氮掺杂碳包覆的ZnO/CuO微米球作为锂离子电池负极材料的性能研究

doi:10.15541/jim20250409

摘要/Abstract

摘要：

过渡金属氧化物ZnO做为锂电池负极材料, 具有978 mAh·g⁻¹的高理论比容量, 但是ZnO的循环稳定性与比容量保持率仍有待提高。本研究采用Cu-ZnSe微米球为模板, 盐酸多巴胺为原料制备了氮掺杂碳包覆的ZnO/CuO微米球。该合成策略同步实现了活性物质转化、内部孔隙结构构建以及外部导电碳层包覆。氮掺杂形成的吡啶氮、吡咯氮、石墨氮可以增加表面活性位点, 促进离子、电子转移。碳包覆后, 在材料内部产生大量的缺陷, 可以为表面氧化还原反应提供大量活性位点。ZnO/CuO/N-C微米球作为锂离子电池负极材料表现出优异的电化学性能。在0.1 A·g⁻¹电流密度下200次循环后表现出1010.4 mAh·g^-1的高比容量; 在1 A·g^-1高电流密度下1000次循环后比容量为447.1 mAh·g⁻¹。其储锂过程具有较高的赝电容贡献, 确保了优异的倍率性能。性能提升主要归因于以下因素: 氮掺杂碳层有效缓冲了体积膨胀并维持了结构完整性; 内部孔隙促进了电解液浸润与离子传输; ZnO与CuO的转化与合金化反应产生了高容量。

关键词: ZnO/CuO, 氮掺杂碳包覆, 微米球, 锂电池负极

Abstract:

ZnO, a transition metal oxide, possesses a high theoretical capacity of 978 mAh·g⁻¹ as an anode for lithium batteries. However, its cycling stability and capacity retention still need to be improved. Therefore, ZnO/CuO microspheres modified with nitrogen-doped carbon-coating (ZnO/CuO/N-C) were synthesized using Cu-ZnSe microspheres as a template and dopamine hydrochloride as raw material. This synthesis strategy simultaneously achieves the conversion of active materials, construction of internal pore structure, and coating of external conductive carbon layer. The electrochemical properties of ZnO/CuO microspheres anode are greatly improved after the treatment of nitrogen-doped carbon-coating. The pyridine nitrogen, pyrrole nitrogen, and graphite nitrogen are formed after nitrogen doping into ZnO/CuO microspheres, significantly increasing surface active sites and promoting ion and electron transfer. A large number of defects are generated in the inner composites after carbon coating, advantageous for providing more active sites for surface redox reactions. The ZnO/CuO/N-C microspheres, as anode material of Li-ion batteries, exhibit excellent electrochemical properties. They still display a high specific capacity of 1010.4 mAh·g⁻¹ at 0.1 A·g⁻¹after 200 cycles. The specific capacity of ZnO/CuO/N-C microspheres anode could reach 447.1 mAh·g⁻¹ at a high current density of 1 A·g⁻¹after 1000 cycles. The excellent rate performance is exhibited in the process of Li⁺ ions insertion, ascribed to a high contribution of pseudocapacitance. The improved electrochemical properties of ZnO/CuO/N-C microspheres can be ascribed to the following factors. The structural integrity of composites could be maintained by buffering volume expansion after carbon-coating. The electrolyte infiltration and ion transport can be promoted due to the existence of internal pores. A high capacity is caused through the conversion and alloying reactions between ZnO and CuO.

Key words: ZnO/CuO, nitrogen-doped carbon-coating, microsphere, lithium-ion battery anode

中图分类号:

TB332

张高举, 任海波, 李文正, 王刚. 氮掺杂碳包覆的ZnO/CuO微米球作为锂离子电池负极材料的性能研究[J]. 无机材料学报, 2026, 41(9): 1211-1219.

ZHANG Gaoju, REN Haibo, LI Wenzheng, WANG Gang. ZnO/CuO Microspheres Modified with Nitrogen-doped Carbon-coating for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2026, 41(9): 1211-1219.

图/表 12

图1 (a) Cu-ZnSe与(b) ZnO/CuO/N-C的XRD谱图

Fig. 1 XRD patterns of (a) Cu-ZnSe and (b) ZnO/CuO/N-C

图2 ZnO/CuO/N-C的XPS谱图

Fig. 2 XPS spectra of ZnO/CuO/N-C (a) Full spectrum; (b) Zn2p; (c) O1s; (d) C1s; (e) N1s; (f) Cu2p

图3 (a~c) Cu-ZnSe、(d~f) ZnO/CuO/N-C和(g~i) ZnO/CuO的SEM照片; ZnO/CuO/N-C的(j, k) TEM和(l) HRTEM照片

Fig. 3 SEM images of (a-c) Cu-ZnSe, (d-f) ZnO/CuO/N-C and (g-i) ZnO/CuO; (j, k) TEM and (l) HRTEM images of ZnO/CuO/N-C

图4 ZnO/CuO/N-C的拉曼光谱图

Fig. 4 Raman spectrum of ZnO/CuO/N-C

图5 (a) ZnO/CuO/N-C在1 mV·s−1的扫描速率下初始4次的CV曲线; (b) ZnO/CuO/N-C在0.1 A·g−1下第1、2、3、10、20、50、100、200次循环的充放电曲线; (c) ZnO/CuO/N-C、Cu-ZnSe与ZnO/CuO负极材料在0.1 A·g−1电流密度下的循环性能; (d) ZnO/CuO/N-C、Cu-ZnSe与ZnO/CuO负极材料的倍率性能

Fig. 5 (a) Initial four CV curves of ZnO/CuO/N-C anode at a scan rate of 1 mV·s−1; (b) Charge-discharge curves for the 1st, 2nd, 3rd, 10th, 20th, 50th, 100th and 200th cycle at a current density of 0.1 A·g−1 of ZnO/CuO/N-C anode; (c) Cycling performance of ZnO/CuO/N-C, ZnO/CuO and Cu-ZnSe anodes at 0.1 A·g−1; (d) Rate performance of ZnO/CuO/N-C, Cu-ZnSe and ZnO/CuO anodes Colorful figures are available on website

图6 (a) ZnO/CuO/N-C负极在不同扫速下的CV曲线; (b) lgi-lgv拟合直线; (c)不同扫速下的赝电容行为占比柱状图; (d) 1 mV·s−1扫速下CV曲线赝电容行为面积占比拟合

Fig. 6 (a) CV curves of ZnO/CuO/N-C anode at different scan rates; (b) lgi-lgv fitting lines; (c) Capacitance control proportion histogram at different sweep speeds; (d) Fitting areas of capacitance control in CV curves at a scan rate of 1 mV·s−1 Colorful figures are available on website

图7 (a) ZnO/CuO/N-C、ZnO/CuO和Cu-ZnSe电池的Nyquist曲线; (b) ZnO/CuO/N-C、ZnO/CuO和Cu-ZnSe的Warburg阻抗拟合图

Fig.7 (a) Nyquist plots of ZnO/CuO/N-C, ZnO/CuO and Cu-ZnSe batteries; (b)Warburg impedance linear fitting diagram of ZnO/CuO/N-C, ZnO/CuO and Cu-ZnSe anodes

图S1 ZnO/CuO/N-C微米球材料合成示意图

Fig. S1 Schematic diagram of ZnO/CuO/N-C microsphere material synthesis

图S2 (a) Cu-ZnSe、(b) ZnO/CuO和(c) ZnO/CuO/N-C氮气吸附脱附曲线, 插图为对应的孔尺寸分布

Fig. S2 Nitrogen adsorption-disadsorption isotherms of (a) Cu-ZnSe, (b) ZnO/CuO and (c) ZnO/CuO/N-C with insets showing the corresponding pore size distributions

图S3 (a) ZnO/CuO/N-C、Cu-ZnSe与ZnO/CuO负极材料在1 A·g−1电流密度下500次循环性能; (b) ZnO/CuO/N-C在1 A·g−1电流密度下1000次循环性能

Fig. S3 (a) Performance of ZnO/CuO/N-C, ZnO/CuO and Cu-ZnSe for 500 cycles at 1 A·g−1; (b) Performance of ZnO/CuO/N-C for 1000 cycles at 1 A·g−1

表S1 ZnO/CuO/N-C和文献报道的ZnO基负极材料循环性能

Table S1 Electrochemical properties of ZnO/CuO/N-C and reported ZnO-based anodes

Material	Current density/(A·g⁻¹)	Cycle number	Specific capacity/(mAh·g⁻¹)	Ref.
ZnO/CuO/N-C	0.1	200	1010.4	This work
ZnO/CuO/N-C	1	1000	447.1	This work
ZnO/MnO	1	1000	315.0	[S1]
ZnO@C	0.1	100	500.0	[S2]
ZnO/CuO/GNS	0.3	50	186.1	[S3]
CuO-ZnO@Al₂O₃	0.1	50	715.0	[S4]
CS-ZnO-60@NC	0.2	500	940.9	[S5]

图S4 (a~c) Cu-ZnSe、(d~f) ZnO/CuO与(g~i) ZnO/CuO/N-C 200次循环后的SEM照片

Fig. S4 SEM images of (a-c) Cu-ZnSe, (d-f) ZnO/CuO and (g-i) ZnO/CuO/N-C after 200 cycles

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