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

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

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出版历程
- 收稿日期: 2022-01-01
- 网络出版日期: 2022-04-01

An Innovative and Efficient Preparation of Mesocarbon Microbeads by The Delayed Capillary Breakup Method and Their Electrochemical Performance

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:
DONG Si-lin, Email: silindong@hnu.edu.cn

Corresponding author: YANG Jian-xiao, Email: yangjianxiao@hnu.edu.cn

摘要

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Abstract: An innovative and efficient preparation method of mesocarbon microbeads (MCMBs) was developed based on the dripping behavior and rheological theory of pitch during the melt-spinning process, named as the delayed capillary breakup (DCB) method. In this work, the MCMBs were prepared by the DCB method with different receiving solvents (water or tetrahydrofuran (THF)), and their microstructure evolutions were compared systematically. Moreover, the MCMBs were further activated with KOH at 750 °C or graphitized at 2800 °C to prepare the A-MCMBs or G-MCMBs, and their electrochemical performance as electrode materials for electronic double layer capacitors (EDLC) or lithium-ion batteries (LIB) was investigated, respectively. The results showed that both MCMB-W prepared from water and MCMB-T prepared from THF had great spherical structure with the size of 1~2 μm. In addition, A-MCMB-T had a high specific surface area (1391 m² g⁻¹), micropore volume (0.55 cm³ g⁻¹) and mesopore volume (0.24 cm³ g⁻¹), exhibiting 30% higher specific capacitance than the original material, and its capacitance retention was also significantly improved when it was used as an electrode material for EDLC. Moreover, G-MCMB-T had high graphitization degree (0.895) and orderly lamellar structure, which demonstrated high specific capacity of 353.5 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹ when it was used as an electrode material for LIB. Therefore, this work proposed and verified a new preparation method of MCMBs, which could provide a strategy for designing and developing traditional energy storage materials.
- Mesophase pitch /
- Mesocarbon microbeads /
- Delayed capillary breakup /
- Lithium-ion batteries /
- Electronic double layer capacitors

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Figure 1. The preparation progress 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 in nitrogen atmosphere (a, b) and in air atmosphere (c, d), and TG-DSC curves of O-MP, O-MS-W, O-MS-T in nitrogen atmosphere (e, f).

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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 and nitrogen adsorption isotherms (d), pore size distributions (e) and Raman spectra (f) of A-MCMBs.

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

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Figure 7. CV curves at the scanning speed of 100 mV s⁻¹ (a), GCD curves at a current density of 0.5 A g⁻¹ (b) and EIS curves (c) 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. Raman spectra (a), nitrogen adsorption isotherms (b) and XRD patterns (c) of G-MCMBs.

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