源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料

doi:10.15541/jim20200525

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 929-935.DOI: 10.15541/jim20200525

源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料

李昆儒¹(), 胡省辉¹, 张正富¹, 郭玉忠¹(), 黄瑞安²()

1.昆明理工大学材料科学与工程学院, 昆明 650093
2.昆明理工大学真空冶金国家工程实验室, 昆明 650093

收稿日期:2020-09-08 修回日期:2020-11-08 出版日期:2021-09-20 网络出版日期:2020-12-10
通讯作者: 郭玉忠, 教授. E-mail: yzguocn62@sina.com; 黄瑞安, 副教授. E-mail: hruian@siom.ac.cn
作者简介:李昆儒(1996-), 男, 硕士研究生. E-mail: likunru@stu.kust.edu.cn
基金资助:
国家自然科学基金(51464025)

Three-dimensional Porous Biogenic Si/C Composite for High Performance Lithium-ion Battery Anode Derived from Equisetum Fluviatile

LI Kunru¹(), HU Xinghui¹, ZHANG Zhengfu¹, GUO Yuzhong¹(), HUANG Ruian²()

1. Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China
2. National Engineering Laboratory for Vacuum Metallurgy, Kunming University of Science and Technology, Kunming 650093, China

Received:2020-09-08 Revised:2020-11-08 Published:2021-09-20 Online:2020-12-10
Contact: GUO Yuzhong, professor. E-mail: yzguocn62@sina.com; HUANG Ruian, associate professor. E-mail: hruian@siom.ac.cn
About author:LI Kunru(1996-), male, Master candidate. E-mail: likunru@stu.kust.edu.cn
Supported by:
National Natural Science Foundation of China(51464025)

摘要/Abstract

摘要：

锂离子电池硅基负极材料的理论比容量比传统石墨材料高10倍, 是最有前途的锂离子电池负极材料之一。然而硅基纳米材料的制备工艺复杂、成本高昂, 严重限制了锂离子电池硅负极的商业应用。本工作采用溪木贼为原料, 通过深度还原、浅度氧化和碳包覆工艺制备了三维多孔生物质硅/碳复合材料(多孔3D-bio-Si/C)。三维多孔结构不仅有利于Li⁺的快速传输, 而且提供足够的空隙缓解在脱-嵌锂过程中发生的体积变化。得益于三维结构中大量的孔隙和高强度的外部碳层, 多孔3D-bio-Si/C制备的电极表现出优异的电化学性能。当电流密度为1 A/g时, 多孔3D-bio-Si/C的可逆容量为1243.2 mAh/g, 循环400次后仍可保持933.4 mAh/g, 容量保持率高达89%。利用溪木贼作为生物质硅源制备高性能硅基负极材料, 实现了低成本、可规模化、绿色和可持续的合成路线, 有望为Si基锂离子电池负极材料的商业应用打下基础。

关键词: 溪木贼, 锂离子电池, 多孔硅, 硅/碳复合材料, 负极材料

Abstract:

Silicon-based materials are one of the most promising anode materials for lithium-ion batteries (LIBs) because of their theoretical capacity which is ten times higher than that of conventional graphite. However, the complex fabrication process and the high cost of silicon-based nanomaterials limit their practical application. In this study, equisetum fluviatile was used as raw material to prepare a three-dimensional porous biogenic Si/C composite (3D-bio-Si/C) by deep reduction, mild oxidation and carbon coating processes. The three-dimensional porous structure not only allows rapid diffusion of Li⁺, but also provides enough voids to accommodate the volume change on Li⁺ insertion and extraction. Benefiting from the abundant internal porosity and the high-strength outer carbon film of the three-dimensional porous structure, the obtained 3D-bio-Si/C shows remarkable electrochemical performance. This 3D-bio-Si/C can deliver reversible specific capacity of 1243.2 mAh/g at a current density of 1 A/g, and maintain 933.4 mAh/g after 400 cycles. This low-cost, scalable, green and sustainable route to synthesize high-performance silicon-based anode material derived from equisetum fluviatile lays a foundation for the commercial preparation of Si based lithium-ion battery anode materials.

Key words: equisetum fluviatile, lithium-ion battery, porous silicon, silicon/carbon composite, anode material

中图分类号:

TQ152

李昆儒, 胡省辉, 张正富, 郭玉忠, 黄瑞安. 源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料[J]. 无机材料学报, 2021, 36(9): 929-935.

LI Kunru, HU Xinghui, ZHANG Zhengfu, GUO Yuzhong, HUANG Ruian. Three-dimensional Porous Biogenic Si/C Composite for High Performance Lithium-ion Battery Anode Derived from Equisetum Fluviatile[J]. Journal of Inorganic Materials, 2021, 36(9): 929-935.

图/表 9

图1 多孔3D-bio-Si/C合成过程示意图

Fig. 1 Schematic illustration for the fabrication of 3D-bio-Si/C

图2 多孔3D-bio-Si/C制备过程中不同阶段产物的XRD图谱

Fig. 2 XRD patterns for products in different preparation stages of 3D-bio-Si/C

图3 多孔3D-bio-Si和多孔3D-bio-Si/C的拉曼光谱图

Fig. 3 Raman spectra of 3D-bio-Si and 3D-bio-Si/C

图4 多孔3D-bio-Si的Si2p高分辨X射线光电子能谱图

Fig. 4 High-resolution Si2p XPS spectrum of 3D-bio-Si

图5 (a~c)多孔3D-bio-SiO2和(d~f)多孔3D-bio-Si的(a, d)扫描电镜照片、(b, e)透射电镜照片和(c, f)高分辨透射电镜照片

Fig. 5 (a, d) SEM, (b, e) TEM and (c, f) HRTEM images of (a-c) 3D-bio-SiO2 and (d-f) 3D-bio-Si

图6 多孔3D-bio-Si/C的(a)扫描电镜照片、(b)透射电镜照片和(c)高分辨透射电镜照片

Fig. 6 SEM (a), TEM (b) and HRTEM (c) images of 3D-bio-Si/C

图7 多孔3D-bio-SiO2、多孔3D-bio-Si和多孔3D-bio-Si/C的(a)N2吸附-脱附等温线和(b)孔径分布曲线

Fig. 7 (a) Nitrogen adsorption-desorption isotherms and (b) pore size distribution curves for 3D-bio-SiO2, 3D-bio-Si and 3D-bio-Si/C

图8 多孔3D-bio-Si/C (a)在0.05 A/g电流密度下的第1~6圈的充放电曲线, (b)循环伏安(CV)曲线, (c)循环性能曲线(1 A/g)和(d)倍率性能曲线

Fig. 8 (a) Charge and discharge curves for initial 6 cycles at 0.05 A/g, (b) CV curves at a scanning rate of 0.5 mV/s, (c) cycling performance (1 A/g), and (d) rate capability at different rates of 3D-bio-Si/C

表1 不同生物质硅作为锂离子电池负极材料的电化学性能比较

Table 1 Comparison of electrochemical properties for various biomass-derived Si as LIBs anodes

Sample	Si source	Structure	Current density/(A∙g^-1)	Capacity/(mAh∙g^-1) (Cycle number)	Ref.
Si/N-doped C	Rice husk	Spheres	0.5	1031 (100^th)	[10]
Si/C	Rice husk	Spheres	0.1	560 (180^th)	[26]
Si/N-doped C	Bamboo charcoal	Porous	0.2	603 (120^th)	[27]
Si@C/RGO	Bamboo leaf	Nanoparticles	0.84	1900 (100^th)	[28]
Si/N-doped C	Horsetail	Nanoparticles	1	750 (760^th)	[29]
Si/C	Reed plants	Porous	0.5	1050 (200^th)	[30]
Si/C	Rice husk	Bulks	0.1	537 (100^th)	[16]
3D-bio-Si/C	Equisetum fluviatile	Porous	1	933 (400^th)	This work

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源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料

Three-dimensional Porous Biogenic Si/C Composite for High Performance Lithium-ion Battery Anode Derived from Equisetum Fluviatile

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