导电聚合物、过渡金属氧化物、碳材料是新型的超级电容器电极材料,超级电容器的性能与电极材料、电解液及其使用的隔膜有关,而电极材料是其中最主要的影响因素,因为它是超级电容器的重要依托,电极材料性能的好坏直接影响到电容器性能的好坏。故合理构建电极材料结构一直是储能领域的研究热点。采用典型的水热法制备了一种珊瑚状NiCo2O4,在冰水浴条件下通过化学氧化法制备聚苯胺(PANI),并通过原味聚合法合成了PANI包覆的NiCo2O4(PANI@NiCo2O4)复合材料,有效地解决了过渡金属氧化物的导电率差、比表面积低、活性物质易团聚等问题。并对PANI@NiCo2O4纳米复合材料结构和形貌进行表征,将其用作超级电容器的电极材料,在三电极体系下测试电化学性能。结果表明:NiCo2O4@PANI在1A/g的电流密度时比电容为892F/g,相比纯PANI比电容提升207.8%,相比NiCo2O4材料比电容提升75.9%。在10A/g电流密度下4000次充放电循环后比电容保持率为95%,具有良好的循环稳定性。因此,PANI@NiCo2O4是很有前途的超级电容器电极材料。
Conductive polymers,transition metal oxides and carbon materials are new supercapacitor electrode materials.The performance of supercapacitor is related to the electrode materials,electrolyte and its used diaphragm,and the electrode materials are the main influencing factor,because they are the important components supporting the supercapacitor,and the performance of electrode materials directly affects the performance of capacitor.Therefore,the reasonable construction of electrode material structure has been a hot research topic in the field of energy storage.A coral-like NiCo2O4 was prepared by a typical hydrothermal method,and polyaniline (PANI) was prepared by chemical oxidation under ice-water bath conditions,and then PANI-coated NiCo2O4 (PANI@NiCo2O4) composites were synthesized by the in-situ polymerization method,which effectively solved the problems of poor electrical conductivity,low specific surface area and easy agglomeration of active substances of transition metal oxides.The structure and morphology of PANI@NiCo2O4 nanocomposite were also characterized,and it was used as an electrode material for supercapacitors.The electrochemical properties were tested in a three-electrode system.The results showed that the specific capacitance of NiCo2O4@PANI was 892F/g at a current density of 1A/g,which was 207.8% higher than that of pure PANI and 75.9% higher than that of NiCo2O4 material.The retention rate of specific capacitance was 95% after 4000 charge/discharge cycles at 10A/g current density,which had good cycling stability.The results indicated that PANI@NiCo2O4 composites were promising electrode materials for supercapacitors.
[1] Wang G,Zhang L,Zhang J.A review of electrode materials for electrochemical supercapacitors[J].Chemical Society Reviews,2012,41(2):797-828.
[2] Scibioh M A,Viswanathan B.Materials for supercapacitor applications[M].Amsterdam:Elsevier,2020:1-13.
[3] Li Kunshan,Lu Xinyu,Zhang You,et al.Bi3TaO7/Ti3C2 heterojunctions for enhanced photocatalytic removal of water-borne contaminants-ScienceDirect[J].Environmental Research,2020,185:109409.
[4] Kim E,Kim S,Choi Y M,et al.Ultrathin hematite on mesoporous WO3 from atomic layer deposition for minimal charge recombination[J].ACS Sustainable Chemistry & Engineering,2020,8(30):11358-11367.
[5] González A,Goikolea E,Barrena J A,et al.Review on supercapacitors:technologies and materials[J].Renewable and Sustainable Energy Reviews,2016,58:1189-1206.
[6] Najib S,Erdem E.Current progress achieved in novel materials for supercapacitor electrodes:mini review[J].Nanoscale Advances,2019,1(8):2817-2827.
[7] Xin L,Wei B.Supercapacitors based on nanostructured carbon[J].Nano Energy,2012,2(2):159-173.
[8] Huang Y,Yang H,Xiong T,et al.Adsorption energy engineering of nickel oxide hybrid nanosheets for high areal capacity flexible lithium-ion batteries[J].Energy Storage Materials,2019,25:41-51.
[9] Xiong T,Su H,Yang F,et al.Harmonizing self-supportive VN/MoS2 pseudocapacitance core-shell electrodes for boosting the areal capacity of lithium storage[J].Materials Today Energy,2020,17:100461.
[10] Dai J,Fu K,Palanisamy R,et al.A solid state energy storage device with supercapacitor-battery hybrid design[J].Journal of Materials Chemistry A,2017,5(29):15266-15272.
[11] Dubal D P,Ayyad O,Ruiz V,et al.Hybrid energy storage:the merging of battery and supercapacitor chemistries[J].Chemical Society Reviews,2015,44(7):1777-1790.
[12] Béguin François,Presser Volker,Balducci Andrea,et al.Carbons and electrolytes for advanced supercapacitors[J].Advanced Materials,2014,26(14):2219-2251.
[13] Chouduary N,Li C,Moore J,et al.Asymmetric supercapacitor electrodes and devices[J].Advanced Materials,2017,29(21):1605336-1-1605336-30.
[14] Borenstein A,Hanna O,Ran A,et al.Carbon-based composite materials for supercapacitor electrodes:a review[J].Journal of Materials Chemistry A,2017,5(25):12653-12672.
[15] Sun L,Shi Y,He Z,et al.Synthesis and characterization of SnO2/polyaniline nanocomposites by sol-gel technique and microemulsion polymerization[J].Synthetic Metals,2012,162(24):2183-2187.
[16] 宁轲,刘含笑.基于MIL-88电极材料的锌离子电容器储能性能研究[J].赤峰学院学报(自然科学版),2023,39(9):35-38.
[17] Lu Y,Deng B L,Liu Y B,et al.Nanostructured Co3O4for achieving high-performance supercapacitor[J].MaterialsLetters,2021,285:129101-129110.
[18] Zhang Z F,Su X R,Zhu Y Y,et al.Porous multishelled NiO hollow microspheres encapsulated within three-dimensional graphene as flexible free-standing electrodes for high-performance supercapacitors[J].Nanoscale,2019,11(34):16071-16079.
[19] Zhang Z F,Su X R,Zhu Y Y,et al.Polypyrrole encapsulation-protected porous multishelled Co3O4 hollow microspheres for advanced all-solid-state asymmetric supercapacitors with boosted reaction kinetics and stability[J].Nano-Technology,2020,31(25):255403-255412.
[20] Huang M,Li F,Ji J Y,et al.Facile synthesis of singlecrystalline NiO nanosheet arrays on Ni foam for high-performance supercapacitors[J].CrystEngComm,2014,16(14):2878-2884.
[21] 郭容男,李太文,王栋,等.超级电容器用MOFs衍生纳米电极材料的研究进展[J].人工晶体学报,2023,52(11):1922-1930.
[22] 吴怡芳,崇少坤,柳永宁,等.碳纳米材料构建高性能锂离子和锂硫电池研究进展[J].材料工程,2020,48(4):25-35.
[23] 董瑞婷.泡沫镍基底表面氢氧化镍电极材料的原位生长及其电化学性能测试[J].河南科技,2023,42(18):66-69.
[24] Xin Y X,Wang Z Y,Jiang Y Y,et al.Effect of carriers on deposition morphologies and catalytic performances of NiCo2O4[J].Ceramics International,2020,46(8):11499-11507.
[25] Wang Y,Hu X,Li W,et al.Preparation of boron nitrogen co-doped carbon quantum dots for rapid detection of Cr(Ⅵ)[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2020,243:118807.
[26] Wang Yong,Zhuang Qianfen,Ni Yongnian,et al.Facile microwave-assisted solid-phase synthesis of highly fluorescent nitrogen-sulfur-codoped carbon quantum dots for cellular imaging applications[J].Chemistry A European Journal,2015,21(37):13004-13011.
[27] Sahu S,Behera B,Maiti T K,et al.Simple one-step synthesis of highly luminescent carbon dots from orange juice:application as excellent bio-imaging agents[J].Chemical Communications,2012,48(70):8835-8837.
[28] Mehta V N,Jha S,Kailasa S K.One-pot green synthesis of carbon dots by using Saccharum officinarum juice for fluorescent imaging of bacteria (Escherichia coli) and yeast (Saccharomyces cerevisiae) cells[J].Materials Science & Engineering C,2014,38(9):20-27.
[29] Zhang Z,Hao J,Zhang J,et al.Protein as the source for synthesizing fluorescent carbon dots by a one-pot hydrothermal route[J].RSC Advances,2012,2(23):8599-8601.
[30] Tang Q,Zhu W,He B,et al.Rapid conversion from carbohydrates to large-scale carbon quantum dots for all-weather solar cells[J].ACS Nano,2017,11(2):1540-1547.
[31] Fan G,Wang H,Xiang X,et al.Co-Al mixed metal oxides/carbon nanotubes nanocomposite prepared via a precursor route and enhanced catalytic property[J].Journal of Solid State Chemistry,2013,197:14-22.
[32] Wang Y,Yang W,Yang J.A Co-Al layered double hydroxides nanosheets thin-film electrode:fabrication and electrochemical study[J].Electrochemical and Solid State Letters,2007,10(10):A233.
[33] Ansaldo A,Bondavalli P,Bellani S,et al.High-power graphene-carbon nanotube hybrid supercapacitors[J].ChemNanoMat,2017,DOI:10.1002/cnma.201700093.
[34] 覃奇贤,刘淑兰.电极的极化和极化曲线(Ⅰ)——电极的极化[J].电镀与精饰,2008,30(6):28-30.
[35] Hosseini Mir Ghasem,Shahryari Elham.Synthesis,characterization and electrochemical study of graphene oxide-multi walled carbon nanotube-manganese oxide-polyaniline electrode as supercapacitor[J].Journal of Materials Science & Technology,2016(8):763-773.
[36] 王文聪.层状双金属氢氧化物超级电容器电极材料的制备和电化学性能研究[D].杭州:浙江大学,2019.
[37] Ajami N.PANOA/MnO2/MWCNT nanocomposite:synthesis,characterization,and electrochemical performance as efficient electrode materials for supercapacitors[J].Journal of Macromolecular Science:Pure & Applied Chemistry,2020,57(1):1-8.
[38] Chen S,Zhao L,Wei W,et al.A novel strategy to synthesize NiCo layered double hydroxide nanotube from metal organic framework composite for high-performance supercapacitor[J].Journal of Alloys and Compounds,2020,831:154794.
基金资助
浙江工业大学平湖新材料研究院科研团队项目(平村院发[2021]23号);南京市江宁区科技局创新基金资助项目(2021JSCX00449)
PDF
