Chen Nan, Gao Yu, Zhang Meina, Meng Xing, Wang Chunzhong, Wei Yingjin, Du Fei, Chen Gang
Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun, 130012, P.R. China.
State Key Laboratory of Superhard Materials, Jilin University, Changchun, 130012, P.R. China.
Chemistry. 2016 May 17;22(21):7248-54. doi: 10.1002/chem.201600224. Epub 2016 Apr 9.
Silver molybdate, Ag2 Mo2 O7 , has been prepared by a conventional solid-state reaction. Its electrochemical properties as an anode material for sodium-ion batteries (SIBs) have been comprehensively examined by means of galvanostatic charge-discharge cycling, cyclic voltammetry, and rate performance measurements. At operating voltages between 3.0 and 0.01 V, the electrode delivered a reversible capacity of nearly 190 mA h g(-1) at a current density of 20 mA g(-1) after 70 cycles. Ag2 Mo2 O7 also demonstrated a good rate capability and long-term cycle stability, the capacity reaching almost 100 mA h g(-1) at a current density of 500 mA g(-1) , with a capacity retention of 55 % over 1000 cycles. Moreover, the sodium storage process of Ag2 Mo2 O7 has been investigated by means of ex situ XRD, Raman spectroscopy, and HRTEM. Interestingly, the anode decomposes into Ag metal and Na2 MoO4 during the initial discharge process, and then Na(+) ions are considered to be inserted into/extracted from the Na2 MoO4 lattice in the subsequent cycles governed by an intercalation/deintercalation mechanism. Ex situ HRTEM images revealed that Ag metal not only remains unchanged during the sodiation/desodiation processes, but is well dispersed throughout the amorphous matrix, thereby greatly improving the electronic conductivity of the working electrode. The "in situ" decomposition behavior of Ag2 Mo2 O7 is distinct from that of chemically synthesized, metal-nanoparticle-coated electrode materials, and provides strong supplementary insight into the mechanism of such new anode materials for SIBs and may set a precedent for the design of further materials.
钼酸银(Ag₂Mo₂O₇)通过传统的固态反应制备而成。通过恒电流充放电循环、循环伏安法和倍率性能测试等手段,对其作为钠离子电池(SIBs)负极材料的电化学性能进行了全面研究。在3.0至0.01 V的工作电压下,该电极在70次循环后,于20 mA g⁻¹的电流密度下提供了近190 mA h g⁻¹的可逆容量。Ag₂Mo₂O₇还表现出良好的倍率性能和长期循环稳定性,在500 mA g⁻¹的电流密度下容量达到近100 mA h g⁻¹,在1000次循环中的容量保持率为55%。此外,通过非原位XRD、拉曼光谱和高分辨透射电子显微镜(HRTEM)研究了Ag₂Mo₂O₇的储钠过程。有趣的是,在初次放电过程中负极分解为金属银和Na₂MoO₄,然后在随后的循环中,Na⁺离子被认为是通过嵌入/脱嵌机制插入/脱出Na₂MoO₄晶格。非原位HRTEM图像显示,金属银不仅在钠化/脱钠过程中保持不变,而且在整个非晶基体中均匀分散,从而大大提高了工作电极的电子导电性。Ag₂Mo₂O₇的“原位”分解行为与化学合成的、金属纳米颗粒包覆的电极材料不同,为这类新型SIBs负极材料的机理提供了有力的补充见解,并可能为进一步的材料设计开创先例。