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，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5 C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 h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:

The chromium oxide (Cr₈O₂₁) primary battery has emerged as a research hotspot in aerospace and military applications owing to its high energy density and high operating voltage. However, its use under extreme conditions is constrained by the inherent trade-off between high current discharge capacity and high-temperature storage life, which conventional electrolytes cannot simultaneously optimize. To address this issue, a multi-component electrolyte design strategy was proposed. A mixed solvent of ethylene carbonate (EC, high dielectric constant) and methyl ethyl carbonate (EMC, low viscosity) was employed to enhance lithium-salt dissociation and ion migration efficiency. Propylene carbonate (PC, high boiling point) was incorporated to improve electrolyte thermal stability, while a dual-salt system of lithium hexafluorophosphate (LiPF₆) and lithium bis(oxalato)borate (LiBOB) was used to regulate solvation structure and form a stable solid electrolyte interphase (SEI) film enriched with LiF and B—O species. This strategy ensures high ionic conductivity, a low desolvation energy barrier, elevated thermal decomposition temperature, and strong interfacial passivation, thereby overcoming the functional limitations of single-component electrolytes. Experimental results demonstrate that the specific discharge capacity of the Cr₈O₂₁||Li primary battery at a 5 C rate is 1.53 times higher than that with a commercial electrolyte of lithium tetrafluoroborate (LiBF₄) in PC + ethylene glycol dimethyl ether (DME). Moreover, the high-temperature storage life at 60 ℃ is extended more than fivefold, with a capacity retention of 89% after 720 h. This work establishes a new paradigm for electrolyte design and interface control in high-reliability primary batteries for extreme environments, offering significant engineering value for spacecraft power systems and other specialized applications.

Key words: Cr₈O₂₁, primary battery, high current discharge, high-temperature storage life, synergistic effect

中图分类号:

TM 911.11

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, 2025, 14(11): 4123-4132.

Yan ZHANG, Hongmei ZHANG, Li LIAO, Xuanzhong WEN, Mingshan WANG, Xing LI. 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, 2025, 14(11): 4123-4132.

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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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