Preparation and Electrochemical Properties of Calcium Bronze/Carbon Nanotubes Composites †

doi:10.7503/cjcu20190397

Abstract

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

CLC Number:

O646
O611.6

TrendMD:

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

Figures/Tables 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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