烟煤衍生炭材料的炭化机制及其在锂/钠离子电池中的应用

TIAN Qing-qing; LI Xiao-ming; XIE Li-jing; SU Fang-yuan; YI Zong-lin; DONG Liang; CHEN Cheng-meng

doi:10.1016/S1872-5805(23)60759-0

烟煤衍生炭材料的炭化机制及其在锂/钠离子电池中的应用

doi: 10.1016/S1872-5805(23)60759-0

田青青^{1, 3,},
李晓明²,
谢莉婧²,
苏方远²,
易宗琳²,
董良^{1, 3, ,},
陈成猛^2, ,

1.
中国矿业大学煤炭加工与高效洁净利用教育部重点实验室，江苏徐州 221116
2.
中国科学院山西煤炭化学研究所炭材料重点实验室，山西太原 030001
3.
中国矿业大学化工学院，江苏徐州 221116

基金项目: 陕西省自然科学基础研究计划 (2019JLZ-10)；国家自然科学基金委员会面上基金项目 (22179139)；山西省基础研究计划面上基金项目 (20210302123008, 20210302124101)；山西省重点研发计划项目 (2022ZDYF028)

详细信息

通讯作者:
董　良，教授. E-mail：dongl@cumt.edu.cn

陈成猛，研究员. E-mail：ccm@sxicc.ac.cn

中图分类号: 127.1⁺1
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出版历程
- 收稿日期: 2023-03-07
- 录用日期: 2023-06-12
- 修回日期: 2023-06-12
- 网络出版日期: 2023-06-16
- 刊出日期: 2023-10-01

Insights into the carbonization mechanism of bituminous coal-derived carbon materials for lithium-ion and sodium-ion batteries

1.
Key Laboratory of Coal Processing and Efficient Utilization, China University of Mining and Technology, Xuzhou 221116, China
2.
CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
School of Chemical Engineering & Technology, China University of Mining & Technology, Xuzhou 221116, China

More Information

Author Bio:
田青青，硕士研究生. E-mail：tianqingqing032@163.com

Corresponding author: DONG Liang. E-mail: dongl@cumt.edu.cn; CHEN Cheng-meng. E-mail: ccm@sxicc.ac.cn

摘要

摘要: 近年来，人们对利用低温炭化工艺制备煤基无定形炭材料作为锂离子电池（LIBs）和钠离子电池（SIBs）的负极材料产生了兴趣。然而，煤衍生炭材料的炭化机制仍然不太清楚。因此，本文选取烟煤为原料，探究了煤炭到无定形炭材料的化学、微晶和孔隙结构演变过程。随着温度的升高（低于1 000 ℃），材料结构发生局部变化，碳层的迁移和小分子物质的释放导致了层间距（3.69-3.82 Å）和缺陷密度（1.26-1.90）逐渐增大，并且产生了丰富的纳米微孔结构。当温度升至1000~1600 °C时，层间距和缺陷密度开始逐渐减小。在LIBs中，经1 000 °C炭化制备的样品表现出最佳的电化学性能。在0.1 C倍率测试下可逆容量达到384 mAh g^–1，在5 C倍率下仍能保持170 mAh g^–1，表现出优异的倍率性能。在SIBs中，经1200 °C炭化制备的样品在0.1 C倍率测试下具有270.1 mAh g^–1的可逆容量和高达86.8%的首次库伦效率。本研究为煤基炭材料的精细化制备提供了理论支撑。
- 煤 /
- 炭化机制 /
- 炭材料 /
- 锂离子电池 /
- 钠离子电池
Abstract: Despite recent interest in the low-temperature carbonization of coal to prepare disordered carbon materials for the anodes of lithium-ion (LIBs) and sodium-ion batteries (SIBs), the carbonization mechanism is still poorly understood. We selected bituminous coal as the raw material and investigated the chemical, microcrystal, and pore structure changes during the carbonization process from coal to the resulting disordered carbon. These structural changes with temperature below 1 000 °C show an increase in both interlayer spacing (3.69–3.82 Å) and defect concentration (1.26–1.90), accompanied by the generation of a large amount of nano-microporous materials. These changes are attributed to the migration of the local carbon layer and the release of small molecules. Furthermore, a decrease in interlayer spacing and defect concentration occurs between 1 000 °C and 1 600 °C. In LIBs, samples carbonized at 1000 °C showed the best electrochemical performance, with a reversible capacity of 384 mAh g⁻¹ at 0.1 C and excellent rate performance, maintaining 170 mAh g⁻¹ at 5 C. In SIBs, samples carbonized at 1 200 °C had a reversible capacity of 270.1 mAh g⁻¹ at 0.1 C and a high initial Coulombic efficiency of 86.8%. This study offers theoretical support for refining the preparation of carbon materials derived from coal.
- Coal /
- Carbonization mechanism /
- Carbon materials /
- Lithium-ion batteries /
- Sodium-ion batteries

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FIG. 2656. FIG. 2656.

FIG. 2656.. FIG. 2656.

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Figure 1. (a) TG-DTG curves of CC. (b) MS spectra of evolving gas from TG of CC. (c) O/C and H/C atomic ratio of CC and coal-derived disordered carbon materials. (d) FTIR spectrum, and (e) High-resolution O1s spectra of CC and coal-derived disordered carbon materials at different carbonization temperatures

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Figure 2. (a-f) HR-TEM and SAED images of coal-derived disordered carbon materials. (g) Schematic illustration of the structural transformation from a highly-disordered state to a graphite-like structure

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Figure 3. (a) XRD patterns of CC and coal-derived disordered carbon materials. (b) Schematic definition of the parameter R. (c) Variation curve of R values of CC and coal-derived disordered carbon materials at different carbonization temperatures. (d) Fitted Raman spectra, (e) Values of d₀₀₂ and A_D1/A_G, (f) N₂ adsorption-desorption isotherms, and (g) total open pore volume and average pore diameter of CC and coal-derived disordered carbon materials

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Figure 4. (a) GCD curves at 0.1C, (b) Variation curve of specific capacity and ICE, and (c) Rate capacity at different current rates of coal-derived disordered carbon materials. (d) The three CV curves of CC-600, CC-1000 and CC-1400. (e) The CV curves at different rates of CC-1000. (f) A linear relationship between log (Peak Currents) and log (Sweep Rate), (g) Nyquist plots of the fresh cells of coal-derived disordered carbon materials. (h) GITT curves of the CC-1000 during the discharge/charge process in LIBs

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Figure 5. (a) GCD curves at 0.1C, (b) Variation curve of specific capacity and ICE, and (c) Rate capacity at different current rates of coal-derived disordered carbon materials. (d) The 3 CV curves of CC-600, CC-1200 and CC-1400. (e) The CV curves at different rates of CC-1200. (f) A linear relationship between log (Peak Currents) and log (Sweep Rate), (g) Nyquist plots of the fresh cells of coal-derived disordered carbon materials. (h) GITT curves of the CC-1200 in SIBs

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Figure 6. Possible carbonization mechanism of coal and the correlated structure-performance relationship in LIBs and SIBs

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Table 1. The contents of O1s peaks of coal-derived disordered carbon materials

B.E. (eV)	Assignment	CC	CC-600	CC-800	CC-1000	CC-1200	CC-1400	CC-1600
534.8	O―H	1.03	1.05	1.08	1.00	1.24	1.30	0.93
533.4	C―O	5.50	3.48	2.27	2.69	2.52	2.09	2.07
532.1	C＝O	6.85	2.35	1.95	2.42	2.01	1.77	1.84

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Table 2. Physical parameters of coal-derived disordered carbon materials

Sample	CC	CC-600	CC-800	CC-1000	CC-1200	CC-1400	CC-1600
R	2.03	1.50	1.90	2.17	2.20	2.35	3.17
2θ (°)	24.12	24.00	23.54	23.29	23.54	23.72	24.78
d₀₀₂ (Å)	3.69	3.71	3.78	3.82	3.78	3.75	3.59
A_D1/A_G	1.26	1.72	1.73	1.90	1.73	1.50	1.49

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Table 3. Pore structure parameters of coal-derived disordered carbon materials

Sample	S_BET^a (m² g^–1)	V_tot^a (cm³ g^–1)	D_ave^a (nm)	Ture density^b (g cm^–3)	V_{close pores} (cm³ g^–1)	S_BET^c (m² g^–1)
CC	2.72	0.0080	11.71	1.36	0.29	133.70
CC-600	272.97	0.0152	2.23	1.55	0.20	289.28
CC-800	38.56	0.0249	2.59	1.79	0.11	318.95
CC-1000	4.14	0.0073	7.06	1.85	0.10	293.47
CC-1200	2.03	0.0067	13.13	1.98	0.06	81.49
CC-1400	2.11	0.0069	13.07	1.73	0.14	2.55
CC-1600	2.36	0.0080	13.47	1.54	0.21	1.69
Note: ^a Testing under N₂ atmosphere. ^b Testing under He atmosphere. ^c Testing under CO₂ atmosphere.

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