微扩层改性对煤基石墨微观结构和储锂性能的影响

doi:10.16085/j.issn.1000-6613.2023-0121

化工进展 ›› 2023, Vol. 42 ›› Issue (12): 6259-6269.DOI: 10.16085/j.issn.1000-6613.2023-0121

• 能源加工与技术 • 上一篇

微扩层改性对煤基石墨微观结构和储锂性能的影响

李龙¹(), 邢宝林²^,³(), 鲍倜傲²^,³, 靳鹏¹, 曾会会²^,³, 郭晖²^,³, 张越², 张文豪²

^1.炼焦煤资源开发及综合利用国家重点实验室，中国平煤神马控股集团有限公司，河南平顶山 467000
^2.河南省煤炭绿色转化重点实验室，河南理工大学化学化工学院，河南焦作 454000
^3.煤炭安全生产河南省协同创新中心，河南焦作 454000

收稿日期:2023-02-01 修回日期:2023-03-18 出版日期:2023-12-25 发布日期:2024-01-08
通讯作者: 邢宝林
作者简介:李龙（1987—），男，硕士，工程师，研究方向为煤化工与新材料。E-mail：lilongskl@163.com。
基金资助:
国家自然科学基金(52274261);国家级大学生创新创业训练计划(202110460011)

Effect of mildly-expanded modification on coal-based graphite microstructure and lithium storage performance

LI Long¹(), XING Baolin²^,³(), BAO Ti'ao²^,³, JIN Peng¹, ZENG Huihui²^,³, GUO Hui²^,³, ZHANG Yue², ZHANG Wenhao²

^1.State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization, China Pingmei Shenma Group, Pingdingshan 467000, Henan, China
^2.Henan Key Laboratory of Coal Green Conversion, College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, Henan, China
^3.State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454000, Henan, China

Received:2023-02-01 Revised:2023-03-18 Online:2023-12-25 Published:2024-01-08
Contact: XING Baolin

摘要/Abstract

摘要：

以自制煤基石墨为前体，浓硫酸为插层剂，高锰酸钾为氧化剂，采用液相氧化插层-热处理工艺对煤基石墨进行微扩层改性处理，制备出微扩层煤基石墨。利用X射线衍射仪、扫描电子显微镜、透射电子显微镜、拉曼光谱测试、低温氮气吸附和X射线光电子能谱等手段分析不同微扩层煤基石墨的微观结构，并测试其用作锂离子电池负极材料的电化学储锂特性，系统研究微扩层改性对煤基石墨微观结构和储锂性能的影响。研究表明，微扩层改性处理不仅可增加石墨微晶片层的层间距，还可以在石墨基体中引入纳米孔道和C $̿$ O、C—O—H及C—O—C等含氧官能团。氧化剂用量是影响微扩层煤基石墨微观结构的重要因素。通过调节氧化剂用量可实现微扩层煤基石墨微晶层间距、纳米孔道和表面官能团等微观结构的有效调控。当氧化剂用量为煤基石墨的0.30倍时，微扩层煤基石墨的层间距为0.3374nm，其纳米孔道主要由1~2nm微孔和2~6nm中孔组成，比表面积为24.6m²/g，且富含C $̿$ O、C—O—H及C—O—C等含氧官能团。微扩层煤基石墨用作锂离子电池负极材料展现出优异的电化学储锂性能，其在0.1C低电流密度下的可逆比容量最高可达511.1mAh/g，在5C高电流密度下为348.7mAh/g，且经300次循环充放电后，其比容量仍可维持在313.3mAh/g，容量保持率为89.9%，综合性能远高于煤基石墨。微扩层煤基石墨优异的电化学储能特性与其微观结构中富含石墨微晶片层、纳米孔道和含氧官能团等密切相关。

关键词: 煤基石墨, 微扩层改性, 微观结构, 负极材料, 电化学性能

Abstract:

The mildly-expanded coal-based graphite was prepared from coal-based graphite via liquid oxidation-thermal reduction process using concentrated H₂SO₄ as intercalator and KMnO₄ as oxidant. The microstructures of mildly-expanded coal-based graphite were characterized by XRD、SEM、TEM、Raman、nitrogen adsorption-desorption and XPS, and their lithium ions storage performance and the effect of the degree of mildly-expanded modification on their structure were further investigated. The results demonstrated that the mildly-expanded modification not only could expand the interlayer spacing of graphite crystallites, decrease the crystallite size and increase the content of nanopores, but also could introduce oxygen-containing functional groups such as carbonyl, hydroxyl and alkoxy groups into coal-based graphite. When the amount of oxidant is 0.30 times that of coal-based graphite, the interlayer distance of the mildly-expanded coal-based graphite was 0.3374nm, and its nanopore channels mainly consisted of 1—2nm micropores and 2—6nm mesopores with a specific surface area of 24.6m²/g and was rich in oxygen-containing functional groups such as C $̿$ O, C—O—H and C—O—C. Mildly-expanded coal-based graphite as anode for lithium-ion batteries exhibited excellent electrochemical performance, in which the reversible specific capacity could reach up to 511.1mAh/g at 0.1C and 348.7mAh/g at high current density of 5C, and the specific capacity at 5C could still be maintained at 313.3mAh/g after 300 cycles with a capacity retention rate of 89.9%. Its comprehensive performance was much higher than that of coal-based graphite. The excellent electrochemical energy storage properties of mildly-expanded coal-based graphite were closely related to its microstructure, which is rich in graphite microcrystal layers, nanopores and oxygen-containing functional groups.

Key words: coal-based graphite, mildly-expanded modification, microstructure, anode material, electrochemical performance

中图分类号:

TQ536

李龙, 邢宝林, 鲍倜傲, 靳鹏, 曾会会, 郭晖, 张越, 张文豪. 微扩层改性对煤基石墨微观结构和储锂性能的影响[J]. 化工进展, 2023, 42(12): 6259-6269.

LI Long, XING Baolin, BAO Ti'ao, JIN Peng, ZENG Huihui, GUO Hui, ZHANG Yue, ZHANG Wenhao. Effect of mildly-expanded modification on coal-based graphite microstructure and lithium storage performance[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6259-6269.

图/表 10

表1 太西无烟煤的工业分析与元素分析

工业分析/%				元素分析/%
M_ad	A_d	V_daf	FC_daf	C_daf	H_daf	O^*_daf	N_daf	S_daf
1.17	3.60	8.75	91.25	94.80	3.61	0.70	0.76	0.03

图1 煤基石墨的微扩层改性处理流程示意图

图2 煤基石墨和微扩层煤基石墨的XRD谱图

表2 煤基石墨和微扩层煤基石墨的微晶参数

样品	2θ₍₀₀₂₎/(°)	d₀₀₂/nm	L_a/nm	L_c/nm	G/%
CG-2600	26.520	0.3358	28.2	13.9	95.3
ECG-0.25	26.462	0.3365	21.1	11.1	86.6
ECG-0.30	26.390	0.3374	20.6	10.7	76.2
ECG-0.35	26.387	0.3375	17.1	10.6	75.7
ECG-0.40	26.295	0.3386	16.1	10.3	62.2

图3 煤基石墨和微扩层煤基石墨ECG-0.30的SEM图

图4 煤基石墨和微扩层煤基石墨ECG-0.30的TEM图

图5 煤基石墨和微扩层煤基石墨的Raman图谱

图6 煤基石墨和微扩层煤基石墨的氮气吸附脱附曲线与DFT孔径分布曲线

图7 煤基石墨和微扩层煤基石墨ECG-0.30的XPS图谱

图8 煤基石墨和微扩层煤基石墨的电化学性能

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微扩层改性对煤基石墨微观结构和储锂性能的影响

Effect of mildly-expanded modification on coal-based graphite microstructure and lithium storage performance

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