一步水热法制备纳米<strong>SnO<sub>2</sub>@C</strong>复合材料及其储锂性能研究

doi:10.11901/1005.3093.2019.604

材料研究学报

2020, Vol. 34

Issue (8): 591-598 DOI: 10.11901/1005.3093.2019.604

研究论文

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一步水热法制备纳米SnO₂@C复合材料及其储锂性能研究

李玲芳¹, 曾斌¹, 原志朋², 范长岭²(

)

1 湖南文理学院机械工程学院常德 415000
2 湖南大学材料科学与工程学院长沙 410082

One Step Hydrothermal Preparation of SnO₂@C Composite and Its Lithium Storage Performance

LI Lingfang¹, ZENG Bin¹, YUAN Zhipeng², FAN Changling²(

)

1 College of Mechanical Engineering, Hunan University of Arts and Science, Changde 415000, China
2 College of Materials Science and Engineering, Hunan University, Changsha 410082, China

引用本文:

李玲芳, 曾斌, 原志朋, 范长岭. 一步水热法制备纳米SnO₂@C复合材料及其储锂性能研究[J]. 材料研究学报, 2020, 34(8): 591-598.
Lingfang LI, Bin ZENG, Zhipeng YUAN, Changling FAN. One Step Hydrothermal Preparation of SnO₂@C Composite and Its Lithium Storage Performance[J]. Chinese Journal of Materials Research, 2020, 34(8): 591-598.

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摘要:

以两种糖类化合物(葡萄糖与水溶性淀粉)为碳源，以SnCl₄.5H₂O为锡源用一步水热法制备了SnO₂@C复合物。使用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、N₂吸脱附法和透射电镜(TEM)表征其组成和微观结构，并采用恒电流充放电测试、循环伏安法(CV)和电化学阻抗谱(EIS)表征其作为锂离子电池负极材料的电化学性能。结果表明，糖类前驱体衍生的热解炭和直径为4~5 nm的SnO₂纳米点生成了稳定的复合结构，炭基体的缓冲作用和材料纳米化缓解了SnO₂的体积膨胀效应，使材料的结构稳定性和电化学性能提高。由于葡萄糖热解炭的有序度比淀粉热解炭更高，这组试样具有更好的循环性能和倍率性能，在2 A/g大电流密度下其比容量高于400 mAh/g。

关键词 ：复合材料, SnO₂, 热解硬炭, 纳米颗粒, 锂离子电池负极材料

Abstract：

Two kinds of SnO₂@C composite were successfully prepared by a facile and cost-effective method through one-pot hydrothermal treatment of a mixture of Sn⁴⁺, and different carbohydrates (glucose and starch). The composition and microstructure of resultants were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), N₂ Adsorption-desorption method and Transmission Electron Microscope (TEM). The electrochemical performance as anode material for lithium-ion batteries was confirmed by galvanostatic charge-discharge test and Cyclic Voltammetry (CV) method. Results show that the pyrolytic carbon derived from carbohydrate precursors forms a stable composite structure with 4~5 nm SnO₂nanocrystals. The large volume variation of SnO₂ during the Li⁺ insertion-extraction process is effectively alleviated by the buffering effect of carbon matrix. Whatsmore, small SnO₂ nanoparticles can also effectively reduce this volume change, improving the electrode structural stability and electrochemical properties. Because the degree of order of glucose pyrolytic carbon is higher than that of starch pyrolytic carbon, correspondingly its composite shows better cycle and rate performance, which can stably release >400 mAh/g specific capacity at high current density of 2 A/g.

Key words： composite tin dioxide pyrolytic hard carbon nanoparticles anode of lithium ion batteries

收稿日期: 2019-12-30

ZTFLH:

TM912.9

基金资助:国家自然科学基金(51802096);国家自然科学基金(51672079);国家自然科学基金(51972104);湖南省自然科学基金(2020JJ4449)

作者简介: 李玲芳，女，1981年生，博士，副教授

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.604 或 https://www.cjmr.org/CN/Y2020/V34/I8/591

图1 近年来SnO2基锂离子电池阳极材料的循环次数和容量报道[20]

图2 TOC-G和TOC-S的XRD图谱

图3 试样的红外光谱(a)、N2吸脱附曲线和孔径分布(b)

图4 TOC-G(a)和TOC-S(b)的TEM和HRTEM照片

图5 试样的循环性能(a)和倍率性能(b)

图6 TOC-G 和TOC-S 的充放电曲线以及锂离子在炭基体中的插层和吸附示意图

图7 TOC-G试样(a)和TOC-S试样(b)的循环伏安曲线(前三次循环和第100次循环)

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