ZnO-GA anode with gradient-pore distribution for lithium-ion battery

doi:10.11949/0438-1157.20241498

Abstract

Abstract:

The graphene aerogel (GA) anode for lithium-ion battery with a gradient porous structure was prepared with graphene oxide by freeze-drying and thermal annealing. Zinc oxide (ZnO) was doped into the porous structure of GA to obtain the anode ZnO-GA with high capacity and good stability. The results of X-ray diffractometer (XRD), Raman spectroscopy, infrared spectroscopy (FTIR), thermogravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and transmission electron microscopy (TEM) showed that ZnO particles were uniformly distributed in GA with pore size of 20—50 nm. In the half-cell test at 1 mA·cm^-2 and 1 mAh·cm^-2, high coulombic efficiency of 97.5% after 200 cycles was obtained. Under current density of 200 mA·g^-1, the reversible capacity after 100 cycles was 2050.1 mAh·g^-1. In the full cell of ZnO-GA@Li and LiFePO₄, the reversible capacity was 121.3 mAh·g^-1 after 1000 cycles at 1C. ZnO nanoparticles addtion could enhance the battery capacity. The GA with gradient-pore distribution could not only increase the contact area between the anode and the electrolyte, but also provide space for the volume expansion during the reaction of ZnO and lithium ions, therefore bringing higher stability and safety of battery.

Key words: lithium-ion battery, graphene aerogel anode, gradient-pore distribution, ZnO, freeze-drying

摘要：

以氧化石墨烯为原料采用冷冻干燥-热退火制备具有梯度孔结构的石墨烯气凝胶（GA）负极材料，在此基础上掺杂氧化锌（ZnO）得到具有容量高、稳定性好的锂离子电池负极ZnO-GA。X射线衍射仪（XRD）、拉曼光谱、红外光谱（FTIR）、热重分析（TG）、X射线光电子能谱（XPS）、扫描电镜（SEM）、能谱仪（EDS）和透射电子显微镜（TEM）结果表明，ZnO颗粒均匀分布在孔径为20~50 nm的GA中。组装纽扣半电池在1 mA·cm^-2、1 mAh·cm^-2条件下，循环200圈后仍具有97.50%的库仑效率，在200 mA·g^-1经过100次循环后的可逆容量达2050.1 mAh·g^-1。ZnO-GA@Li与LiFePO₄全电池在1C条件下，循环1000圈后，仍能保持121.3 mAh·g^-1的可逆容量。ZnO纳米颗粒掺杂可以提高负极容量，三维石墨烯增大负极与电解液的接触面积，而梯度孔结构可以为ZnO与锂离子反应发生的膨胀提供体积变化的空间，赋予电池更高的稳定性和安全性。

关键词: 锂离子电池, 石墨烯气凝胶负极, 梯度孔结构, ZnO, 冷冻干燥

CLC Number:

TQ 912

Chuanfu SUN, Guilin HU, Junjie CAO, Qibin ZUO, Mei CHEN, Yuzhen XIA. ZnO-GA anode with gradient-pore distribution for lithium-ion battery[J]. CIESC Journal, 2025, 76(7): 3710-3718.

孙传付, 胡桂林, 曹俊杰, 左启斌, 陈媚, 夏玉珍. 梯度孔分布ZnO-GA锂离子电池负极材料研究[J]. 化工学报, 2025, 76(7): 3710-3718.

Figures/Tables 8

Fig.1 Flow chart of ZnO-GA anode preparation

Fig.2 TG, XRD, Raman spectroscopy and FTIR of GO, GA and ZnO-GA

Fig.3 XPS spectra of GA and Zn-GA

Fig.4 Structural analysis of GA and ZnO-GA

Fig.5 Li||Cu battery test of Cu, GA and ZnO-GA at 1 mA·cm-2 and 1 mAh·cm-2

Fig.6 CV and constant current charge/discharge curves for GA and ZnO-GA

Fig.7 Performance testing of Cu@Li, GA@Li and ZnO-GA@Li in Li||LiFePO4 full cells

Fig.8 Impedance curves of the Cu, GA, and ZnO-GA assembled Li||Cu half-cells before charging

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