Journal of Energy Storage ( IF 8.9 ) Pub Date : 2023-03-23 , DOI: 10.1016/j.est.2023.107208 Jia-Xuan Cai , Yong-Xin Qi , Wei Liu , Yu-Jun Bai
Rechargeable Li-ion batteries with fast-charging performance, long cycle life and safety are desirable. Herein, an efficient hydrothermal avenue was adopted to modify Li2ZnTi3O8 (LZTO) with trithiocyanuric acid (TCA). The two isomers of keto and enol TCA undergo different evolutions in the hydrothermal and electrochemical processes. For the enol TCA in the hydrothermal process, the HS– bonds close to LZTO react with LZTO to introduce superficial S-doping to facilitate electron conductance, and the others oxidize into –SO3– groups which transform into –SO3Li groups in lithiation process to favor Li+ migration. The keto TCA is stable in the hydrothermal process, yet the CS groups oxidize into –SO3– groups in anodic process and yield –SO3Li groups in subsequent cathodic process for Li+ diffusion. Despite these changes, the six-membered cyclic structures in both the keto and enol TCA are stable and coordinate with LZTO to create coating layer. The organic coating with good mechanical performance and strong interaction with PVDF protects LZTO from electrolyte corrosion and side reactions. Therefore, the TCA-modified LZTO demonstrates accelerated Li-ion migration and electron transfer, significantly enhanced rate capability and cycling stability.
中文翻译:
三硫氰尿酸异构体衍生物赋予 Li2ZnTi3O8 负极优异的稳定性和电化学性能
具有快速充电性能、长循环寿命和安全性的可充电锂离子电池是可取的。在此,采用有效的水热途径用三硫氰尿酸 (TCA)对 Li 2 ZnTi 3 O 8 (LZTO) 进行改性。酮和烯醇 TCA 的两种异构体在水热和电化学过程中经历了不同的演变。对于水热过程中的烯醇TCA,靠近LZTO的HS-键与LZTO反应引入表面S-掺杂以促进电子电导,其他氧化成-SO 3 -基团,在锂化过程中转化为-SO 3 Li基团有利于 Li +迁移的过程。酮 TCA 在水热过程中稳定,但 CS 基团在阳极过程中氧化成 –SO 3 – 基团,并在随后的用于 Li +扩散的阴极过程中产生 –SO 3 Li 基团。尽管发生了这些变化,但酮和烯醇 TCA 中的六元环结构是稳定的,并与 LZTO 协调形成涂层。具有良好机械性能和与 PVDF 强相互作用的有机涂层保护 LZTO 免受电解质腐蚀和副反应。因此,TCA 修饰的 LZTO 表现出加速的锂离子迁移和电子转移,显着增强的倍率性能和循环稳定性。