389: 240-248. DOI: 10.1016/j.jpowsour.2018.03.071.
14	孟庆飞, 杨睿, 金成龙, 等. 铬氧化物作为高容量锂电池正极材料的制备及其性能研究[J]. 储能科学与技术, 2023, 12(10): 3049-3055. DOI: 10.19799/j.cnki.2095-4239.2023.0396.
	MENG Q F, YANG R, JIN C L, et al. Preparation and performance of high-capacity Cr₈O₂₁ as a cathode material for lithium batteries[J]. Energy Storage Science and Technology, 2023, 12(10): 3049-3055. DOI: 10.19799/j.cnki.2095-4239.2023.0396.
15	WANG Q D, YAO Z P, ZHAO C L, et al. Interface chemistry of an amide electrolyte for highly reversible lithium metal batteries[J]. Nature Communications, 2020, 11(1): 4188. DOI: 10.1038/s41467-020-17976-x.
16	VALIYAVEETTIL-SOBHANRAJ S, GŁUCHOWSKI P, LÓPEZ-ARANGUREN P, et al. High-pressure low-temperature densification of NASICON-based LATP electrolytes for solid-state lithium batteries[J]. Materialia, 2024, 33: 101999. DOI: 10.1016/j.mtla. 2023.101999.
17	WAETZIG K, ROST A, HEUBNER C, et al. Synthesis and sintering of Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) electrolyte for ceramics with improved Li⁺ conductivity[J]. Journal of Alloys and Compounds, 2020, 818: 153237. DOI: 10.1016/j.jallcom.2019.153237.
18	CHANG Z, QIAO Y, DENG H, et al. A liquid electrolyte with de-solvated lithium ions for lithium-metal battery[J]. Joule, 2020, 4(8): 1776-1789. DOI: 10.1016/j.joule.2020.06.011.
19	FAN X L, JI X, CHEN L, et al. All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents[J]. Nature Energy, 2019, 4(10): 882-890. DOI: 10.1038/s41560-019-0474-3.
20	LIU Y Y, XU X Y, SADD M, et al. Insight into the critical role of exchange current density on electrodeposition behavior of lithium metal[J]. Advanced Science, 2021, 8(5): 2003301. DOI: 10.1002/advs.202003301.
21	NOERSKOV J K, BLIGAARD T, LOGADOTTIR A, et al. Trends in the exchange current for hydrogen evolution[J]. ChemInform, 2005, 36(24): DOI: 10.1002/chin.200524023.

材料	规格及参数
Cr₈O₂₁-LATP正极	活性物质比例/%	95
	面密度/(mg/cm²)	23
	压实密度/(g/cm³)	2.1
	面容量/(mAh/cm²)	8

锂负极	厚度/μm	100
PP隔膜	厚度/μm	12
铝箔	厚度/μm	10

N/P比	1.5
电解液	FB55

正极材料	电解液	体系简称
Cr₈O₂₁	1 mol/L LiBF₄-PC+DME	B
Cr₈O₂₁	1 mol/L LiFSI-PC+MB	F
Cr₈O₂₁	0.7 mol/L LiFSI+0.3 mol/L LiBF₄-PC+MB	FB73
Cr₈O₂₁	0.5 mol/L LiFSI+0.5 mol/L LiBF₄-PC+MB	FB55
Cr₈O₂₁	0.3 mol/L LiFSI+0.7 mol/L LiBF₄-PC+MB	FB37
Cr₈O₂₁-5%LATP	0.5 mol/L LiFSI+0.5 mol/L LiBF₄-PC+MB	FB55-5%
Cr₈O₂₁-10%LATP	0.5 mol/L LiFSI+0.5 mol/L LiBF₄-PC+MB	FB55-10%
Cr₈O₂₁-15%LATP	0.5 mol/L LiFSI+0.5 mol/L LiBF₄-PC+MB	FB55-15%

[1]	刘顺新, 许令平, 张建兴, 曾光, 李昊阳. 基于双通道并行串联式液冷板下锂电池温升特性数值分析[J]. 储能科学与技术, 2025, 14(4): 1496-1506.
[2]	彭鹏, 王成东, 陈满, 王青松, 雷旗开, 金凯强. 某钛酸锂电池储能电站热失控致灾危害评价[J]. 储能科学与技术, 2025, 14(4): 1617-1630.
[3]	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.
[4]	肖子信, 张泓, 徐林. 纳米线调控固态电池离子输运与界面[J]. 储能科学与技术, 2025, 14(3): 1026-1039.
[5]	张新新, 岑官骏, 乔荣涵, 朱璟, 郝峻丰, 孙蔷馥, 田孟羽, 金周, 詹元杰, 闫勇, 贲留斌, 俞海龙, 刘燕燕, 周洪, 黄学杰. 锂电池百篇论文点评（2024-12-01—2025-01-31）[J]. 储能科学与技术, 2025, 14(3): 1310-1330.
[6]	朱鹏杰, 李伟, 张楚, 宋浩, 李贝贝, 刘秀梅, 刘利利. 基于烟气扩散的储能柜内锂电池热失控预警研究[J]. 储能科学与技术, 2025, 14(2): 624-635.
[7]	黎家玮, 刘祯. 锂电池湿式冷却系统数值模拟及性能分析[J]. 储能科学与技术, 2025, 14(2): 717-727.
[8]	黄怀宇, 黄思林, 赵荣超, 肖质文, 侯军辉, 闫力玮. 磷酸铁锂电池铝塑膜壳体绝缘失效触发热失控特性实验研究[J]. 储能科学与技术, 2025, 14(2): 613-623.
[9]	江训昌, 喻科霖, 杨大祥, 廖敏会, 周洋. 原位聚合制备PDOL基固态电解质及其在锂金属电池中的应用[J]. 储能科学与技术, 2025, 14(1): 1-12.
[10]	周洪, 俞海龙, 王丽平, 黄学杰. 基于BERTopic主题模型的锂电池前沿监测及主题分析研究[J]. 储能科学与技术, 2025, 14(1): 406-416.
[11]	刘迎迎, 张孝远, 刘梦楠, 孙俊章, 张艳. 基于自适应最优组合核函数高斯过程回归的锂电池健康状态区间估计[J]. 储能科学与技术, 2025, 14(1): 346-357.
[12]	郝峻丰, 岑官骏, 乔荣涵, 朱璟, 孙蔷馥, 张新新, 田孟羽, 金周, 詹元杰, 闫勇, 贲留斌, 俞海龙, 刘燕燕, 周洪, 黄学杰. 锂电池百篇论文点评（2024.10.1—2024.11.30）[J]. 储能科学与技术, 2025, 14(1): 388-405.
[13]	陈星光, 沈逸凡, 邵裕新, 郑岳久, 孙涛, 来鑫, 沈凯, 韩雪冰. 面向实车应用的磷酸铁锂电池容量辨识及特异性优化方法研究[J]. 储能科学与技术, 2024, 13(9): 2963-2971.
[14]	黎耀康, 杨海东, 徐康康, 蓝昭宇, 章润楠. 基于加权UMAP和改进BLS的锂电池温度预测[J]. 储能科学与技术, 2024, 13(9): 3006-3015.
[15]	焦君宇, 张全權, 陈宁波, 王冀钰, 芦秋迪, 丁浩浩, 彭鹏, 宋孝河, 张帆, 郑家新. 电池大数据智能分析平台的研发与应用[J]. 储能科学与技术, 2024, 13(9): 3198-3213.

Li/Cr₈O₂₁ 电池宽温电解液的设计与应用

Design and application of wide-temperature electrolytes for Li/Cr₈O₂₁ batteries

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价