PC基电解液对Li/CrO<i><sub>x</sub></i>一次电池高倍率性能的影响

引用本文: 杨睿, 李惠, 孟庆飞, 李文杰, 吴际良, 方永进, 黄驰, 曹余良. PC基电解液对Li/CrO_x一次电池高倍率性能的影响[J]. 物理化学学报, 2024, 40(9): 230805. doi: 10.3866/PKU.WHXB202308053 shu

Citation: Rui Yang, Hui Li, Qingfei Meng, Wenjie Li, Jiliang Wu, Yongjin Fang, Chi Huang, Yuliang Cao. Influence of PC-based Electrolyte on High-Rate Performance in Li/CrO_x Primary Battery[J]. Acta Physico-Chimica Sinica, 2024, 40(9): 230805. doi: 10.3866/PKU.WHXB202308053 shu

PC基电解液对Li/CrO_x一次电池高倍率性能的影响

杨睿 ^1, ,
李惠 ^1, ,
孟庆飞 ^2, ,
李文杰 ^2, ,
吴际良 ^2, ,
方永进 ^1, ,
黄驰 ^{1,
,} ,
曹余良 ^{1,
,}

1.
武汉大学化学与分子科学学院, 武汉 430072;
2.
武汉中原长江科技发展有限公司, 武汉 430090

通讯作者: 黄驰,Email:chihuang@whu.edu.cn; 曹余良,Email:ylcao@whu.edu.cn

基金项目:
国防基础科研计划(JCKY2021211B014)资助项目

摘要: Li/CrO_x电池具有高能量密度和优异的倍率性能，成为高性能一次锂电池的研究热点。而基于发展具有宽温域和高介电常数的碳酸丙烯酯(PC)电解液体系，对于开发功率高和环境耐受性强的锂一次电池具有重要的应用价值。在本工作中，我们研究了CrO_x在PC基电解液中的放电行为，筛选了适配于大电流放电的电解液体系：1 mol∙L⁻¹ LiTFSI PC : DOL (1,3-二氧环戊烷) = 1 : 2；并揭示了在PC基电解液中影响CrO_x大电流放电的规律：Li⁺溶剂化鞘层中溶剂分子配位数以及参与配位的粒子类型，会极大地影响Li/CrO_x电池体系的倍率放电性能。低的配位数以及阴离子参与的溶剂化鞘层结构更加适配Li/CrO_x电池体系，能够实现大电流放电。这些规律的认识对于推动PC基电解液应用于大倍率Li/CrO_x电池体系具有重要指导意义。

关键词:

English

Influence of PC-based Electrolyte on High-Rate Performance in Li/CrO_x Primary Battery

Rui Yang ^1, ,
Hui Li ^1, ,
Qingfei Meng ^2, ,
Wenjie Li ^2, ,
Jiliang Wu ^2, ,
Yongjin Fang ^1, ,
Chi Huang ^{1,
,} ,
Yuliang Cao ^{1,
,}

1.
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;
2.
Wuhan Zhongyuan Changjiang Technology Development Co. Ltd., Wuhan 430090, China

Corresponding author: Chi Huang, ; Yuliang Cao,

Received Date: 31 August 2023
Accepted Date: 06 October 2023
Revised Date: 27 September 2023
Available Online: 16 October 2023
Fund Project:
The project was supported by the Defense Industrial Technology Development Program (JCKY2021211B014).

Abstract: The Li/CrO_x battery has gained attention in the construction of smart cities, aerospace, and national defense and military applications due to its high energy density and excellent rate performance. Developing a Li/CrO_x battery with high specific capacity, high energy density, excellent magnification performance, long storage life, and low cost is a primary goal. In this pursuit, the role of the electrolyte in battery performance for Li/CrO_x primary batteries cannot be underestimated. However, current research on Li/CrO_x primary batteries has primarily focused on electrode materials, with limited attention given to the electrolyte. Propylene carbonate (PC) solvent possesses a wide temperature range for melting and boiling points (−48.8 to 242 °C) and a high dielectric constant of 64.92. As a result, it is frequently used as a key component in electrolytes that operate under extreme temperatures and high rates. Nevertheless, its use in Li/CrO_x batteries remains limited. Developing electrolyte systems based on PC with a wide temperature range and high dielectric constant is crucial for the advancement of high-power and environmentally robust lithium primary batteries. In this study, we investigated the discharge behavior of CrO_x in PC-based electrolytes and identified suitable electrolyte systems for high-current discharge, specifically a 1 mol∙L⁻¹ LiTFSI PC : DOL (1,3-dioxolane) = 1 : 2 ratio. We also demonstrated that the coordination number of solvent molecules in the solvation sheath layer around Li⁺ ions and the solvated structure involved in coordination significantly influence the rate performance of Li/CrO_x battery systems in PC-based electrolytes. Reducing the coordination number of solvent molecules facilitates the desolvation behavior of solvated Li⁺, thereby enhancing the desolvation process on the material surface. Furthermore, lowering the coordination number of solvent molecules promotes the involvement of anions in the solvated sheath structure. When the coordination number of solvent molecules falls below 3, it tends to form a solvated coordination structure involving anions with a higher lowest unoccupied molecular orbital (LUMO) level. This enables anions to participate in forming a solid electrolyte interface (SEI), resulting in a thinner and denser SEI film that significantly improves battery performance. Ultimately, modifying the coordination number for PC-based electrolytes is a practical and effective approach to enhance the rate performance of solvated sheath structures. The coordination number and the solvated sheath structure of Li⁺ in PC-based electrolytes have a profound impact on the high-current-discharge performance of the Li/CrO_x battery system. A lower coordination number and the participation of anions in the solvated sheath structure effectively accommodate the high-rate discharge characteristics of the Li/CrO_x battery. Among several selected electrolyte solvents, an electrolyte with DOL (a cyclic ether) and PC reduces the solvent’s coordination number to less than four, thereby enabling high-rate discharge. Understanding these principles is crucial for advancing the application of PC-based electrolytes in high-rate Li/CrO_x battery systems.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

PC基电解液对Li/CrO_x一次电池高倍率性能的影响

通讯作者: 黄驰,Email:chihuang@whu.edu.cn; 曹余良,Email:ylcao@whu.edu.cn

English

Influence of PC-based Electrolyte on High-Rate Performance in Li/CrO_x Primary Battery

Corresponding author: Chi Huang, ; Yuliang Cao,

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PC基电解液对Li/CrOx一次电池高倍率性能的影响

通讯作者: 黄驰,Email:chihuang@whu.edu.cn; 曹余良,Email:ylcao@whu.edu.cn

English

Influence of PC-based Electrolyte on High-Rate Performance in Li/CrOx Primary Battery

Corresponding author: Chi Huang, ; Yuliang Cao,

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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