Tailoring Ca2+/Li+ Dual-Cation Gel Polymer Electrolytes via Cross-Linking for Reductive and Oxidative Stability in Ca-Metal Batteries

IF 5.4 3区材料科学 Q2 CHEMISTRY, PHYSICAL

ACS Applied Energy Materials Pub Date : 2025-03-12 DOI:10.1021/acsaem.4c0306510.1021/acsaem.4c03065

Takara Shinohara, Kazuaki Kisu*, Shohichi Furukawa, Kenji Zushida and Shin-ichi Orimo*,

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Abstract

Calcium–metal batteries with polymer electrolytes are emerging as promising next-generation energy systems owing to their high energy density, natural abundance of Ca in the Earth’s crust, and inherent safety. However, developing suitable polymer electrolytes for Ca-metal batteries remains challenging owing to compatibility issues with Ca-metal anodes and high-voltage cathodes. Herein, we report a dual-cation (Ca²⁺/Li⁺) gel polymer electrolyte (GPE), designed using calcium monocarborane (Ca(CB₁₁H₁₂)₂) and adjusting the lithium borohydride (LiBH₄) concentration, which enhanced oxidation stability while maintaining compatibility with Ca metal. The incorporation of the CB₁₁H₁₂^– anion improved the oxidation stability of the electrolyte, increasing the oxidation potential from 2.2 to 2.6 V (vs Ca²⁺/Ca). Cyclic voltammetry and galvanostatic tests demonstrated reversible plating/stripping properties and high stability against Ca-metal anodes. The reversible operation of the Ca-metal battery was confirmed using a titanium disulfide (TiS₂) cathode, which achieved an initial discharge capacity of 188.5 mA h g^–1. Exsitu X-ray diffraction analysis corroborated this finding by revealing crystallographic changes in TiS₂. This Ca-GPE, with its enhanced oxidation stability, paves the way for developing high-voltage Ca metal–polymer batteries.

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通过交联剪裁Ca2+/Li+双阳离子凝胶聚合物电解质用于钙金属电池的还原和氧化稳定性

聚合物电解质的钙金属电池由于其高能量密度、地壳中天然丰富的钙以及固有的安全性，正在成为有前途的下一代能源系统。然而，由于与钙金属阳极和高压阴极的兼容性问题，开发适合钙金属电池的聚合物电解质仍然具有挑战性。本文报道了一种双阳离子（Ca2+/Li+）凝胶聚合物电解质（GPE），采用单碳硼烷钙（Ca(CB11H12)2）设计，并调节硼氢化锂（LiBH4）浓度，增强了氧化稳定性，同时保持了与金属Ca的相容性。CB11H12 -阴离子的掺入提高了电解质的氧化稳定性，将氧化电位从2.2 V （vs Ca2+/Ca）提高到2.6 V。循环伏安法和恒流试验证明了可逆的镀/剥离性能和对金属钙阳极的高稳定性。使用二硫化钛（TiS2）阴极证实了锂离子电池的可逆操作，其初始放电容量为188.5 mA h g-1。原位x射线衍射分析通过揭示TiS2的晶体学变化证实了这一发现。这种Ca- gpe具有增强的氧化稳定性，为开发高压Ca金属聚合物电池铺平了道路。

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来源期刊

ACS Applied Energy Materials Materials Science-Materials Chemistry

CiteScore

10.30

自引率

6.20%

发文量

1368

期刊介绍： ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.