多组分电解液协同效应提升Cr8O21||Li一次电池倍率性能和高温贮存寿命研究

doi:10.19799/j.cnki.2095-4239.2025.0459

摘要/Abstract

摘要：

铬氧化物(Cr₈O₂₁)一次电池由于其高能量密度和高工作电压等特性，成为航天军事领域的研究热点。然而，一次电池在极端工况下的应用受限于大电流放电能力与高温贮存寿命的固有矛盾，而传统电解液又难以实现二者同步优化。针对这一矛盾，本研究提出多组分电解液协同设计策略：通过高介电常数EC(碳酸乙烯酯)与低黏度EMC(碳酸甲乙酯)复合溶剂优化锂盐解离与离子迁移效率，配合同样高沸点的PC(碳酸丙烯酯)提高电解液热稳定性，并结合LiPF₆(六氟磷酸锂)与LiBOB(二草酸硼酸锂)双盐体系调控溶剂化结构并构建含LiF与B-O组分的稳定SEI膜。该设计兼顾高离子电导率、低去溶剂化能垒、高热分解温度及界面钝化能力，突破了单一组分功能局限。实验表明，该体系使Cr₈O₂₁||Li一次电池在5C倍率下放电比容量达到商用电解液[LiBF₄(四氟硼酸锂)-PC+DME(乙二醇二甲醚)]的1.53倍。同时在60℃下的高温贮存寿命相比商用电解液延长5倍以上，且在60℃贮存720小时后容量保持率仍能达到89%。本研究通过多组分电解液策略为极端环境下高可靠性一次电池的开发提供了电解液设计与界面调控的新范式，对航天器电源系统等特殊场景应用具有重要工程价值。

关键词: Cr₈O₂₁, 一次电池, 大电流放电, 高温贮存寿命, 协同效应

Abstract:

Chromium oxide (Cr₈O₂₁) primary battery has become a research hotspot in the field of aerospace and military because of its high energy density and high working voltage. However, the application of primary batteries in extreme conditions is limited by the inherent contradiction between high current discharge capacity and high temperature storage life, but the traditional electrolyte is difficult to achieve synchronous optimization of the two. In view of this contradiction, this study proposed a multi-component electrolyte collaborative design strategy: through the high dielectric constant EC (ethylene carbonate) and low viscosity EMC (methyl ethyl carbonate) composite solvent to optimize the lithium salt dissociation and ion migration efficiency, combined with the same high boiling point PC (propylene carbonate) to improve the thermal stability of the electrolyte, and combined with LiPF₆ (lithium hexafluorophosphate) and LiBOB (lithium oxalate borate) double salt system to control the solvation structure and construct a stable SEI film containing LiF and B-O components. The design takes into account high ionic conductivity, low desolvation energy barrier, high thermal decomposition temperature and interface passivation ability, breaking through the functional limitations of a single component. The experimental results show that the specific discharge capacity of Cr₈O₂₁||Li primary battery at 5C rate is 1.53 times that of commercial electrolyte [LiBF₄(lithium tetrafluoroborate) - PC+DME (ethylene glycol dimethyl ether)]. At the same time, the high temperature storage life at 60℃ is more than 5 times longer than that of commercial storage, and the capacity retention rate reaches 89% after 720 hours of storage at 60℃. This study provides a new paradigm of electrolyte design and interface control for the development of high reliability primary batteries in extreme environments through the multi-component electrolyte strategy, which has important engineering value for the application of spacecraft power system and other special scenarios.

Key words: Cr₈O₂₁, Primary battery, High current discharge, High temperature storage life, synergistic effect

中图分类号:

TM911.11

张岩, 张红梅, 廖丽, 文炫中, 王明珊, 李星. 多组分电解液协同效应提升Cr₈O₂₁||Li一次电池倍率性能和高温贮存寿命研究[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0459.

Yan Zhang, Hongmei Zhang, Mingshan Wang, Xing Ling. Synergistic effect of multi-component electrolyte on the rate performance and high temperature storage life of Cr₈O₂₁||Li primary battery[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0459.

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参考文献 24

1	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. 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]. 储能科学与技术, 2023, 12(10): 3049-3055.
2	Liu J, Wang Z, Li H; Huang X, et al. Synthesis and characterization of Cr₈O₂₁ as cathode material for rechargeable lithium batteries. Solid State Ion. 2006, 177((26/32)): 2675–2678.
3	Belt J, Utgikar V, Bloom I. Calendar and PHEV cycle life aging of high-energy, lithium-ion cells containing blended spinel and layered-oxide cathodes[J]. Journal of Power Sources, 2011, 196(23): 10213-10221.
4	Fang Z, Yang Y, Zheng T, et al. An all-climate CFx/Li battery with mechanism-guided electrolyte[J]. Energy Storage Materials, 2021, 42: 477-483.
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): 2308053. 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): 2308053-2308053.
6	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.
7	金成龙,孙梦婷,孟庆飞,等. Cr₈O₂₁/Li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. JIN C L, SUN M T, MENG Q F, et al. Design and application of wide temperature electrolytes for Cr₈O₂₁/Libatteries[J]. Energy Storage Science and Technology, 2025, 14(4): 1369-1376
8	Zhou S Z, Liu X Y, Ji W W, et al. Electrolyte design for a high energy density Li/Cr₈O₂₁ primary battery in a wide-temperature range[J]. Journal of Power Sources, 2024, 614: 235006-235006.
9	Xiao Z X,Wu SY,Ren X Z, et al. Superior High-Rate Ni-Rich Lithium Batteries Based on Fast Ion-Desolvation and Stable Solid-Electrolyte Interphase[J]. Advanced science, 2025, 12(12): e2413419.
10	Chen X X, Liu G P, Fu A, et al. Electrolyte Strategy Enables High-Rate Lithium Carbon Fluoride (Li/CFx) Primary Batteries in All-Climate Environments[J]. Advanced Functional Materials, 2025, 35(3): 2413423.
11	Xu Kang. Electrolytes and Interphases in Li-Ion Batteries and Beyond[J]. Chemical Reviews, 2014, 114(23): 11503-11618.
12	Li Z H, Yao X Y, Zheng M T, et al. Electrolyte Design Enables Rechargeable LiFePO4/Graphite Batteries from -80℃ to 80℃[J]. Angew Chem Int Ed, 2024, 64(2): e202409409.
13	Jiang Z P, Mo J S, Li C, et al. Anion-Regulated Weakly Solvating Electrolytes for High-Voltage Lithium Metal Batteries[J]. Energy Environ Materials. 2023, 6(6): e12440.
14	Ming J, Cao Z, Li Q, et al. Molecular-Scale Interfacial Model for Predicting Electrode Performance in Rechargeable Batteries[J]. Acs Energy Letters, 2019, 4(7): 1584-1593.
15	Shen C, Guan D, Liu W, et a. Synergistic Solvent Design for Fluorine-Free Electrolytes in High-Performance Lithium-Ion Batteries[J]. Advanced Functional Materials, 2025,2503713.
16	Xiao G Y,Yang K, Qiu Y, et al. Dielectric-Tailored Space Charge Layer and Ion Coordination Structure for High-Voltage Polymer All-Solid-State Lithium Batteries[J]. Advanced materials, 2025, e2415411.
17	Fan Z, Zhang J, Wu L, et al. Solvation structure dependent ion transport and desolvation mechanism for fast-charging Li-ion batteries[J]. Chemical Science, 2024, 15(41): 17161–17172.
18	CHEN L, NIAN Q S, RUAN D G, et al. High-safety and highefficiency electrolyte design for 4.6 V-class lithium-ion batteries with a non-solvating flame-retardant[J]. Chemical Science, 2022, 14(5): 1184-1193.
19	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.
20	广玉, 刘新伟, 梅悦旎, 等. 锂离子电池高温贮存容量衰减分析[J]. 储能科学与技术, 2022, 11(5): 1339-1349. Guang Y, Liu X W, Mei Y N,Capacity fading analysis of lithium-ion battery after high temperature storage[J]. Energy Storage Science and Technology, 2022, 11(5): 1339-1349.
21	Zhu Y L, Zhu J G, Jiang B, et al. Insights on the degradation mechanism for large format prismatic graphite/LiFePO₄ battery cycled under elevated temperature[J]. Journal of Energy Storage, 2023, 60: 106624.
22	Kum K S, Song M K, Kim Y T, et al. The effect of mixed salts in gel-coated polymer electrolyte for advanced lithium battery[J]. Electrochimica Acta, 2004, 50(2-3): 285-288.
23	Luo Z, 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 (Weinheim an der Bergstrasse, Germany), 2024, 20(7): e2305980-e2305980.
24	Du Z, Wood D L, Belharouak I. Enabling fast charging of high energy density Li-ion cells with high lithium transport electrolytes[J]. Electrochemistry Communications, 2019, 103: 109-113.

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多组分电解液协同效应提升Cr₈O₂₁||Li一次电池倍率性能和高温贮存寿命研究

Synergistic effect of multi-component electrolyte on the rate performance and high temperature storage life of Cr₈O₂₁||Li primary battery

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