双离子液体基多孔炭的制备与电化学性能

doi:10.7503/cjcu20190703

摘要/Abstract

摘要：

以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVImHSO₄)为主炭源, 以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF₆)为助剂, 在氮气气氛、 1000 ℃下一步炭化得到氮、磷、硫共掺杂多孔炭. 通过N₂吸附-脱附、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、 X射线衍射(XRD)、拉曼光谱(Raman)、热重分析(TGA)和X射线光电子能谱(XPS)等技术对多孔炭进行了分析表征. 结果表明, 多孔炭的孔结构以微孔为主, 最高比表面积可达1111 m²/g, 其微晶结构中无定形碳和石墨化碳并存; 多孔炭中的氮主要以季氮(N-Q)、吡咯氮(N-5)和吡啶氮(N-6)的形式存在, 磷以磷-氧(N—O—P)键合形式为主, 硫主要以噻吩硫(C—S—C)为主. 在6 mol/L KOH溶液、三电极体系中, 多孔炭在0.5 A/g电流密度下的比电容为138 F/g; 在10 A/g电流密度下的比电容为100 F/g; 在2 A/g电流密度下循环充放电10000次, 其比电容保持率为95.8%, 显示出良好的电化学性能.

关键词: 离子液体, 一步炭化, 氮、磷、硫共掺杂, 比电容, 保持率

Abstract:

Nitrogen, phosphorus and sulfur co-doped porous carbons(PCs) were prepared with a protic ionic liquid 1-hydrogen-3-butylimidazolium hydrogen sulfate(HVImHSO₄) as precursor and 1-butyl-3-methylimi-dazolium hexafurophosphate(BMImPF₆) as assistant through one-step carbonization process at 1000 ℃ in nitrogen atmosphere. The PCs were characterized by nitrogen adsorption-desorption, scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), Raman spectroscopy, thermo-gravimetric analysis(TGA) and X-ray photoelectron spectroscopy(XPS). The results showed that the PCs mainly had micro pores and the specific surface area could be up to 1111 m²/g under m(BMImPF₆)/m(HVImHSO₄)=0.4. The amorphous and disordered graphitic layers were dominant in PCs. Nitrogen bonding state was mainly N-Q(N substituted groups of aromatic graphite structure), phosphorus was mainly in O—P type groups, and sulfur was attributed to C—S—C of thiophene-type sulfur. Meanwhile, the capacitance of PC-BMImPF₆-0.5 was 138 F/g at 0.5 A/g and 100 F/g at 10 A/g, the retention ratio was 95.8% after being cycled for 10000 times at 2 A/g in the electrolyte of 6 mol/L KOH. A simple and easy method for preparation of N, P and S co-doped PCs from ionic liquids has been provided, and the PCs have a certain extent application prospect in supercapacitor electrode materials.

Key words: Ionic liquid, One-step carbonization process, N, P, S co-doping, Specific capacitance, Retention ratio

中图分类号:

O646

TrendMD:

程时富,胡皓,陈必华,吴海虹,高国华,何鸣元. 双离子液体基多孔炭的制备与电化学性能. 高等学校化学学报, 2020, 41(5): 1048.

CHENG Shifu,HU Hao,CHEN Bihua,WU Haihong,GAO Guohua,HE Mingyuan. Preparation and Electrochemical Performance of Porous Carbons Prepared from Binary Ionic Liquids ^†. Chem. J. Chinese Universities, 2020, 41(5): 1048.

图/表 10

Fig.1 N2 adsorption-desorption isotherms of PCs

Table 1 Yield, specific surface area and porosity of PCs

Entry	Sample	Yield(%)	S_BET/(m²·g^-1)	V_t/(cm³·g^-1)	Averagepore size/nm
1	PC-0	8.43	144	0.13	3.7
2	PC-BMImCl-0.3	8.83	3	0.02	33.7
3	PC-BMImBr-0.3	9.16	22	0.05	9.3
4	PC-BMImPF₆-0.3	13.24	452	0.24	2.2
5	PC-EMImBF₄-0.3	12.11	37	0.03	3.5
6	PC-BMImBF₄-0.3	11.27	151	0.11	2.9
7	PC-OMImBF₄-0.3	13.33	176	0.26	6.0
8	PC-BMImPF₆-0.1	13.42	126	0.09	2.7
9	PC-BMImPF₆-0.4	12.24	1111	0.55	2.0
10	PC-BMImPF₆-0.5	13.53	1018	0.52	2.1
11	PC-BMImPF₆-0.75	12.83	685	0.46	2.7

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of PC-0 and PC-BMImPF6-X

Fig.3 SEM images of PC-BMImPF6-0.3(A), PC-BMImPF6-0.4(B), PC-BMImPF6-0.5(C) and TEM image of PC-BMImPF6-0.5(D)

Fig.4 XRD patterns(A) and Raman spectra(B) of PC-0 and PC-BMImPF6-X

Fig.5 TG curves(A) and DTG curves(B) of PC-0 and PC-BMImPF6-X

Fig.6 XPS survey(A) and high resolution patterns of C1s(B), N1s(C), O1s(D), P2p(E), S2p(F) of PC-BMImPF6-0.3

Table 2 Elementalal analysis of PC-0 and PC-BMImPF6-X(X=0.3, 0.4, 0.5)

Sample	CHNS analysis(%)					XPS analysis(%)
Sample	C	H	N	S	Others^*	C	N	S	P	O
PC-0	81.81	0.20	3.81	4.03	10.15	83.74	1.55	2.09	0	12.62
PC-BMImPF₆-0.3	79.02	1.15	2.92	1.91	14.99	74.50	1.66	0.61	2.80	20.43
PC-BMImPF₆-0.4	75.76	1.27	3.08	1.98	17.92	72.22	2.26	0.17	4.81	20.04
PC-BMImPF₆-0.5	60.58	1.47	3.40	1.43	33.13	65.39	1.79	0.10	3.31	29.41

Fig.7 CV curves at 5 mV/s of PC-0 and PC-BMImPF6-X(A), CV curves at 5—100 mV/s of PC-BMImPF6-0.5(B), GCD curves at 1.0 A/g(C) and EIS curves(D) of PC-0 and PC-BMImPF6-X

Fig.8 Specific capacitance at 0.5—10 A/g(A) of PC-0, PC-BMImPF6-X and AC-CEP-21KSW and GCD life of PC-BMImPF6-0.5 at 2.0 A/g(B) Inset: GCD curves of the first and last 10 cycles) of PC-BMImPF6-0.5.

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