对苯二酚增强纤维素/石墨烯电极的制备
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摘要
目的以纳米纤维素气凝胶为骨架,对苯二酚为增强相,并加入还原氧化石墨烯,制备纳米纤维素/还原氧化石墨烯复合电极薄膜,将其应用于超级电容器。方法采用超声处理制备纳米纤维素/氧化石墨烯混合溶液;在高温高压的环境下,加入对苯二酚,采用水热合成法和冷冻干燥法制备纳米纤维素/还原氧化石墨烯气凝胶,并最终制成电极膜。结果在纳米纤维素/还原氧化石墨烯复合气凝胶中,石墨烯可将纳米纤维素均匀包裹,形成三维多孔网络结构;纳米纤维素/还原氧化石墨烯复合电极具有良好的电化学性能,在1mol/L的H_2SO_4溶液中,当电流扫描速率为1mA/cm~2时,超级电容器比面积电容高达1.621 F/cm~2,且在2000次循环测试后,电容保留率为88.3%。结论以纳米纤维素为基体制备的纳米纤维素/还原氧化石墨复合电极具有良好的电化学性能,可以用作超级电容器电极。
The work aims to prepare the cellulose nanofibers/reduced graphene oxide(CNFs/RGO) composite electrode film with CNFs aerogel as the skeleton, hydroquinone as the reinforcing phase and added with reduced graphene oxide, and to apply the film to the supercapacitor. CNFs/RGO solution was prepared by ultrasonic treatment. CNFs/RGO aerogel was prepared by hydrothermal synthesis and freeze-drying with hydroquinone added at high temperature and pressure, and the electrode film was finally made. In the CNFs/RGO composite aerogel, the graphene could evenly wrap the CNFs to form a three-dimensional porous network structure. The CNFs/RGO composite electrode had excellent electrochemical performance. In 1 mol/L H_2 SO_4 solution, when the current scan rate was 1 mA/cm~2, the specific area capacitance of the supercapacitor was as high as 1.621 F/cm~2, and the capacitance retention rate was 88.3% after 2,000 cycles of testing. The CNFs/RGO composite electrode prepared with cellulose nanofibers as the substrate has excellent electrochemical performance and can be used as the supercapacitor electrode.
The work aims to prepare the cellulose nanofibers/reduced graphene oxide(CNFs/RGO) composite electrode film with CNFs aerogel as the skeleton, hydroquinone as the reinforcing phase and added with reduced graphene oxide, and to apply the film to the supercapacitor. CNFs/RGO solution was prepared by ultrasonic treatment. CNFs/RGO aerogel was prepared by hydrothermal synthesis and freeze-drying with hydroquinone added at high temperature and pressure, and the electrode film was finally made. In the CNFs/RGO composite aerogel, the graphene could evenly wrap the CNFs to form a three-dimensional porous network structure. The CNFs/RGO composite electrode had excellent electrochemical performance. In 1 mol/L H_2 SO_4 solution, when the current scan rate was 1 mA/cm~2, the specific area capacitance of the supercapacitor was as high as 1.621 F/cm~2, and the capacitance retention rate was 88.3% after 2,000 cycles of testing. The CNFs/RGO composite electrode prepared with cellulose nanofibers as the substrate has excellent electrochemical performance and can be used as the supercapacitor electrode.
引文
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[2]XIE X,ZHANG C,YANG Q.The Development of Electrode Materials for Supercapacitors[J].Chemical Industry and Engineering,2014,31(1):63-71.
[3]PETER J H,MOJTABA M S,ISOBEL F,et al.Energy Storage in Electrochemical Capacitors:Designing Functional Materials to Improve Performance[J].Energy&Environmetal Science,2010,3:1238-1251.
[4]WENG Z,SU Y,WANG D W,et al.Graphenecellulose Paper Flexible Supercapacitors[J].Advanced Energy Materials,2011,5:917-922.
[5]SHAO Y L,MAHER F.Mousaviae and Richard B.Kaner.Graphene-based Materials for Flexible Supercapacitors[J].Chemical Society Reviews,2015,44:3639-3665.
[6]SI W,WU X Z,ZHOU J,et al.Reduced Graphene Oxide Aerogel with High-rate Supercapacitive Performance in Aqueous Electrolytes[J].Nano Express2013,8:247-254.
[7]STOLLER MD,PARK S,ZHU Y,et al.Graphene-based Ultracapacitors[J].Nano Letters,2008,8(10):3498-502.
[8]VIVEKCHAND S R C,ROUT C SSUBRAHMANYAM KS,et al.Graphene-based Electrochemical Supercapacitor[J].Journal of Chemical Science,2008,120(1):9-13.
[9]XU Z Y,ZHOU H.Facile Synthesis of Reduced Graphene Oxide/Trimethyl Chlorosilane-coated Cellulose Nanofibres Aerogel for Oil Absorption[J].IET Nanotechnology,2017,8(11):929-934.
[10]WU Z Y,LI C,LIANG H W,et al.Ultralight,Flexible,and Fire-resistant Carbon Nanofiber Aerogels from Bacterial Cellulose[J].Angewandte Chemie International Edition,2013,52(10):2925-2929.
[11]祝晓,魏晓奕,李积华,等.纳米纤维素的应用研究进展[J].化工新型材料,2015,43(2):212-217.ZHU Xiao,WEI Xiao-yi,LI Ji-hua,et al.Research on Application of Nano-crystalline Cellulose[J].New Chemical Materials,2015,43(2):212-217.
[12]CHEN W S,YU H P,LIU Y X.Preparation of Millimeter-long Cellulose Nanofibers with Diameters of30-80 nm from Bamboo Fibers[J].Carbohydrate Polymers,2011,86:453-461.
[13]WILLIAM S,HUMMERS J R.Richard Preparation of Graphitic Oxide[J].Chemical Society,1958,80(6):1339.
[14]梁敏,王羽,宋树鑫,等.生物可降解高分子材料在食品包装中的应用[J].塑料工业,2015,43(10):1-5.LIANG Min,WANG Yu,SONG Shu-xin,et al.Application of Biodegradable Maerials in Food Packaging[J].China Plastics Industry,2015,43(10):1-5.
[15]罗福生,邵庆益,周宝艳,等.硼磷掺杂小直径单壁碳纳米管的第一性原理研究[J].原子与分子物理学报,2014,31(1):117-121.LUO Fu-sheng,SHAO Qing-yi,ZHOU Bao-yan,et al.First-principles Study on the Boron-phosphorus Doping Small Diameter Carbon Nanotubes[J].Journal of Atomic and Molecular Physics,2014,31(1):117-121
[16]WANG Z,TAMMELA P,STROMME M,et al.Cellulose-based Supercapacitors:Material and Performance Considerations[J].Advanced Energy Materials2017,7(18):30.
[17]钱少平.竹纳米纤维素晶须增强聚乳酸复合材料界面结合及强化机理研究[D].杭州:浙江大学,2016.QIAN Shao-ping.Toughen Mechanism and Interphase Interaction of Bamboo Cellulose Nanowisker Reinforced Poly(Lacti Acid)Composites[D].Hangzhou:Zhejiang University,2016.
[18]PATIL D S,PAWAR S A,HWANG J,et al.Silver Incorporated PEDOT:PSS for Enhanced Electrochemical Performance[J].Journal of Industrial and Engineering Chemistry,2016,42:113-120.
[19]PARK M S,KANG Y M,WANG G X,et al.The Effect of Morphological Modification on the Electrochemical Properties of SnO2 Nanomaterials[J].Advanced Functional Materials,2008,18:455-461.
[20]HABIBI Y,LUCIA L A,ROJAS,O J.Cellulose Nanocrystals:Chemistry,Self-assembly,and Applications[J].Chemical Reviews,2010,6(6):3479-3500.
[21]DU A,ZHOU B,ZHANG Z H,et al.A Special Material or a New State of Matter:a Review and Reconsideration of the Aerogel[J].Materials,2013,6(3):941-968.
[22]ROMAN M,WILLIAM W T.Effect of Sulfate Groups from Sulfuric Acid Hydrolysis on the Thermal Degradation Behavior of Bacterial Cellulose[J].Biomacromolecules,2004,5(5):1671-1677.