Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany.
Angew Chem Int Ed Engl. 2013 May 3;52(19):4998-5026. doi: 10.1002/anie.201205569. Epub 2013 Apr 29.
The thermodynamics of electrochemical lithium storage are examined by taking into account that it is the point defects that enable storage. While the Li defects are mobile, most of the other point defects have to be considered as frozen owing to the performance temperature being low compared to the melting point of the electrode materials. The defect chemistry needs to be considered to fully understand equilibrium charge/discharge curves. On this basis, single phase and multiphase storage mechanisms can be discussed in terms of theoretical storage capacity and theoretical voltage. Of paramount interest in the field of Li batteries are metastable materials, in particular nanocrystalline and amorphous materials. The thermodynamics of storage and voltage, also at interfaces, thus deserve a special treatment. The relationship between reversible cell voltage and lithium content is derived for the novel job-sharing mechanism. With respect to the classic storage modes, thermodynamic differences for cathodes and anodes are elaborated with a special attention being paid to the search for new materials. As this contribution concentrates on the equilibrium state, current-related phenomena (irreversible thermodynamics) are only briefly touched upon.
通过考虑到是点缺陷使存储成为可能，来研究电化学锂存储的热力学。虽然 Li 缺陷是可移动的，但由于性能温度与电极材料的熔点相比较低，大多数其他点缺陷必须被视为冻结。为了充分理解平衡充放电曲线，需要考虑缺陷化学。在此基础上，可以根据理论存储容量和理论电压讨论单相和多相存储机制。在锂电池领域，亚稳材料，特别是纳米晶和非晶材料，是至关重要的。因此，存储和电压的热力学，包括界面，都值得特别处理。针对新的共享机制，推导出了可逆电池电压和锂含量之间的关系。与经典的存储模式相比，详细阐述了阴极和阳极的热力学差异，并特别关注新材料的寻找。由于本贡献集中在平衡状态，因此仅简要涉及与电流相关的现象（不可逆热力学）。
