Bimetallic Cyanide-Bridged Coordination Polymers as Lithium Ion Cathode Materials: Core@Shell Nanoparticles with Enhanced Cyclability

详细信息    查看全文

• 作者：Daisuke Asakura ; Carissa H. Li ; Yoshifumi Mizuno ; Masashi Okubo ; Haoshen Zhou ; Daniel R. Talham
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：February 20, 2013
• 年：2013
• 卷：135
• 期：7
• 页码：2793-2799
• 全文大小：483K
• 年卷期：v.135,no.7(February 20, 2013)
• ISSN：1520-5126

文摘

Prussian blue analogues (PBAs) have recently been proposed as electrode materials for low-cost, long-cycle-life, and high-power batteries. However, high-capacity bimetallic examples show poor cycle stability due to surface instabilities of the reduced states. The present work demonstrates that, relative to single-component materials, higher capacity and longer cycle stability are achieved when using Prussian blue analogue core@shell particle heterostructures as the cathode material for Li-ion storage. Particle heterostructures with a size dispersion centered at 210 nm composed of a high-capacity K_0.1Cu[Fe(CN)₆]_0.7路3.8H₂O (CuFe-PBA) core and lower capacity but highly stable shell of K_0.1Ni[Fe(CN)₆]_0.7路4.1H₂O have been prepared and characterized. The heterostructures lead to the coexistence of both high capacity and long cycle stability because the shell protects the otherwise reactive surface of the highly reduced state of the CuFe-PBA core. Furthermore, interfacial coupling to the shell suppresses a known structural phase transition in the CuFe-PBA core, providing further evidence of synergy between the core and shell. The structure and chemical state of the heterostructure during electrochemical cycling have been monitored with ex situ X-ray diffraction and X-ray absorption experiments and compared to the behavior of the individual components.