将溶解平衡热力学与电池的电解质运输动力学联系起来
Jianwei Lai1, Yanjun Guo1, Hao-En Lai2
1John and Willie Leone Family Department of Energy and Mineral Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, United States.
温度变化驱动离子溶解平衡,将溶剂分离离子对 (SSIP) 转换为接触离子对 (CIP) 和反向. 这揭示了电解质的差异,并将热力学特性与离子运输相关联.
科学领域:
- 电化学
- 材料科学
- 物理化学
背景情况:
- 了解离子溶解对于设计高级电解质至关重要.
- 之前的研究缺乏关于广泛温度范围内的溶解平衡的基本热力学数据.
- 主要的物理化学特性如溶解力和溶解能量已经被探索,但不是协调的动态演变.
研究的目的:
- 系统地研究电解质中的+溶剂和离子协调的动态演变.
- 将溶解平衡的热力学特性与传输特性相关联.
- 建立电池电解质设计的基准标准.
主要方法:
- 使用温度分辨率的红外和拉曼光谱.
- 在-60°C的温度范围内研究了典型的和碳酸电解质.
- 量化温度响应的平均协调数和酸盐物种度.
主要成果:
- 在溶剂分离离子对 (SSIP) 和接触离子对 (CIP) 之间确定了温度驱动的平衡.
- 在温度变化下观察到SSIP和CIP之间的可逆转换.
- 在碳酸电解质与以太电解质相比显示出偏好的CIP协会.
- 在Gibbs自由能量变化和Li+转移数量之间发现了强烈的相关性.
结论:
- 溶解平衡的热力学特性为动态溶解结构提供了新的描述.
- 这些发现为广泛的电池电解质提供了基准.
- 这项工作为基于溶解结构和热力学的合理电解质设计奠定了基础.
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