用于高性能超级电容器电极的栓皮栎基多孔活性炭的制备

doi:10.15541/jim20180426

摘要/Abstract

摘要：

本研究以空腔细胞组成的栓皮栎为原料, KOH为活化剂制备了具有多孔结构的栓皮栎软木基多孔活性炭。以此方法制得的活性炭呈薄片状外形, 最大比表面积达到2312 m ²/g, 具有特殊的微孔-介孔结构。在呈碱性的KOH三电极体系中, 0.1 A/g电流密度时比电容达296 F/g; 两电极体系中, 5 A/g时的比电容达到201 F/g, 循环5000次后电容保持率达99.5%。在呈中性的Na₂SO₄两电极体系中, 电流密度0.5 A/g (174 F/g)至50 A/g (140 F/g)时电容保持率达80.5%, 倍率性能良好, 能量密度高达19.62 Wh/kg。

关键词: 软木, 活性炭, 互联孔结构, 超级电容器

Abstract:

The quercus variabilis cork made up of cavity cells is used as raw material. Herein, the cork-derived activated carbon with the various pores was successfully prepared by the facile carbonization of cork followed by chemical activation. The as-prepared activated carbon sheets possess large specific surface area (2312 m ²/g) and unique interconnected pores. As a result, it shows excellent electrochemical performance as electrode material for supercapacitors. In three electrode system of KOH, it exhibits a high specific capacitance of 296 F/g at a current density of 0.1 A/g. The assembled symmetric supercapacitor shows a high specific capacitance of 201 F/g at 5 A/g, with a good cycling stability of 99.5 % capacitance retention after 5000 cycles. In two electrode system of Na₂SO₄, the symmetric supercapacitor displays a good rate performance of 80.5% retention from 0.5 A/g (174 F/g) to 50 A/g (140 F/g) and a high energy density of 19.62 Wh/kg.

Key words: cork, activated carbon, interconnected pores, supercapacitor

中图分类号:

O613

许伟佳, 邱大平, 刘诗强, 李敏, 杨儒. 用于高性能超级电容器电极的栓皮栎基多孔活性炭的制备[J]. 无机材料学报, 2019, 34(6): 625-632.

Wei-Jia XU, Da-Ping QIU, Shi-Qiang LIU, Min LI, Ru YANG. Preparation of Cork-derived Porous Activated Carbon for High Performance Supercapacitors[J]. Journal of Inorganic Materials, 2019, 34(6): 625-632.

图/表 11

图1 软木基多孔活性炭片制备流程及超级电容器应用

Fig. 1 Schematic illustration of the preparation process for cork-derived porous activated carbon sheets and application of supercapacitor

图2 软木原料的TG/DTG曲线

Fig. 2 TG/DTG curves of raw cork in a flow of nitrogen gas

图3 (a)~(c)样品CC和(d)~(f)样品COAC-4.5的(a, d) SEM和(b, c, e, f)TEM照片

Fig. 3 (a, d) SEM and (b, c, e, f) TEM images of (a-c) CC and (d-f) COAC-4.5

图4 样品COAC-n的(a)N2 (77K)吸脱附等温线和(b)孔径分布曲线

Fig. 4 (a) N2 (77 K) adsorption/desorption isotherms and (b) pore size distribution curves of COAC-n samples

表S1 样品COAC-n的孔结构参数

Table S1 Porosity parameters of the COAC-n samples

Samples	S_BET/ (m²?g^-1)	^aD_ave/ nm	V_t/ (cm³?g^-1)	DFT Method
Samples	S_BET/ (m²?g^-1)	^aD_ave/ nm	V_t/ (cm³?g^-1)	S_{<1 nm}/ (m²?g^-1)	S_{1-2 nm}/ (m²?g^-1)	S_{2-4 nm}/ (m²?g^-1)	V_{<1 nm}/ (cm³?g^-1)	V_{1-2 nm}/ (cm³?g^-1)	V_{2-4 nm}/ (cm³?g^-1)
COAC-3.5	1044	2.19	0.57	1097	115	29	0.34	0.08	0.04
COAC-4.0	2169	2.20	1.19	975	554	221	0.33	0.37	0.26
COAC-4.5	2312	2.22	1.28	1191	485	247	0.40	0.35	0.29
COAC-5.0	1929	2.18	1.05	1087	423	172	0.36	0.29	0.21

图5 样品COAC-n的XRD图谱

Fig. 5 XRD patterns of the COAC-n samples

图6 (a)样品COAC-n的XPS图谱, 样品COAC-4.5的(b)C1s图谱和(c)O1s图谱

Fig. 6 (a) XPS spectra of COAC-n, (b) C1s and (c) O1s XPS spectra of COAC-4.5

表S2 XPS分析样品COAC-n的C, O和N元素含量

Table S2 C, O and N contents of COAC-n samples from XPS analysis

Samples	N/at%	C/at%	O/at%	O-I/at%	O-II/at%	O-III/at%
COAC-3.5	—	86.65	13.35	5.85	4.58	2.92
COAC-4.0	1.42	81.51	17.07	7.87	5.78	3.42
COAC-4.5	1.34	86.12	12.54	4.04	3.77	4.73
COAC-5.0	1.37	82.79	15.84	7.78	5.24	2.82

图7 样品COAC-n在6 mol/L KOH三电极体系的电化学性能: 在扫描速率(a) 1和200 mV/s(b)下的循环伏安曲线; (c)在电流密度0.1 A/g下的恒电流充放电曲线; (d) 比电容与电流密度函数关系曲线; (e) Nyquist图谱

Fig. 7 Electrochemical performance characteristics of COAC-n measured in a three-electrode system in the 6 mol/L KOH electrolyte: CV curves at (a) 1 mV/s and (b) 200 mV/s; (c) Galvanostatic charge/discharge curves at a current density of 0.1 A/g; (d) Specific capacitances at different current densities; (e) Nyquist plots in the frequency range from 10 kHz to 10 mHz with inset showing magnified figure of arc part

图S1 样品COAC-4.5在6 mol/L KOH两电极体系的电化学性能: (a)在扫描速率1~50 mV/s下的循环伏安曲线; (b)在扫描速率100~500 mV/s下的循环伏安曲线; (c)在电流密度10~50 A/g下的恒电流充放电曲线; (d)比电容与电流密度函数关系曲线; (e)能量密度与功率密度关系曲线; (f) 在电流密度5 A/g下循环5000次的长循环曲线(插图为第1次与第5000次循环恒电流充放电曲线)

Fig. S1 Electrochemical performance of COAC-4.5 measured in two electrode system with 6 mol/L KOH electrolyte:(a), (b) CV curves at different scan rates; (c) Galvanostatic charge-discharge curves at different current densities; (d) Specific capacitances for a single electrode at different current densities; (e) Ragone plot of the symmetrical system; (f) Cycling stability at a current density of 5 A/g and inset is the charge-discharge curves of first cycle and 5000th cycle

图S2 样品COAC-4.5在1 mol/L Na2SO4两电极体系的电化学性能: (a)在不同电势窗口、扫描速率50 mV/s下的循环伏安曲线; (b)在电流密度5-50 A/g下的恒电流充放电曲线; (c)比电容与电流密度函数关系曲线; (d)能量密度与功率密度关系曲线

Fig. S2 Electrochemical performance of COAC-4.5 measured in two electrode system with 1 mol/L Na2SO4 electrolyte: (a) CV curves of the cell operated in different voltage windows at a scan rate of 50 mV/s; (b) Galvanostatic charge/discharge curves of the cell at various current densities; (c) Specific capacitances for a single electrode at different current densities; (d) Ragone plot of COAC-4.5 and other carbon-based symmetrical supercapacitors

参考文献 34

[1]	DE WIT M, FAAIJ A . European biomass resource potential and costs. Biomass and Bioenergy, 2010,34(2):188-202. DOI URL
	HAO Y X, QIAN M, XU J J , et al. Synthesis, microstructure and superconductivity of cotton-based porous carbon materials. Journal of Inorganic Materials, 2018,33(1):93-99.
[2]	SEVILLA M, MOKAYA R . Energy storage applications of activated carbons: supercapacitors and hydrogen storage. Energy & Environmental Science, 2014,7(4):1250-1280.
[3]	WICKRAMARATNE N P, XU J, WANG M , et al. Nitrogen enriched porous carbon spheres: attractive materials for supercapacitor electrodes and CO₂ adsorption. Chemistry of Materials, 2014,26(9):2820-2828. DOI URL
[4]	ZHAI Y, DOU Y, ZHAO D , et al. Carbon materials for chemical capacitive energy storage. Advanced Materials, 2011,23(42):4828-4850. DOI URL
[5]	ZHANG L L, ZHAO X S . Carbon-based materials as supercapacitor electrodes. Chemical Society Reviews, 2009,38(9):2520-2531. DOI URL
[6]	TIAN X, MA H, LI Z , et al. Flute type micropores activated carbon from cotton stalk for high performance supercapacitors. Journal of Power Sources, 2017,359:88-96. DOI URL
[7]	YU K, ZHU H, QI H , et al. High surface area carbon materials derived from corn stalk core as electrode for supercapacitor. Diamond and Related Materials, 2018,88:18-22. DOI URL
[8]	YANG C S, JANG Y S, JEONG H K . Bamboo-based activated carbon for supercapacitor applications. Curr. Appl. Phys., 2014,14(12):1616-1620. DOI URL
[9]	CHEN C, ZHANG Y, LI Y , et al. All-wood, low tortuosity, aqueous, biodegradable supercapacitors with ultra-high capacitance. Energy & Environmental Science, 2017,10(2):538-545.
[10]	YANG R, WANG Y, LI M , et al. A new carbon/ferrous sulfide/ iron composite prepared by an in situ carbonization reduction method from hemp (Cannabis sativa L.) stems and its Cr (VI) removal ability. ACS Sustainable Chemistry & Engineering, 2014,2(5):1270-1279.
[11]	YU Z F, WANG X Z, HOU Y N , et al. Preparation of nitrogen- doped porous carbon by molten salt method and its catalytic desulfurization performance. Journal of Inorganic Materials, 2017,32(7):770-776. DOI URL
[12]	ATANES E NIETO-MÁRQUEZ A, CAMBRA A, , et al. Adsorption of SO₂ onto waste cork powder-derived activated carbons. Chemical Engineering Journal, 2012,211(22):60-67.
[13]	JAIN A, BALASUBRAMANIAN R, SRINIVASAN M P . Production of high surface area mesoporous activated carbons from waste biomass using hydrogen peroxide-mediated hydrothermal treatment for adsorption applications. Chemical Engineering Journal, 2015,273:622-629. DOI URL
[14]	KIM M J, JUNG M J, KIM M I , et al. Adsorption characteristics of toluene gas using fluorinated phenol-based activated carbons. Applied Chemistry for Engineering, 2015,26(5):587-592. DOI URL
[15]	ROSAS J M, RUIZ-ROSAS R, RODRÍGUEZ-MIRASOL J , et al. Kinetic study of SO₂, removal over lignin-based activated carbon. Chemical Engineering Journal, 2017,307:707-721. DOI URL
[16]	LULAI E C, CORSINI D L . Differential deposition of suberin phenolic and aliphatic domains and their roles in resistance to infection during potato tuber (Solanum tuberosum L.) wound-healing. Physiological and Molecular Plant Pathology, 1998,53(4):209-222. DOI URL
[17]	PILAO R, RAMALHO E, PINHO C . Overall characterization of cork dust explosion. Journal of Hazardous Materials, 2006,133(1):183-195. DOI URL
[18]	YANG H P, YAN R, CHEN H P , et al. Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel, 2007,86(12):1781-1788. DOI URL
[19]	CORDEIRO N, BELGACEM N M, GANDINI A , et al. Cork suberin as a new source of chemicals: 2. Crystallinity, thermal and rheological properties. Bioresource Technology, 1998,63(2):153-158. DOI URL
[20]	JIANG G, NOWAKOWSKI D J, BRIDGWATER A V . A systematic study of the kinetics of lignin pyrolysis. Thermochimica Acta, 2010,498(1):61-66. DOI URL
[21]	JOHN M J, THOMAS S . Biofibres and biocomposites. Carbohydrate Polymers, 2008,71(3):343-364. DOI URL
[22]	RAYMUNDO-PIÑERO E, LEROUX F, BÉGUIN F . A high- performance carbon for supercapacitors obtained by carbonization of a seaweed biopolymer. Advanced Materials, 2006,18(14):1877-1882. DOI URL
[23]	LI Y, ZHAO Y, CHENG H , et al. Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. Journal of the American Chemical Society, 2011,134(1):15-18.
[24]	BINIAK S, SZYMAŃSKI G, SIEDLEWSKI J , et al. The characterization of activated carbons with oxygen and nitrogen surface groups. Carbon, 1997,35(12):1799-1810. DOI URL
[25]	ZHAO Y F, RAN W, HE J , et al. Oxygen-rich hierarchical porous carbon derived from artemia cyst shells with superior electrochemical performance. ACS Applied Materials & Interfaces, 2015,7(2):1132-1139.
[26]	ZHU H, WANG X L, YANG F , et al. Promising carbons for supercapacitors derived from fungi. Advanced Materials, 2011,23(24):2745-2748. DOI URL
[27]	JIANG L, SHENG L, LONG C , et al. Functional pillared graphene frameworks for ultrahigh volumetric performance supercapacitors. Advanced Energy Materials, 2015, 5(15): 1500771-1-9.
[28]	XU B, HOU S, CAO G , et al. Sustainable nitrogen-doped porous carbon with high surface areas prepared from gelatin for supercapacitors. Journal of Materials Chemistry, 2012,22(36):19088-19093. DOI URL
[29]	ZHONG C, DENG Y D, HU W B , et al. A review of electrolyte materials and compositions for electrochemical supercapacitors. Chemical Society Reviews, 2015,44(21):7484-7539. DOI URL
[30]	YU A, CHABOT V, ZHANG J. Electrochemical supercapacitors for energy storage and delivery:fundamentals and applications. CRC Press, 2013.
[31]	WANG Q, YAN J, WANG Y B , et al. Three-dimensional flower-like and hierarchical porous carbon materials as high-rate performance electrodes for supercapacitors. Carbon, 2014,67(2):119-127. DOI URL
[32]	SUN G L, LI B, RAN J B , et al. Three-dimensional hierarchical porous carbon/graphene composites derived from graphene oxide- chitosan hydrogels for high performance supercapacitors. Electrochimica Acta, 2015,171:13-22. DOI URL
[33]	LONG C L, CHEN X, JIANG L L , et al. Porous layer-stacking carbon derived from in-built template in biomass for high volumetric performance supercapacitors. Nano Energy, 2015,12:141-151. DOI URL
[34]	YAN J, WANG Q, WEI T, FAN Z J . Recent advances in design and fabrication of electrochemical supercapacitors with high energy densities. Adv. Energy Mater., 2014, 4(4): 1300816-1-43.