WO2022094871A1 - Composite electrode material for super capacitor, manufacturing method therefor, and super capacitor - Google Patents

Composite electrode material for super capacitor, manufacturing method therefor, and super capacitor Download PDF

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WO2022094871A1
WO2022094871A1 PCT/CN2020/126778 CN2020126778W WO2022094871A1 WO 2022094871 A1 WO2022094871 A1 WO 2022094871A1 CN 2020126778 W CN2020126778 W CN 2020126778W WO 2022094871 A1 WO2022094871 A1 WO 2022094871A1
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preparation
nio
nickel
electrode material
aqueous solution
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PCT/CN2020/126778
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French (fr)
Chinese (zh)
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李高仁
吴金齐
古林非
谢灵杰
李成飞
赵佳伟
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中山大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention belongs to the field of supercapacitor electrode materials, relates to a composite electrode material for supercapacitors, a preparation method thereof, and a supercapacitor, in particular to a Co3O4 / NiO nanosheet array composite material, a preparation method thereof, and a supercapacitor . Application in supercapacitor electrode materials.
  • supercapacitors As an efficient energy storage platform, supercapacitors have received extensive attention in recent decades. It has high energy density, long cycle life, can achieve rapid charge and discharge, is environmentally friendly and safe, and can be used in electronic equipment, defense technology and energy fields. Supercapacitors can be divided into electric double layer capacitors and pseudocapacitors. The specific capacitance and energy density of pseudocapacitance are higher than that of electric double layer capacitance. Therefore, the research on pseudocapacitance is more extensive.
  • Transition metal oxides have abundant valence states and variable electronic structures, can rapidly undergo redox reactions, and are a class of promising capacitor materials, such as RuO 2 , Mn 3 O 4 , MnO 2 and so on.
  • Co3O4 as an ideal capacitor material, has high theoretical capacitance, is cheap, and is abundant and easy to obtain on earth.
  • Due to the poor conductivity, small specific surface area, and low electron and ion transport efficiency of bulk Co3O4 it is difficult to achieve its theoretical capacitance, which greatly limits its large - scale application.
  • the purpose of the present invention is to provide a Co3O4 /NiO nanosheet array composite material for supercapacitors and a preparation method thereof.
  • the O 4 /NiO nanosheet array composite is a Co-ZIF nanosheet array synthesized on nickel foam (NF), supported by nickel hydroxide (Ni(OH) 2 ) and then thermally treated to obtain Co 3 O 4 /NiO nanosheet array .
  • the material can accelerate the electron and ion transport efficiency, greatly improve the specific surface area, and greatly improve the specific capacitance of the Co 3 O 4 /NiO nanosheet array.
  • the technical scheme adopted in the present invention is: a composite electrode material for a super capacitor, a preparation method thereof, and a super capacitor.
  • a composite electrode material for a super capacitor of the present invention is a Co 3 O 4 /NiO nanosheet array composite material composed of Co 3 O 4 and NiO.
  • Co-ZIF nanosheet arrays were grown on NF by chemical deposition method, and then Ni(OH) 2 was supported on the obtained material by immersion method, and then Co 3 O 4 /NiO composite material was obtained by heat treatment, forming a highly Ordered nanosheet array composite structure.
  • the preparation method of the composite electrode material for supercapacitor of the present invention comprises the following steps:
  • step (2) Loading Ni(OH) 2 by immersion method: the ethanol solution containing nickel compound is placed in a constant temperature water bath at a constant temperature of 30°C, and then the material in step (1) is immersed in the ethanol solution containing nickel compound, and the temperature is kept constant. Take out after treatment, wash and dry to obtain step (2) material;
  • Step (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: placing the material in step (2) in a tube furnace and annealing in air to obtain Co 3 O 4 /NiO nanosheet composite array material, That is, the composite electrode material for supercapacitor of the present invention.
  • the concentration of the cobalt nitrate aqueous solution in step (1) is 0.04-0.08 mol/L respectively, and the concentration of the 2-methylimidazole aqueous solution is 0.4-0.8 mol/L.
  • the soaking time in step (1) is 6-18 hours; more preferably, it is about 12 hours.
  • the volume of ethanol in the ethanol solution containing the nickel compound in step (2) is 8-25 mL, and the content of the nickel-containing compound is 0.03-0.09 g.
  • the time of constant temperature treatment in step (2) is 0.5-2 hours.
  • the nickel-containing compound in step (2) includes, but is not limited to, one or more of nickel nitrate, nickel chloride, and nickel sulfate.
  • the annealing temperature in step (3) is 300°C-500°C; more preferably, it is about 350°C.
  • the time of the annealing treatment in step (3) is 1-3 hours.
  • the time of the annealing treatment in step (3) is about 1 hour.
  • a supercapacitor of the present invention includes the above-mentioned composite electrode material for a supercapacitor.
  • the present invention utilizes the characteristics of large specific surface area and porosity of the metal-organic framework, and can prepare a Co 3 O 4 nanosheet array with good dispersion, so that it has a high specific surface area, which can promote ion transport and improve its specific capacitance.
  • the Co 3 O 4 /NiO nanosheet array composite material of the present invention has good capacitance characteristics, and can be used as an ideal supercapacitor electrode material.
  • FIG. 1 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 1.
  • FIG. 1 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 1.
  • FIG. 2 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 2.
  • FIG. 2 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 2.
  • FIG. 3 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 3.
  • FIG. 3 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 3.
  • FIG. 4 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite synthesized in Example 4.
  • FIG. 4 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite synthesized in Example 4.
  • FIG. 5 is a SEM image of the Co 3 O 4 nanosheet array material synthesized in Comparative Example 1.
  • FIG. 6 is the cyclic voltammetry curves of the Co 3 O 4 /NiO nanosheet array composites synthesized in Example 3 at different scan rates.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Ni(OH) 2 loaded by immersion method firstly, 0.03 g of nickel nitrate hexahydrate was dissolved in 15 mL of ethanol to obtain a 6.88 mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 1 hour, taken out, washed and dried.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Ni(OH) 2 loaded by immersion method firstly, 0.03 g of nickel nitrate hexahydrate was dissolved in 15 mL of ethanol to obtain a 6.88 mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30°C, the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Ni(OH) 2 loaded by immersion method firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 1 hour, taken out, washed and dried.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Ni(OH) 2 loaded by immersion method firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30°C, the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Co-ZIF supported by chemical deposition method First, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100 mL of deionized water to prepare an aqueous solution of cobalt nitrate with a concentration of 0.04 mol/L and a concentration of 0.4 mol/L, respectively. mol/L of 2-methylimidazole aqueous solution; take 20 mL of cobalt nitrate aqueous solution and mix with 20 mL of 2-methylimidazole aqueous solution, put the material obtained in (1) into the above mixed solution and soak it for 12 hours. Wash with water and dry.
  • Co 3 O 4 /ZnO composite material by heat treatment method: placing the material prepared in (2) in a quartz boat, placing the quartz boat in a tube furnace, and annealing in air at 350° C. for 1 hour to obtain
  • the Co 3 O 4 /ZnO composite material is the composite electrode material for the supercapacitor of this comparative example.
  • a preparation method of a composite electrode material for a supercapacitor comprising the following steps:
  • Co-ZIF supported by chemical deposition method First, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100 mL of deionized water to prepare an aqueous solution of cobalt nitrate with a concentration of 0.04 mol/L and a concentration of 0.4 mol/L, respectively. mol/L of 2-methylimidazole aqueous solution; take 20 mL of cobalt nitrate aqueous solution and mix with 20 mL of 2-methylimidazole aqueous solution, put the material obtained in (1) into the above mixed solution and soak it for 12 hours. Wash with water and dry.
  • Ni(OH) 2 loaded by immersion method firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (2) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
  • Electrochemical performance test method The prepared electrode material, mercury/mercury oxide electrode and carbon rod are used as the working electrode respectively, the reference electrode and the counter electrode form a three-electrode system, and the electrolyte is an aqueous solution of potassium hydroxide with a molar concentration of 6 mol/L.
  • CHI760E electrochemical workstation was used to calculate the specific capacitance with the cyclic voltammetry curve obtained at a scan rate of 0.04 V/s.
  • Table 1 Calculated specific capacitance of the electrode materials obtained in Examples 1-4 and Comparative Examples 1-3 at a scan rate of 0.04 V/s.
  • Example 1 Example 2 Example 3
  • Example 4 Specific capacitance (F/g) 480.74 496.78 515.35 536.52 Comparative Example 1 Comparative Example 2 Comparative Example 3 Specific capacitance (F/g) 236.32 53.05 88.65

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Abstract

Disclosed are a composite electrode material for a super capacitor, a manufacturing method therefor and a super capacitor. The composite electrode material for a super capacitor of the present invention is a highly ordered Co3O4/NiO nanosheet array composite material consisting of Co3O4 and NiO. The manufacturing method comprises: growing a Co-ZIF nanosheet array by means of a chemical deposition method; loading Ni(OH)2 by means of an impregnation method; and manufacturing the Co3O4/NiO nanosheet array composite material by means of a heat treatment method. The Co3O4 nanosheet array with good dispersity is manufactured by utilizing the characteristics of a large specific surface area and the porosity of a metal organic framework; by compounding Co3O4 and NiO, various oxidation states are provided, enriching redox reactions, and an electron interaction between composite interfaces can promote fast transfer of electrons; and compared with the capacitance performance of Co3O4, the Co3O4/NiO nanosheet array composite material of the present invention has good capacitance characteristics.

Description

一种超级电容器用复合电极材料及其制备方法和超级电容器A kind of composite electrode material for supercapacitor and its preparation method and supercapacitor 技术领域technical field
本发明属于超级电容器电极材料领域，涉及一种超级电容器用复合电极材料及其制备方法和超级电容器，具体地说是涉及一种Co 3O 4/NiO纳米片阵列复合材料及其制备方法和其在超级电容器电极材料中的应用。 The invention belongs to the field of supercapacitor electrode materials, relates to a composite electrode material for supercapacitors, a preparation method thereof, and a supercapacitor, in particular to a Co3O4 / NiO nanosheet array composite material, a preparation method thereof, and a supercapacitor . Application in supercapacitor electrode materials.
背景技术Background technique
超级电容器作为一种高效的能量储存平台，在近几十年得到了广泛的关注。它具有较高能量密度，较长循环寿命，可实现快速充放电，对环境友好并且安全，可应用于电子设备，国防科技及能源领域等。超级电容器可分为双电层电容和赝电容。其中赝电容的比电容和能量密度高于双电层电容。因此赝电容的研究更加广泛。As an efficient energy storage platform, supercapacitors have received extensive attention in recent decades. It has high energy density, long cycle life, can achieve rapid charge and discharge, is environmentally friendly and safe, and can be used in electronic equipment, defense technology and energy fields. Supercapacitors can be divided into electric double layer capacitors and pseudocapacitors. The specific capacitance and energy density of pseudocapacitance are higher than that of electric double layer capacitance. Therefore, the research on pseudocapacitance is more extensive.
过渡金属氧化物具有丰富的价态和可变的电子结构，可快速发生氧化还原反应，是一类具有发展前景的电容器材料，如RuO 2，Mn 3O 4，MnO 2等。其中，Co 3O 4作为一种理想的电容器材料，它具有很高的理论电容量，价格便宜，在地球上含量丰富且容易获得。然而，由于块状Co 3O 4的导电性很差，比表面积小，电子和离子传输效率低，导致很难达到它的理论电容量，极大地限制了它的大规模应用。 Transition metal oxides have abundant valence states and variable electronic structures, can rapidly undergo redox reactions, and are a class of promising capacitor materials, such as RuO 2 , Mn 3 O 4 , MnO 2 and so on. Among them, Co3O4 , as an ideal capacitor material, has high theoretical capacitance, is cheap, and is abundant and easy to obtain on earth. However, due to the poor conductivity, small specific surface area, and low electron and ion transport efficiency of bulk Co3O4, it is difficult to achieve its theoretical capacitance, which greatly limits its large - scale application.
发明内容SUMMARY OF THE INVENTION
为克服现有的基于Co 3O 4制备的超级电容器电极材料的问题，本发明的目的在于提供一种用于超级电容器的Co 3O 4/NiO纳米片阵列复合材料及其制备方法，Co 3O 4/NiO纳米片阵列复合材料是在泡沫镍(NF)上合成Co-ZIF纳米片阵列，负载氢氧化镍(Ni(OH) 2)之后通过热处理来获得Co 3O 4/NiO纳米片阵列。该材料作为超级电容器材料，可以加速电子和离子传输效率，比表面积大大提高，Co 3O 4/NiO纳米片阵列的比电容会得到极大的提升。 In order to overcome the existing problems of supercapacitor electrode materials prepared based on Co3O4, the purpose of the present invention is to provide a Co3O4 /NiO nanosheet array composite material for supercapacitors and a preparation method thereof. The O 4 /NiO nanosheet array composite is a Co-ZIF nanosheet array synthesized on nickel foam (NF), supported by nickel hydroxide (Ni(OH) 2 ) and then thermally treated to obtain Co 3 O 4 /NiO nanosheet array . As a supercapacitor material, the material can accelerate the electron and ion transport efficiency, greatly improve the specific surface area, and greatly improve the specific capacitance of the Co 3 O 4 /NiO nanosheet array.
本发明采用的技术方案是：一种超级电容器用复合电极材料及其制备方法和超级电容器。The technical scheme adopted in the present invention is: a composite electrode material for a super capacitor, a preparation method thereof, and a super capacitor.
本发明的一种超级电容器用复合电极材料是由Co 3O 4和NiO组成的Co 3O 4/NiO纳米片阵列复合材料。首先，通过化学沉积法在NF上生长Co-ZIF纳米片阵列，之后将上述得到的材料上通过浸泡法负载Ni(OH) 2，随即通过热处理得到Co 3O 4/NiO复合材料，形成了高度有序的纳米片阵列复合结构。 A composite electrode material for a super capacitor of the present invention is a Co 3 O 4 /NiO nanosheet array composite material composed of Co 3 O 4 and NiO. First, Co-ZIF nanosheet arrays were grown on NF by chemical deposition method, and then Ni(OH) 2 was supported on the obtained material by immersion method, and then Co 3 O 4 /NiO composite material was obtained by heat treatment, forming a highly Ordered nanosheet array composite structure.
另一方面，本发明超级电容器用复合电极材料的制备方法包括如下步骤：On the other hand, the preparation method of the composite electrode material for supercapacitor of the present invention comprises the following steps:
(1)化学沉积法生长Co-ZIF纳米片阵列：将硝酸钴水溶液与2-甲基咪唑水溶液混合； 然后将处理干净的NF浸入所述的混合溶液中，浸泡数小时后取出，用去离子水洗涤干净，得到步骤(1)材料备用；(1) Growth of Co-ZIF nanosheet array by chemical deposition method: mix cobalt nitrate aqueous solution and 2-methylimidazole aqueous solution; then immerse the cleaned NF in the mixed solution, soak for several hours, take out, and deionize Wash with water, obtain step (1) material for subsequent use;
(2)浸泡法负载Ni(OH) 2：将含镍化合物的乙醇溶液置于恒温水浴锅中恒温到30℃，然后将步骤(1)材料浸入所述的含镍化合物的乙醇溶液中，恒温处理后取出，洗涤并干燥，得到步骤(2)材料； (2) Loading Ni(OH) 2 by immersion method: the ethanol solution containing nickel compound is placed in a constant temperature water bath at a constant temperature of 30°C, and then the material in step (1) is immersed in the ethanol solution containing nickel compound, and the temperature is kept constant. Take out after treatment, wash and dry to obtain step (2) material;
(3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将步骤(2)材料置于管式炉中，在空气中退火处理，得到Co 3O 4/NiO纳米片复合阵列材料，即本发明超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: placing the material in step (2) in a tube furnace and annealing in air to obtain Co 3 O 4 /NiO nanosheet composite array material, That is, the composite electrode material for supercapacitor of the present invention.
优选地，步骤(1)中硝酸钴水溶液的浓度分别为0.04-0.08mol/L，2-甲基咪唑水溶液的浓度为0.4-0.8mol/L。Preferably, the concentration of the cobalt nitrate aqueous solution in step (1) is 0.04-0.08 mol/L respectively, and the concentration of the 2-methylimidazole aqueous solution is 0.4-0.8 mol/L.
优选地，步骤(1)中浸泡的时间为6-18小时；进一步优选为约12小时。Preferably, the soaking time in step (1) is 6-18 hours; more preferably, it is about 12 hours.
优选地，步骤(2)中含镍化合物的乙醇溶液中乙醇的体积为8-25mL，含镍化合物的含量为0.03-0.09g。Preferably, the volume of ethanol in the ethanol solution containing the nickel compound in step (2) is 8-25 mL, and the content of the nickel-containing compound is 0.03-0.09 g.
优选地，步骤(2)中恒温处理的时间为0.5-2小时。Preferably, the time of constant temperature treatment in step (2) is 0.5-2 hours.
优选地，步骤(2)中含镍化合物包括但不限于硝酸镍、氯化镍和硫酸镍等中的一种或多种。Preferably, the nickel-containing compound in step (2) includes, but is not limited to, one or more of nickel nitrate, nickel chloride, and nickel sulfate.
优选地，步骤(3)中退火处理温度为300℃-500℃；进一步优选为约350℃。Preferably, the annealing temperature in step (3) is 300°C-500°C; more preferably, it is about 350°C.
优选地，步骤(3)中退火处理的时间为1-3小时。Preferably, the time of the annealing treatment in step (3) is 1-3 hours.
优选地，步骤(3)中退火处理的时间为约1小时。Preferably, the time of the annealing treatment in step (3) is about 1 hour.
另一方面，本发明的一种超级电容器包括上述超级电容器用复合电极材料。In another aspect, a supercapacitor of the present invention includes the above-mentioned composite electrode material for a supercapacitor.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明利用金属有机框架比表面积大和多孔性的特点，可以制备出分散性很好的Co 3O 4纳米片阵列，使其具有高的比表面积，可促进离子传输，提高其比电容。 1. The present invention utilizes the characteristics of large specific surface area and porosity of the metal-organic framework, and can prepare a Co 3 O 4 nanosheet array with good dispersion, so that it has a high specific surface area, which can promote ion transport and improve its specific capacitance.
2、通过将Co 3O 4与NiO复合，提供了多种氧化态，丰富氧化还原反应，复合物界面之间的电子相互作用可以促进电子的快速转移。 2. By compounding Co3O4 with NiO, various oxidation states are provided, which enriches the redox reaction, and the electronic interaction between the complex interfaces can promote the rapid transfer of electrons.
3、与Co 3O 4的电容性能相比，本发明的Co 3O 4/NiO纳米片阵列复合材料具有很好的电容特性，可作为一种理想的超级电容器电极材料。 3. Compared with the capacitance performance of Co 3 O 4 , the Co 3 O 4 /NiO nanosheet array composite material of the present invention has good capacitance characteristics, and can be used as an ideal supercapacitor electrode material.
附图说明Description of drawings
图1为实施例1合成的Co 3O 4/NiO纳米片阵列复合材料的SEM图。 FIG. 1 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 1. FIG.
图2为实施例2合成的Co 3O 4/NiO纳米片阵列复合材料的SEM图。 FIG. 2 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 2. FIG.
图3为实施例3合成的Co 3O 4/NiO纳米片阵列复合材料的SEM图。 FIG. 3 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite material synthesized in Example 3. FIG.
图4为实施例4合成的Co 3O 4/NiO纳米片阵列复合材料的SEM图。 FIG. 4 is a SEM image of the Co 3 O 4 /NiO nanosheet array composite synthesized in Example 4. FIG.
图5为对比例1合成的Co 3O 4纳米片阵列材料的SEM图。 FIG. 5 is a SEM image of the Co 3 O 4 nanosheet array material synthesized in Comparative Example 1. FIG.
图6为实施例3合成的Co 3O 4/NiO纳米片阵列复合材料在不同扫速下的循环伏安曲线。 FIG. 6 is the cyclic voltammetry curves of the Co 3 O 4 /NiO nanosheet array composites synthesized in Example 3 at different scan rates.
具体实施方式Detailed ways
实施例1Example 1
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)化学沉积法在NF上生长Co-ZIF纳米片阵列：将一块NF分别用丙酮和3mol/L盐酸水溶液超声清洗30分钟，去除表面的油污和氧化镍，然后依次用乙醇和去离子水清洗3次。之后将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将处理干净的NF浸入所述的混合溶液中，浸泡12小时后取出，用去离子水洗涤干净并干燥。(1) Growth of Co-ZIF nanosheet arrays on NF by chemical deposition method: a piece of NF was ultrasonically cleaned with acetone and 3 mol/L hydrochloric acid aqueous solution for 30 minutes to remove oil stains and nickel oxide on the surface, and then sequentially washed with ethanol and deionized water Wash 3 times. Then, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100mL of deionized water, respectively, to prepare a cobalt nitrate aqueous solution with a concentration of 0.04mol/L and a 2-methylimidazole aqueous solution of 0.4mol/L; Mix 20 mL of cobalt nitrate aqueous solution with 20 mL of 2-methylimidazole aqueous solution, immerse the cleaned NF in the mixed solution, soak for 12 hours, take out, wash with deionized water and dry.
(2)浸泡法负载Ni(OH) 2：首先将0.03g六水合硝酸镍溶于15mL乙醇中制得6.88mmol/L的硝酸镍乙醇溶液；再将硝酸镍乙醇溶液置于恒温水浴锅中恒温到30℃，之后将(1)制备的纳米棒阵列浸入硝酸镍乙醇溶液中，恒温浸泡1小时后取出，洗涤并干燥。 (2) Ni(OH) 2 loaded by immersion method: firstly, 0.03 g of nickel nitrate hexahydrate was dissolved in 15 mL of ethanol to obtain a 6.88 mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 1 hour, taken out, washed and dried.
(3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将(2)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/NiO纳米片复合材料，即得本实施例超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: put the material prepared in (2) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350°C for 1 hours, the Co 3 O 4 /NiO nanosheet composite material was obtained, that is, the composite electrode material for the supercapacitor of this embodiment was obtained.
实施例2Example 2
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)化学沉积法在NF上生长Co-ZIF纳米片阵列：将一块NF分别用丙酮和3mol/L盐酸水溶液超声清洗30分钟，去除表面的油污和氧化镍，然后依次用乙醇和去离子水清洗3次。之后将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将处理干净的NF浸入所述的混合溶液中，浸泡12小时后取出，用去离子水洗涤干净并干燥。(1) Growth of Co-ZIF nanosheet arrays on NF by chemical deposition method: A piece of NF was ultrasonically cleaned with acetone and 3 mol/L hydrochloric acid aqueous solution for 30 minutes to remove oil stains and nickel oxide on the surface, and then sequentially washed with ethanol and deionized water. Wash 3 times. Then, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100mL of deionized water, respectively, to prepare a cobalt nitrate aqueous solution with a concentration of 0.04mol/L and a 2-methylimidazole aqueous solution of 0.4mol/L; Mix 20 mL of cobalt nitrate aqueous solution with 20 mL of 2-methylimidazole aqueous solution, immerse the cleaned NF in the mixed solution, soak for 12 hours, take out, wash with deionized water and dry.
(2)浸泡法负载Ni(OH) 2：首先将0.03g六水合硝酸镍溶于15mL乙醇中制得6.88mmol/L的硝酸镍乙醇溶液；再将硝酸镍乙醇溶液置于恒温水浴锅中恒温到30℃，之后将(1)制备的纳米棒阵列浸入硝酸镍乙醇溶液中，恒温浸泡2小时后取出，洗涤并干燥。 (2) Ni(OH) 2 loaded by immersion method: firstly, 0.03 g of nickel nitrate hexahydrate was dissolved in 15 mL of ethanol to obtain a 6.88 mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30°C, the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
(3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将(2)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/NiO纳米片 复合材料，即得本实施例超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: put the material prepared in (2) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350°C for 1 hours, the Co 3 O 4 /NiO nanosheet composite material was obtained, that is, the composite electrode material for the supercapacitor of this embodiment was obtained.
实施例3Example 3
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)化学沉积法在NF上生长Co-ZIF纳米片阵列：将一块NF分别用丙酮和3mol/L盐酸水溶液超声清洗30分钟，去除表面的油污和氧化镍，然后依次用乙醇和去离子水清洗3次。之后将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将处理干净的NF浸入所述的混合溶液中，浸泡12小时后取出，用去离子水洗涤干净并干燥。(1) Growth of Co-ZIF nanosheet arrays on NF by chemical deposition method: A piece of NF was ultrasonically cleaned with acetone and 3 mol/L hydrochloric acid aqueous solution for 30 minutes to remove oil stains and nickel oxide on the surface, and then sequentially washed with ethanol and deionized water. Wash 3 times. Then, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100mL of deionized water, respectively, to prepare a cobalt nitrate aqueous solution with a concentration of 0.04mol/L and a 2-methylimidazole aqueous solution of 0.4mol/L; Mix 20 mL of cobalt nitrate aqueous solution with 20 mL of 2-methylimidazole aqueous solution, immerse the cleaned NF in the mixed solution, soak for 12 hours, take out, wash with deionized water and dry.
(2)浸泡法负载Ni(OH) 2：首先将0.06g六水合硝酸镍溶于15mL乙醇中制得13.76mmol/L的硝酸镍乙醇溶液；再将硝酸镍乙醇溶液置于恒温水浴锅中恒温到30℃，之后将(1)制备的纳米棒阵列浸入硝酸镍乙醇溶液中，恒温浸泡1小时后取出，洗涤并干燥。 (2) Ni(OH) 2 loaded by immersion method: firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 1 hour, taken out, washed and dried.
(3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将(2)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/NiO纳米片复合材料，即得本实施例超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: put the material prepared in (2) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350°C for 1 hours, the Co 3 O 4 /NiO nanosheet composite material was obtained, that is, the composite electrode material for the supercapacitor of this embodiment was obtained.
实施例4Example 4
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)化学沉积法在NF上生长Co-ZIF纳米片阵列：将一块NF分别用丙酮和3mol/L盐酸水溶液超声清洗30分钟，去除表面的油污和氧化镍，然后依次用乙醇和去离子水清洗3次。之后将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将处理干净的NF浸入所述的混合溶液中，浸泡12小时后取出，用去离子水洗涤干净并干燥。(1) Growth of Co-ZIF nanosheet arrays on NF by chemical deposition method: A piece of NF was ultrasonically cleaned with acetone and 3 mol/L hydrochloric acid aqueous solution for 30 minutes to remove oil stains and nickel oxide on the surface, and then sequentially washed with ethanol and deionized water. Wash 3 times. Then, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100mL of deionized water, respectively, to prepare a cobalt nitrate aqueous solution with a concentration of 0.04mol/L and a 2-methylimidazole aqueous solution of 0.4mol/L; Mix 20 mL of cobalt nitrate aqueous solution with 20 mL of 2-methylimidazole aqueous solution, immerse the cleaned NF in the mixed solution, soak for 12 hours, take out, wash with deionized water and dry.
(2)浸泡法负载Ni(OH) 2：首先将0.06g六水合硝酸镍溶于15mL乙醇中制得13.76mmol/L的硝酸镍乙醇溶液；再将硝酸镍乙醇溶液置于恒温水浴锅中恒温到30℃，之后将(1)制备的纳米棒阵列浸入硝酸镍乙醇溶液中，恒温浸泡2小时后取出，洗涤并干燥。 (2) Ni(OH) 2 loaded by immersion method: firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30°C, the nanorod array prepared in (1) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
(3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将(2)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/NiO纳米片复合材料，即得本实施例超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: put the material prepared in (2) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350°C for 1 hours, the Co 3 O 4 /NiO nanosheet composite material was obtained, that is, the composite electrode material for the supercapacitor of this embodiment was obtained.
对比例1Comparative Example 1
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)化学沉积法在NF上生长Co-ZIF纳米片阵列：将一块NF分别用丙酮和3mol/L盐酸水溶液超声清洗30分钟，去除表面的油污和氧化镍，然后依次用乙醇和去离子水清洗3次。之后将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将处理干净的NF浸入所述的混合溶液中，浸泡12小时后取出，用去离子水洗涤干净并干燥。(1) Growth of Co-ZIF nanosheet arrays on NF by chemical deposition method: A piece of NF was ultrasonically cleaned with acetone and 3 mol/L hydrochloric acid aqueous solution for 30 minutes to remove oil stains and nickel oxide on the surface, and then sequentially washed with ethanol and deionized water. Wash 3 times. Then, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100mL of deionized water, respectively, to prepare a cobalt nitrate aqueous solution with a concentration of 0.04mol/L and a 2-methylimidazole aqueous solution of 0.4mol/L; Mix 20 mL of cobalt nitrate aqueous solution with 20 mL of 2-methylimidazole aqueous solution, immerse the cleaned NF in the mixed solution, soak for 12 hours, take out, wash with deionized water and dry.
(2)热处理法制备Co 3O 4纳米片阵列：将(1)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4纳米片阵列，即得本对比例超级电容器用复合电极材料。 (2) Preparation of Co 3 O 4 nanosheet array by heat treatment method: put the material prepared in (1) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350° C. for 1 hour to obtain Co 3 O 4 nanosheet array, namely the composite electrode material for supercapacitor of this comparative example.
对比例2Comparative Example 2
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)电化学沉积法制备ZnO纳米棒阵列：首先将2.98g六水合硝酸锌和4.00g硝酸铵溶于1000mL H 2O中配制含有硝酸锌浓度为0.01mol/L和硝酸铵浓度为0.05mol/L混合水溶液；将清洗后的碳布作为阴极，石墨棒电极作为阳极，置于上述含有硝酸锌和硝酸铵的水溶液的电解槽中，通过施加1.6A的恒定电流电沉积1小时制备得到ZnO纳米棒阵列；用去离子水洗掉表面附着的硝酸锌和硝酸铵。 (1) Preparation of ZnO nanorod arrays by electrochemical deposition method: First, 2.98 g of zinc nitrate hexahydrate and 4.00 g of ammonium nitrate were dissolved in 1000 mL of H 2 O to prepare a concentration of 0.01 mol/L of zinc nitrate and 0.05 mol of ammonium nitrate. /L mixed aqueous solution; the cleaned carbon cloth was used as the cathode, and the graphite rod electrode was used as the anode, placed in the above electrolytic cell containing the aqueous solution of zinc nitrate and ammonium nitrate, and ZnO was prepared by applying a constant current of 1.6A for 1 hour by electrodeposition. Nanorod array; surface-attached zinc nitrate and ammonium nitrate were washed away with deionized water.
(2)化学沉积法负载Co-ZIF：首先将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将(1)获得的材料置入上述混合溶液中浸泡12小时后取出，用去离子水洗涤干净并干燥。(2) Co-ZIF supported by chemical deposition method: First, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100 mL of deionized water to prepare an aqueous solution of cobalt nitrate with a concentration of 0.04 mol/L and a concentration of 0.4 mol/L, respectively. mol/L of 2-methylimidazole aqueous solution; take 20 mL of cobalt nitrate aqueous solution and mix with 20 mL of 2-methylimidazole aqueous solution, put the material obtained in (1) into the above mixed solution and soak it for 12 hours. Wash with water and dry.
(3)热处理法制备Co 3O 4/ZnO复合材料：将(2)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/ZnO复合材料，即得本对比例超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /ZnO composite material by heat treatment method: placing the material prepared in (2) in a quartz boat, placing the quartz boat in a tube furnace, and annealing in air at 350° C. for 1 hour to obtain The Co 3 O 4 /ZnO composite material is the composite electrode material for the supercapacitor of this comparative example.
对比例3Comparative Example 3
一种超级电容器用复合电极材料的制备方法，包括以下步骤：A preparation method of a composite electrode material for a supercapacitor, comprising the following steps:
(1)电化学沉积法制备ZnO纳米棒阵列：首先将2.98g六水合硝酸锌和4.00g硝酸铵溶于1000mL H 2O中配制含有硝酸锌浓度为0.01mol/L和硝酸铵浓度为0.05mol/L混合水溶液；将清洗后的碳布作为阴极，石墨棒电极作为阳极，置于上述含有硝酸锌和硝酸铵的水溶液的电解槽中，通过施加1.6A的恒定电流电沉积1小时制备得到ZnO纳米棒阵列；用去离子水洗掉表面附着的硝酸锌和硝酸铵。 (1) Preparation of ZnO nanorod arrays by electrochemical deposition method: First, 2.98 g of zinc nitrate hexahydrate and 4.00 g of ammonium nitrate were dissolved in 1000 mL of H 2 O to prepare a concentration of 0.01 mol/L of zinc nitrate and 0.05 mol of ammonium nitrate. /L mixed aqueous solution; the cleaned carbon cloth was used as the cathode, and the graphite rod electrode was used as the anode, placed in the above electrolytic cell containing the aqueous solution of zinc nitrate and ammonium nitrate, and ZnO was prepared by applying a constant current of 1.6A for 1 hour by electrodeposition. Nanorod array; surface-attached zinc nitrate and ammonium nitrate were washed away with deionized water.
(2)化学沉积法负载Co-ZIF：首先将1.16g六水合硝酸钴及3.28g 2-甲基咪唑分别 溶于100mL去离子水中，配制得到浓度分别为0.04mol/L的硝酸钴水溶液及0.4mol/L的2-甲基咪唑水溶液；取20mL的硝酸钴水溶液与20mL的2-甲基咪唑水溶液混合，将(1)获得的材料置入上述混合溶液中浸泡12小时后取出，用去离子水洗涤干净并干燥。(2) Co-ZIF supported by chemical deposition method: First, 1.16g of cobalt nitrate hexahydrate and 3.28g of 2-methylimidazole were dissolved in 100 mL of deionized water to prepare an aqueous solution of cobalt nitrate with a concentration of 0.04 mol/L and a concentration of 0.4 mol/L, respectively. mol/L of 2-methylimidazole aqueous solution; take 20 mL of cobalt nitrate aqueous solution and mix with 20 mL of 2-methylimidazole aqueous solution, put the material obtained in (1) into the above mixed solution and soak it for 12 hours. Wash with water and dry.
(3)浸泡法负载Ni(OH) 2：首先将0.06g六水合硝酸镍溶于15mL乙醇中制得13.76mmol/L的硝酸镍乙醇溶液；再将硝酸镍乙醇溶液置于恒温水浴锅中恒温到30℃，之后将(2)制备的纳米棒阵列浸入硝酸镍乙醇溶液中，恒温浸泡2小时后取出，洗涤并干燥。 (3) Ni(OH) 2 loaded by immersion method: firstly, 0.06g of nickel nitrate hexahydrate was dissolved in 15mL of ethanol to obtain a 13.76mmol/L nickel nitrate ethanol solution; then the nickel nitrate ethanol solution was placed in a constant temperature water bath at a constant temperature After reaching 30° C., the nanorod array prepared in (2) was immersed in a nickel nitrate ethanol solution, soaked at a constant temperature for 2 hours, taken out, washed and dried.
(4)热处理法制备Co 3O 4/NiO/ZnO复合材料：将(3)制备的材料置于石英舟中，将石英舟放入管式炉中，在350℃的空气中退火处理1小时，得到Co 3O 4/NiO/ZnO复合材料，即得本对比例超级电容器用复合电极材料。 (4) Preparation of Co 3 O 4 /NiO/ZnO composite material by heat treatment method: put the material prepared in (3) in a quartz boat, put the quartz boat in a tube furnace, and anneal it in air at 350° C. for 1 hour , the Co 3 O 4 /NiO/ZnO composite material is obtained, that is, the composite electrode material for the supercapacitor of this comparative example is obtained.
为了验证本发明技术方案制备所得复合材料的性能，分别将实施例1-4和对比例1-3所制备的电极材料进行电化学性能测试，具体结果如表1。In order to verify the performance of the composite materials prepared by the technical solution of the present invention, the electrode materials prepared in Examples 1-4 and Comparative Examples 1-3 were respectively subjected to electrochemical performance tests. The specific results are shown in Table 1.
电化学性能测试方法：将准备好的电极材料，汞/氧化汞电极和碳棒分别作为工作电极，参比电极和对电极组成三电极系统，电解液为摩尔浓度为6mol/L氢氧化钾水溶液，采用CHI760E电化学工作站，以扫描速率为0.04V/s所得的循环伏安曲线来计算比电容。Electrochemical performance test method: The prepared electrode material, mercury/mercury oxide electrode and carbon rod are used as the working electrode respectively, the reference electrode and the counter electrode form a three-electrode system, and the electrolyte is an aqueous solution of potassium hydroxide with a molar concentration of 6 mol/L. , CHI760E electrochemical workstation was used to calculate the specific capacitance with the cyclic voltammetry curve obtained at a scan rate of 0.04 V/s.
表1实施例1-4和对比例1-3所得的电极材料在0.04V/s扫描速率下所计算的比电容。Table 1 Calculated specific capacitance of the electrode materials obtained in Examples 1-4 and Comparative Examples 1-3 at a scan rate of 0.04 V/s.
   实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4
比电容(F/g)Specific capacitance (F/g) 480.74480.74 496.78496.78 515.35515.35 536.52536.52
   对比例1Comparative Example 1 对比例2Comparative Example 2 对比例3Comparative Example 3   
比电容(F/g)Specific capacitance (F/g) 236.32236.32 53.0553.05 88.6588.65   
从实施例1-4和对比例1-3的比电容可看出，对比例1纯的Co 3O 4纳米片阵列的比电容为236.32F/g，而负载了NiO之后，比电容大大增加，可达到纯的Co 3O 4纳米片阵列的2倍多，说明本发明制备的Co 3O 4/NiO纳米片阵列是很好的超级电容的电极材料。从对比例2和对比例3的比电容来看，直接生长Co 3O 4在基底上比利用ZnO纳米棒阵列为模板获得的材料的性能更优异。此外，负载NiO之后的性能均有提升，说明本发明技术方案是可行并且有益的。 From the specific capacitances of Examples 1-4 and Comparative Examples 1-3, it can be seen that the specific capacitance of the pure Co 3 O 4 nanosheet array of Comparative Example 1 is 236.32 F/g, while the specific capacitance is greatly increased after NiO is loaded. , which can reach more than 2 times that of pure Co 3 O 4 nano-sheet array, indicating that the Co 3 O 4 /NiO nano-sheet array prepared by the present invention is a very good electrode material for super capacitor. From the specific capacitances of Comparative Example 2 and Comparative Example 3 , the direct growth of Co3O4 on the substrate has better performance than the material obtained by using the ZnO nanorod array as a template. In addition, the performance after loading NiO is improved, indicating that the technical solution of the present invention is feasible and beneficial.

Claims (13)

  1. 一种超级电容器用复合电极材料，其特征在于，所述复合电极材料是由Co 3O 4和NiO组成的Co 3O 4/NiO纳米片阵列复合材料。 A composite electrode material for supercapacitors, characterized in that the composite electrode material is a Co 3 O 4 /NiO nanosheet array composite material composed of Co 3 O 4 and NiO.
  2. 权利要求1所述的超级电容器用复合电极材料的制备方法，其特征在于，包括以下步骤：The preparation method of composite electrode material for supercapacitor according to claim 1, is characterized in that, comprises the following steps:
    (1)化学沉积法生长Co-ZIF纳米片阵列：将硝酸钴水溶液与2-甲基咪唑水溶液混合；然后将处理干净的NF浸入所述的混合溶液中，浸泡数小时后取出，用去离子水洗涤干净，得到步骤(1)材料，备用；(1) Growth of Co-ZIF nanosheet array by chemical deposition method: Mix cobalt nitrate aqueous solution and 2-methylimidazole aqueous solution; then immerse the cleaned NF in the mixed solution, soak for several hours, take out, and deionize Wash with water to obtain the material of step (1), for subsequent use;
    (2)浸泡法负载Ni(OH) 2：将含镍化合物的乙醇溶液置于恒温水浴锅中恒温到30℃，然后将步骤(1)材料浸入所述的含镍化合物的乙醇溶液中，恒温处理后取出，洗涤并干燥，得到步骤(2)材料； (2) Loading Ni(OH) 2 by immersion method: the ethanol solution containing nickel compound is placed in a constant temperature water bath at a constant temperature of 30°C, and then the material in step (1) is immersed in the ethanol solution containing nickel compound, and the temperature is kept constant. Take out after treatment, wash and dry to obtain step (2) material;
    (3)热处理法制备Co 3O 4/NiO纳米片阵列复合材料：将步骤(2)材料置于管式炉中，在空气中退火处理，得到超级电容器用复合电极材料。 (3) Preparation of Co 3 O 4 /NiO nanosheet array composite material by heat treatment method: the material in step (2) is placed in a tube furnace and annealed in air to obtain a composite electrode material for supercapacitors.
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中硝酸钴水溶液的浓度为0.04-0.08mol/L，2-甲基咪唑水溶液的浓度为0.4-0.8mol/L。The preparation method according to claim 2, wherein the concentration of the cobalt nitrate aqueous solution in step (1) is 0.04-0.08mol/L, and the concentration of the 2-methylimidazole aqueous solution is 0.4-0.8mol/L.
  4. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中浸泡的时间为6-18小时。The preparation method according to claim 2, wherein the soaking time in step (1) is 6-18 hours.
  5. 根据权利要求4所述的制备方法，其特征在于，步骤(1)中浸泡的时间为约12小时。The preparation method according to claim 4, wherein the soaking time in step (1) is about 12 hours.
  6. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中含镍化合物的乙醇溶液中乙醇的体积为8-25mL，含镍化合物含量为0.03-0.09g。The preparation method according to claim 2, wherein in step (2), the volume of ethanol in the ethanol solution containing the nickel compound is 8-25 mL, and the content of the nickel-containing compound is 0.03-0.09 g.
  7. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中恒温处理的时间为0.5-2小时。The preparation method according to claim 2, wherein the time of constant temperature treatment in step (2) is 0.5-2 hours.
  8. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中含镍化合物包括硝酸镍、氯化镍和硫酸镍中的一种或多种。The preparation method according to claim 2, wherein the nickel-containing compound in step (2) comprises one or more of nickel nitrate, nickel chloride and nickel sulfate.
  9. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中退火处理的温度为300℃-500℃。The preparation method according to claim 2, wherein the temperature of the annealing treatment in step (3) is 300°C-500°C.
  10. 根据权利要求9所述的制备方法，其特征在于，步骤(3)中退火处理的温度为约350℃。The preparation method according to claim 9, wherein the temperature of the annealing treatment in step (3) is about 350°C.
  11. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中退火处理的时间为1-3小时。The preparation method according to claim 2, wherein the annealing treatment time in step (3) is 1-3 hours.
  12. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中退火处理的时间为约1小时。The preparation method according to claim 2, wherein the annealing treatment time in step (3) is about 1 hour.
  13. 一种超级电容器，包括权利要求1所述的超级电容器用复合电极材料。A supercapacitor, comprising the composite electrode material for a supercapacitor according to claim 1.
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CN115536112A (en) * 2022-11-03 2022-12-30 西安建筑科技大学 Preparation method of capacitive deionization electrode for selectively removing lead ions in drinking water
CN115536112B (en) * 2022-11-03 2024-04-26 西安建筑科技大学 Preparation method of capacitive deionization electrode for selectively removing lead ions in drinking water
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CN118173394A (en) * 2024-05-14 2024-06-11 山东海化集团有限公司 Preparation method and application of cobalt nickel zinc trimetallic oxide porous carbon material

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