CN105480962A - Preparation method of in-situ self-assembling N-doped super-hydrophilic carbon aerogel supercapacitor electrode material - Google Patents
Preparation method of in-situ self-assembling N-doped super-hydrophilic carbon aerogel supercapacitor electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000004966 Carbon aerogel Substances 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- -1 Borate ions Chemical class 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 15
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 10
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
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- 230000008569 process Effects 0.000 claims description 5
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 claims description 4
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 5
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical group [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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- H01G11/32—Carbon-based
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- 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
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- H01G11/48—Conductive polymers
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Abstract
本发明公开了一种原位自组装氮掺杂超亲水碳气凝胶超级电容器电极材料的制备方法，将含氮导电聚合物和硼酸根骨架引进凝胶三维网络结构中，高温活化后，制得具有多级孔结构的超亲水高比电容氮掺杂碳气凝胶超级电容器电极材料，氮元素起到增加材料赝电容和提高电子传输能力的双重作用，硼酸根离子不仅作为交联剂维持凝胶骨架，而且具有自组装模板的功效促进大孔空隙的生成。本发明没有经过紫外光照射或额外表面化学修饰等处理即呈现优良的超亲水性能；不需要采用溶剂交换，使用冷冻干燥技术、成本低廉，既简单易行，又保持了凝胶内部特殊的三维网络结构，环境友好。
The invention discloses a preparation method of an in-situ self-assembled nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material. A nitrogen-containing conductive polymer and a borate skeleton are introduced into the three-dimensional network structure of the gel, and after high-temperature activation, A super-hydrophilic high-capacitance nitrogen-doped carbon airgel supercapacitor electrode material with a hierarchical pore structure is prepared. The nitrogen element plays a dual role in increasing the pseudocapacitance of the material and improving the electron transport ability. Borate ions not only serve as cross-linking The agent maintains the gel skeleton, and has the effect of self-assembly template to promote the generation of macroporous voids. The present invention exhibits excellent superhydrophilic properties without ultraviolet light irradiation or additional surface chemical modification; it does not need to use solvent exchange, uses freeze-drying technology, and is low in cost. Three-dimensional network structure, environment-friendly.
Description
技术领域 technical field
本发明属于超级电容器电极材料的合成技术领域，具体涉及一种原位自组装氮掺杂超亲水碳气凝胶超级电容器电极材料的制备方法。 The invention belongs to the technical field of synthesis of supercapacitor electrode materials, and in particular relates to a preparation method of an in-situ self-assembled nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material.
背景技术 Background technique
多孔碳材料由于其孔径分布和结构的可控性在催化剂载体、二氧化碳存储和超级电容器领域发挥了巨大的应用价值。在超级电容器中，多孔碳材料大孔用于存储电解液，介孔用于离子的快速传输，微孔用于离子积累的有效场所，因而具有大比表面积与微孔-介孔-大孔孔隙结构合理分配的多孔碳材料是极具发展潜力的超级电容器电极材料。鉴于碳材料表面的化学惰性，引入非金属杂原子，不仅可以增加碳材料的浸润性，而且可以贡献一定的赝电容。非金属元素掺杂后的碳材料在能量存储领域具有尤为优异的表现。采用模板法有利于合成孔径均一可调控的内部结构，从而改善其性能。 Due to its controllable pore size distribution and structure, porous carbon materials have played a huge application value in the fields of catalyst supports, carbon dioxide storage and supercapacitors. In a supercapacitor, the large pores of the porous carbon material are used to store the electrolyte, the mesopores are used for the rapid transport of ions, and the micropores are used as an effective place for ion accumulation, so they have a large specific surface area and micropore-mesopore-macropore pores. Porous carbon materials with reasonable structure distribution are great potential electrode materials for supercapacitors. In view of the chemical inertness of the surface of carbon materials, the introduction of non-metallic heteroatoms can not only increase the wettability of carbon materials, but also contribute a certain amount of pseudocapacitance. Carbon materials doped with non-metallic elements have particularly excellent performance in the field of energy storage. The template method is beneficial to the synthesis of internal structures with uniform and adjustable pore size, thereby improving their performance.
目前，公开号为CN102013335A的专利公开了一种合成非金属磷或硼掺杂的有序介孔碳的方法，尽管该方法中非金属磷或硼的掺杂增加了材料的亲水性，但由于使用了表面活性剂给后处理增加了能耗，并且制备的材料比表面积较小。公开号为CN102107863A的专利公开了一种采用鱼鳞作为碳源和天然模板，同时使用碱性活化剂制备多孔碳材料的方法，所述的多孔呈连续性分布，比表面积高达2300m2/g，但鱼鳞资源较少难以收集。此外，虽然模板法为定向合成孔道有序、高比面积的碳材料提供了捷径，但是以中孔分子筛为代表的“硬模板”在制备中孔炭材料时面临制备周期长、合成工艺复杂且模板剂去除等问题；以表面活性剂及其聚集体为代表的“软模板”法也存在制备的材料电化学性能较差等缺陷。因此，探索出一种自组装模板制备多孔碳是研究的热点。碳气凝胶具有高的孔隙度（80%~98%）、高的导电率（25-100S/cm）、丰富的比表面积（>400m2/g）、可调控的孔结构和较低的离子传输阻力，并兼具特殊的三维网络结构，是一种新型轻质纳米多孔碳材料，在超级电容器领域有着可观的应用前景（Pekala,R.W.;Farmer,J.C.;Alviso,C.T.;etal.J.Non-crystsolids,1998,225,74-80.）。 At present, the patent with publication number CN102013335A discloses a method for synthesizing ordered mesoporous carbon doped with non-metallic phosphorus or boron, although the doping of non-metallic phosphorus or boron in this method increases the hydrophilicity of the material, but Due to the use of surfactants, the post-treatment increases energy consumption, and the specific surface area of the prepared material is small. The patent with the publication number CN102107863A discloses a method of using fish scales as a carbon source and a natural template, and at the same time using an alkaline activator to prepare a porous carbon material. Fish scale resources are rare and difficult to collect. In addition, although the template method provides a shortcut for the directional synthesis of carbon materials with ordered pores and high specific area, the "hard template" represented by mesoporous molecular sieves faces long preparation cycles, complex synthesis processes and Template removal and other issues; the "soft template" method represented by surfactants and their aggregates also has defects such as poor electrochemical properties of the prepared materials. Therefore, exploring a self-assembled template to prepare porous carbon is a research hotspot. Carbon airgel has high porosity (80%~98%), high electrical conductivity (25-100S/cm), abundant specific surface area (>400m 2 /g), adjustable pore structure and low Ion transport resistance, and with a special three-dimensional network structure, is a new type of lightweight nanoporous carbon material, which has considerable application prospects in the field of supercapacitors (Pekala, RW; Farmer, JC; Alviso, CT; etal.J. Non-crystsolids, 1998, 225, 74-80.).
发明内容 Contents of the invention
本发明解决的技术问题是提供了一种原位自组装氮掺杂超亲水碳气凝胶超级电容器电极材料的制备方法，制得的材料是具有大的比表面积、大的孔体积、亲水性好、比容高、功率密度和能量密度大的超级电容器电极材料。 The technical problem solved by the present invention is to provide a method for preparing an in-situ self-assembled nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material. The prepared material has a large specific surface area, a large pore volume, and a hydrophilic Supercapacitor electrode materials with good water properties, high specific volume, high power density and energy density.
本发明为解决上述技术问题采用如下技术方案，一种原位自组装氮掺杂超亲水碳气凝胶超级电容器电极材料的制备方法，其特征在于包括以下步骤： In order to solve the above-mentioned technical problems, the present invention adopts the following technical scheme, a preparation method of an in-situ self-assembled nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material, which is characterized in that it comprises the following steps:
步骤1，在60~85℃的水浴温度下，将水溶性聚合物溶于无机酸中并搅拌1~3h，转至室温下，加入含氮有机单体并搅拌30~60min，再加入氧化剂过硫酸铵并搅拌30~60min，然后加入硼酸溶液并于室温老化24~48h，冷冻干燥得到气凝胶A，所述水溶性聚合物为聚乙烯醇、聚乙烯基吡咯烷酮、聚丙烯酸、聚丙烯酰胺、聚氧乙烯或聚甲基丙烯酸羟乙酯，所述无机酸为摩尔浓度为0.1~1mol/L的盐酸溶液或硫酸溶液，所述含氮有机单体为苯胺、N-甲基苯胺或N-羟乙基苯胺中的至少一种； Step 1: Dissolve the water-soluble polymer in the mineral acid at a water bath temperature of 60-85°C and stir for 1-3 hours, then transfer to room temperature, add nitrogen-containing organic monomers and stir for 30-60 minutes, then add an oxidizing agent to ammonium sulfate and stirred for 30-60min, then added boric acid solution and aged at room temperature for 24-48h, freeze-dried to obtain airgel A, the water-soluble polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide , polyoxyethylene or polyhydroxyethyl methacrylate, the inorganic acid is a hydrochloric acid solution or a sulfuric acid solution with a molar concentration of 0.1 to 1 mol/L, and the nitrogen-containing organic monomer is aniline, N-methylaniline or N - at least one of hydroxyethylaniline;
步骤2，将步骤1得到的气凝胶A在惰性气体下炭化处理得到材料B，炭化处理的具体过程是以5~10℃/min的升温速率由室温升至500~1000℃恒温2~4h，再将得到的材料B与碱性活化剂以质量比为1:2~1:5的比例在水溶液中混合6~12h，置于烘箱中于105℃干燥，然后置于管式炉中，在惰性气体下高温活化，高温活化的具体过程是以5~10℃/min的升温速率由室温升至500~1000℃恒温2~4h，将高温活化后的材料在摩尔浓度为2mol/L的盐酸溶液中浸泡12h，过滤，使用纯水洗至中性，再置于烘箱中于105℃干燥24h制得超亲水氮掺杂氮碳气凝胶，所述惰性气体为氮气或氩气，所述碱性活化剂为氢氧化钾、氢氧化钠或碳酸钾中的至少一种。 Step 2: Carbonize the airgel A obtained in step 1 under inert gas to obtain material B. The specific process of carbonization is to raise the temperature from room temperature to 500~1000℃ at a constant temperature of 2~10℃/min. 4h, then mix the obtained material B with the alkaline activator in the aqueous solution at a mass ratio of 1:2~1:5 for 6~12h, dry in an oven at 105°C, and then place in a tube furnace , high-temperature activation under inert gas. The specific process of high-temperature activation is to raise the temperature from room temperature to 500-1000 °C at a constant temperature of 2-4 hours at a rate of 5-10 °C/min. Soak in L of hydrochloric acid solution for 12 hours, filter, wash with pure water until neutral, then place in an oven and dry at 105°C for 24 hours to obtain superhydrophilic nitrogen-doped nitrogen-carbon airgel, the inert gas is nitrogen or argon , the alkaline activator is at least one of potassium hydroxide, sodium hydroxide or potassium carbonate.
进一步优选，步骤1中原料水溶性聚合物、无机酸、含氮有机单体、过硫酸铵和硼酸的质量比为2.0~6.0:0.2~2.0:0.06~0.6:0.1~3.0:1.0~3.0。 Further preferably, the mass ratio of the raw material water-soluble polymer, inorganic acid, nitrogen-containing organic monomer, ammonium persulfate and boric acid in step 1 is 2.0-6.0:0.2-2.0:0.06-0.6:0.1-3.0:1.0-3.0.
本发明与现有技术相比具有以下优点： Compared with the prior art, the present invention has the following advantages:
1、采用原位掺杂和自组装模板法将含氮导电聚合物与硼酸根离子骨架引进凝胶三维网络结构中，高温活化后，制得多级孔结构的高比容氮掺杂碳气凝胶超级电容器电极材料，氮元素起到增加材料赝电容和提高电子传输能力的双重作用，硼酸根离子不仅作为交联剂，而且具有自组装模板的功能； 1. Using in-situ doping and self-assembly template method to introduce nitrogen-containing conductive polymer and borate ion skeleton into the three-dimensional network structure of the gel, after high-temperature activation, a high-specificity nitrogen-doped carbon gas with a multi-level pore structure is produced Gel supercapacitor electrode material, nitrogen plays a dual role in increasing the pseudocapacitance of the material and improving the electron transport ability, borate ion not only acts as a cross-linking agent, but also has the function of self-assembly template;
2、本发明所制备的碳气凝胶具有超亲水性，这种超亲水表面无需经过紫外光照射或额外表面化学修饰等处理，不仅降低成本，而且有利于电极材料与电解质的接触，促进离子由本体溶液向电极表面的传输，从而降低电极材料与集流体的接触电阻，进而提高其在高倍率下的电容性能。 2. The carbon airgel prepared by the present invention has superhydrophilicity. This superhydrophilic surface does not need to be treated by ultraviolet light or additional surface chemical modification, which not only reduces the cost, but also facilitates the contact between the electrode material and the electrolyte. Promote the transport of ions from the bulk solution to the electrode surface, thereby reducing the contact resistance between the electrode material and the current collector, thereby improving its capacitive performance at high rates.
3、本发明不需要采用溶剂交换，使用冷冻干燥技术既简单易行、成本低廉，又保持了凝胶内部特殊的三维网络结构。 3. The present invention does not need solvent exchange, and the use of freeze-drying technology is simple, low-cost, and maintains the special three-dimensional network structure inside the gel.
附图说明 Description of drawings
图1是本发明实施例1制得的超亲水氮掺杂超亲水碳气凝胶超级电容器电极材料的SEM图； Fig. 1 is the SEM picture of the superhydrophilic nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material that the embodiment of the present invention 1 makes;
图2是本发明实施例1制得的超亲水氮掺杂超亲水碳气凝胶超级电容器电极材料的孔径分布图； Fig. 2 is the pore size distribution figure of the superhydrophilic nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material that the embodiment 1 of the present invention makes;
图3是本发明实施例1制得的超亲水氮掺杂超亲水碳气凝胶超级电容器电极材料的接触角图； Fig. 3 is the contact angle figure of superhydrophilic nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material that the embodiment 1 of the present invention makes;
图4是本发明实施例1制得的超亲水氮掺杂超亲水碳气凝胶超级电容器电极材料在三电极体系中的充放电图。 Fig. 4 is a charge-discharge diagram of the superhydrophilic nitrogen-doped superhydrophilic carbon airgel supercapacitor electrode material prepared in Example 1 of the present invention in a three-electrode system.
具体实施方式 detailed description
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。 The above-mentioned contents of the present invention are described in further detail below through the embodiments, but this should not be interpreted as the scope of the above-mentioned themes of the present invention being limited to the following embodiments, and all technologies realized based on the above-mentioned contents of the present invention all belong to the scope of the present invention.
实施例1 Example 1
在80℃水浴温度下，将10g聚乙烯醇（PVA）溶于100mL摩尔浓度为0.5mol/L盐酸溶液中，搅拌2h，转至室温下，加入1.715gN-羟乙基苯胺，搅拌30min，加入5mL溶有2.853g过硫酸铵的溶液，搅拌30min，然后加入100mL溶有5g硼酸的溶液，室温老化24h，冷冻干燥得到A1； Dissolve 10g of polyvinyl alcohol (PVA) in 100mL of hydrochloric acid solution with a molar concentration of 0.5mol/L at 80°C in a water bath, stir for 2h, turn to room temperature, add 1.715g of N-hydroxyethylaniline, stir for 30min, add 5mL solution containing 2.853g ammonium persulfate, stirred for 30min, then added 100mL solution containing 5g boric acid, aged at room temperature for 24h, freeze-dried to obtain A1;
将A1在氮气气氛下，以5℃/min的升温速率升温至700℃炭化2h得到B1，再将B1与氢氧化钾活化剂以质量比1:4在水溶液中混合12h，在105℃烘箱中干燥，然后置于管式炉中，在氮气气氛下，以5℃/min的升温速率升温至700℃活化2h，将活化后的材料浸泡在摩尔浓度为2mol/L的盐酸溶液中12h，过滤，用纯水洗至中性，于105℃烘箱中干燥24h得到气凝胶C1。 Under a nitrogen atmosphere, heat up A1 to 700°C at a rate of 5°C/min and carbonize it for 2 hours to obtain B1, then mix B1 and potassium hydroxide activator in an aqueous solution at a mass ratio of 1:4 for 12 hours, and place in an oven at 105°C Dry it, then place it in a tube furnace, and activate it at a rate of 5°C/min to 700°C for 2 hours under a nitrogen atmosphere, soak the activated material in a hydrochloric acid solution with a molar concentration of 2mol/L for 12 hours, and filter , washed with pure water until neutral, and dried in an oven at 105°C for 24 hours to obtain airgel C1.
将75wt%的气凝胶C1与10wt%的导电炭黑混合，依次加入15wt%聚四氟乙烯和10倍于聚四氟乙烯质量的N-甲基吡咯烷酮，搅拌成糊状，采用不锈钢网作为集流体，将混合好的材料均匀涂在集流体不锈钢网上，制成超级电容器电极。 Mix 75wt% airgel C1 with 10wt% conductive carbon black, add 15wt% polytetrafluoroethylene and N-methylpyrrolidone 10 times the mass of polytetrafluoroethylene in turn, stir to form a paste, use stainless steel mesh as Current collector, the mixed material is evenly coated on the stainless steel mesh of the current collector to make a supercapacitor electrode.
将制备好的超级电容器电极在100℃真空干燥12h，然后把干燥好的电极在摩尔浓度为1mol/L的硫酸溶液中浸泡12h。采用三电极体系进行电化学性能测试，以不锈钢片电极作为对电极，硫酸亚汞电极作为参比电极，测试电压范围为-0.8~0.2V；恒定电流密度0.5、1、2、5、10、20、30A/g进行循环测试，并计算出各电流密度下的比电容。同时采用对称两电极体系进行电化学性能测试。 The prepared supercapacitor electrode was vacuum-dried at 100° C. for 12 h, and then the dried electrode was soaked in a sulfuric acid solution with a molar concentration of 1 mol/L for 12 h. A three-electrode system is used for electrochemical performance testing, with a stainless steel sheet electrode as the counter electrode and a mercurous sulfate electrode as the reference electrode. The test voltage range is -0.8~0.2V; the constant current density is 0.5, 1, 2, 5, 10, 20, 30A/g cycle test, and calculate the specific capacitance under each current density. At the same time, a symmetrical two-electrode system was used to test the electrochemical performance.
本发明自组装模板机理在于，水溶性聚合物分子链的羟基和含氮前驱体的羟基分别与硼酸根离子发生脱水反应，交联生成三维的网络结构。结构式如下： The mechanism of the self-assembly template of the present invention lies in that the hydroxyl groups of the water-soluble polymer molecular chain and the hydroxyl groups of the nitrogen-containing precursor undergo dehydration reactions with borate ions respectively, and cross-link to form a three-dimensional network structure. The structural formula is as follows:
本实施例制备的超级电容器电极材料具有大的比表面积2016.02m2/g、大的孔体积1.179cm3/g、和超亲水性（接触角为1.4°），制成的超级电容器在电流密度为1A/g时，比容高达284F/g，三电极体系中电容达467F/g（1A/g）、循环寿命长（在电流密度为20A/g和30A/g时电容保持率分别为90.9%和85.7%）、功率密度和能量密度高（分别为262.5W/kg和22.75Wh/kg），能使发光二极管发光。 The supercapacitor electrode material prepared in this example has a large specific surface area of 2016.02m 2 /g, a large pore volume of 1.179cm 3 /g, and superhydrophilicity (the contact angle is 1.4°). When the density is 1A/g, the specific volume is as high as 284F/g, the capacitance in the three-electrode system is as high as 467F/g (1A/g), and the cycle life is long (at the current density of 20A/g and 30A/g, the capacitance retention rate is respectively 90.9% and 85.7%), high power density and energy density (respectively 262.5W/kg and 22.75Wh/kg), which can make light-emitting diodes emit light.
实施例2 Example 2
在60℃水浴温度下，将10g聚乙烯基吡咯烷酮（PVP）溶于100mL摩尔浓度为1.0mol/L的盐酸溶液中，搅拌1h，转至室温下，加入1.164g苯胺，搅拌30min，加入5mL溶有2.853g过硫酸铵的溶液，搅拌60min，然后加入100mL溶有5g硼酸的溶液，室温老化24h，冷冻干燥得到A2； Dissolve 10g of polyvinylpyrrolidone (PVP) in 100mL of hydrochloric acid solution with a molar concentration of 1.0mol/L at a water bath temperature of 60°C, stir for 1h, turn to room temperature, add 1.164g of aniline, stir for 30min, add 5mL of A solution containing 2.853g of ammonium persulfate was stirred for 60 minutes, then 100mL of a solution containing 5g of boric acid was added, aged at room temperature for 24 hours, and freeze-dried to obtain A2;
将A2在氮气气氛下，以5℃/min的升温速率升温至600℃炭化3h得到B2，再将B2与氢氧化钠活化剂以质量比1:2在水溶液中混合12h，在105℃烘箱中干燥，然后置于管式炉中，在氮气气氛下，以10℃/min的升温速率升温至800℃活化2h，将活化后的材料浸泡在摩尔浓度为2mol/L的盐酸溶液中12h，过滤，用纯水洗至中性，于105℃烘箱中干燥24h得到气凝胶C2。 Under a nitrogen atmosphere, heat up A2 to 600°C at a rate of 5°C/min and carbonize it for 3 hours to obtain B2, then mix B2 and sodium hydroxide activator in an aqueous solution at a mass ratio of 1:2 for 12 hours, and place in an oven at 105°C Dry it, then place it in a tube furnace, and activate it at a rate of 10°C/min to 800°C for 2 hours under a nitrogen atmosphere, soak the activated material in a hydrochloric acid solution with a molar concentration of 2mol/L for 12 hours, filter , washed with pure water until neutral, and dried in an oven at 105°C for 24 hours to obtain airgel C2.
将85wt%的气凝胶C2与5wt%的导电炭黑混合，依次加入10wt%聚四氟乙烯和5倍于聚四氟乙烯质量的N-甲基吡咯烷酮，搅拌成糊状，采用不锈钢网作为集流体，将混合好的材料均匀涂在集流体不锈钢网上，制成超级电容器电极。 Mix 85wt% airgel C2 with 5wt% conductive carbon black, add 10wt% polytetrafluoroethylene and N-methylpyrrolidone 5 times the mass of polytetrafluoroethylene in turn, stir into a paste, use stainless steel mesh as Current collector, the mixed material is evenly coated on the stainless steel mesh of the current collector to make a supercapacitor electrode.
将制备好的超级电容器电极在100℃真空干燥12h，然后把干燥好的电极在摩尔浓度为1mol/L的硫酸溶液中浸泡12h。采用三电极体系进行电化学性能测试，以不锈钢片电极作为对电极，硫酸亚汞电极作为参比电极，测试电压范围为-0.8~0.2V；恒定电流密度0.5、1、2、5、10、20、30A/g进行循环测试，并计算出各电流密度下的比电容。同时采用对称两电极体系进行电化学性能测试。 The prepared supercapacitor electrode was vacuum-dried at 100° C. for 12 h, and then the dried electrode was soaked in a sulfuric acid solution with a molar concentration of 1 mol/L for 12 h. A three-electrode system is used for electrochemical performance testing, with a stainless steel sheet electrode as the counter electrode and a mercurous sulfate electrode as the reference electrode. The test voltage range is -0.8~0.2V; the constant current density is 0.5, 1, 2, 5, 10, 20, 30A/g cycle test, and calculate the specific capacitance under each current density. At the same time, a symmetrical two-electrode system was used to test the electrochemical performance.
本实施例制备的超级电容器电极材料具有较高的比表面积1294m2/g、孔体积为0.694cm3/g、和较好的亲水性（接触角为3.8°），制成的超级电容器在电流密度为1A/g时，比容高达227F/g，三电极体系中电容达410F/g（1A/g）、在电流密度为20A/g和30A/g时电容保持率分别为85.5%和74.5%、功率密度和能量密度分别为234.38W/kg和21.28Wh/kg。 The supercapacitor electrode material prepared in this example has a high specific surface area of 1294m 2 /g, a pore volume of 0.694cm 3 /g, and good hydrophilicity (contact angle is 3.8°). When the current density is 1A/g, the specific volume is as high as 227F/g, and the capacitance in the three-electrode system reaches 410F/g (1A/g). When the current density is 20A/g and 30A/g, the capacitance retention rate is 85.5% and 74.5%, power density and energy density are 234.38W/kg and 21.28Wh/kg respectively.
实施例3 Example 3
在85℃水浴温度下，将12g聚丙烯酰胺（PAAm）溶于100mL摩尔浓度为0.5mol/L的硫酸溶液中，搅拌3h，转至室温下，加入1.327gN-甲基苯胺，搅拌45min，然后加入5mL溶有2.853g过硫酸铵的溶液，搅拌30min，然后加入100mL溶有6g硼酸的溶液，室温老化36h，冷冻干燥得到A3； Dissolve 12g of polyacrylamide (PAAm) in 100mL of sulfuric acid solution with a molar concentration of 0.5mol/L at a water bath temperature of 85°C, stir for 3h, turn to room temperature, add 1.327g of N-methylaniline, stir for 45min, then Add 5 mL of a solution containing 2.853 g of ammonium persulfate, stir for 30 minutes, then add 100 mL of a solution containing 6 g of boric acid, age at room temperature for 36 hours, and freeze-dry to obtain A3;
将A3在氩气气氛下，以5℃/min的升温速率升温至500℃炭化4h得到B3，再将B3与碳酸钾活化剂以质量比1:5在水溶液中混合12h，在105℃烘箱中干燥，然后置于管式炉中，在氩气气氛下，以10℃/min的升温速率升温至900℃活化2h，将活化后的材料浸泡在摩尔浓度为2mol/L的盐酸溶液中12h，过滤，用纯水洗至中性，于105℃烘箱中干燥24h得到气凝胶C3。 Under an argon atmosphere, heat A3 up to 500°C at a rate of 5°C/min and carbonize it for 4 hours to obtain B3, then mix B3 and potassium carbonate activator in an aqueous solution at a mass ratio of 1:5 for 12 hours, and place in an oven at 105°C Dry it, then place it in a tube furnace, and activate it at a rate of 10°C/min to 900°C for 2 hours under an argon atmosphere, and soak the activated material in a hydrochloric acid solution with a molar concentration of 2mol/L for 12 hours. Filter, wash with pure water until neutral, and dry in an oven at 105°C for 24 hours to obtain airgel C3.
将90wt%的气凝胶C3与5wt%的导电炭黑混合，依次加入5wt%聚四氟乙烯和15倍于聚四氟乙烯质量的N-甲基吡咯烷酮，搅拌成糊状，采用不锈钢网作为集流体，将混合好的材料均匀涂在集流体不锈钢网上，制成超级电容器电极。 Mix 90wt% airgel C3 with 5wt% conductive carbon black, add 5wt% polytetrafluoroethylene and N-methylpyrrolidone 15 times the mass of polytetrafluoroethylene in turn, stir into a paste, use stainless steel mesh as Current collector, the mixed material is evenly coated on the stainless steel mesh of the current collector to make a supercapacitor electrode.
将制备好的超级电容器电极在100℃真空干燥12h，然后把干燥好的电极在摩尔浓度为1mol/L硫酸溶液浸泡12h。采用三电极体系进行电化学性能测试，以不锈钢片电极作为对电极，硫酸亚汞电极作为参比电极，测试电压范围为-0.8~0.2V；恒定电流密度0.5、1、2、5、10、20、30A/g进行循环测试，并计算出各电流密度下的比电容。同时采用对称两电极体系进行电化学性能测试。 The prepared supercapacitor electrode was vacuum-dried at 100° C. for 12 hours, and then the dried electrode was soaked in a sulfuric acid solution with a molar concentration of 1 mol/L for 12 hours. A three-electrode system is used for electrochemical performance testing, with a stainless steel sheet electrode as the counter electrode and a mercurous sulfate electrode as the reference electrode. The test voltage range is -0.8~0.2V; the constant current density is 0.5, 1, 2, 5, 10, 20, 30A/g cycle test, and calculate the specific capacitance under each current density. At the same time, a symmetrical two-electrode system was used to test the electrochemical performance.
本实施例制备的超级电容器电极材料具有大的比表面积1573m2/g、孔体积为1.357cm3/g、和较好的亲水性（接触角为8.9°），制成的超级电容器在电流密度为1A/g时，比容高达217F/g，三电极体系中电容达390F/g（1A/g）、循环寿命测试表明在电流密度为20A/g和30A/g时电容保持率分别为80.5%和78.5%、功率密度和能量密度分别为247.45W/kg和18.14Wh/kg。 The supercapacitor electrode material prepared in this example has a large specific surface area of 1573m 2 /g, a pore volume of 1.357cm 3 /g, and good hydrophilicity (contact angle is 8.9°). When the density is 1A/g, the specific volume is as high as 217F/g, and the capacitance in the three-electrode system is as high as 390F/g (1A/g). The cycle life test shows that when the current density is 20A/g and 30A/g, the capacitance retention rate is respectively 80.5% and 78.5%, power density and energy density are 247.45W/kg and 18.14Wh/kg respectively.
实施例4 Example 4
在70℃水浴温度下，将8g聚甲基丙烯酸羟乙酯（PHEMA）溶于100mL摩尔浓度为1.0mol/L的硫酸溶液中，搅拌3h，转至室温下，加入0.858gN-羟乙基苯胺，搅拌60min，加入5mL溶有1.426g过硫酸铵的溶液，搅拌30min，然后加入100mL溶有4g硼酸的溶液，室温老化48h，冷冻干燥得到A4； Dissolve 8g of polyhydroxyethyl methacrylate (PHEMA) in 100mL of sulfuric acid solution with a molar concentration of 1.0mol/L at a water bath temperature of 70°C, stir for 3h, turn to room temperature, and add 0.858g of N-hydroxyethylaniline , stirred for 60 minutes, added 5 mL of a solution containing 1.426 g of ammonium persulfate, stirred for 30 minutes, then added 100 mL of a solution containing 4 g of boric acid, aged at room temperature for 48 hours, and freeze-dried to obtain A4;
将A4在氩气气氛下，以10℃/min的升温速率升温至1000℃炭化2h得到B4，再将B4与氢氧化钾活化剂以质量比1:3在水溶液中混合6h，在105℃烘箱中干燥，然后置于管式炉中，在氩气气氛下，以5℃/min的升温速率升温至600℃活化4h，将活化后的材料浸泡在摩尔浓度为2mol/L的盐酸溶液中12h，过滤，使用纯水洗至中性，于105℃烘箱中干燥24h得到气凝胶C4。 Under an argon atmosphere, heat A4 up to 1000°C at a rate of 10°C/min and carbonize it for 2 hours to obtain B4, then mix B4 and potassium hydroxide activator in an aqueous solution at a mass ratio of 1:3 for 6 hours, and place in an oven at 105°C Then put it in a tube furnace and activate it at a rate of 5°C/min to 600°C for 4 hours under an argon atmosphere, and soak the activated material in a hydrochloric acid solution with a molar concentration of 2mol/L for 12 hours , filtered, washed with pure water until neutral, and dried in an oven at 105°C for 24 hours to obtain airgel C4.
将80wt%的气凝胶C4与10wt%的导电炭黑混合，依次加入10wt%聚四氟乙烯和10倍于聚四氟乙烯质量的N-甲基吡咯烷酮，搅拌成糊状，采用不锈钢网作为集流体，将混合好的材料均匀涂在集流体不锈钢网上，制成超级电容器电极。 Mix 80wt% airgel C4 with 10wt% conductive carbon black, add 10wt% polytetrafluoroethylene and N-methylpyrrolidone 10 times the mass of polytetrafluoroethylene in turn, stir to form a paste, use stainless steel mesh as Current collector, the mixed material is evenly coated on the stainless steel mesh of the current collector to make a supercapacitor electrode.
将制备好的超级电容器电极在100℃真空干燥12h，然后把干燥好的电极在摩尔浓度为1mol/L的硫酸溶液中浸泡12h。采用三电极体系进行电化学性能测试，以不锈钢片电极作为对电极，硫酸亚汞电极作为参比电极，测试电压范围为-0.8~0.2V；恒定电流密度0.5、1、2、5、10、20、30A/g进行循环测试，并计算出各电流密度下的比电容。同时采用对称两电极体系进行电化学性能测试。 The prepared supercapacitor electrode was vacuum-dried at 100° C. for 12 h, and then the dried electrode was soaked in a sulfuric acid solution with a molar concentration of 1 mol/L for 12 h. A three-electrode system is used for electrochemical performance testing, with a stainless steel sheet electrode as the counter electrode and a mercurous sulfate electrode as the reference electrode. The test voltage range is -0.8~0.2V; the constant current density is 0.5, 1, 2, 5, 10, 20, 30A/g cycle test, and calculate the specific capacitance under each current density. At the same time, a symmetrical two-electrode system was used to test the electrochemical performance.
本实施例制备的超级电容器电极材料具有大的比表面积1502m2/g、孔体积0.829cm3/g、和较好的亲水性（接触角为5.1°），制成的超级电容器在电流密度为1A/g时，比容高达206F/g，三电极体系中电容达385F/g（1A/g）、在电流密度为20A/g和30A/g时电容保持率分别为83.6%和76.8%、功率密度和能量密度分别为248.2W/kg和16.85Wh/kg。 The supercapacitor electrode material prepared in this example has a large specific surface area of 1502m 2 /g, a pore volume of 0.829cm 3 /g, and good hydrophilicity (the contact angle is 5.1°). When the current density is 1A/g, the specific volume is as high as 206F/g, the capacitance in the three-electrode system is 385F/g (1A/g), and the capacitance retention rate is 83.6% and 76.8% when the current density is 20A/g and 30A/g , power density and energy density are 248.2W/kg and 16.85Wh/kg respectively.
实施例5 Example 5
在80℃水浴温度下，将10g聚乙烯醇（PVA）溶于100mL摩尔浓度为0.1mol/L盐酸溶液中，搅拌2h，转至室温下，加入1.164g苯胺，搅拌30min，加入5mL溶有2.853g过硫酸铵的溶液，搅拌60min，然后加入100mL溶有5g硼酸的溶液，室温老化24h，冷冻干燥得到A5； At 80°C water bath temperature, dissolve 10g polyvinyl alcohol (PVA) in 100mL hydrochloric acid solution with a molar concentration of 0.1mol/L, stir for 2h, turn to room temperature, add 1.164g of aniline, stir for 30min, add 5mL to dissolve 2.853 g ammonium persulfate solution, stirred for 60min, then added 100mL solution containing 5g boric acid, aged at room temperature for 24h, and freeze-dried to obtain A5;
将A5在氮气气氛下，以5℃/min的升温速率升温至700℃炭化2h得到B5，再将B5与氢氧化钾活化剂以质量比1:4在水溶液中混合12h，在105℃烘箱中干燥，然后置于管式炉中，在氮气气氛下，以5℃/min的升温速率升温至700℃活化2h，将活化后的材料浸泡在摩尔浓度为2mol/L盐酸溶液中12h，过滤，用纯水洗至中性，于105℃烘箱中干燥24h得到气凝胶C5。 Under a nitrogen atmosphere, heat A5 to 700°C at a rate of 5°C/min and carbonize it for 2 hours to obtain B5, then mix B5 and potassium hydroxide activator in an aqueous solution at a mass ratio of 1:4 for 12 hours, and place in an oven at 105°C Dry it, then place it in a tube furnace, and in a nitrogen atmosphere, raise the temperature to 700°C at a rate of 5°C/min for activation for 2h, soak the activated material in a hydrochloric acid solution with a molar concentration of 2mol/L for 12h, filter, Wash with pure water until neutral, and dry in an oven at 105°C for 24 hours to obtain airgel C5.
将75wt%的气凝胶C5与10wt%的导电炭黑混合，依次加入15wt%聚四氟乙烯和10倍于聚四氟乙烯质量的N-甲基吡咯烷酮，搅拌成糊状，采用不锈钢网作为集流体，将混合好的材料均匀涂在集流体不锈钢网上，制成超级电容器电极。 Mix 75wt% airgel C5 with 10wt% conductive carbon black, add 15wt% polytetrafluoroethylene and N-methylpyrrolidone 10 times the mass of polytetrafluoroethylene in turn, stir into a paste, use stainless steel mesh as Current collector, the mixed material is evenly coated on the stainless steel mesh of the current collector to make a supercapacitor electrode.
将制备好的超级电容器电极在100℃真空干燥12h，然后把干燥好的电极片在摩尔浓度为1mol/L的硫酸溶液中浸泡12h。采用三电极体系进行电化学性能测试，以不锈钢片电极作为对电极，硫酸亚汞电极作为参比电极，测试电压范围为-0.8~0.2V；恒定电流密度0.5、1、2、5、10、20、30A/g进行循环测试，并计算出各电流密度下的比电容。同时采用对称两电极体系进行电化学性能测试。 The prepared supercapacitor electrode was vacuum-dried at 100° C. for 12 h, and then the dried electrode sheet was soaked in a sulfuric acid solution with a molar concentration of 1 mol/L for 12 h. A three-electrode system is used for electrochemical performance testing, with a stainless steel sheet electrode as the counter electrode and a mercurous sulfate electrode as the reference electrode. The test voltage range is -0.8~0.2V; the constant current density is 0.5, 1, 2, 5, 10, 20, 30A/g cycle test, and calculate the specific capacitance under each current density. At the same time, a symmetrical two-electrode system was used to test the electrochemical performance.
本实施例制备的超级电容器电极材料具比表面积为1021m2/g、孔体积为0.558cm3/g、和超亲水性（接触角为3.0°），制成的超级电容器在电流密度为1A/g时，比容高达207F/g，三电极体系中电容达379F/g（1A/g）、在电流密度为20A/g和30A/g时电容保持率分别为85.5%和80.4%、功率密度和能量密度分别为245W/kg和17.2Wh/kg。 The supercapacitor electrode material prepared in this example has a specific surface area of 1021m 2 /g, a pore volume of 0.558cm 3 /g, and superhydrophilicity (a contact angle of 3.0°). The supercapacitor produced at a current density of 1A When the current density is 20A/g and 30A/g, the specific volume is as high as 207F/g, the capacitance in the three-electrode system is 379F/g (1A/g), and the capacitance retention rate is 85.5% and 80.4% when the current density is 20A/g and 30A/g. The density and energy density are 245W/kg and 17.2Wh/kg, respectively.
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。 The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.
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