毛细管破裂法制备中间相炭微球及其电化学性能

DONG Si-lin; YANG Jian-xiao; CHANG Sheng-kai; SHI Kui; LIU Yue; ZOU Jia-ling; LI Jun

doi:10.1016/S1872-5805(22)60606-1

毛细管破裂法制备中间相炭微球及其电化学性能

doi: 10.1016/S1872-5805(22)60606-1

董斯琳^1,,
杨建校^1, ,,
常胜凯¹,
石奎¹,
刘越¹,
邹嘉玲¹,
李君²

1.
湖南大学材料科学与工程学院，先进炭材料及应用技术湖南省重点实验室，湖南长沙 410082
2.
长沙理工大学化学与生物工程学院，湖南长沙 410114

基金项目: 国家自然科学基金青年科学基金(5172094)；湖南省自然科学基金(2020JJ4203，2019JJ50651)

详细信息

通讯作者:
杨建校，副教授. E-mail：yangjianxiao@hnu.edu.cn

中图分类号: TQ127.1⁺1
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出版历程
- 收稿日期: 2022-01-04
- 修回日期: 2022-03-15
- 网络出版日期: 2022-04-01
- 刊出日期: 2023-01-06

An innovative and efficient method for the preparation of mesocarbon microbeads and their use in the electrodes of lithium ion batteries and electric double layer capacitors

1.
Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, College of Materials Science and Engineering, Hunan University, Changsha 410082, China
2.
School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410114, China

More Information

Author Bio:
董斯琳. E-mail：silindong@hnu.edu.cn

Corresponding author: YANG Jian-xiao, Associate professor. E-mail: yangjianxiao@hnu.edu.cn

摘要

摘要: 基于沥青在熔融纺丝过程中的滴落行为和流变学理论，提出了一种新型高效的中间相炭微球（MCMB）制备方法—毛细管破裂法（DCB法）。本实验以中间相沥青为原料，采用DCB法考察了不同接收相（水或THF）对MCMB制备的影响规律，并系统研究了相应MCMB微观结构的演变规律。在此基础上，所制MCMB经750 °C的KOH活化制备了A-MCMB，以及经2800 °C的石墨化制备了G-MCMB，并分别探究了它们作为超级电容器（EDLC）和锂离子电池（LIB）电极材料的电化学性能。结果表明：采用DCB方法所制备的水接收相的MCMB-W和THF接收相的MCMB-T均呈现尺寸约1~2 μm的球形结构特征。此外，A-MCMB-T具有高比表面积1391 m² g⁻¹、微孔体积0.55 cm³ g⁻¹和中孔体积0.24 cm³ g⁻¹，作为EDLC的电极材料时，其比电容比MP衍生的炭材料提高了30%，且电容保持率也显著提升。同时，G-MCMB-T具有较高的石墨化度0.895和有序的层状结构，作为LIB的负极材料时，在100 mA g⁻¹下进行100次循环后，具有353.5 mAh g⁻¹的高比容量。因此，本文提出并验证了一种新的MCMB制备方法，有望为储能材料的设计和开发提供了一种思路和途径。
- 中间相沥青 /
- 中间相炭微球 /
- 毛细管破裂法 /
- 锂离子电池 /
- 超级电容器
Abstract: An innovative and efficient method for preparation of mesocarbon microbeads (MCMBs) was developed based on the dripping behavior and rheological properties of molten pitch during melt-spinning, where a string of beads was formed after the pitch was extruded from spinnerets and dropped into a receiving solvent (tetrohydrofuran or water). The pitch droplets were first carbonized, then activated by KOH or graphitized at 2800 °C to prepare A-MCMBs or G-MCMBs, respectively, and these were respectively used as the electrode materials for electric double layer capacitors (EDLCs) and lithium-ion batteries (LIBs). Results showed that both MCMB-W prepared using water as the receiving solvent and MCMB-T prepared using tetrohydrofuran as the receiving solvent had a spherical shape with sizes of 1-2 μm. A-MCMB-T had a high specific surface area (1 391 m² g⁻¹), micropore volume (0.55 cm³ g⁻¹) and mesopore volume (0.24 cm³ g⁻¹), with a 30% higher specific capacitance than an activated mesophase carbon prepared under the same conditions, and its capacitance retention was significantly improved when it was used as an electrode material for EDLCs. G-MCMB-T had a high degree of graphitization (0.895) and when it was used as an electrode material for LIBs it had a high specific capacity of 353.5 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹. This work reports a new preparation method for MCMBs, which could be used to prepare energy storage materials.
- Mesophase pitch /
- Mesocarbon microbeads /
- Delayed capillary breakup /
- Lithium-ion batteries /
- Electronic double layer capacitors

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FIG. 2070. FIG. 2070.

FIG. 2070.. FIG. 2070.

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Figure 1. The preparation process of MCMBs by the DCB method

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Figure 2. SEM images of (a, b) C-MP, (c, d) C-MS-W and (e, f) C-MS-T

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Figure 3. TG-DSC curves of MP, MS-W, MS-T (a, b) in nitrogen atmosphere and (c, d) in air atmosphere. (e, f) TG-DSC curves of O-MP, O-MS-W, O-MS-T in nitrogen atmosphere

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Figure 4. FTIR and Raman spectra of (a, d) MP, MS-W, MS-T, (b, e) O-MP, O-MS-W, O-MS-T and (c, f) C-MP, C-MS-W, C-MS-T

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Figure 5. TEM images of (a) A-MP, (b) A-MS-W, (c) A-MS-T. (d) Nitrogen adsorption isotherms, (e) pore size distributions and (f) Raman spectra of A-MCMBs

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Figure 6. (a) FTIR and (b) XPS spectra, and (c) the high resolution of C1s XPS spectra and (d) the O1s XPS spectra of A-MCMBs

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Figure 7. (a) CV curves at the scanning speed of 100 mV s⁻¹, (b) GCD curves at a current density of 0.5 A g⁻¹ and (c) EIS curves of A-MCMBs

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Figure 8. TEM images of (a, b, c) G-MP, (d, e, f) G-MS-W and (g, h, i) G-MS-T

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Figure 9. (a) Raman spectra, (b) nitrogen adsorption isotherms and (c) XRD patterns of G-MCMBs

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Figure 10. (a）The 1st discharge/charge curves between 0.005 and 3.0 V at a current density of 100 mA g⁻¹ . (b) The capacities at current densities from 0.05 to 2 A g⁻¹. (c) Cycling performance and coulombic efficiency at 100 mA g⁻¹ and (d) Nyquist plots of G-MCMBs

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Table 1. Relevant analysis results of samples

Samples	Yield	TG (in N₂)		DSC (in air)			FTIR			Raman
Samples	Yield	T_d (°C)	W	△T (°C)	△H (J/g)	△H/△T	I_OS	I_CHS	I_A	I_D/I_G	I_A/I_G
MP	─	235	54%	207	291	1.41	0.225	0.501	0.503	0.69	0.40
MS-W	─	241	52%	218	405	1.86	0.224	0.500	0.502	0.64	0.35
MS-T	─	305	72%	221	209	0.95	0.212	0.498	0.501	0.60	0.32
O-MP	103%	291	77%	─	─	─	0.243	0.500	0.500	0.83	0.45
O-MS-W	104%	296	77%	─	─	─	0.241	0.495	0.501	0.69	0.38
O-MS-T	105%	301	80%	─	─	─	0.239	0.494	0.499	0.62	0.33
C-MP	70%	─	─	─	─	─	0.250	0.499	0.500	1.14	0.53
C-MS-W	72%	─	─	─	─	─	0.249	0.498	0.499	1.12	0.51
C-MS-T	74%	─	─	─	─	─	0.247	0.497	0.498	1.08	0.45

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Table 2. Microstructure and porosity parameters of A-MCMBs

Samples	Raman		Parameters of pore structure
Samples	I_D/I_G	I_A/I_G	S_BET (m² g⁻¹)	V_mic (cm³ g⁻¹)	V_mes (cm³ g⁻¹)	V_tot (cm³ g⁻¹)	D (nm)
A-MP	0.99	0.60	1222	0.16	0.49	0.65	5.04
A-MS-W	0.96	0.71	1190	0.33	0.17	0.50	5.00
A-MS-T	0.94	0.72	1391	0.37	0.24	0.61	4.19

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Table 3. FTIR and XPS analysis results of A-MCMBs

Samples	FTIR			XPS (at%)		percentage of total C1s				percentage of total O1s
Samples	I_OS	I_CHS	I_A	C	O	C=C	C―O	C＝O	COOH	C＝O	C―O	COOH
A-MP	0.251	0.500	0.502	90.03	8.70	35.29	23.73	19.85	21.13	31.66	35.91	32.43
A-MS-W	0.231	0.480	0.482	90.45	8.39	35.26	23.75	19.87	21.12	32.46	36.04	31.50
A-MS-T	0.220	0.460	0.462	91.28	7.64	34.32	24.28	21.27	20.13	32.96	37.20	29.84

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Table 4. Electrochemical properties of different A-MCMBs

Samples	Specific capacitance(F/g)					Capacitance retention(%)	R_ct(Ω)
Samples	0.5 A g⁻¹	1 A g⁻¹	2 A g⁻¹	5 A g⁻¹	10 A g⁻¹	Capacitance retention(%)	R_ct(Ω)
A-MP	156.9	131.1	118.8	108.5	100.0	63.7	0.6
A-MS-W	178.6	169.5	153.4	145.0	139.0	77.8	0.5
A-MS-T	193.5	166.2	147.0	135.5	129.0	66.6	0.3

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Table 5. Parameters of pore structure and graphite microcrystallite s of G-MCMBs

Samples	I_D/I_G	I_D’/I_G	S_BET (m² g⁻¹)	d₀₀₂ (nm)	L_c (nm)	L_a (nm)	N (n)	G
G-MP	0.21	0.05	1.60	0.3366	0.6582	1.3976	2.96	0.861
G-MS-W	0.18	0.04	2.25	0.3366	0.6973	1.9862	3.07	0.861
G-MS-T	0.14	0.02	3.53	0.3363	0.5680	2.4556	2.69	0.895

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Table 6. Cycle performance of different G-MCMBs

Samples	Specific capacity (mAh g⁻¹)					ICE (%)	Capacity retention (%)	R_ct (Ω)
Samples	D₁	C₁	D₂	D₃	D₁₀₀	ICE (%)	Capacity retention (%)	R_ct (Ω)
G-MP	329.4	277.6	285.1	277.1	255.3	84.27	77.50	295.9
G-MS-W	401.4	346.9	354.0	349.6	313.6	86.42	78.13	301.9
G-MS-T	408.1	353.0	366.6	362.4	353.5	86.50	86.62	95.5

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