CN103646788A - Nickel oxalate based asymmetrical supercapacitor and preparation method thereof - Google Patents
Nickel oxalate based asymmetrical supercapacitor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 239000003990 capacitor Substances 0.000 claims abstract description 25
- VNYOIRCILMCTHO-UHFFFAOYSA-L nickel(2+);oxalate;dihydrate Chemical compound O.O.[Ni+2].[O-]C(=O)C([O-])=O VNYOIRCILMCTHO-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 239000002114 nanocomposite Substances 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229920006280 packaging film Polymers 0.000 claims abstract description 10
- 239000012785 packaging film Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- -1 RuO 2 Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
Classifications
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- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明属于电容器制备技术领域,涉及一种草酸镍基非对称型超级电容器及其制备方法。本发明草酸镍基非对称型超级电容器包括正极极片、负极极片、电解液、隔离膜和包装膜，其特征是正极极片是镍/二水合草酸镍纳米复合材料，基底为平板或者泡沫形态的镍,包覆层是纳米结构的二水合草酸镍膜层，厚度50纳米～100微米；负极极片是活性炭极片；电解液为1～6mol/L的氢氧化钾或氢氧化钠溶液。上述草酸镍基非对称型超级电容器的制备方法，包括正负极片的制备、电容器的组装和封装。本发明草酸镍基非对称型超级电容器比电容大，比功率、比能量密度高，制备方法简单易行，可控性高。The invention belongs to the technical field of capacitor preparation, and relates to a nickel oxalate-based asymmetric supercapacitor and a preparation method thereof. The nickel oxalate-based asymmetric supercapacitor of the present invention comprises a positive pole piece, a negative pole piece, an electrolyte, a separator and a packaging film, and is characterized in that the positive pole piece is a nickel/nickel oxalate dihydrate nanocomposite material, and the substrate is a flat plate or a foam Form of nickel, the coating layer is a nanostructured nickel oxalate dihydrate film with a thickness of 50 nanometers to 100 microns; the negative electrode is an activated carbon electrode; the electrolyte is 1 to 6 mol/L potassium hydroxide or sodium hydroxide solution . The preparation method of the above-mentioned nickel oxalate-based asymmetric supercapacitor includes the preparation of the positive and negative plates, the assembly and packaging of the capacitor. The nickel oxalate-based asymmetric supercapacitor of the invention has large specific capacitance, high specific power and specific energy density, simple and easy preparation method and high controllability.
Description
技术领域technical field
本发明属于电容器制备领域，特别是一种草酸镍基非对称型超级电容器及其制备方法。The invention belongs to the field of capacitor preparation, in particular to a nickel oxalate-based asymmetric supercapacitor and a preparation method thereof.
背景技术Background technique
超级电容器(Super Capacitor)是一种介于常规电容器与化学电池之间的新型储能元件，兼具传统电容器高的比功率和化学电池高的比能量的特点。是一种高效、实用、环保的能量存储装置，它优越的性能得到各方的重视。根据不同的标准，超级电容器有不同的分类。按照不同的储存电能的机理，超级电容器分为两类:一类是双电层电容器，其电容的产生主要是基于高比表面积碳材料与溶液间界面双电层原理的双电层电容器(Electric Double Capacitors，EDLC)；另一类是法拉第赝电容器(Faraday Pseudo-capacitor)，其电容的产生是基于电极材料表面或体相的二维或准二维空间上，电活性物质进行欠电位沉积,发生高度可逆的化学吸附-脱附或氧化-还原反应，产生与电极充电电位有关的电容。Supercapacitor (Super Capacitor) is a new type of energy storage element between conventional capacitors and chemical batteries. It has the characteristics of high specific power of traditional capacitors and high specific energy of chemical batteries. It is an efficient, practical and environmentally friendly energy storage device, and its superior performance has attracted the attention of all parties. There are different classifications of supercapacitors according to different standards. According to different mechanisms for storing electric energy, supercapacitors are divided into two categories: one is electric double layer capacitors, and its capacitance is mainly based on the principle of an electric double layer at the interface between a carbon material with a high specific surface area and a solution. Double Capacitors, EDLC); the other is Faraday Pseudo-capacitor (Faraday Pseudo-capacitor), the generation of its capacitance is based on the two-dimensional or quasi-two-dimensional space of the surface or bulk phase of the electrode material, and the underpotential deposition of electroactive substances. A highly reversible chemisorption-desorption or oxidation-reduction reaction occurs, resulting in a capacitance that is related to the electrode charge potential.
赝电容材料包括导电聚合物，比如聚吡咯、聚噻吩、聚苯胺等，还有金属氧化物，比如RuO2,MnO2,Co3O4等。金属氧化物相较于活性炭，有较高的能量密度，相较于导电聚合物，电化学稳定性更高。金属氧化物的形态对电容有很大的影响，纳米结构的电容远大于块体,这是因为纳米结构有更大的比表面积，使得更多的活性材料能形成双电层或者发生氧化还原反应而产生更大的电容。Pseudocapacitive materials include conductive polymers, such as polypyrrole, polythiophene, polyaniline, etc., and metal oxides, such as RuO 2 , MnO 2 , Co 3 O 4 , etc. Compared with activated carbon, metal oxides have higher energy density and higher electrochemical stability than conductive polymers. The morphology of metal oxides has a great influence on the capacitance. The capacitance of the nanostructure is much larger than that of the bulk. This is because the nanostructure has a larger specific surface area, so that more active materials can form an electric double layer or undergo redox reactions. resulting in greater capacitance.
以多孔活性炭为电极材料的双电层电容器能有较好的功率性能，但具有较低的比能量；以金属氧化物（如氧化钌）为电极材料的赝电容器虽然具有较高的比能量，但是其原料成本较高；另一类以聚合物(如聚苯胺）为电极材料的赝电容器也具有较高的比能量，但是其循环性能和导电性能较差。Electric double layer capacitors with porous activated carbon as electrode materials can have better power performance, but have lower specific energy; although pseudocapacitors with metal oxides (such as ruthenium oxide) as electrode materials have higher specific energy, But its cost of raw materials is high; another type of pseudocapacitor with polymer (such as polyaniline) as electrode material also has high specific energy, but its cycle performance and conductivity are poor.
为了同时获得较高的能量密度和功率密度，人们开始设计新型的非对称型超级电容器，即电容器的一极是双电层电极，另一极为法拉第赝电容电极。非对称型电化学超级电容器综合了两类电化学电容器的优点，可更好地满足实际应用中负载对电源系统的能量密度和功率密度的整体要求。In order to obtain higher energy density and power density at the same time, people began to design a new type of asymmetric supercapacitor, that is, one pole of the capacitor is an electric double layer electrode, and the other pole is a Faraday pseudocapacitive electrode. The asymmetric electrochemical supercapacitor combines the advantages of the two types of electrochemical capacitors, and can better meet the overall requirements of the load for the energy density and power density of the power supply system in practical applications.
制备金属氧化物电极的方法主要有电化学沉积、水热法、模板法、化学气相沉积等。例如在中国专利201210142685中，张克金等用水热法制备二氧化锰或纳米二氧化锰/活性炭复合材料然后将其与导电剂、粘结剂按照一定配比制成浆料涂覆在泡沫镍上，制成正极。该方法要分布操作，耗时长、操作复杂；涂刷制备电极的方法不如原位生长均匀稳定。The methods for preparing metal oxide electrodes mainly include electrochemical deposition, hydrothermal method, template method, chemical vapor deposition and so on. For example, in Chinese patent 201210142685, Zhang Kejin et al. prepared manganese dioxide or nano manganese dioxide/activated carbon composite material by hydrothermal method, and then prepared slurry with conductive agent and binder according to a certain ratio and coated it on foamed nickel. Make a positive electrode. This method requires distributed operations, which is time-consuming and complicated; the method of preparing electrodes by brushing is not as uniform and stable as in-situ growth.
发明内容Contents of the invention
本发明针对现有技术的不足，提供了一种基于镍/二水合草酸镍纳米复合材料的草酸镍基非对称型超级电容器及制备方法。Aiming at the deficiencies of the prior art, the invention provides a nickel oxalate-based asymmetric supercapacitor based on nickel/nickel oxalate dihydrate nanocomposite material and a preparation method thereof.
本发明是通过以下方式实现的：The present invention is achieved in the following ways:
一种草酸镍基非对称型超级电容器，包括正极极片、负极极片、电解液、隔离膜和包装膜，电解液填充于包装膜构成的密闭容器中，正极极片、负极极片置于电解液中，正极极片、负极极片由隔离膜隔开；其特征是正极极片是镍/二水合草酸镍纳米复合材料，基底为平板或者泡沫形态的镍,包覆层是纳米结构的二水合草酸镍膜层，厚度50纳米～100微米；负极极片是活性炭极片；电解液为1～6mol/L的氢氧化钾或氢氧化钠溶液。A nickel oxalate-based asymmetric supercapacitor, comprising a positive pole piece, a negative pole piece, an electrolyte, a separator and a packaging film, the electrolyte is filled in a closed container formed by the packaging film, and the positive pole piece and the negative pole piece are placed In the electrolyte, the positive pole piece and the negative pole piece are separated by a separator; the feature is that the positive pole piece is nickel/nickel oxalate dihydrate nanocomposite material, the substrate is nickel in the form of flat plate or foam, and the coating layer is nanostructured. The dihydrate nickel oxalate film layer has a thickness of 50 nanometers to 100 microns; the negative pole piece is an activated carbon pole piece; the electrolyte is 1-6 mol/L potassium hydroxide or sodium hydroxide solution.
上述草酸镍基非对称型超级电容器的制备方法，包括正负极片的制备、电容器的组装和封装，其特征是包括以下步骤：The preparation method of the above-mentioned nickel oxalate-based asymmetric supercapacitor includes the preparation of positive and negative plates, the assembly and packaging of capacitors, and is characterized in that it includes the following steps:
（1）制备镍/二水合草酸镍纳米复合材料正极极片；按照0.01～1.5mol/L的浓度配制草酸溶液；将平板或泡沫镍置于上述所制备的草酸溶液中，用恒电压法或恒电流法进行阳极氧化处理，在金属镍表面生成厚度为50纳米～100微米的二水合草酸镍包覆层，制得镍/二水合草酸镍纳米复合材料正极极片；(1) Prepare nickel/nickel oxalate dihydrate nanocomposite material positive pole piece; prepare oxalic acid solution according to the concentration of 0.01-1.5mol/L; place flat plate or nickel foam in the oxalic acid solution prepared above, and use constant voltage method or Anode oxidation treatment is carried out by the constant current method, and a coating layer of nickel oxalate dihydrate with a thickness of 50 nanometers to 100 microns is formed on the surface of the metal nickel to prepare a nickel/nickel oxalate dihydrate nanocomposite positive electrode sheet;
（2）制备活性炭负极极片；按照8:1:1的比例称量活性炭、炭黑和聚偏氟乙烯并混合均匀备用；在活性炭、炭黑和聚偏氟乙烯的混合物中加入适量的氮-甲基吡咯烷酮作为溶剂，搅拌均匀，获得具有一定黏度的均匀浆料，涂刷在剪切好的泡沫镍上；干燥箱中80摄氏度干燥4～5个小时，制得活性炭负极极片，取出备用；(2) Prepare the activated carbon negative electrode sheet; weigh the activated carbon, carbon black and polyvinylidene fluoride according to the ratio of 8:1:1 and mix them evenly for later use; add an appropriate amount of nitrogen to the mixture of activated carbon, carbon black and polyvinylidene fluoride -Methylpyrrolidone is used as a solvent, stirred evenly to obtain a uniform slurry with a certain viscosity, and brushed on the sheared nickel foam; dried in a drying oven at 80 degrees Celsius for 4 to 5 hours to prepare an activated carbon negative electrode sheet, and take it out spare;
（3）组装电容器：取步骤（1）制备的镍/二水合草酸镍纳米复合材料正极极片与步骤（2）制备的活性炭负极极片，中间加隔离膜，相对叠加对齐，装入包装膜内，滴入电解液，正极极片和负极极片露出上部金属部分以便连接导线。(3) Assembling the capacitor: Take the nickel/nickel oxalate dihydrate nanocomposite positive pole piece prepared in step (1) and the activated carbon negative pole piece prepared in step (2), add a separator in the middle, stack and align them, and put them into the packaging film Inside, the electrolyte is dripped, and the positive pole piece and the negative pole piece expose the upper metal part for connecting wires.
上述草酸镍基非对称型超级电容器的制备方法，其特征是步骤（1）中恒电压法的反应条件为：反应电位1～100伏，反应时间10秒～1小时，反应温度-10～90摄氏度。恒电流法的反应条件为：反应电流10毫安～30安，反应时间10秒～1小时，反应温度-10～90摄氏度。The preparation method of the above-mentioned nickel oxalate-based asymmetric supercapacitor is characterized in that the reaction conditions of the constant voltage method in step (1) are: reaction potential 1-100 volts, reaction time 10 seconds-1 hour, reaction temperature -10-90 Celsius. The reaction conditions of the constant current method are as follows: a reaction current of 10 milliamps to 30 amps, a reaction time of 10 seconds to 1 hour, and a reaction temperature of -10 to 90 degrees Celsius.
本发明草酸镍基非对称型超级电容器及其制备方法具有以下优点：The nickel oxalate-based asymmetric supercapacitor and the preparation method thereof of the present invention have the following advantages:
（1）本发明所述的草酸镍基非对称型超级电容器容量大，比能量、比功率高；超级电容器所用到的镍/二水合草酸镍纳米复合材料极片采用平板或者泡沫形态的金属镍做基底，可同时作为支撑衬底和集流器，简化超级电容器的制作过程，减轻了超级电容器的负载；(1) The nickel oxalate-based asymmetric supercapacitor described in the present invention has large capacity, high specific energy and high specific power; the nickel/nickel oxalate dihydrate nanocomposite pole piece used in the supercapacitor adopts metal nickel in the form of a flat plate or a foam As a base, it can be used as a supporting substrate and a current collector at the same time, which simplifies the manufacturing process of supercapacitors and reduces the load on supercapacitors;
（2）本发明所述制备方法，可选择性控制电容器的厚度和电容大小，通过控制镍/二水合草酸镍纳米复合材料电极制备时电解液的浓度、体积和配比以及温度、电压、反应时间、电极间距等参数，调节生成的氧化物的结构和厚度，以达到控制电容器电容大小的目的，可控性高；(2) The preparation method of the present invention can selectively control the thickness and capacitance of the capacitor, by controlling the concentration, volume and proportion of the electrolyte, as well as the temperature, voltage, and reaction Time, electrode spacing and other parameters, adjust the structure and thickness of the generated oxide, in order to achieve the purpose of controlling the capacitance of the capacitor, with high controllability;
（3）本发明所述的制备方法，简单易行，适用范围广泛。(3) The preparation method of the present invention is simple and easy to implement, and has a wide range of applications.
具体实施方式Detailed ways
下面给出本发明的五个最佳实施例，但本发明所保护范围不限于此。Five best embodiments of the present invention are given below, but the protection scope of the present invention is not limited thereto.
实施例1Example 1
一种草酸镍基非对称型超级电容器，包括正极极片、负极极片、电解液、隔离膜和包装膜，电解液填充于包装膜构成的密闭容器中，正极极片、负极极片置于电解液中，由隔离膜隔开。所述正极极片是泡沫镍/二水合草酸镍纳米复合材料，基底为2毫米厚的泡沫镍，包覆层是纳米结构的金属氧化物膜层。所述负极极片是活性炭极片。电解液为氢氧化钾溶液。A nickel oxalate-based asymmetric supercapacitor, comprising a positive pole piece, a negative pole piece, an electrolyte, a separator and a packaging film, the electrolyte is filled in a closed container formed by the packaging film, and the positive pole piece and the negative pole piece are placed The electrolyte is separated by a separator. The positive pole piece is a nickel foam/nickel oxalate dihydrate nanocomposite material, the substrate is nickel foam with a thickness of 2 mm, and the coating layer is a metal oxide film layer with a nanostructure. The negative pole piece is an activated carbon pole piece. The electrolyte is potassium hydroxide solution.
上述草酸镍基非对称型超级电容器的制备方法，包括正负极片的制备、电容器的组装和封装，具体步骤如下：The preparation method of the above-mentioned nickel oxalate-based asymmetric supercapacitor includes the preparation of the positive and negative plates, the assembly and packaging of the capacitor, and the specific steps are as follows:
一种镍/二水合草酸镍纳米复合材料正极极片的制备方法如下：A kind of preparation method of nickel/nickel oxalate dihydrate nanocomposite positive electrode sheet is as follows:
（1）配制0.5mol/L的草酸溶液备用；(1) Prepare 0.5mol/L oxalic acid solution for later use;
（2）将2厘米×2厘米,2毫米厚的泡沫镍置于（1）所述的电解液中，连接导线，泡沫镍做正极，平板镍片做负极；(2) Put 2 cm × 2 cm, 2 mm thick nickel foam into the electrolyte described in (1), connect the wires, the nickel foam is used as the positive electrode, and the flat nickel sheet is used as the negative electrode;
（3）零下10摄氏度恒电位50伏电压下对泡沫镍进行阳极氧化处理，反应5分钟，制得泡沫镍/二水合草酸镍复合材料。二水合草酸镍均匀分布在泡沫镍韧带上。(3) Perform anodic oxidation treatment on nickel foam at a constant potential of 50 volts at minus 10 degrees Celsius, and react for 5 minutes to prepare a nickel foam/nickel oxalate dihydrate composite material. Nickel oxalate dihydrate was evenly distributed on the nickel foam ligament.
一种活性炭负极极片的制备方法如下：A kind of preparation method of activated carbon negative pole sheet is as follows:
（1）按照8:1:1的比例称量活性炭、炭黑和聚偏氟乙烯(PVDF)备用；(1) Weigh activated carbon, carbon black and polyvinylidene fluoride (PVDF) according to the ratio of 8:1:1 for later use;
（2）加入氮-甲基吡咯烷酮适量，搅拌均匀，涂刷在剪切好的泡沫镍上；(2) Add an appropriate amount of nitrogen-methylpyrrolidone, stir evenly, and brush on the sheared foam nickel;
（3）干燥箱中80摄氏度干燥5个小时，取出备用。(3) Dry in a drying oven at 80°C for 5 hours, take it out and set aside.
电容器的组装：Capacitor assembly:
（1）配制2mol/L的氢氧化钾溶液备用；(1) Prepare 2mol/L potassium hydroxide solution for later use;
（2）将制备的活性炭负极极片和泡沫镍/二水合草酸镍纳米复合材料正极极片的纯金属部分剪切，使整体呈“7”型，用隔离膜分离两电极，叠加对齐，装入包装膜中，滴入电解液，极片露出上部金属部分以便连接导线，封装。(2) Cut the pure metal part of the prepared activated carbon negative pole piece and nickel foam/nickel oxalate dihydrate nanocomposite positive pole piece so that the whole is in a "7" shape, separate the two electrodes with a separator, stack and align them, and install Put it into the packaging film, drop the electrolyte, expose the upper metal part of the pole piece to connect the wire, and package.
实施例2Example 2
一种草酸镍基非对称型超级电容器及其制备方法，除镍/二水合草酸镍纳米复合材料正极极片制备中使用1mol/L的草酸溶液作为电解液，零下10摄氏度恒电位30伏电压下对泡沫镍进行阳极氧化处理10分钟，电容器组装采用4mol/L的氢氧化钾溶液外，其余同实施例1。A nickel oxalate-based asymmetric supercapacitor and a preparation method thereof, using 1mol/L oxalic acid solution as electrolyte in the preparation of nickel-removing/nickel oxalate dihydrate nanocomposite positive electrode sheet, under minus 10 degrees Celsius constant potential and 30 volts The nickel foam was anodized for 10 minutes, and the capacitor was assembled with 4 mol/L potassium hydroxide solution, and the others were the same as in Example 1.
实施例3Example 3
一种草酸镍基非对称型超级电容器及其制备方法，除镍/二水合草酸镍纳米复合材料正极极片制备中使用0.2mol/L的草酸溶液作为电解液，零下5摄氏度恒电位50伏电压下对平板进行阳极氧化处理15分钟，电容器组装采用1mol/L的氢氧化钠溶液外，其余同实施例1。A nickel oxalate-based asymmetric supercapacitor and a preparation method thereof, using 0.2mol/L oxalic acid solution as the electrolyte in the preparation of nickel-removing/nickel oxalate dihydrate nanocomposite positive electrode sheet, and a constant potential of 50 volts at minus 5 degrees Celsius Next, carry out anodic oxidation treatment on the plate for 15 minutes, except that 1 mol/L sodium hydroxide solution is used for assembling the capacitor, the rest is the same as in Example 1.
实施例4Example 4
一种草酸镍基非对称型超级电容器及其制备方法，除镍/二水合草酸镍纳米复合材料正极极片制备中使用0.6mol/L的草酸溶液作为电解液，零下5摄氏度恒电位40伏电压下对平板镍进行阳极氧化处理10分钟，电容器组装采用6mol/L的氢氧化钠溶液外，其余同实施例1。A nickel oxalate-based asymmetric supercapacitor and a preparation method thereof, using 0.6mol/L oxalic acid solution as the electrolyte in the preparation of nickel-removing/nickel oxalate dihydrate nanocomposite positive electrode sheet, and a constant potential of 40 volts at minus 5 degrees Celsius Next, carry out anodic oxidation treatment to flat nickel for 10 minutes, except that 6 mol/L sodium hydroxide solution is used for capacitor assembly, the others are the same as in Example 1.
实施例5Example 5
一种草酸镍基非对称型超级电容器及其制备方法，除镍/二水合草酸镍纳米复合材料正极极片制备中使用0.5mol/L的草酸溶液作为电解液，25摄氏度恒电位40伏电压下对平板镍进行阳极氧化处理10分钟，电容器组装采用6mol/L的氢氧化钾溶液外，其余同实施例1。A nickel oxalate-based asymmetric supercapacitor and a preparation method thereof, using 0.5 mol/L oxalic acid solution as electrolyte in the preparation of nickel-removing/nickel oxalate dihydrate nanocomposite positive electrode sheet, under constant potential of 25 degrees Celsius and 40 volts The flat nickel was anodized for 10 minutes, and the capacitor was assembled with 6 mol/L potassium hydroxide solution, and the others were the same as in Example 1.
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| CN104795243A (en) * | 2015-02-04 | 2015-07-22 | 三峡大学 | Asymmetric supercapacitor and preparation method thereof |
| CN109727784A (en) * | 2017-10-27 | 2019-05-07 | 北京碳阳科技有限公司 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
| CN112133574A (en) * | 2020-11-09 | 2020-12-25 | 湖南科技大学 | A kind of preparation method of foamed nickel@nickel micro-nanorod array electrode |
| CN114334485A (en) * | 2022-01-24 | 2022-04-12 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104795243A (en) * | 2015-02-04 | 2015-07-22 | 三峡大学 | Asymmetric supercapacitor and preparation method thereof |
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| CN109727784A (en) * | 2017-10-27 | 2019-05-07 | 北京碳阳科技有限公司 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
| CN112133574A (en) * | 2020-11-09 | 2020-12-25 | 湖南科技大学 | A kind of preparation method of foamed nickel@nickel micro-nanorod array electrode |
| CN114334485A (en) * | 2022-01-24 | 2022-04-12 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
| CN114334485B (en) * | 2022-01-24 | 2023-06-16 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
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