东北师范大学吴兴隆团队报道了用于超长寿命铝离子水电池的低应变约束相变熵调节阴极。相关研究成果发表在2024年1月29日出版的《德国应用化学》。

在多价离子插入过程中，电荷载体和主体之间的强烈静电相互作用，使高性能可逆铝离子存储仍然是一个难以捉摸的目标。由于强的静电排斥和较差的稳健性，包括普鲁士蓝类似物（PBAs）在内的金属有机框架，在可逆的Al³⁺插入过程中不可避免地会发生大的应变和相变。

该文中，研究人员展示了一种基于中熵PBAs（ME PBAs）宿主的熵驱动策略，以实现超长寿命的水性铝离子电池（AIBs）。通过引入多个氧化还原活性中心，可以同时增强本征的不良导电性和放电电压平台，从而产生卓越的电化学铝离子存储能力。同时，PBA框架中金属位点的共占据也可以增加M-N键的强度，这有利于在连续Al³⁺可逆插入过程中实现对相变的约束，从而实现超过10000次循环的延长寿命。

根据不同操作状态下的计算，ME-PBA晶格参数的波动仅在1.2%的范围内。与MoO₃阳极组装，全电池AIBs也可以提供出色的电化学性能。熵调节策略揭示了长期可逆Al³⁺存储对应变和相变的等时约束。

附：英文原文

Title: Entropy-Regulated Cathode with Low Strain and Constraint Phase-Change Toward Ultralong-Life Aqueous Al-Ion Batteries

Author: Yan-Ning Liu, Jia-Lin Yang, Zhen-Yi Gu, Xin-Yi Zhang, Yue Liu, Meng-Yuan Su, Xue-Li Zhang, Igor V. Zatovsky, Kai Li, Jun-Ming Cao, Xing-Long Wu

Issue&Volume: 2024-01-29

Abstract: During multivalent ions insertion processes, intense electrostatic interaction between charge carriers and host makes the high-performance reversible Al-ions storage remains an elusive target. On account of the strong electrostatic repulsion and poor robustness, metal organic frameworks, including Prussian Blue analogues (PBAs), severely suffers from the inevitable and large strain and phase change during reversible Al3+ insertion. Herein, we demonstrate an entropy-driven strategy to realize ultralong life aqueous Al-ion batteries (AIBs) based on medium entropy PBAs (ME-PBAs) host. By virtue of multiple redox active centers introduction, the intrinsic poor conductivity and discharging voltage platform can be enhanced simultaneously, resulting in outstanding capabilities of electrochemical Al ions storage. Meanwhile, the co-occupation at metal sites in PBA frameworks can also increase the M-N bond intensity, which is beneficial for achieving the constrain on phase change during consecutive Al3+ reversible insertion, to realize an extended lifespan over 10,000 cycles. Based on the calculation at different operation states, the fluctuation of ME-PBA lattice parameters is varied in a range of only 1.2%. Assembled with MoO3 anodes, the full cells AIBs can also deliver outstanding electrochemical properties. The entropy regulation strategy uncover the isochronous constrain on both strain and phase transition for long-term reversible Al3+ storage.

DOI: 10.1002/anie.202316925

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202316925