Gheytani Saman, Liang Yanliang, Wu Feilong, Jing Yan, Dong Hui, Rao Karun K, Chi Xiaowei, Fang Fang, Yao Yan
Department of Electrical and Computer Engineering and Materials Science and Engineering Program University of Houston Houston TX 77204 USA.
Department of Materials Science Fudan University Shanghai 200433 China.
Adv Sci (Weinh). 2017 Oct 26;4(12):1700465. doi: 10.1002/advs.201700465. eCollection 2017 Dec.
Multivalent-ion batteries are emerging as low-cost, high energy density, and safe alternatives to Li-ion batteries but are challenged by slow cation diffusion in electrode materials due to the high polarization strength of Mg- and Al-ions. In contrast, Ca-ion has a low polarization strength similar to that of Li-ion, therefore a Ca-ion battery will share the advantages while avoiding the kinetics issues related to multivalent batteries. However, there is no battery known that utilizes the Ca-ion chemistry due to the limited success in Ca-ion storage materials. Here, a safe and low-cost aqueous Ca-ion battery based on a highly reversible polyimide anode and a high-potential open framework copper hexacyanoferrate cathode is demonstrated. The prototype cell shows a stable capacity and high efficiency at both high and low current rates, with an 88% capacity retention and an average 99% coloumbic efficiency after cycling at 10C for 1000 cycles. The Ca-ion storage mechanism for both electrodes as well as the origin of the fast kinetics have been investigated. Additional comparison with a Mg-ion cell with identical electrodes reveals clear kinetics advantages for the Ca-ion system, which is explained by the smaller ionic radii and more facile desolvation of hydrated Ca-ions.
多价离子电池正在成为锂离子电池低成本、高能量密度且安全的替代品,但由于镁离子和铝离子的高极化强度,电极材料中的阳离子扩散缓慢,这对其构成了挑战。相比之下,钙离子的极化强度与锂离子相似,因此钙离子电池将兼具锂离子电池的优点,同时避免与多价离子电池相关的动力学问题。然而,由于钙离子存储材料方面成效有限,目前还没有已知的利用钙离子化学性质的电池。在此,展示了一种基于高度可逆的聚酰亚胺阳极和高电位开放框架六氰合铁酸铜阴极的安全、低成本水系钙离子电池。该原型电池在高电流率和低电流率下均表现出稳定的容量和高效率,在10C下循环1000次后容量保持率为88%,平均库仑效率为99%。对两个电极的钙离子存储机制以及快速动力学的起源进行了研究。与具有相同电极的镁离子电池进行的额外比较揭示了钙离子体系明显的动力学优势,这可以通过水合钙离子较小的离子半径和更易脱溶剂化来解释。