Zheng Jiening, Yi Ke, Chang Chengkang
School of Materials Science and Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai, 201418, China.
Small Methods. 2025 Apr;9(4):e2401000. doi: 10.1002/smtd.202401000. Epub 2024 Aug 30.
Nonaqueous aluminum-ion batteries (AIBs) provide advantages, such as high energy density, enhanced safety, and reduced corrosion, making them ideal for advanced energy storage solutions. A key challenge faced by AIBs is the lack of suitable cathode materials for rapid Al-ion insertion /extraction. Herein, KMn[Fe(CN)] 2HO (KMHCF) is innovatively chosen as a model to investigate the aluminum storage performance of Prussian blue analogues in nonaqueous AIBs. As anticipated, the KMHCF allows for reversible aluminum storage and exhibits characteristic charge/discharge plateaus. Furthermore, carbon combined highly crystalline KMHCF (HC-KMHCF@C) is synthesized through a chelator-assisted preparation method in combination with an in situ carbon compositing technique. With reduced [Fe(CN)]⁻ defects, lower interstitial water content, and enhanced conductivity, HC-KMHCF@C exhibits a high aluminum storage capacity (146.2 mAh g⁻¹ at 0.5 A g⁻¹) and satisfactory cycling performance (maintaining 86.4 mAh g⁻¹ after 800 cycles). The electrochemical reaction mechanism of HC-KMHCF@C is investigated in detail. During the initial charge, K⁺ ions are extracted, shifting the structure from monoclinic to cubic. In subsequent cycles, reversible Al insertion and extraction cause the structure to alternate between monoclinic and cubic phases.
非水铝离子电池（AIBs）具有诸多优势，如高能量密度、更高的安全性以及减少的腐蚀性，使其成为先进储能解决方案的理想选择。AIBs面临的一个关键挑战是缺乏适用于快速铝离子嵌入/脱出的阴极材料。在此，创新性地选择KMn[Fe(CN)]·2H₂O（KMHCF）作为模型，来研究普鲁士蓝类似物在非水AIBs中的储铝性能。正如预期的那样，KMHCF能够实现可逆的铝存储，并呈现出特征性的充放电平台。此外，通过螯合剂辅助制备方法结合原位碳复合技术合成了碳复合的高结晶度KMHCF（HC-KMHCF@C）。由于[Fe(CN)]⁻缺陷减少、间隙水含量降低以及导电性增强，HC-KMHCF@C表现出高的储铝容量（在0.5 A g⁻¹时为146.2 mAh g⁻¹）和令人满意的循环性能（800次循环后保持86.4 mAh g⁻¹）。详细研究了HC-KMHCF@C的电化学反应机理。在初次充电过程中，K⁺离子脱出，结构从单斜相转变为立方相。在随后的循环中，可逆的铝嵌入和脱出导致结构在单斜相和立方相之间交替。
