Improving Li3V2(PO4)3 cathode performance by Mn2+ doping for high-rate aqueous zinc ion hybrid batteries
Improving Li3V2(PO4)3 cathode performance by Mn2+ doping for high-rate aqueous zinc ion hybrid batteries
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通过Mn2掺杂提高高倍率水系锌离子混合电池Li3V2(PO4)3正极性能
DOI：
10.1007/s11581-022-04561-z
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发表时间：
2022-05
期刊：
影响因子：
2.8
通讯作者：
Lizhi Xiong
中科院分区：
文献类型：
--
作者：
Youliang Jiang;Yanhong Xiang;Qiuling Zou;Baocheng Liu;Saiqiu Liu;Hanzhang Zeng;Leyan Chen;Jian Li;Xianwen Wu;Lizhi Xiong
采用冷冻干燥辅助溶胶凝胶法合成了水基锌离子混合电池正极材料Li3V2-xMnx(PO4)3(x=0，0.02，0.04，0.06和0.1)。研究了Mn2+掺杂对样品结构、形貌和电化学性能的影响。X射线衍射结果表明，合成的Li3V2-xMnx(PO4)3产物属于Li3V2(PO4)3结构(P21/n)。X射线光电子能谱分析表明，材料中的Mn2p1/2和Mn2p2/3分别位于653.94 eV和642.46 eV处，并有微量的Mn掺杂。扫描电子显微镜照片表明，Li3V1.94Mn0.06(PO4)3样品在形貌上更加分散，颗粒尺寸更小，EDAX证实了Li3V1.94Mn0.06(PO4)3样品中元素(V，Mn，P，O)在先驱体复合材料中的均匀分布。锌//Li3V1.94Mn0.06(PO4)3电池在2C电流密度(106.5 mA g−1)下具有良好的初始容量(200 mA g−1)、出色的循环稳定性(50次循环容量保持率为98%)和卓越的倍率性能(当电流密度达到20 C时，可逆容量为98mAhg−1)。循环伏安测试结果表明，锌离子在Li3V1.94Mn0.06(PO4)3电极中的扩散系数为1.3×10-12cm2 S−1，大于其他四种电极。交流阻抗谱结果表明，Li3V1.94Mn0.06(PO4)3的RCT值最低(243.5Ω)，这与倍率性能和循环结果一致。非原位X射线衍射结果表明，Li+离子在充放电过程中可以可逆地插入或脱出。
Li3V2-xMnx(PO4)3 (x = 0, 0.02, 0.04, 0.06 and 0.1) cathode materials for aqueous zinc-ion hybrid batteries (AZHBs) have been synthesized by freeze-drying-assisted sol–gel method. The effects of Mn2+ dopping content on the structure, morphology, and electrochemical performance of the samples were investigated. XRD results indicated that the Li3V2-xMnx(PO4)3 products belong to the Li3V2(PO4)3 structure (P21/n). XPS results indicate that Mn2p1/2 and Mn2p2/3 are located at 653.94 eV and 642.46 eV, respectively, with trace amounts of Mn doping in the material. SEM images show that Li3V1.94Mn0.06(PO4)3 sample has more dispersed and smaller particle size in morphology, and the uniform distribution of elements of Li3V1.94Mn0.06(PO4)3 sample (V, Mn, P, O) in the precursor composites was confirmed by EDAX. The Zn// Li3V1.94Mn0.06(PO4)3 battery delivers a superior initial capacity of 106.5 mAh g−1 at the current density of 2 C (200 mA g−1), remarkable cycle stability (98% capacity retention for 50th cycles) and superior rate capability (when current density reaches up to 20 C, the reversible capacities are 98mAh g−1). The results of CV indicated that the diffusion coefficient of zinc ion in Li3V1.94Mn0.06(PO4)3 electrode is 1.30 × 10–12 cm2 s−1, which is larger than the other four electrodes. The result of EIS demonstrated that the Rct value.of Li3V1.94Mn0.06(PO4)3 is the lowest (243.5 Ω), which is in good agreement with rate capability and cyclic results. ex situ XRD results demonstrate that Li+ ion can be inserted or de-inserted reversibly during charge and discharge.
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