类松果状NiMoO_4/MnO_2复合材料的合成及超级电容性能
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摘要
以Na_2MoO_4·2H_2O、Ni SO_4·6H_2O和MnO_2为原料,采用水热法成功制备了类松果状NiMoO_4/MnO_2复合材料.通过X射线衍射、扫描电子显微镜、恒电流充放电、循环伏安和交流阻抗对材料进行表征.结果表明,MnO_2的最佳质量分数为10%,所得NiMoO_4/MnO_2复合材料具有类松果状形貌,其颗粒直径为200～600 nm,且表面粗糙、多孔;在1 A·g~(-1)的电流密度下,MnO_2质量分数为0、5%、10%、15%、20%时,所得复合材料NM0、NM5、NM10、NM15和NM20的放电比电容分别为260、248、650、420和305 F·g~(-1).在电流密度为10 A·g~(-1)下,最佳样品NM10复合材料的首次放电比容量为102 F·g~(-1),经过100次循环后,其放电比电容稳定在147 F·g~(-1).该性能的提高,主要是由于MnO_2的引入弥补了NiMoO_4单一材料存在的不足,从而达到协同增效的作用.
Supercapacitors,also called electrochemical capacitors or ultracapacitors,have attracted increasing attention owing to their high specific capacitance,high power density,long lifecycle,fast charge-discharge ability,wide working temperature range,and environmental friendliness for mobile electronics,power grids,and hybrid electric vehicles. The electrode is the most important part of supercapacitors; therefore,the electrode material is the chief factor that determines the properties of supercapacitors. To enhance the performance of a supercapacitor,particularly its specific energy while retaining its intrinsic high specific power,several researchers have focused mainly on improving the properties of electrode materials. The major classes of materials applied for supercapacitors include various forms of carbon,transition metal oxides,and conductive polymers. Compared to the carbon materials and conducting polymer materials,transition metal oxides can achieve a much higher specific capacitance because of their high theoretical capacitance,well-defined electrochemical redox activity,low cost,and abundant resources. In particular,binary metal oxides,such as NiMoO_4,MnMoO_4,and Co MoO_4,have been extensively studied as pseudocapacitor electrode materials because of their good electronic conductivity and rich redox reactions. In this study,pinecone-like NiMoO_4/MnO_2 composite materials were successfully synthesized using a facile hydrothermal method. Na_2 MoO_4·2 H_2O,Ni SO_4·6 H_2O,and MnO_2 were used as raw materials. The as-products were characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge-discharge,cyclic voltammetry(CV),and electrochemical impedance spectroscopy(EIS). The results show that when the optimal content of MnO_2 reaches 10%,the obtained NiMoO_4/MnO_2 composite materials exhibits a pinecone-like porous morphology,with the particle size ranging from 200 to600 nm. The results show that NiMoO_4/MnO_2 composite materials have excellent electrochemical properties. The discharge specific capacitance of NM0,NM5,NM10,NM15,and NM20 composites with corresponding MnO_2 contents of 0%,5%,10%,15%,and20% are 260,248,650,420,and 305 F·g-1,respectively,at a current density of 1 A·g-1. When the current density is up to 10 A·g-1,the initial discharge specific capacitance is 102 F·g-1. After 100-week cycles,the discharge specific capacitance of the NM10 sample is still 147 F·g-1. The improvements can be mainly attributed to the introduction of MnO_2 in the NiMoO_4/MnO_2 composite materials to overcome the shortcomings of single NiMoO_4.
Supercapacitors,also called electrochemical capacitors or ultracapacitors,have attracted increasing attention owing to their high specific capacitance,high power density,long lifecycle,fast charge-discharge ability,wide working temperature range,and environmental friendliness for mobile electronics,power grids,and hybrid electric vehicles. The electrode is the most important part of supercapacitors; therefore,the electrode material is the chief factor that determines the properties of supercapacitors. To enhance the performance of a supercapacitor,particularly its specific energy while retaining its intrinsic high specific power,several researchers have focused mainly on improving the properties of electrode materials. The major classes of materials applied for supercapacitors include various forms of carbon,transition metal oxides,and conductive polymers. Compared to the carbon materials and conducting polymer materials,transition metal oxides can achieve a much higher specific capacitance because of their high theoretical capacitance,well-defined electrochemical redox activity,low cost,and abundant resources. In particular,binary metal oxides,such as NiMoO_4,MnMoO_4,and Co MoO_4,have been extensively studied as pseudocapacitor electrode materials because of their good electronic conductivity and rich redox reactions. In this study,pinecone-like NiMoO_4/MnO_2 composite materials were successfully synthesized using a facile hydrothermal method. Na_2 MoO_4·2 H_2O,Ni SO_4·6 H_2O,and MnO_2 were used as raw materials. The as-products were characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge-discharge,cyclic voltammetry(CV),and electrochemical impedance spectroscopy(EIS). The results show that when the optimal content of MnO_2 reaches 10%,the obtained NiMoO_4/MnO_2 composite materials exhibits a pinecone-like porous morphology,with the particle size ranging from 200 to600 nm. The results show that NiMoO_4/MnO_2 composite materials have excellent electrochemical properties. The discharge specific capacitance of NM0,NM5,NM10,NM15,and NM20 composites with corresponding MnO_2 contents of 0%,5%,10%,15%,and20% are 260,248,650,420,and 305 F·g-1,respectively,at a current density of 1 A·g-1. When the current density is up to 10 A·g-1,the initial discharge specific capacitance is 102 F·g-1. After 100-week cycles,the discharge specific capacitance of the NM10 sample is still 147 F·g-1. The improvements can be mainly attributed to the introduction of MnO_2 in the NiMoO_4/MnO_2 composite materials to overcome the shortcomings of single NiMoO_4.
引文
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[6] Lee G H,Lee S,Kim J C,et al. MnMoO4electrocatalysts for superior long-life and high-rate lithium-oxygen batteries. Adv Energy Mater,2017,7(6):1601741
[7] Deng T. Investigations of Co-based Electrode Materials for Supercapacitors and the Atomic-Level Energy Storage Mechanism[Dissertation]. Changchun:Jilin University,2017(邓霆.超级电容器钴基电极材料制备及其储能机理的研究[学位论文].长春:吉林大学,2017)
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[9] LüJ L,Miura H,Yang M. A novel mesoporous Ni Mo O4@r GO nanostructure for supercapacitor applications. Mater Lett,2017,194:94
[10] Zhou D,Cheng P P,Luo J X,et al. Facile synthesis of graphene@Ni Mo O4nanosheet arrays on Ni foam for a high-performance asymmetric supercapacitor. J Mater Sci,2017,52(24):13909
[11] Zhang Z,Liu Y D,Huang Z Y,et al. Facile hydrothermal synthesis of Ni Mo O4@CoMoO4hierarchical nanospheres for supercapacitor applications. Phys Chem Chem Phys,2015,17(32):20795
[12] Cao M L,Bu Y,LüX W,et al. Three-dimensional Ti O2nanowire@Ni Mo O4ultrathin nanosheet core-shell arrays for lithium ion batteries. Appl Surf Sci,2018,435:641
[13] Chen H,Yu L,Zhang J M,et al. Construction of hierarchical Ni Mo O4@MnO2nanosheet arrays on titanium mesh for supercapacitor electrodes. Ceram Int,2016,42(16):18058
[14] Zhao X,Wang H E,Chen X X,et al. Tubular Mo O2organized by 2D assemblies for fast and durable alkali-ion storage. Energy Storage Mater,2018,11:161
[15] Li Y F,Jian J M,Fan Y,et al. Facile one-pot synthesis of a NiMo O4/reduced graphene oxide composite as a pseudocapacitor with superior performance. RSC Adv,2016,6(73):69627
[16] Gao H L,Wang L Z,Zhang Y,et al. Synthesis and electrochemical performances of Li2Fe SiO4/C composite materials. J Chin Ceramic Soc,2014,42(4):528(高海丽,王力臻,张勇,等. Li2Fe SiO4/C复合材料的制备及电化学性能.硅酸盐学报,2014,42(4):528)
[17] Wang X X,Zhang B Q,Yu M X,et al. Enhanced microwave absorption capacity of hierarchical structural MnO2@Ni Mo O4composites. RSC Adv,2016,6(43):36484
[18] Cai D P,Wang D D,Liu B,et al. Three-dimensional Co3O4@Ni Mo O4core/shell nanowire arrays on Ni foam for electrochemical energy storage. ACS Appl Mater Interfaces,2014,6(7):5050
[19] Pang M J,Jiang S,Ji Y,et al. Comparison ofα-Ni Mo O4nanorods and hierarchicalα-Ni Mo O4@δ-MnO2core-shell hybrid nanorod/nanosheet aligned on Ni foam for supercapacitors. J Alloys Compd,2017,708:14
[20] Ma X J,Zhang W B,Kong L B,et al. Ni Mo O4-modified MnO2hybrid nanostructures on nickel foam:electrochemical performance and supercapacitor applications. New J Chem,2015,39(8):6207
[21] Sun W. The Preparation of Nanometer Nickel(Cobalt)Hydroxide Electrode Materials and Their Electrchemical Properties[Dissertation]. Harbin:Harbin Engineering University,2012(孙薇.纳米氢氧化镍(钴)电极材料的制备及其电化学性能研究[学位论文].哈尔滨:哈尔滨工程大学,2012)
[22] Wang X H,Xia H Y,Gao J,et al. Enhanced cycle performance of ultraflexible asymmetric supercapacitors based on a hierarchical MnO2@Ni Mo O4core-shell nanostructure and porous carbon. J Mater Chem A,2016,4(46):18181
[23] Kazemi S H,Bahmani F,Kazemi H,et al. Binder-free electrodes of Ni Mo O4/graphene oxide nanosheets:synthesis,characterization and supercapacitive behavior. RSC Adv, 2016, 6(112):111170
[24] Lin J H,Liang H Y,Jia H N,et al. Hierarchical CuCo2O4@Ni Mo O4core-shell hybrid arrays as a battery-like electrode for supercapacitors. Inorg Chem Front,2017,4(9):1575
[2] Zhao X,Qiu P D,Jiang H J,et al. Latest research progress of electrode materials for supercapacitor. Electr Comp Mater,2015,34(1):1(赵雪,邱平达,姜海静,等.超级电容器电极材料研究最新进展.电子元件与材料,2015,34(1):1)
[3] Oudghiri-Hassani H,Al Wadaani F. Preparation,characterization and catalytic activity of nickel molybdate(Ni Mo O4)nanoparticles. Molecules,2018,23(2):273.
[4] Fang L X,Wang F,Zhai T L,et al. Hierarchical CoMoO4nanoneedle electrodes for advanced supercapacitors and electrocatalytic oxygen evolution. Electrochim Acta,2018,259:552
[5] Li M G,Yang W W,Huang Y R,et al. Hierarchical mesoporous Co3O4@ZnCo2O4hybrid nanowire arrays supported on Ni foam for high-performance asymmetric supercapacitors. Sci China Mater,2018,61(9):1167
[6] Lee G H,Lee S,Kim J C,et al. MnMoO4electrocatalysts for superior long-life and high-rate lithium-oxygen batteries. Adv Energy Mater,2017,7(6):1601741
[7] Deng T. Investigations of Co-based Electrode Materials for Supercapacitors and the Atomic-Level Energy Storage Mechanism[Dissertation]. Changchun:Jilin University,2017(邓霆.超级电容器钴基电极材料制备及其储能机理的研究[学位论文].长春:吉林大学,2017)
[8] Zhang Y,Feng H,Wu X B,et al. Progress of electrochemical capacitor electrode materials:a review. Int J Hydrogen Energy,2009,34(11):4889
[9] LüJ L,Miura H,Yang M. A novel mesoporous Ni Mo O4@r GO nanostructure for supercapacitor applications. Mater Lett,2017,194:94
[10] Zhou D,Cheng P P,Luo J X,et al. Facile synthesis of graphene@Ni Mo O4nanosheet arrays on Ni foam for a high-performance asymmetric supercapacitor. J Mater Sci,2017,52(24):13909
[11] Zhang Z,Liu Y D,Huang Z Y,et al. Facile hydrothermal synthesis of Ni Mo O4@CoMoO4hierarchical nanospheres for supercapacitor applications. Phys Chem Chem Phys,2015,17(32):20795
[12] Cao M L,Bu Y,LüX W,et al. Three-dimensional Ti O2nanowire@Ni Mo O4ultrathin nanosheet core-shell arrays for lithium ion batteries. Appl Surf Sci,2018,435:641
[13] Chen H,Yu L,Zhang J M,et al. Construction of hierarchical Ni Mo O4@MnO2nanosheet arrays on titanium mesh for supercapacitor electrodes. Ceram Int,2016,42(16):18058
[14] Zhao X,Wang H E,Chen X X,et al. Tubular Mo O2organized by 2D assemblies for fast and durable alkali-ion storage. Energy Storage Mater,2018,11:161
[15] Li Y F,Jian J M,Fan Y,et al. Facile one-pot synthesis of a NiMo O4/reduced graphene oxide composite as a pseudocapacitor with superior performance. RSC Adv,2016,6(73):69627
[16] Gao H L,Wang L Z,Zhang Y,et al. Synthesis and electrochemical performances of Li2Fe SiO4/C composite materials. J Chin Ceramic Soc,2014,42(4):528(高海丽,王力臻,张勇,等. Li2Fe SiO4/C复合材料的制备及电化学性能.硅酸盐学报,2014,42(4):528)
[17] Wang X X,Zhang B Q,Yu M X,et al. Enhanced microwave absorption capacity of hierarchical structural MnO2@Ni Mo O4composites. RSC Adv,2016,6(43):36484
[18] Cai D P,Wang D D,Liu B,et al. Three-dimensional Co3O4@Ni Mo O4core/shell nanowire arrays on Ni foam for electrochemical energy storage. ACS Appl Mater Interfaces,2014,6(7):5050
[19] Pang M J,Jiang S,Ji Y,et al. Comparison ofα-Ni Mo O4nanorods and hierarchicalα-Ni Mo O4@δ-MnO2core-shell hybrid nanorod/nanosheet aligned on Ni foam for supercapacitors. J Alloys Compd,2017,708:14
[20] Ma X J,Zhang W B,Kong L B,et al. Ni Mo O4-modified MnO2hybrid nanostructures on nickel foam:electrochemical performance and supercapacitor applications. New J Chem,2015,39(8):6207
[21] Sun W. The Preparation of Nanometer Nickel(Cobalt)Hydroxide Electrode Materials and Their Electrchemical Properties[Dissertation]. Harbin:Harbin Engineering University,2012(孙薇.纳米氢氧化镍(钴)电极材料的制备及其电化学性能研究[学位论文].哈尔滨:哈尔滨工程大学,2012)
[22] Wang X H,Xia H Y,Gao J,et al. Enhanced cycle performance of ultraflexible asymmetric supercapacitors based on a hierarchical MnO2@Ni Mo O4core-shell nanostructure and porous carbon. J Mater Chem A,2016,4(46):18181
[23] Kazemi S H,Bahmani F,Kazemi H,et al. Binder-free electrodes of Ni Mo O4/graphene oxide nanosheets:synthesis,characterization and supercapacitive behavior. RSC Adv, 2016, 6(112):111170
[24] Lin J H,Liang H Y,Jia H N,et al. Hierarchical CuCo2O4@Ni Mo O4core-shell hybrid arrays as a battery-like electrode for supercapacitors. Inorg Chem Front,2017,4(9):1575