Methylnaphthalene Pitch-based Ordered Mesoporous Carbon: Synthesis and Electrochemical Properties

doi:10.15541/jim20200690

Abstract

Abstract:

Ordered mesoporous carbon was synthesized by liquid impregnation, using polymerized pitch prepared from 1-methylnaphthalene through thermal bromination with dehydrobromination as precursor and mesoporous silica SBA-15 as template. Microstructure and electrochemical properties of mesoporous carbon were characterized. It was found that the optimal preparation conditions were template/pitch mass ratio of 1:1, carbonization temperature of 900 ℃, and heating rate of 1 ℃·min^-1. The optimal sample exhibits highly ordered two-dimensional hexagonal channels, with specific surface area of 675 m²·g^-1, pore volume of 1 cm³·g^-1, and pore diameter concentrated at about 3.84 nm. The Li-S batteries with this mesoporous carbon as the sulfur host showed excellent electrochemical performance. After 300 cycles, the specific discharge capacity and capacity retention were 688 mAh·g^-1 and 67.1% at a current density of 0.2C (1C=1675 mA·g^-1), respectively, while the specific capacity could reach 556 mAh·g^-1 at a current density of 3C.

Key words: methylnaphthalene pitch, hard template method, ordered mesoporous carbon, Li-S battery

CLC Number:

TQ127

TANG Jiawei, WANG Yongbang, MA Cheng, YANG Haixiao, WANG Jitong, QIAO Wenming, LING Licheng. Methylnaphthalene Pitch-based Ordered Mesoporous Carbon: Synthesis and Electrochemical Properties[J]. Journal of Inorganic Materials, 2021, 36(10): 1031-1038.

Figures/Tables 19

Fig. 1 SEM images of mesoporous carbon obtained at template/pitch mass ratios of (a, b) 0.6, (c, d) 0.8, (e, f) 1.0, and (g, h) 1.2

Fig. 2 TEM images of mesoporous carbon along (a-d) [100] and (e-h) [001] orientations obtained at template/pitch mass ratios of (a, e) 0.6, (b, f) 0.8, (c, g) 1.0 and (d, h) 1.2

Fig. 3 (a) N2 adsorption-desorption isotherms and (b) BJH pore size distributions of mesoporous carbon obtained from various addition amounts of SBA-15

Fig. 4 Small-angle XRD patterns of mesoporous carbon obtained from various addition amounts of SBA-15

Table 1 Porous structural parameters of mesoporous carbon obtained under different process conditions

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	D_ave^a/nm	d₁₀₀^b/nm	a₀^c/nm	Wall thickness^d/nm
SBA-15^e	488	1.24	8.31	10.23	11.81	3.50
POMC0.6-800	654	0.94	3.84	9.71	11.21	7.37
POMC0.8-800	653	0.94	3.85	9.71	11.21	7.36
POMC1.0-800	703	1.05	4.11	9.48	10.95	6.84
POMC1.2-800	684	0.98	4.10	8.73	10.08	5.98
POMC1.0-800-F	681	0.93	3.85	8.72	10.07	6.22
POMC1.0-700	749	1.16	4.12	9.46	10.92	6.80
POMC1.0-900	675	1.00	3.84	9.28	10.72	6.88
POMC1.0-1000	676	0.95	3.85	8.71	10.06	6.21

Fig. 5 (a, b) SEM and (c, d) TEM images of POMC1.0-800-F

Fig. 6 Small-angle XRD patterns of mesoporous carbon prepared under different heating rates

Fig. 7 SEM images of mesoporous carbon obtained under carbonization temperatures of (a, b) 700, (c, d) 800, (e, f) 900 and (g, h) 1000 ℃

Fig. 8 TEM images of mesoporous carbon obtained under carbonization temperatures of (a, e) 700, (b, f) 800, (c, g) 900 and (d, h) 1000 ℃

Fig. 9 (a) TG and DTG curves, (b) cycling performance at 0.2C rate, (c) EIS spectra and (d) rate performance of sample POMCt/60S, (e) CV curves and (f) long cycling performance at 0.2C rate of sample POMC900/60S

Fig. S1 Apparent viscosity vs. temperature correlation curves of methylnaphthalene pitch T290

Fig. S2 Synthesis of methylnaphthalene pitch

Table S1 General physical properties of methylnaphthalene pitch T290

Elemental analysis/wt%				SP^a/℃	CY^b/wt%	Solubility/wt%
C	H	Br(diff.)	H/C	SP^a/℃	CY^b/wt%	TS	TI-THFS	THFI-QS	QI
93.65	4.63	1.72	0.59	278	56.3	89.8	6.9	3.3	0

Fig. S3 XRD patterns of mesoporous carbon prepared under various carbonization temperatures in the (a) low-angle and (b) wide-angle regions

Table S2 Distributions of aliphatic and aromatic carbons in methylnaphthalene pitch T290

Pitch	Aliphatic carbons/%			Aromatic carbons/%		f_a
Pitch	CH₃^a	CH₂^b	C_chain^c	Car₁^d	Car₂^e	f_a
T290	2.31	3.09	7.83	59.49	27.28	0.87

Fig. S4 Solid-state 13C-NMR spectra of methylnaphthalene pitch T290

Fig. S5 FT-IR spectra of T290 and derived carbon prepared under various carbonization temperatures

Fig. S6 UV-Vis absorption spectra of the Li2S6 solution before and after adding POMC prepared under various carbonization temperatures (inset: digital image of pure Li2S6 solution and Li2S6 solutions after adding POMC for 2 h)

Table S3 Comparison of electrochemical performance of POMC with similar carbon hosts for Li-S batteries

Carbon-based sulfur host	Precursor	Sulfur content /wt%	Initial capacity /(mAh·g^-1)	Retention	Rate performance /(mAh·g^-1)	Ref.
Hierarchical structure ordered mesoporous carbon	Phenolic resin	60	1138 at 0.1C	~70% after 80 cycles	761 at 2.7C	[30]
Core-shell structure ordered meso@microporous carbon	Sucrose	60	1037 at 0.5C	~81% after 200 cycles	605 at 2C	[31]
Hierarchical microporous-mesoporous carbon	Phenolic resin	60	939 at 0.3C	~78% after 150 cycles	561 at 2C	[33]
Mesoporous hollow carbon	Petroleum pitch	70	1071 at 0.5C	~91% after 100 cycles	450 at 3C	[34]
Ordered mesoporous carbon	Methylnaphthalene pitch	60	1095 at 0.2C	~78% after 100 cycles	651 at 2C, 556 at 3C	This work

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