甲基萘沥青基有序中孔炭的制备及电化学性能

doi:10.15541/jim20200690

无机材料学报 ›› 2021, Vol. 36 ›› Issue (10): 1031-1038.DOI: 10.15541/jim20200690 CSTR: 32189.14.10.15541/jim20200690

甲基萘沥青基有序中孔炭的制备及电化学性能

汤嘉伟¹(), 王永邦¹^,², 马成¹, 杨海潇¹, 王际童¹, 乔文明¹(), 凌立成¹

1.华东理工大学化学工程联合国家重点实验室, 上海 200237
2.中国石化炼油销售公司, 上海 200050

收稿日期:2020-12-01 修回日期:2021-02-22 出版日期:2021-10-20 网络出版日期:2021-03-12
通讯作者: 乔文明, 教授. E-mail: qiaowm@ecust.edu.cn
作者简介:汤嘉伟(1996-), 男, 硕士研究生. E-mail: 15216726632@163.com
基金资助:
国家自然科学基金(U1710252);国家自然科学基金(21978097);中国石油化工有限公司基金(218025)

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

TANG Jiawei¹(), WANG Yongbang¹^,², MA Cheng¹, YANG Haixiao¹, WANG Jitong¹, QIAO Wenming¹(), LING Licheng¹

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2. Sinopec Refinery Product Sales Company Limited, Shanghai 200050, China

Received:2020-12-01 Revised:2021-02-22 Published:2021-10-20 Online:2021-03-12
Contact: QIAO Wenming, professor. E-mail: qiaowm@ecust.edu.cn
About author:TANG Jiawei (1996-), male, Master candidate. E-mail: 15216726632@163.com
Supported by:
National Natural Science Foundation of China(U1710252);National Natural Science Foundation of China(21978097);Foundation of Sinopec(218025)

摘要/Abstract

摘要：

以1-甲基萘热溴化/脱溴聚合沥青为前驱体, 中孔二氧化硅SBA-15为模板, 采用液相浸渍法合成有序中孔炭。通过不同测试手段对中孔炭的微观结构和电化学性能进行了研究。当模板剂和沥青质量比为1:1, 升温速率为 1 ℃·min^-1, 碳化温度为900 ℃时, 所制备的中孔炭性能最优, 具有高度有序的二维六方孔道结构, 比表面积为675 m²·g^-1, 孔容为1 cm³·g^-1, 孔径集中在3.84 nm左右。该中孔炭用于Li-S电池的正极载体材料表现出良好的电化学性能, 在0.2C(1C=1675 mA·g^-1)电流密度下经300次循环后放电比容量和容量保持率分别为688 mAh·g^-1和67.1%, 在3C电流密度下比容量可达556 mAh·g^-1。

关键词: 甲基萘沥青, 硬模板法, 有序中孔炭, 锂硫电池

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

中图分类号:

TQ127

汤嘉伟, 王永邦, 马成, 杨海潇, 王际童, 乔文明, 凌立成. 甲基萘沥青基有序中孔炭的制备及电化学性能[J]. 无机材料学报, 2021, 36(10): 1031-1038.

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.

图/表 19

图1 模板剂和沥青质量比为(a, b)0.6、(c, d)0.8、(e, f)1.0和(g, h)1.2时所制中孔炭的SEM照片

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

图2 模板剂和沥青质量比为(a, e)0.6、(b, f)0.8、(c, g)1.0和(d, h)1.2时所制中孔炭沿(a~d) [100]和(e~h) [001]晶向的TEM照片

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

图3 不同SBA-15添加量时中孔炭的(a)氮气吸脱附等温线及(b)BJH孔径分布图

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

图4 不同SBA-15添加量时中孔炭的小角XRD谱图

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

表1 在不同工艺条件下所制备中孔炭的孔结构参数

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

图5 POMC1.0-800-F的(a, b)SEM和(c, d)TEM照片

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

图6 不同升温速率所得中孔炭的小角XRD谱图

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

图7 碳化温度为(a, b)700、(c, d)800、(e, f)900和(g, h)1000 ℃时所制中孔炭的SEM照片

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 ℃

图8 碳化温度为(a, e) 700、(b, f) 800、(c, g) 900和(d, h) 1000 ℃时所制中孔炭的TEM照片

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 ℃

图9 POMCt/60S的(a)热失重曲线、(b)0.2C下的循环性能、(c)交流阻抗谱和(d)倍率性能, POMC900/60S的(e)CV曲线和(f)0.2C下的长循环稳定性

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

图S1 甲基萘沥青T290的表观粘度-温度曲线

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

图S2 甲基萘沥青的合成过程

Fig. S2 Synthesis of methylnaphthalene pitch

表S1 甲基萘沥青T290的一般物性参数

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

图S3 不同碳化温度所制中孔炭的(a)小角和(b)广角XRD谱图

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

表S2 甲基萘沥青T290的脂肪碳和芳香碳的分布

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

图S4 甲基萘沥青T290的固态核磁碳谱

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

图S5 甲基萘沥青T290在不同温度碳化前后的红外光谱图

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

图S6 加入不同碳化温度所制中孔炭前后Li2S6溶液的紫外-可见吸收光谱图(插图为加入中孔炭2 h后的照片)

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)

表S3 甲基萘沥青基中孔炭与同类用于锂硫电池的碳基载体材料的电化学性能对比

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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甲基萘沥青基有序中孔炭的制备及电化学性能

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

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