高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能

doi:10.15541/jim20230009

无机材料学报 ›› 2023, Vol. 38 ›› Issue (8): 947-953.DOI: 10.15541/jim20230009 CSTR: 32189.14.10.15541/jim20230009

所属专题：【能源环境】锂离子电池(202409)

高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能

苏楠¹(), 邱介山¹^,³(), 王治宇¹^,²()

1.大连理工大学化工学院, 精细化工国家重点实验室,大连 116024
2.中节能万润股份有限公司新材料开发分公司, 烟台 265503
3.北京化工大学化工学院, 北京 100029

收稿日期:2023-01-05 修回日期:2023-02-20 出版日期:2023-08-20 网络出版日期:2023-03-06
通讯作者: 王治宇, 教授. E-mail: zywang@dlut.edu.cn;
邱介山, 教授. E-mail: jqiu@dlut.edu.cn
作者简介:苏楠(1998-), 女, 硕士研究生. E-mail: 18895369203@163.com
基金资助:
国家自然科学基金(51972040);国家重点研发计划(2022YFB4101600);中央高校基本科研业务费(DUT22LAB125);有机无机复合材料国家重点实验室开放课题(oic-202201003)

F-doped Carbon Coated Nano-Si Anode with High Capacity: Preparation by Gaseous Fluorination and Performance for Lithium Storage

SU Nan¹(), QIU Jieshan¹^,³(), WANG Zhiyu¹^,²()

1. State Key Lab of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
2. Branch of New Material Development, Valiant Co., Ltd., Yantai 265503, China
3. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2023-01-05 Revised:2023-02-20 Published:2023-08-20 Online:2023-03-06
Contact: WANG Zhiyu, professor. E-mail: zywang@dlut.edu.cn;
QIU Jieshan, professor. E-mail: jqiu@dlut.edu.cn
About author:SU Nan (1998-), female, Master candidate. E-mail: 18895369203@163.com
Supported by:
National Natural Science Foundation of China(51972040);National Key R&D Program of China(2022YFB4101600);The Fundamental Research Funds for the Central Universities(DUT22LAB125);Open project of State Key Laboratory of Organic-Inorganic Composites(oic-202201003)

摘要/Abstract

摘要：

具有超高储锂比容量的硅材料是备受瞩目的高性能锂离子电池负极材料, 但硅嵌锂时巨大的体积膨胀效应使之快速失效, 从而限制了其应用性能。本研究提出一种简易低毒的气相氟化方法制备氟掺杂碳包覆纳米硅材料。通过在纳米硅表面包覆高缺陷度的氟掺杂碳层, 抑制硅材料嵌锂体积膨胀, 提供丰富的锂离子输运通道, 同时形成富含LiF的稳定SEI膜。获得的氟掺杂碳包覆纳米硅负极在0.2~5.0 A·g^-1电流密度下, 比容量达1540~ 580 mAh·g^-1, 循环200次后容量保持率>75%。本方法解决了传统氟化技术氟源(如XeF₂、F₂等)高成本、高毒性的问题。

关键词: 锂离子电池, 硅负极, 氟掺杂碳, 气相氟化法

Abstract:

Si anodes hold immense potential in developing high-energy Li-ion batteries. But fast failure due to huge volume change upon Li uptake impedes their application. This work reports a facile yet low-toxic gas fluorination way for yielding F-doped carbon-coated nano-Si anode materials. Coating of nano-Si with F-doped carbon containing high defects can effectively protect Si from huge volume change upon Li storage while facilitating Li⁺ transport and formation of stable LiF-rich solid electrolyte interphase (SEI). This anode exhibits high capacities of 1540-580 mAh·g^-1 at various current rates of 0.2-5.0 A·g^-1, while retaining >75% capacity after 200 cycles. This method also addresses the issues of high cost and toxicity of traditional fluorination techniques that use fluorine sources such as XeF₂ and F₂.

Key words: Li-ion battery, Si anode, F-doped carbon, gaseous fluorination method

中图分类号:

TQ152

苏楠, 邱介山, 王治宇. 高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能[J]. 无机材料学报, 2023, 38(8): 947-953.

SU Nan, QIU Jieshan, WANG Zhiyu. F-doped Carbon Coated Nano-Si Anode with High Capacity: Preparation by Gaseous Fluorination and Performance for Lithium Storage[J]. Journal of Inorganic Materials, 2023, 38(8): 947-953.

图/表 9

图1 氟掺杂碳包覆纳米硅材料的制备过程示意图

Fig. 1 Schematic illustration of the production of Si@C-F

图2 Si@C和Si@C-F的(a)XRD谱图, (b)Raman谱图, (c)XPS全谱图, 高分辨(d)F1s和(e)Si2p XPS谱图; (f)Si@C-F的TGA曲线

Fig. 2 (a) XRD patterns, (b) Raman spectra, (c) XPS survey scan, (d) high-resolution F1s and (e) Si2p XPS spectra of Si@C and Si@C-F, (f) TGA curve of Si@C-F

图3 Si@C-F材料的(a~c)SEM照片, (d~f)TEM照片及其(g~i)元素分布谱图

Fig. 3 (a-c) SEM images, (d-f) TEM images and (g-i) elemental mapping of Si@C-F

图4 (a, c, e) Si@C和(b, d, f) Si@C-F负极在 (a, b) 0.1 mV·s-1扫速下的CV曲线, 电流密度为(c, d) 0.2和(e, f) 0.4 A·g-1时的充放电曲线

Fig. 4 (a, b) CV curves at a scan rate of 0.1 mV·s-1 and charge-discharge voltage curves at (c, d) 0.2 and (e, f) 0.4 A·g-1 for (a, c, e) Si@C and (b, d, f) Si@C-F anodes

图5 Si@C和Si@C-F负极(a)在电流密度为0.4 A·g-1时的循环性能(先在0.2 A·g-1电流密度下活化4圈); (b)在电流密度0.2~5.0 A·g−1范围的倍率性能; (c)在电流密度为0.2 A·g-1时的长循环容量保持率

Fig. 5 (a) Cycling stability at a current density of 0.4 A·g-1 with anodes activated by 4 cycles at 0.2 A·g-1 before cycling, and (b) rate capability at various current densities ranging from 0.2 to 5.0 A·g−1 and (c) capacity retention at a current density of 0.2 A·g-1 for lithium storage in Si@C and Si@C-F anode Colorful figures are available on website

表1 Si@C-F负极与文献报道硅负极的电化学性能比较

Table 1 Comparison of Si@C-F anode with reported Si-based anode in electrochemical performance

Materials	Initial CE	Initial capacity/(mAh·g^-1)	Capacity retention	Ref.
Si@C-F	65.9%	2640	85% (100 cycles) 75 % (cycles)	This work
nano-Si/TiN@ carbon	71%	2716	59.4% (110 cycles)	[20]
Si@C@RGO	74.5%	1474	48.9% (40 cycles)	[21]
Si@FA	65%	1334	68.7% (100 cycles)	[22]
p-Si@C	58%	3460	57.5% (100 cycles)	[23]
Si@void@C	-	900	70% (100 cycles)	[24]
Si/C@C	-	1120	80% (100 cycles)	[25]

图6 不同氟掺杂量Si@C-F负极在0.4 A·g-1电流密度的循环性能(先在0.2 A·g-1电流密度下活化4~10圈)

Fig. 6 Cycling stability of Si@C-F anodes with different F ratios at a current density of 0.4 A·g-1 with anodes activated by 4-10 cycles at 0.2 A·g-1 before cycling Colorful figures are available on website

图7 Si@C和Si@C-F负极在循环(a)前(b)后的电化学阻抗谱图(电流密度为0.4 A·g-1)

Fig. 7 Nyquist plots of the Si@C and Si@C-F anodes (a) before and (b) after cycling at a current density of 0.4 A·g-1

图8 (a)充放电循环后的Si@C和(d)Si@C-F负极的表面SEM照片; (b, e)循环前和(c, f)循环后(b, c)Si@C和(e, f) Si@C-F负极截面的SEM照片; 充放电循环后Si@C和Si@C-F负极表面SEI膜的高分辨(g)F1s及(h)Li1s XPS谱图

Fig. 8 Top SEM images of (a) Si@C and (d) Si@C-F anodes after cycling; Cross-section SEM images of (b, c) Si@C and (e, f) Si@C-F anodes (b, e) before and (c, f) after cycling; High-resolution (g) F1s and (h) Li1s XPS spectra of SEI on Si@C and Si@C-F anodes after cycling

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高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能

F-doped Carbon Coated Nano-Si Anode with High Capacity: Preparation by Gaseous Fluorination and Performance for Lithium Storage

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