Song Zhihao, Yin Qing, Yang Shuhan, Miao Yidong, Wu Yunjia, Li Yong-Zhi, Ren Yaojian, Sui Yanwei, Qi Jiqiu, Han Jingbin
Jiangsu Province Engineering Laboratory of High Efficient Energy Storage Technology and Equipments, School of Materials and Physics, China University of Mining and Technology, Xuzhou, 221116, P. R. China.
State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, P. R. China.
Small. 2023 Oct;19(43):e2302896. doi: 10.1002/smll.202302896. Epub 2023 Jun 27.
Chloride-ion batteries (CIBs) have drawn growing attention in large-scale energy storage applications owing to their comprehensive merits of high theoretical energy density, dendrite-free characteristic, and abundance of chloride-containing materials. Nonetheless, cathodes for CIBs are plagued by distinct volume effect and sluggish Cl diffusion kinetics, leading to inferior rate capability and short cycling life. Herein, an unconventional Ni Ti-Cl LDH is reported with a high nickel ratio as a cathode material for CIB. The reversible capacity of Ni Ti-Cl LDH retains 127.9 mAh g over 1000 cycles at a large current density of 1000 mA g , which exceeds that of ever reported CIBs, with extraordinary low volume change of 1.006% during a whole charge/discharge process. Such superior Cl-storage performance is attributed to synergetic contributions consisting of high redox activity from Ni /Ni and pinning Ti that restrains local structural distortion of LDH host layers and enhances adsorption intensity of chloride atoms during the reversible Cl intercalation/de-intercalation in LDH gallery, which are revealed by a comprehensive study including X-ray photoelectron spectroscopy, kinetic investigations, and DFT calculations. This work provides an effective strategy to design low-cost LDHs materials for high-performance CIBs, which are also applicable to other types of halide-ion batteries (e.g., fluoride-ion and bromide-ion batteries).
氯离子电池（CIBs）因其在高理论能量密度、无枝晶特性以及含氯材料丰富等综合优点，在大规模储能应用中受到越来越多的关注。尽管如此，CIBs的阴极却受到明显的体积效应和缓慢的Cl扩散动力学的困扰，导致倍率性能较差和循环寿命较短。在此，报道了一种具有高镍比例的非常规Ni Ti-Cl LDH作为CIB的阴极材料。Ni Ti-Cl LDH在1000 mA g的大电流密度下，经过1000次循环后可逆容量保持在127.9 mAh g，超过了以往报道的CIBs，在整个充放电过程中的体积变化极低，仅为1.006%。这种优异的Cl存储性能归因于协同作用，包括Ni /Ni的高氧化还原活性和固定Ti，后者抑制了LDH主体层的局部结构畸变，并增强了在LDH层间可逆Cl嵌入/脱嵌过程中氯原子的吸附强度，这通过包括X射线光电子能谱、动力学研究和密度泛函理论计算在内的综合研究得以揭示。这项工作为设计用于高性能CIBs的低成本LDHs材料提供了一种有效策略，该策略也适用于其他类型的卤离子电池（如氟离子电池和溴离子电池）。
