生物质炭@MnO<sub>2</sub>基超级电容器电极材料研究进展

张亚林; 陈兴刚; 王梦倩; 任梦雅; 蔡艳青; 许莹

doi:10.13801/j.cnki.fhclxb.20221109.001

生物质炭@MnO₂基超级电容器电极材料研究进展

doi: 10.13801/j.cnki.fhclxb.20221109.001

华北理工大学　材料科学与工程学院，河北省无机非金属材料重点实验室，唐山 063021

基金项目: 河北省省属高校基本科研业务费研究项目(JST2022005)；华北理工大学大学生创新创业训练项目(T2022047)

详细信息

通讯作者:
蔡艳青，博士，副教授，硕士生导师，研究方向为储能材料、熔盐电化学、医用生物材料等　E-mail: caiyanqing126@126.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-09-20
- 修回日期: 2022-10-25
- 录用日期: 2022-10-29
- 网络出版日期: 2022-11-10
- 刊出日期: 2023-07-15

Research progress of biomass carbon@MnO₂-based electrode materials for supercapacitors

Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China

Funds: Basic Research Funds of Hebei Provincial Universities (JST2022005); Innovation and Entrepreneurship Training Program for College Students of North China University of Science and Technology (T2022047)

摘要

摘要: 基于能源危机、环境污染等问题，开发新型的高性能储能装置至关重要，超级电容器因具有高比能量、稳定性好等优异性能而受到研究者青睐。生物质炭是由生物质材料经过预碳化和活化处理后获得的，具有发达的孔径、较高的活性比表面积，且资源廉价丰富，作为超级电容器材料具有较好的应用前景。为了满足超级电容器高比容量和高循环稳定性，目前有效的方法是将生物炭材料与赝电容材料相结合。过渡金属氧化物MnO₂具有高的理论比电容、宽的电位窗口、低成本、环境友好性而成为最有应用前途的赝电容材料。研究表明：由生物炭与过渡金属氧化物复合材料制备的超级电容器，其比电容和能量密度有了明显提高。本文主要介绍了生物质炭的来源、特点及制备方法，并介绍了生物质炭与MnO₂的复合制备方法及生物质炭@MnO₂复合材料用于超级电容器的研究现状，最后展望了生物质炭@MnO₂基超级电容器的发展趋势。
- 生物质炭 /
- MnO₂ /
- 超级电容器 /
- 比电容 /
- 赝电容材料
Abstract: Based on the problems of energy crisis and environmental pollution, it is very important to develop new high-performance energy storage devices. Supercapacitors are favored by researchers because of their high specific energy and good stability. Biomass carbon is obtained by pre-carbonization and activation of biomass materials, with developed pore size, high active specific surface area, and rich resources, which has good application prospects as a supercapacitor material. In order to meet the high specific capacity and high cycle stability of supercapacitors, the current effective method is to combine biomass carbon materials with pseudo capacitor materials. Transition metal oxide MnO₂ has become the most promising pseudocapacitor material due to its high theoretical specific capacitance, wide potential window, low cost and environmental friendliness. The research shows that the specific capacitance and energy density of the supercapacitor made of the composite material of biomass carbon and transition metal oxide are significantly improved. This paper mainly introduces the source, characteristics and preparation methods of biomass carbon, also introduces the composite methods of biomass carbon and MnO₂ and the research progress of biomass carbon@MnO₂ composite materials, and finally looks forward to the development trend of biomass carbon@MnO₂ based supercapacitors.
- biomass carbon /
- MnO₂ /
- supercapacitors /
- specific capacitance /
- pseudo capacitor materials

HTML全文

图 1 钾单质插入碳层造孔机制图^[31]

Figure 1. Pore forming mechanism diagram of potassium inserted into carbon layer^[31]

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图 2 在5 A/g电流密度下木质素生物质炭电极(a)和木质素生物质炭和MnO₂复合材料电极(b)循环稳定性和库伦效率图^[41]

Figure 2. Cyclic stability and coulomb efficiency of lignin biochar electrode (a) and lignin biochar and MnO₂ composite electrode (b) at 5 A/g current density^[41]

WDB—Wood-derived biochar

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图 3 (a) 无复合MnO₂多孔碳复合材料；在油浴中复合不同时间的多孔碳@MnO₂：(b) 1 h；(c) 3 h；(d) 8 h；(e) 9 h；(f) 15 h^[42]

Figure 3. (a) No composite MnO₂ porous carbon composite; Porous carbon@MnO₂ composite in oil bath for different time: (b) 1 h; (c) 3 h; (d) 8 h; (e) 9 h; (f) 15 h^[42]

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图 4 多孔碳@MnO₂的制作流程^[14]

Figure 4. Production process of porous carbon@MnO₂^[14]

HPC—Hierarchical porous carbon

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图 5 生物质碳预碳化及分级多孔碳和MnO₂复合过程中结构示意图^[14]

Figure 5. Schematic structural diagram of biomass carbon pre carbonization and hierarchical porous carbon and MnO₂ composite process^[14]

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图 6 制备不同玉米芯碳基底超级电容器示意图^[45]

Figure 6. Schematic diagram of preparing supercapacitors with different corn cob carbon substrates^[45]

CC—Corncob carbon; AC—Activated carbon; PVA—Polyvinyl alcohol; ASC—All-solid-state supercapacitor

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图 7 ((a), (b)) 沉积5 min活化生物质炭@MnO₂的SEM和HR-SEM图像；((c), (d)) 沉积2 h碳化的生物质炭@MnO₂的SEM和HR-SEM图像；((e), (f)) 沉积2 h碳化生物质炭@MnO₂ TEM和HR-TEM图像(插图：选定区域电子衍射)^[45]

Figure 7. ((a), (b)) SEM and HR-SEM images of 5 min activated biochar@MnO₂ deposited; ((c), (d)) SEM and HR-SEM images of deposited 2 h carbonized biomass carbon@MnO₂; ((e), (f)) TEM and HR-TEM images of deposited 2 h carbonized biomass carbon@MnO₂(Inset: Electron diffraction in selected areas)^[45]

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图 8 经过活化和只碳化的两种生物质碳表面电沉积MnO₂的示意图^[45]

Figure 8. Schematic diagram of MnO₂ electrodeposition on carbon surface of two kinds of biomass after activation and carbonization only^[45]

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图 9 ((a), (b)) KOH活化处理的多孔碳的SEM图像；(c) KOH活化处理的多孔碳的TEM图像；((d), (e)) 3 h水热复合多孔碳@MnO₂ SEM图像；(f) 3 h水热复合多孔碳@MnO₂的TEM图像；(g) 3 h水热复合多孔碳@MnO₂ EDS图像^[51]

Figure 9. ((a), (b)) SEM images of KOH activated porous carbon; (c) TEM image of KOH activated porous carbon; ((d), (e)) SEM images of 3 h hydrothermal composite MnO₂@porous carbon; (f) TEM image of 3 h hydrothermal composite porous carbon@MnO₂; (g) EDS diagram of 3 h hydrothermal composite porous carbon@MnO₂^[51]

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图 10 (a) 25 mV/s时EC、MnO₂和MnO₂/EC复合材料的CV曲线；(b) 0.5 A/g时EC、MnO₂和MnO₂/EC复合材料的恒流充放电曲线；(c) MnO₂/EC复合材料在10、25、50、75和100 mV/s下的CV曲线；(d) MnO₂/EC复合材料在0.5、1.0、2.0、5.0和10 A/g下的恒流充放电曲线；(e) 不同电流密度下EC、MnO₂和MnO₂/EC复合材料的比电容；(f) EC、MnO₂和MnO₂/EC的电化学阻抗谱^[52]

Figure 10. (a) CV curves of EC, MnO₂ and MnO₂/EC composites at 25 mV/s; (b) Galvanostatic charge/discharge curves of EC, MnO₂ and MnO₂/EC composites at 0.5 A/g; (c) CV curves of MnO₂/EC composites at 10, 25, 50, 75 and 100 mV/s; (d) Galvanostatic charge/discharge curves of MnO₂/EC composites at 0.5, 1.0, 2.0, 5.0 and 10 A/g; (e) Specific capacitance of EC, MnO₂ and MnO₂/EC composites at different current densities; (f) Electrochemical impedance spectroscopy of EC, MnO₂ and MnO₂/EC^[52]

EC—Eggplant carbon; Z'—Real part of impedance; Z"—Imaginary part of impedance

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表 1 木材、香蕉皮、茶叶、稻壳、柚皮、塔松、水稻秸秆的微观结构和电化学性能^[28]

Table 1. Microstructure and electrochemical properties of wood, banana peel, tea, rice husk, pomelo peel, tarzon and rice straw^[28]

Biomass carbon precursor	Biomass carbon morphology	Electrochemical performance







Notes: PC—Direct pyrolysis of wood chips; RC—PC delignified treatment; TARC—Carbonized wood chips; TARC-N—TARC treated twice in N₂; KB—KHCO₃; AC—Porous carbon; X—KHCO₃(KOH)/HC mass radio; HC—Hydrothermal carbon.

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参考文献(52)

[1]	ZHANG X Q, CHENG X B, ZHANG Q. Nanostructured energy materials for electrochemical energy conversion and storage: A review[J]. Journal of Energy Chemistry,2016,25(6):967-984. doi: 10.1016/j.jechem.2016.11.003
[2]	CHAO D L, XIA X H, ZHU C R, et al. Hollow nickel nanocorn arrays as three-dimensional and conductive support for metal oxides to boost supercapacitive performance[J]. Nanoscale,2014,6(11):5691-5697. doi: 10.1039/C4NR01119H
[3]	CHENG Y W, LU S T, ZHANG H B, et al. Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors[J]. Nano Letters,2012,12(8):4206-4211. doi: 10.1021/nl301804c
[4]	HE N F, YILDIZ O, PAN Q, et al. Pyrolytic-carbon coating in carbon nanotube foams for better performance in supercapacitors[J]. Journal of Power Sources,2017,343:492-501. doi: 10.1016/j.jpowsour.2017.01.091
[5]	HU M L, LIU Y H, ZHANG M, et al. Wire-type MnO₂/multilayer graphene/Ni electrode for high-performance supercapacitors[J]. Journal of Power Sources,2016,335:113-120. doi: 10.1016/j.jpowsour.2016.10.043
[6]	LEI W, LIU H P, XIAO J L, et al. Moss-derived mesoporous carbon as Bi-functional electrode materials for lithium-sulfur batteries and supercapacitors[J]. Nanomaterials,2019,9(1):84. doi: 10.3390/nano9010084
[7]	ZHANG Z T, WANG L, LI Y M, et al. Nitrogen-doped core-sheath carbon nanotube array for highly stretchable supercapacitor[J]. Advanced Energy Materials,2017,7(5):1601814. doi: 10.1002/aenm.201601814
[8]	HTUT K Z, KIM M, LEE E, et al. Biodegradable polymer-modified graphene/polyaniline electrodes for supercapacitors[J]. Synthetic Metals,2017,227:61-70. doi: 10.1016/j.synthmet.2017.03.005
[9]	SANTINO L M, ACHARYA S, D'ARCY J M. Low-temperature vapour phase polymerized polypyrrole nanobrushes for supercapacitors[J]. Journal of Materials Chemistry A,2017,5(23):11772-11780. doi: 10.1039/C7TA00369B
[10]	GUO D, ZHANG H M, YU X Z, et al. Facile synthesis and excellent electrochemical properties of CoMoO₄ nanoplate arrays as supercapacitors[J]. Journal of Materials Chemistry A,2013,1(24):7247-7254. doi: 10.1039/c3ta10909g
[11]	KULAL P M, DUBAL D P, LOKHANDE C D, et al. Chemical synthesis of Fe₂O₃ thin films for supercapacitor application[J]. Journal of Alloys and Compounds,2011,509(5):2567-2571. doi: 10.1016/j.jallcom.2010.11.091
[12]	XU J, WANG Q F, WANG X W, et al. Flexible asymmetric supercapacitors based upon Co₉S₈ nanorod//Co₃O₄@RuO₂ nanosheet arrays on carbon cloth[J]. ACS Nano,2013,7(6):5453-5462. doi: 10.1021/nn401450s
[13]	李学林. 二维Ti₃C₂T_X基复合材料的改性及其超级电容器性能研究[D]. 西安: 陕西科技大学, 2021. LI Xuelin. Study on modification of two-dimensional Ti₃C₂T_X-based composites and their supercapacitor properties[D]. Xi'an: Shaanxi University of Science and Technology, 2021(in Chinese).
[14]	LI X Y, HAN D, GONG Z Q, et al. Nest-like MnO₂ nanowire/hierarchical porous carbon composite for high-performance supercapacitor from oily sludge[J]. Nanomaterials,2021,11(10):2715. doi: 10.3390/nano11102715
[15]	DAI C C, WAN J F, YANG J, et al. H₃PO₄ solution hydrothermal carbonization combined with KOH activation to prepare argy wormwood-based porous carbon for high-performance supercapacitors[J]. Applied Surface Science,2018,444:105-117. doi: 10.1016/j.apsusc.2018.02.261
[16]	HOU J H, CAO C B, IDREES F, et al. Hierarchical porous nitrogen-doped carbon nanosheets derived from silk for ultrahigh-capacity battery anodes and supercapacitors[J]. ACS Nano,2015,9(3):2556-2564. doi: 10.1021/nn506394r
[17]	WEI W F, CUI X W, CHEN W X, et al. Manganese oxide-based materials as electrochemical supercapacitor electrodes[J]. Chemical Society Reviews,2011,40(3):1697-1721. doi: 10.1039/C0CS00127A
[18]	宋晓琪, 雷西萍, 樊凯, 等. 基于生物质衍生炭在超级电容器中的研究进展[J]. 复合材料学报, 2023, 40(3):1328-1339. doi: 10.13801/j.cnki.fhclxb.20220628.002 SONG Xiaoqi, LEI Xiping, FAN Kai, et al. Research progress of biomass derived carbon in supercapacitors[J]. Acta Materiae Compositae Sinica,2023,40(3):1328-1339(in Chinese). doi: 10.13801/j.cnki.fhclxb.20220628.002
[19]	CHEN Y D, LI S P, HO S H, et al. Integration of sludge digestion and microalgae cultivation for enhancing bioenergy and biorefinery[J]. Renewable and Sustainable Energy Reviews,2018,96:76-90. doi: 10.1016/j.rser.2018.07.028
[20]	SHAN X F, WU J, ZHANG X T, et al. Review wood for application in electrochemical energy storage devices[J]. Cell Reports Physical Science,2021,2(12):100654. doi: 10.1016/j.xcrp.2021.100654
[21]	TANG Z J, PEI Z X, WANG Z F, et al. Highly anisotropic, multichannel wood carbon with optimized heteroatom doping for supercapacitor and oxygen reduction reaction[J]. Carbon,2018,130:532-543. doi: 10.1016/j.carbon.2018.01.055
[22]	LV Y K, GAN L H, LIU M X, et al. A self-template synthesis of hierarchical porous carbon foams based on banana peel for supercapacitor electrodes[J]. Journal of Power Sources,2012,209:152-157. doi: 10.1016/j.jpowsour.2012.02.089
[23]	SONG X Y, MA X L, LI Y, et al. Tea waste derived microporous active carbon with enhanced double-layer supercapacitor behaviors[J]. Applied Surface Science,2019,487:189-197. doi: 10.1016/j.apsusc.2019.04.277
[24]	XUE B C, JIN L, CHEN Z M, et al. The template effect of silica in rice husk for efficient synthesis of the activated carbon based electrode material[J]. Journal of Alloys and Compounds,2019,789:777-784. doi: 10.1016/j.jallcom.2019.03.012
[25]	WANG Y Y, HOU B H, LU H Y, et al. Hierarchically porous N-doped carbon nanosheets derived from grapefruit peels for high-performance supercapacitors[J]. Chemistryselect,2016,1(7):1441-1447. doi: 10.1002/slct.201600133
[26]	高曼. 松塔生物炭基超级电容器材料的制备与性能研究[D]. 北京: 中国地质大学(北京), 2021. GAO Man. Study on the preparation and performance of pinecone-based carbon supercapacitor materials[D]. Beijing: China University of Geosciences(Beijing), 2021(in Chinese).
[27]	徐增华. 生物质水热炭基多孔炭的制备及其电化学性能研究[D]. 杭州: 浙江大学, 2021. XU Zenghua. Preparation and electrochemical of hydrochar-based porous carbons derived from biomass[D]. Hangzhou: Zhejiang University, 2021(in Chinese).
[28]	芦宇婷. 生物质碳基MnO₂复合材料制备及其电化学性能研究[D]. 大连: 大连海洋大学, 2022. LU Yuting. Preparation of biomass carbon-based MnO₂ composites and study on their electrochemical properties[D]. Dalian: Dalian Ocean University, 2022(in Chinese).
[29]	徐曼曼. 生物质基多孔材料与其在超级电容器中的应用研究[D]. 广州: 华南理工大学, 2017. XU Manman. Study on biomass-based porous materials and their application in supercapacitors[D]. Guangzhou: South China University of Technology, 2017(in Chinese).
[30]	WANG J C, KASKEL S. KOH activation of carbon-based materials for energy storage[J]. Journal of Materials Chemistry,2012,22(45):23710-23725. doi: 10.1039/c2jm34066f
[31]	ROMANOS J, BECKNER M, RASH T, et al. Nanospace engineering of KOH activated carbon[J]. Nanotechnology,2012,23(1):015401. doi: 10.1088/0957-4484/23/1/015401
[32]	WU F M, GAO J P, ZHAI X G, et al. Hierarchical porous carbon microrods derived from albizia flowers for high performance supercapacitors[J]. Carbon,2019,147:242-251. doi: 10.1016/j.carbon.2019.02.072
[33]	WANG C S, LIU T Z. Nori-based N, O, S, Cl co-doped carbon materials by chemical activation of ZnCl₂ for supercapacitor[J]. Journal of Alloys and Compounds,2017,696:42-50. doi: 10.1016/j.jallcom.2016.11.206
[34]	张本镔, 刘运权, 叶跃元. 活性炭制备及其活化机理研究进展[J]. 现代化工, 2014, 34(3):34-39. doi: 10.16606/j.cnki.issn0253-4320.2014.03.016 ZHANG Benbin, LIU Yunquan, YE Yueyuan. Progress in preparation of activated carbon and its activation mechanism[J]. Modern Chemical Industry,2014,34(3):34-39(in Chinese). doi: 10.16606/j.cnki.issn0253-4320.2014.03.016
[35]	DING L L, ZOU B, LI Y N, et al. The production of hydrochar-based hierarchical porous carbons for use as electrochemical supercapacitor electrode materials[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects,2013,423:104-111. doi: 10.1016/j.colsurfa.2013.02.003
[36]	BARBIERI O, HAHN M, HERZOG A, et al. Capacitance limits of high surface area activated carbons for double layer capacitors[J]. Carbon,2005,43(6):1303-1310. doi: 10.1016/j.carbon.2005.01.001
[37]	WANG D W, LI F, LIU M, et al. Mesopore-aspect-ratio dependence of ion transport in rodtype ordered mesoporous carbon[J]. Journal of Physical Chemistry C,2008,112(26):9950-9955. doi: 10.1021/jp800173z
[38]	WANG Q, YAN J, FAN Z J. Carbon materials for high volumetric performance supercapacitors: Design, progress, challenges and opportunities[J]. Energy & Environmental Science,2016,9(3):729-762. doi: 10.1039/c5ee03109e
[39]	YOON S B, CHAI G S, KANG S K, et al. Graphitized pitch-based carbons with ordered nanopores synthesized by using colloidal crystals as templates[J]. Journal of the American Chemical Society,2005,127(12):4188-4189. doi: 10.1021/ja0423466
[40]	KRIVORUCHKO O P, MAKSIMOVA N I, ZAIKOVSKII V I, et al. Study of multiwalled graphite nanotubes and filaments formation from carbonized products of polyvinyl alcohol via catalytic graphitization at 600-800℃ in nitrogen atmosphere[J]. Carbon,2000,38(7):1075-1082. doi: 10.1016/S0008-6223(99)00225-0
[41]	WAN C C, JIAO Y, LI J. Core-shell composite of wood-derived biochar supported MnO₂ nanosheets for supercapacitor applications[J]. RSC Advances,2016,6(69):64811-64817. doi: 10.1039/C6RA12043A
[42]	傅寒立. 虾壳源生物质炭及其MnO₂复合材料的制备与超级电容特性[D]. 杭州: 浙江工业大学, 2020. FU Hanli. Preparation and supercapacitor propreties of shrimp shell-derived carbons and their MnO₂ composites[D]. Hangzhou: Zhejiang University of Technology, 2020(in Chinese).
[43]	BROUSSE T, BÉLANGER D, LONG J W, et al. To be or not to be pseudocapacitive?[J]. Journal of the Electrochemical Society,2015,162:A5185. doi: 10.1149/2.0201505jes
[44]	JIN Y, CHEN H Y, CHEN M H, et al. Graphene-patched CNT/MnO₂ nanocomposite papers for the electrode of high-performance flexible asymmetric supercapacitors[J]. ACS Applied Materials & Interfaces,2013,5(8):3408-3416. doi: 10.1021/am400457x
[45]	LI X S, XU M M, YANG Y, et al. MnO₂@corncob carbon composite electrode and all-solid-state supercapacitor with improved electrochemical performance[J]. Materials,2019,12(15):2379. doi: 10.3390/ma12152379
[46]	CHENG Z Y, TAN G P, QIU Y F, et al. High performance electrochemical capacitors based on MnO₂/activated-carbon-paper[J]. Journal of Materials Chemistry C,2015,3(24):6166-6171. doi: 10.1039/C5TC00645G
[47]	YUAN X M, ZHANG Y, YAN Y S, et al. Tunable synthesis of biomass-based hierarchical porous carbon scaffold@MnO₂ nanohybrids for asymmetric supercapacitor[J]. Chemical Engineering Journal,2020,393:121214. doi: 10.1016/j.cej.2019.03.090
[48]	ZHANG P, LI K X, LIU X H. Carnation-like MnO₂ modified activated carbon air cathode improve power generation in microbial fuel cells[J]. Journal of Power Sources,2014,264:248-253. doi: 10.1016/j.jpowsour.2014.04.098
[49]	FUERTES A B, LOTA G, CENTENO T A, et al. Templated mesoporous carbons for supercapacitor application[J]. Electrochimica Acta,2005,50(14):2799-2805. doi: 10.1016/j.electacta.2004.11.027
[50]	SETARO A. Advanced carbon nanotubes functionalization[J]. Journal of Physics-condensed Matter,2017,29(42):423003. doi: 10.1088/1361-648X/aa8248
[51]	YU J, LI M L, WANG X D, et al. Promising high-performance supercapacitor electrode materials from MnO₂ nanosheets@bamboo leaf carbon[J]. ACS Omega,2020,5(26):16299-16306. doi: 10.1021/acsomega.0c02169
[52]	WANG X, CHU J, YAN H J, et al. Synthesis and characterization of MnO₂/eggplant carbon composite for enhanced supercapacitors[J]. Heliyon, 2022, 8(9): e10631.