CN105742072B - A kind of metal embeds preparation method of the porous carbon to electrode material - Google Patents
A kind of metal embeds preparation method of the porous carbon to electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 title claims description 12
- 239000002184 metal Substances 0.000 title claims description 12
- 239000000499 gel Substances 0.000 claims abstract description 25
- 229920002472 Starch Polymers 0.000 claims abstract description 19
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 239000008107 starch Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000001868 cobalt Chemical class 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 15
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- 108010010803 Gelatin Proteins 0.000 claims abstract description 13
- 239000008273 gelatin Substances 0.000 claims abstract description 13
- 229920000159 gelatin Polymers 0.000 claims abstract description 13
- 235000019322 gelatine Nutrition 0.000 claims abstract description 13
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 13
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 2
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 238000012827 research and development Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BNKWCSJBOZKTJL-UHFFFAOYSA-N [Co].[N].[S] Chemical compound [Co].[N].[S] BNKWCSJBOZKTJL-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- 229920001940 conductive polymer Polymers 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明公开了一种金属内嵌多孔碳对电极材料的制备方法，将可溶性淀粉和明胶粉加入到去离子水中，再将可溶性钴盐和可溶性镍盐加入到上述混合溶液中，于80℃搅拌混合均匀形成溶胶，然后将该溶胶于80℃搅拌24h形成凝胶，再将凝胶置于干燥箱内于80℃干燥形成干凝胶，将所得干凝胶置于管式炉中，在N2气氛条件下于600‑900℃煅烧2h，自然冷却后制得钴镍合金内嵌的氮硫共掺杂多孔碳对电极材料。本发明所用原料均为常见的试剂，成本低廉；制备方法简单，适宜大批量生产；所得产品中的氮硫掺杂使多孔碳表面的电荷分布发生改变，形成不同电性的催化活性位点，同时提高碳材料的表面润湿性，因而具有明显的催化活性。
The invention discloses a method for preparing a metal-embedded porous carbon counter electrode material. Add soluble starch and gelatin powder to deionized water, then add soluble cobalt salt and soluble nickel salt to the above mixed solution, and heat the mixture at 80°C. Stir and mix evenly to form a sol, then stir the sol at 80°C for 24 hours to form a gel, then place the gel in a drying oven at 80°C to form a xerogel, place the obtained xerogel in a tube furnace, and Calcined at 600-900°C for 2 h under N 2 atmosphere, and cooled naturally to prepare a nitrogen-sulfur co-doped porous carbon counter electrode material embedded in a cobalt-nickel alloy. The raw materials used in the present invention are common reagents with low cost; the preparation method is simple and suitable for mass production; the nitrogen and sulfur doping in the obtained product changes the charge distribution on the surface of the porous carbon, forming catalytic active sites with different electrical properties, At the same time, the surface wettability of carbon materials is improved, so it has obvious catalytic activity.
Description
技术领域technical field
本发明属于染料敏化光伏电池电极材料的合成技术领域，具体涉及一种金属内嵌多孔碳对电极材料的制备方法。The invention belongs to the technical field of synthesis of dye-sensitized photovoltaic battery electrode materials, and in particular relates to a method for preparing a metal-embedded porous carbon counter electrode material.
背景技术Background technique
染料敏化光伏电池是一类重要的光伏器件，主要优点是制作工艺简单、成本低廉、环境友好以及光伏效率较高，在学术界和产业界都受到了广泛关注，具有很好的产业化前景。Dye-sensitized photovoltaic cells are an important class of photovoltaic devices. The main advantages are simple manufacturing process, low cost, environmental friendliness and high photovoltaic efficiency. They have received extensive attention in both academia and industry, and have good industrialization prospects. .
染料敏化光伏电池包括敏化光阳极、对电极和电解质三个部分，接受入射光照射激发时，光阳极上的敏化染料将光电子注入光阳极并传输至外电路，自身形成染料正离子，外电路电子传递至对电极，在对电极催化作用下将电解质溶液中的I3 -还原成I-，电解质中I-扩散至光阳极还原染料正离子，完成持续的光电转换。其中对电极的主要作用是接受外电路电子催化还原I3 -，因而应具有良好的导电性、较大的可接触表面积和丰富的表面活性位点。传统的镀Pt对电极催化活性较高，但存在着电解质腐蚀及成本问题，不利于染料敏化光伏电池的商业化推广。廉价高效的非Pt对电极材料是该领域研究开发的热点之一。一系列金属氧族化物、导电聚合物以及碳材料都可用作替代对电极材料，光伏效率逐渐提高。异质元素掺杂多孔碳材料具有丰富的异质元素活性位点、良好的导电性、高比表面积和耐腐蚀性等结构优势，可用作高效对电极材料；此外，铁系金属单质与Pt有相似的价层电子结构，其合金具有良好的催化活性，但是易受电解质腐蚀钝化，稳定性欠佳。将其与异质元素掺杂多孔碳形成复合物不仅能提高碳材料的导电性，而且能提高碳材料的催化活性，因而在染料敏化光伏电池催化对电极材料方面有望获得较高的光伏性能，但是到目前为止，这类材料在对电极方面的研究开发鲜见报道。Dye-sensitized photovoltaic cells include three parts: a sensitized photoanode, a counter electrode and an electrolyte. When excited by incident light, the sensitizing dye on the photoanode injects photoelectrons into the photoanode and transmits them to the external circuit, forming positive dye ions by itself. The electrons from the external circuit are transferred to the counter electrode, and the I 3 - in the electrolyte solution is reduced to I - under the catalysis of the counter electrode, and the I - in the electrolyte diffuses to the photoanode to reduce the dye positive ions to complete the continuous photoelectric conversion. The main function of the counter electrode is to accept electrons from the external circuit to catalyze the reduction of I 3 - , so it should have good conductivity, large accessible surface area and abundant surface active sites. Traditional Pt plating has high catalytic activity on the electrode, but there are electrolyte corrosion and cost problems, which are not conducive to the commercialization of dye-sensitized photovoltaic cells. Cheap and efficient non-Pt counter electrode materials are one of the research and development hotspots in this field. A series of metal oxogenides, conductive polymers, and carbon materials can be used as alternative counter electrode materials, and the photovoltaic efficiency is gradually improved. Heterogeneous element-doped porous carbon materials have structural advantages such as abundant heterogeneous element active sites, good electrical conductivity, high specific surface area, and corrosion resistance, and can be used as high-efficiency counter electrode materials; It has a similar valence layer electronic structure, and its alloy has good catalytic activity, but is susceptible to electrolyte corrosion and passivation, and its stability is not good. Forming a complex with heterogeneous element-doped porous carbon can not only improve the conductivity of carbon materials, but also improve the catalytic activity of carbon materials, so it is expected to obtain higher photovoltaic performance in the catalytic counter electrode material of dye-sensitized photovoltaic cells , but so far, there are few reports on the research and development of this type of material in the counter electrode.
发明内容Contents of the invention
本发明的目的是提供了一种金属内嵌多孔碳对电极材料的制备方法，所制的材料用于染料敏化光伏器件对电极能提供优越的光伏性能。The object of the present invention is to provide a method for preparing a metal-embedded porous carbon counter electrode material, and the prepared material can provide superior photovoltaic performance for the counter electrode of a dye-sensitized photovoltaic device.
本发明为实现上述目的采取如下技术方案，一种金属内嵌多孔碳对电极材料的制备方法，其特征在于金属钴或镍内嵌氮硫共参杂多孔碳对电极材料的具体合成过程为：将可溶性淀粉和明胶粉加入到去离子水中，再将可溶性钴盐或者可溶性镍盐加入到上述混合溶液中，于80℃搅拌混合均匀形成溶胶，然后将该溶胶于80℃搅拌24h形成凝胶，再将凝胶置于干燥箱内于80℃干燥形成干凝胶，将所得干凝胶置于管式炉中，在N2气氛条件下于600-900℃煅烧2h，自然冷却后制得金属钴或镍内嵌的氮硫共掺杂多孔碳对电极材料。In order to achieve the above object, the present invention adopts the following technical scheme, a method for preparing a metal embedded porous carbon counter electrode material, which is characterized in that the specific synthesis process of metal cobalt or nickel embedded nitrogen and sulfur co-doped porous carbon counter electrode material is as follows: Add soluble starch and gelatin powder to deionized water, then add soluble cobalt salt or soluble nickel salt to the above mixed solution, stir and mix evenly at 80°C to form a sol, and then stir the sol at 80°C for 24 hours to form a gel , and then put the gel in a drying oven to dry at 80°C to form a xerogel, place the obtained xerogel in a tube furnace, calcinate at 600-900°C for 2 hours under N2 atmosphere, and cool naturally to obtain Nitrogen-sulfur co-doped porous carbon counter electrode material embedded in metal cobalt or nickel.
进一步优选，所述的可溶性淀粉、明胶粉和可溶性钴盐或可溶性镍盐的质量比为2.5:2-5:2.4-3.2。Further preferably, the mass ratio of the soluble starch, gelatin powder and soluble cobalt salt or soluble nickel salt is 2.5:2-5:2.4-3.2.
本发明所述的金属内嵌多孔碳对电极材料的制备方法，其特征在于钴镍合金内嵌多孔碳对电极材料的具体合成过程为：将可溶性淀粉加入到去离子水中，再将可溶性钴盐和可溶性镍盐加入到上述混合溶液中，于80℃搅拌混合均匀形成溶胶，然后将该溶胶于80℃搅拌24h形成凝胶，再将凝胶置于干燥箱内于80℃干燥形成干凝胶，将所得干凝胶置于管式炉中，在N2气氛条件下于600-900℃煅烧2h，自然冷却后制得钴镍合金内嵌的多孔碳对电极材料。The preparation method of the metal-embedded porous carbon counter electrode material of the present invention is characterized in that the specific synthesis process of the cobalt-nickel alloy embedded porous carbon counter electrode material is: adding soluble starch to deionized water, and then adding soluble cobalt salt Add soluble nickel salt to the above mixed solution, stir and mix evenly at 80°C to form a sol, then stir the sol at 80°C for 24 hours to form a gel, then place the gel in a drying oven at 80°C to form a xerogel , the obtained xerogel was placed in a tube furnace, calcined at 600-900°C for 2h under N 2 atmosphere, and cooled naturally to obtain a porous carbon counter electrode material embedded in a cobalt-nickel alloy.
进一步优选，所述的可溶性淀粉、可溶性钴盐和可溶性镍盐的质量比为2.5:1.2-1.6:1.2-1.6。Further preferably, the mass ratio of the soluble starch, soluble cobalt salt and soluble nickel salt is 2.5:1.2-1.6:1.2-1.6.
本发明所述的金属内嵌多孔碳对电极材料的制备方法，其特征在于钴镍合金内嵌氮硫共掺杂多孔碳对电极材料的具体合成过程为：将可溶性淀粉和明胶粉加入到去离子水中，再将可溶性钴盐和可溶性镍盐加入到上述混合溶液中，于80℃搅拌混合均匀形成溶胶，然后将该溶胶于80℃搅拌24h形成凝胶，再将凝胶置于干燥箱内于80℃干燥形成干凝胶，将所得干凝胶置于管式炉中，在N2气氛条件下于600-900℃煅烧2h，自然冷却后制得钴镍合金内嵌的氮硫共掺杂多孔碳对电极材料。The preparation method of the metal-embedded porous carbon counter electrode material of the present invention is characterized in that the specific synthesis process of the cobalt-nickel alloy embedded nitrogen-sulfur co-doped porous carbon counter electrode material is: adding soluble starch and gelatin powder to Add soluble cobalt salt and soluble nickel salt to the above mixed solution in deionized water, stir and mix evenly at 80°C to form a sol, then stir the sol at 80°C for 24 hours to form a gel, and then place the gel in a drying oven Dried at 80°C to form a xerogel, put the obtained xerogel in a tube furnace, and calcined at 600-900°C for 2 hours under N2 atmosphere, and cooled naturally to obtain a cobalt-nickel alloy-embedded nitrogen-sulfur cobalt Doped porous carbon counter electrode material.
进一步优选，所述的可溶性淀粉、明胶粉、可溶性钴盐和可溶性镍盐的质量比为2.5:2-5:1.2-1.6:1.2-1.6。Further preferably, the mass ratio of the soluble starch, gelatin powder, soluble cobalt salt and soluble nickel salt is 2.5:2-5:1.2-1.6:1.2-1.6.
进一步优选，所述的可溶性钴盐为硝酸钴、硫酸钴或氯化钴。Further preferably, the soluble cobalt salt is cobalt nitrate, cobalt sulfate or cobalt chloride.
进一步优选，所述的可溶性镍盐为硝酸镍、硫酸镍或氯化镍。Further preferably, the soluble nickel salt is nickel nitrate, nickel sulfate or nickel chloride.
本发明通过调节金属盐比例以及金属盐与碳源的比例来优化钴镍合金纳米颗粒粒径和异质元素碳包覆层的厚度，提高其电催化活性以及在染料敏化光伏器件对电极方面的光伏效率。与现有对电极材料制备技术相比，本发明所用原料均为常见的试剂，成本低廉；制备方法简单，适宜大批量生产。所得产品中的氮硫掺杂使多孔碳表面的电荷分布发生改变，形成不同电性的催化活性位点，同时提高碳材料的表面润湿性，因而具有明显的催化活性。此外，合金纳米颗粒自身也具有良好的催化活性，可进一步提高催化活性，同时能有效改善材料导电性，因此可用作高效电催化电极材料。用于染料敏化光伏器件的催化对电极，能提供优越的光伏效率，在染料敏化光伏电池领域有广阔的应用前景。The present invention optimizes the particle size of cobalt-nickel alloy nanoparticles and the thickness of the heterogeneous element carbon coating layer by adjusting the ratio of metal salt and metal salt to carbon source, so as to improve its electrocatalytic activity and improve its performance on the counter electrode of dye-sensitized photovoltaic devices. photovoltaic efficiency. Compared with the existing counter electrode material preparation technology, the raw materials used in the present invention are common reagents with low cost; the preparation method is simple and suitable for mass production. The nitrogen and sulfur doping in the obtained product changes the charge distribution on the surface of the porous carbon, forms catalytic active sites with different electrical properties, and improves the surface wettability of the carbon material, so it has obvious catalytic activity. In addition, the alloy nanoparticles themselves have good catalytic activity, which can further improve the catalytic activity, and can effectively improve the electrical conductivity of the material, so they can be used as high-efficiency electrocatalytic electrode materials. The catalytic counter electrode used for dye-sensitized photovoltaic devices can provide superior photovoltaic efficiency and has broad application prospects in the field of dye-sensitized photovoltaic cells.
附图说明Description of drawings
图1是本发明实施例1制得的钴镍合金内嵌多孔碳对电极材料用于染料敏化光伏器件的光伏曲线图，图中虚线为镀Pt对电极器件的光伏曲线图，由图可知本发明所制对电极材料用于染料敏化光伏器件能提供优越的光伏性能；Fig. 1 is the photovoltaic curve diagram that the cobalt-nickel alloy embedded porous carbon counter electrode material that the embodiment of the present invention makes is used for the dye-sensitized photovoltaic device, and the dotted line in the figure is the photovoltaic curve diagram of the Pt-plated counter electrode device, as can be seen from the figure The counter electrode material prepared by the present invention can provide superior photovoltaic performance when used in dye-sensitized photovoltaic devices;
图2是本发明实施例2制得的钴镍合金内嵌氮硫共掺杂多孔碳对电极材料的SEM图；Fig. 2 is the SEM picture of the cobalt-nickel alloy embedded nitrogen-sulfur co-doped porous carbon counter electrode material that is obtained in Example 2 of the present invention;
图3是本发明实施例2制得的钴镍合金内嵌氮硫共掺杂多孔碳对电极材料的TEM图。FIG. 3 is a TEM image of the cobalt-nickel alloy-embedded nitrogen-sulfur co-doped porous carbon counter electrode material prepared in Example 2 of the present invention.
具体实施方式Detailed ways
下面结合实施例对本发明的上述内容做进一步详细说明。本实施例在以本发明技术方案为前提下实施，给出了详细的实施方式和操作过程，但本发明的保护范围不限于以下实施例。The above content of the present invention will be further described in detail below in conjunction with the embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and the detailed implementation and operation process are given, but the protection scope of the present invention is not limited to the following examples.
实施例1Example 1
将2.5g可溶性淀粉加入到60mL去离子水中，再将1.2g Ni(NO3)2·6H2O和1.2g Co(NO3)2·6H2O加入到上述混合溶液中，在磁力加热搅拌器上于80℃搅拌混合均匀形成溶胶。然后将该溶胶在恒温80℃的条件下搅拌24h形成凝胶。再将凝胶置于干燥箱内于80℃完全干燥形成干凝胶。将所得干凝胶置于管式炉中，在N2气氛条件下于900℃煅烧2h，自然冷却后制得钴镍合金内嵌的多孔碳对电极材料。Add 2.5g soluble starch to 60mL deionized water, then add 1.2g Ni(NO 3 ) 2 6H 2 O and 1.2g Co(NO 3 ) 2 6H 2 O to the above mixed solution, and stir under magnetic heating Stir and mix on a device at 80°C to form a sol evenly. Then the sol was stirred at a constant temperature of 80° C. for 24 h to form a gel. The gel was then placed in a drying oven at 80°C to completely dry to form a xerogel. The obtained xerogel was placed in a tube furnace, calcined at 900 °C for 2 h under N2 atmosphere, and cooled naturally to obtain a porous carbon counter electrode material embedded in a cobalt-nickel alloy.
将所制的钴镍合金内嵌的多孔碳对电极材料用10%聚四氟乙烯（PTFE）制成浆料刮涂在FTO表面作对电极，与N719染料（二-四丁铵-双(异硫氰基)双(2,2'-联吡啶-4,4'-二羧基)钌(II)）敏化TiO2光阳极及I3 -/I-电解质组装染料敏化光伏器件，光伏效率为7.3%（图1）。The prepared cobalt-nickel alloy-embedded porous carbon counter electrode material was made of 10% polytetrafluoroethylene (PTFE) to make a slurry and scrape-coated on the surface of FTO as a counter electrode, and N719 dye (di-tetrabutylammonium-bis(iso Thiocyano)bis(2,2'-bipyridyl-4,4'-dicarboxy)ruthenium(II)) sensitized TiO2 photoanode and I3- / I - electrolyte assembled dye-sensitized photovoltaic devices, photovoltaic efficiency was 7.3% (Figure 1).
实施例2Example 2
将2.5g可溶性淀粉和2g明胶粉加入到60mL去离子水中，再将1.2g Ni(NO3)2·6H2O和1.2g Co(NO3)2·6H2O加入到上述混合溶液中，在磁力加热搅拌器上于80℃搅拌混合均匀形成溶胶。然后将该溶胶在恒温80℃的条件下搅拌24h形成凝胶。再将凝胶置于干燥箱内于80℃完全干燥形成干凝胶。将所得干凝胶置于管式炉中，在N2气氛条件下于900℃煅烧2h，自然冷却后制得钴镍合金内嵌的氮硫共掺杂多孔碳对电极材料（图2）。将所制对电极材料按照实施例1制作对电极并组装染料敏化光伏器件，光伏效率达7.6%。Add 2.5g soluble starch and 2g gelatin powder into 60mL deionized water, then add 1.2g Ni(NO 3 ) 2 ·6H 2 O and 1.2g Co(NO 3 ) 2 ·6H 2 O to the above mixed solution , Stir and mix on a magnetic heating stirrer at 80°C to form a sol evenly. Then the sol was stirred at a constant temperature of 80° C. for 24 h to form a gel. The gel was then placed in a drying oven at 80°C to completely dry to form a xerogel. The obtained xerogel was placed in a tube furnace, calcined at 900 °C for 2 h under N2 atmosphere, and cooled naturally to prepare a nitrogen-sulfur co-doped porous carbon counter electrode material embedded in a cobalt-nickel alloy (Figure 2). The prepared counter electrode material was prepared according to Example 1, and a dye-sensitized photovoltaic device was assembled, and the photovoltaic efficiency reached 7.6%.
实施例3Example 3
将2.5g可溶性淀粉和5g明胶粉加入到60mL去离子水中，再将2.4g Co(NO3)2·6H2O加入到上述混合溶液中，在磁力加热搅拌器上于80℃搅拌混合均匀形成溶胶。然后将该溶胶在恒温80℃条件下搅拌24h形成凝胶。再将凝胶置于干燥箱内于80℃完全干燥形成干凝胶。将所得干凝胶置于管式炉中，在N2气氛条件下于900℃煅烧2h，自然冷却后制得金属钴内嵌的氮硫共掺杂多孔碳对电极材料。将所制对电极材料按照实施例1制作对电极并组装染料敏化光伏器件，光伏效率为7.1%。Add 2.5g soluble starch and 5g gelatin powder into 60mL deionized water, then add 2.4g Co(NO 3 ) 2 ·6H 2 O into the above mixed solution, stir and mix evenly at 80°C on a magnetic heating stirrer form a sol. Then the sol was stirred at a constant temperature of 80° C. for 24 h to form a gel. The gel was then placed in a drying oven at 80°C to completely dry to form a xerogel. The obtained xerogel was placed in a tube furnace, calcined at 900 °C for 2 h under N2 atmosphere, and cooled naturally to prepare a nitrogen-sulfur co-doped porous carbon counter electrode material embedded in metal cobalt. The prepared counter electrode material was prepared according to Example 1, and a dye-sensitized photovoltaic device was assembled, and the photovoltaic efficiency was 7.1%.
实施例4Example 4
将2.5g可溶性淀粉和2g明胶粉加入到60mL去离子水中，再将0.8g Ni(NO3)2·6H2O和1.6g Co(NO3)2·6H2O加入到上述混合溶液中，在磁力加热搅拌器上于80℃搅拌混合均匀形成溶胶。然后将该溶胶在恒温80℃条件下搅拌24h形成凝胶。再将凝胶置于干燥箱内于80℃完全干燥形成干凝胶。将所得干凝胶置于管式炉中，在N2气氛条件下于600℃煅烧2h，自然冷却后制得钴镍合金内嵌的氮硫共掺杂多孔碳对电极材料。将所制对电极材料按照实施例1制作对电极并组装染料敏化光伏器件，光伏效率为5.0%。Add 2.5g soluble starch and 2g gelatin powder into 60mL deionized water, then add 0.8g Ni(NO 3 ) 2 ·6H 2 O and 1.6g Co(NO 3 ) 2 ·6H 2 O to the above mixed solution , Stir and mix on a magnetic heating stirrer at 80°C to form a sol evenly. Then the sol was stirred at a constant temperature of 80° C. for 24 h to form a gel. The gel was then placed in a drying oven at 80°C to completely dry to form a xerogel. The obtained xerogel was placed in a tube furnace, calcined at 600 °C for 2 h under N2 atmosphere, and cooled naturally to prepare a nitrogen-sulfur co-doped porous carbon counter electrode material embedded in a cobalt-nickel alloy. The prepared counter electrode material was prepared according to Example 1, and a dye-sensitized photovoltaic device was assembled, and the photovoltaic efficiency was 5.0%.
实施例5Example 5
将2.5g可溶性淀粉加入到60mL去离子水中，再将1.6g Ni(NO3)2·6H2O和1.6g Co(NO3)2·6H2O加入到上述混合溶液中，在磁力加热搅拌器上于80℃搅拌混合均匀形成溶胶。然后将该溶胶在恒温80℃条件下搅拌24h形成凝胶。再将凝胶置于干燥箱内于80℃完全干燥形成干凝胶。将所得干凝胶置于管式炉中，在N2气氛条件下于600℃煅烧2h，自然冷却后制得钴镍合金内嵌的多孔碳对电极材料。将所制对电极材料按照实施例1制作对电极并组装染料敏化光伏器件，光伏效率为6.8%。Add 2.5g soluble starch to 60mL deionized water, then add 1.6g Ni(NO 3 ) 2 6H 2 O and 1.6g Co(NO 3 ) 2 6H 2 O to the above mixed solution, heat and stir under magnetic force Stir and mix on a device at 80°C to form a sol evenly. Then the sol was stirred at a constant temperature of 80° C. for 24 h to form a gel. The gel was then placed in a drying oven at 80°C to completely dry to form a xerogel. The obtained xerogel was placed in a tube furnace, calcined at 600 °C for 2 h under N2 atmosphere, and cooled naturally to obtain a porous carbon counter electrode material embedded in a cobalt-nickel alloy. The prepared counter electrode material was prepared according to Example 1, and a dye-sensitized photovoltaic device was assembled, and the photovoltaic efficiency was 6.8%.
通过上述实施例可以看出，通过调节碳氮硫源（明胶）质量、可溶性镍盐与可溶性钴盐的质量比及总质量、煅烧碳化温度，均能显著优化金属内嵌多孔碳对电极器件的光伏性能。From the above examples, it can be seen that by adjusting the quality of the carbon, nitrogen and sulfur source (gelatin), the mass ratio and total mass of the soluble nickel salt to the soluble cobalt salt, and the calcination carbonization temperature, the metal-embedded porous carbon counter electrode device can be significantly optimized. Photovoltaic performance.
以上为本发明的典型实施例，这些实施例描述了本发明的主要特征及特定实施条件下的应用性能。应当指出，对于本技术领域的其他技术人员来说，在不脱离本发明原理的前提下，任何对本发明进行的若干改进和修饰，也落入本发明权利要求的保护范围内。The above are typical embodiments of the present invention, and these embodiments describe the main features of the present invention and the application performance under specific implementation conditions. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, any improvements and modifications made to the present invention also fall within the protection scope of the claims of the present invention.
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