钙钒青铜/碳纳米管复合材料的制备及电化学性能

doi:10.7503/cjcu20190397

摘要/Abstract

摘要：

采用水热法制备了具有二维层状结构的钙钒青铜(Ca_xV₂O₅·nH₂O, CVO)水系锌离子电池钒基正极材料, 并通过调控前驱体溶液中碳纳米管的含量, 得到3种钙钒青铜/碳纳米管复合材料(CVO@CNTs). 利用X射线衍射、热重分析、扫描电子显微镜和透射电子显微镜等对材料进行了表征. 结果表明, 所制备的CVO呈纳米带形貌, 长约十几微米, 宽约几百纳米, 选区电子衍射测试表明所得材料为单晶结构. 循环伏安测试结果表明, CVO和CVO@CNTs均具有多个氧化还原峰, 储锌机制包括赝电容行为和电池行为. 在放电倍率1C(1C=300 mA/g)测试条件下, CVO纳米带比容量稳定在210.1 mA·h/g; 与CNTs复合后, CVO@CNTs复合材料的电荷转移阻抗降低, 在相同测试条件下表现出更高的比容量和优异的倍率性能. 其中, CVO@CNTs-40表现出最高的比容量, 在1C倍率测试条件下的比容量可达274.3 mA·h/g, 即使在20C的测试条件下放电比容量仍可达85.2 mA·h/g, 且循环1000次后容量保持率能达到92%.

关键词: 水系锌离子电池, 正极材料, 钙钒青铜, 碳纳米管, 水热反应

Abstract:

A new layered material, calcium bronze(Ca_xV₂O₅·nH₂O, CVO) nanoribbons as cathode materials of aqueous zinc ion batteries(AZIBs) was prepared by hydrothermal method. Three kinds of calcium bronze@carbon nanotubes composites(CVO@CNTs) were synthesized by adjusting the content of CNTs in the precursor solution. The synthesized CVO had a fine nanobelts structure with a length of about 10 μm and a width of several hundred nanometers. Selected area electron diffraction(SAED) spectrum showed that CVO was single crystal. The CV test revealed that the CVO had multiple redox peaks, corresponding to different stages of zinc ion insertion/desertion. The zinc storage mechanism includes pseudocapacitive behavior and battery behavior. When applied as the cathode material of AZIBs, the specific capacity of CVO was stable at 210.1 mA·h/g at a current rate of 1C(1C=300 mA/g). The addition of CNTs could decrease the charge transfer impedance of CVO@CNTs composites. More importantly, the one-dimensional CTNs twisted between the nanoribbons could effectively avoid the stack of nanoribbons, increase the contact area between active materials and electrolyte, and improve the utilization of active materials. Therefore, CVO@CNTs composites exhibited a higher capacity at the same test condition. Among them, CVO@CNTs-40 exhibited a highest specific capacity of 274.3 mA·h/g at a current rate of 1C. What’s more, this cathode material delivered a high rate capability and high capacity retention of more than 92% over 1000 cycles, at a current rate of 20C.

Key words: Aqueous zinc ion battery, Cathode material, Calcium bronze, Carbon nanotubes, Hydrothermal reaction

中图分类号:

O646
O611.6

TrendMD:

刘建,杜海会,孙田将,年庆舜,李海霞,陶占良. 钙钒青铜/碳纳米管复合材料的制备及电化学性能. 高等学校化学学报, 2019, 40(12): 2526.

Jian LIU,Haihui DU,Tianjiang SUN,Qingshun NIAN,Haixia LI,Zhanliang TAO. Preparation and Electrochemical Properties of Calcium Bronze/Carbon Nanotubes Composites ^†. Chem. J. Chinese Universities, 2019, 40(12): 2526.

图/表 12

Fig.1 XRD patterns of as-prepared calcium bronze and its composites(A) and schematic structure illustration of calcium bronze(B)

Fig.2 TG curves of CVO and CVO@CNTs

Fig.3 SEM images of CVO(A), CVO@CNTs-10(B), CVO@CNTs-20(C) and CVO@CNTs-40(D)

Fig.4 TEM image(A), EDS spectrum(B) and HRTEM image(C) of CVO Inset shows the selected area electron diffraction pattern of CVO.

Fig.5 STEM-HAADF image(A) and EDS mapping images of Ca(B), W(C), O(D) of CVO

Fig.6 TEM(A) and HRTEM(B) images of CVO@CNTs-40 Inset shows the selected area electron diffraction pattern of CVO/CNTs-40.

Fig.7 STEM-HAADF image(A) and EDS-mapping images of Ca(B), V(C), O(D), C(E) of CVO@CNTs-40

Fig.8 Cyclic voltammetry profiles of CVO at a scan rate of 0.5 mV/s

Fig.9 CV curves at different scan rates(A), the corresponding plots of lgi vs. lgv at each peak(B) and the capacitive contributions at different scan rates(C) of CVO electrode

Fig.10 CV curves at different scan rates(A), the corresponding plots of lgi vs. lgv at each peak(B) and capacitive contributions at different scan rates(C) of CVO@CNTs-40 electrode

Fig.11 Charge/discharge curve(A) and cycling performance of CVO and CVO@CNTs electrodes at a current rate of 1C(B) and rate performance(C) and long-term cycle life at 20C(D) of CVO@CNTs-40 electrode

Fig.12 EIS plots of CVO and CVO@CNTs electrodes

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