Reaction Mechanism and Structural Evolution of Fluorographite Cathodes in Solid-State K/Na/Li Batteries.

Ding, Zhengping; Yang, Chen; Zou, Jian; Chen, Shulin; Qu, Ke; Ma, Xiumei; Zhang, Jingmin; Lu, Jing et al. · Adv Mater · 2021

basic_science · Level V

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Abstract

Fluorographites (CF<sub>x</sub> ) are ultrahigh-energy-density cathode materials for alkaline-metal primary batteries. However, they are generally not rechargeable. To elucidate the reaction mechanism of CF<sub>x</sub> cathodes, in situ transmission electron microscopy characterizations and ab initio calculations are employed. It is found that it is a two-phase mechanism upon K/Na/Li ion insertion; crystalline KF (crystalline NaF nanoparticles and amorphous LiF) is generated uniformly within the amorphous carbon matrix, retaining an unchanged volume during the discharge process. The diffusivity for K/Na/Li ion migration within the CF<sub>x</sub> is ≈2.2-2.5 × 10<sup>-12</sup> , 3.4-5.3 × 10<sup>-12</sup> , and 1.8-2.5 × 10<sup>-11</sup> cm<sup>2</sup> s<sup>-1</sup> , respectively, which is comparable to the diffusivity of K/Na/Li ions in liquid-state cells. Encouraged by the in situ transmission electron microscopy (TEM) results, a new rechargeable all-solid-state Li/CF<sub>x</sub> battery is further designed that shows a part of the reversible specific discharge capacity at the 2nd cycle. These findings demonstrate that a solid-state electrolyte provides a different reaction process compared with a conventional liquid electrolyte, and enables CF<sub>x</sub> to be partly rechargeable in solid-state Li batteries.