ZnxCo1-xCO3碳酸盐负极材料的制备及其电化学性能研究

doi:10.11949/0438-1157.20191448

摘要/Abstract

摘要：

碳酸钴是一类典型的转换型负极锂电池材料，具有资源丰富、比容量高、安全可靠等优点，但是存在一些尚未解决的问题，例如导电性比较差，同时在锂离子的嵌入和脱出过程中体积变化严重。通过水热法制备了不同组分Zn掺杂Zn_xCo₁_-xCO₃(x=0.12, 0.3, 0.5)，通过调整Zn和Co原材料质量来控制Zn/Co的摩尔比，研究表明当Zn和Co的摩尔比为0.3∶0.7时，掺杂产物有良好的循环和倍率性能，锌离子的掺杂提高了锂离子电导率，对Zn_xCo₁_-xCO₃(x=0.12, 0.3, 0.5)研究表明其在充放电过程中既有合金反应又有转换反应，提高了整个电极的导电性，进而表现出优异的电化学性能。

关键词: 锂离子电池, 碳酸钴, 高振实密度, 掺杂, 电化学, 化学反应, 合成

Abstract:

Cobalt carbonate is a typical type of conversion anode lithium battery material, with rich resources, high capacity, safe and reliable and other advantages, but there are some unresolved problems, such as poor conductivity, at the same time in the lithium ion embedding and excitability process of serious volume changes. In this paper, the different components of Zn doped Zn_xCo_1-_xCO₃ by hydrothermal method, by adjusting the quality of Zn and Co raw materials to control the molar ratio of Zn/Co, the study shows that when molar ratio of Zn and Co is 0.3∶0.7, doping products have good cycle and multiplier performance, zinc ion doping lithium ion conductivity. The study of Zn_xCo₁_-xCO₃ (x=0.12,0.3, 0.5) showed that it had both an alloy and a conversion reaction during charging and discharging process, which improves the conductivity of the whole electrode and then exhibits excellent electrochemical properties.

Key words: lithium ion battery, CoCO₃, high tap density, doping, electrochemistry, chemical reaction, synthesis

中图分类号:

李敬, 杜刚, 殷娟娟. Zn_xCo₁_-xCO₃碳酸盐负极材料的制备及其电化学性能研究[J]. 化工学报, 2020, 71(3): 1390-1397.

Jing LI, Gang DU, Juanjuan YIN. Preparation and electrochemical properties of Zn_xCo₁_-xCO₃ carbonateanode materials[J]. CIESC Journal, 2020, 71(3): 1390-1397.

图/表 13

图1 水热法制备ZnxCo1-xCO3(x=1/3, 1/2, 2/3)的工艺流程

Fig.1 Flowchart for preparation of ZnxCo1-xCO3(x=1/3, 1/2, 2/3)

表1 ZnxCo1-xCO3的理论掺杂量和实际掺杂量

Table 1 Theoretical doping and actual doping of ZnxCo1-xCO3

理论掺杂样品	实际掺杂样品
Zn_0.33Co_0.67CO₃	Zn_0.12Co_0.88CO₃
Zn_0.5Co_0.5CO₃	Zn_0.3Co_0.7CO₃
Zn_0.67Co_0.33CO₃	Zn_0.5Co_0.5CO₃

图2 ZnxCo1-xCO3(x=0,0.12,0.3,0.5)的XRD谱图

Fig.2 XRD patterns of ZnxCo1-xCO3(x=0,0.12,0.3,0.5)

图3 ZnxCo1-xCO3(x=0，0.12, 0.3, 0.5)的SEM图

Fig.3 SEM image of ZnxCo1-xCO3(x=0，0.12, 0.3, 0.5)

表2 ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)的振实密度

Table 2 High tap density of ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)

样品	振实密度/(g·cm^-3)
CoCO₃	1.96
Zn_0.12Co_0.88CO₃	2.11
Zn_0.3Co_0.7CO₃	2.2
Zn_0.5Co_0.5CO₃	2.25

图4 ZnxCo1-xCO3(x=0，0.12，0.3，0.5)的氮气吸附脱附曲线

Fig.4 Nitrogen adsorption–desorption isotherms of ZnxCo1-xCO3(x=0，0.12，0.3，0.5)

图5 ZnxCo1-xCO3(x=0，0.12，0.3，0.5)的TG图

Fig.5 Thermogravimetric analysis of ZnxCo1-xCO3(x=0，0.12，0.3，0.5)

图6 ZnxCo1-xCO3(x=0，0.12，0.3，0.5)在0.1C的电流密度下前2圈的恒流充放电曲线

Fig.6 Constant current charge and discharge curve for first 2 turns at 0.1 C current density of ZnxCo1-xCO3(x=0，0.12，0.3，0.5)

图7 ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)的电化学性能表征结果

Fig.7 Characterization results of electrochemical properties of ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)

表3 图7(b)中ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)在不同倍率下的容量

Table 3 Capacity of ZnxCo1-xCO3 (x=0，0.12，0.3，0.5) [Fig.7(b)] at different ratios/(mA·h·g-1)

样品	0.2 C	0.5 C	1 C	2 C	0.1 C
CoCO₃	1146.7	787.7	479.4	227.8	921
Zn_0.12Co_0.88CO₃	767.8	580.9	546.1	353.4	769
Zn_0.3Co_0.7CO₃	1048.3	809.8	657.1	407.3	935.6
Zn_0.5Co_0.5CO₃	668.5	520.3	440.2	331.2	685.2

图8 ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)在0.1 mV·s-1扫速下前3圈的CV曲线

Fig.8 CV curves of ZnxCo1-xCO3 (x=0，0.12，0.3，0.5) for the first 3 circles at scan rate of 0.1 mV·s-1

图9 ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)循环2圈和102圈的阻抗图谱

Fig.9 Nyquist plots of ZnxCo1-xCO3 (x=0，0.12，0.3，0.5)after 2 and 102 cycles

表4 图9中的EIS曲线的拟合结果

Table 4 Fitting results of EIS curve in Fig.9

样品	循环次数	R_s/Ω	R_SEI/Ω	R_ct/Ω
CoCO₃	2	14.6	87.97	286.7
Zn_0.12Co_0.88CO₃	2	3.76	17.93	138.6
Zn_0.3Co_0.7CO₃	2	12.8	16.5	20.3
Zn_0.5Co_0.5CO₃	2	6.63	63.8	82.6
CoCO₃	102	4.124	150.2	223.7
Zn_0.12Co_0.88CO₃	102	14.7	281.4	406.1
Zn_0.3Co_0.7CO₃	102	7.65	103.6	137.9
Zn_0.5Co_0.5CO₃	102	1.35	137.8	162.4

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Zn_xCo₁_-xCO₃碳酸盐负极材料的制备及其电化学性能研究

Preparation and electrochemical properties of Zn_xCo₁_-xCO₃ carbonateanode materials

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