Huang Jun, Yang Kaihua, Zhang Zhengxi, Yang Li, Hirano Shin-Ichi
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Chem Commun (Camb). 2017 Jul 6;53(55):7800-7803. doi: 10.1039/c7cc03933f.
∼1 V lithium intercalation materials are promising anodes for lithium-ion batteries, because such materials give consideration to both the tolerance of lithium plating (e.g., graphite with ∼0.1 V versus Li/Li easily results in lithium plating due to a too low potential) and the energy density of the batteries (e.g., LiTiO with ∼1.55 V decreases the battery voltage, and thus reduces the energy density). Herein, the layered perovskite compound LiEuTiO4 with a 0.8 V lithium intercalation/deintercalation potential plateau was successfully synthesized by the ion-exchange reaction with NaEuTiO4 prepared via a sol-gel method. LiEuTiO4 can deliver a high capacity of 219.2 mA h g (2nd discharge) at a rate of 100 mA g. Even after 500 cycles, the discharge capacity remains at ∼217 mA h g and the Coulombic efficiency is 99.2%. To our knowledge, the cycle stability of LiEuTiO4 exceeds all previous ∼1 V electrodes. Different from the common lithium intercalation Ti-based electrodes (such as LiTiO) based on the reduction of the Ti to Ti, electrochemical lithium intercalation into LiEuTiO4 leads to the reduction of the Eu to Eu.
约1V的锂嵌入材料是有前景的锂离子电池负极材料,因为这类材料兼顾了锂金属沉积耐受性(例如,相对于Li/Li电位约为0.1V的石墨,由于电位过低容易导致锂金属沉积)和电池的能量密度(例如,电位约为1.55V的LiTiO会降低电池电压,进而降低能量密度)。在此,通过与采用溶胶 - 凝胶法制备的NaEuTiO4进行离子交换反应,成功合成了具有0.8V锂嵌入/脱嵌电位平台的层状钙钛矿化合物LiEuTiO4。LiEuTiO4在100mA g的电流密度下,第二次放电时可提供219.2 mA h g的高容量。即使经过500次循环,放电容量仍保持在约217 mA h g,库仑效率为99.2%。据我们所知,LiEuTiO4的循环稳定性超过了此前所有约1V的电极。与基于Ti还原为Ti的常见锂嵌入钛基电极(如LiTiO)不同,电化学锂嵌入LiEuTiO4会导致Eu还原为Eu。