CN104183392A - Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof - Google Patents
Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 113
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 239000007772 electrode material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229920005546 furfural resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 125000000185 sucrose group Chemical group 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 2
- 238000006703 hydration reaction Methods 0.000 claims 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 239000002736 nonionic surfactant Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000000802 evaporation-induced self-assembly Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000002815 nickel Chemical class 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 239000001569 carbon dioxide Substances 0.000 description 17
- -1 silicon dioxide compound Chemical class 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 239000012456 homogeneous solution Substances 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 150000002484 inorganic compounds Chemical class 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 229940075397 calomel Drugs 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DUKQZMHSXLRNSN-UHFFFAOYSA-N ethanol;nickel Chemical compound [Ni].CCO DUKQZMHSXLRNSN-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 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
本发明公开一种介孔氧化镍/碳复合纳米材料的制备方法。所述介孔氧化镍/碳复合纳米材料，其元素组成按原子百分比计算，氧原子为1%、镍原子为2.72-3.75%，碳原子为96.28-95.25%，其比表面积为435.5～800m2/g、孔体积为1.08～1.5cm3/g，其孔径为2.5～12.0nm。其制备方法即以非离子表面活性剂作为模板剂、以无机镍盐为镍源，通过蒸发诱导自组装的方法制备出一种具有大比表面积和孔体积以及大孔径的介孔氧化镍/碳复合纳米材料，该介孔氧化镍/碳复合纳米材料可用制作超级电容器所用的电极材料。其制备方法简单，原料简单易得，适合大规模生产。
The invention discloses a method for preparing a mesoporous nickel oxide/carbon composite nanometer material. The mesoporous nickel oxide/carbon composite nanomaterial has an elemental composition calculated by atomic percentage, 1% of oxygen atoms, 2.72-3.75% of nickel atoms, 96.28-95.25% of carbon atoms, and a specific surface area of 435.5-800m2 /g, the pore volume is 1.08-1.5cm 3 /g, and the pore diameter is 2.5-12.0nm. The preparation method is to prepare a mesoporous nickel oxide/carbon with large specific surface area, pore volume and large pore diameter by using non-ionic surfactant as template agent and inorganic nickel salt as nickel source through evaporation-induced self-assembly method. Composite nano material, the mesoporous nickel oxide/carbon composite nano material can be used to make electrode materials for supercapacitors. The preparation method is simple, the raw material is simple and easy to obtain, and is suitable for large-scale production.
Description
技术领域 technical field
本发明属于无机材料合成，制备电极材料的领域，具体涉及一种介孔氧化镍/碳复合纳米材料及其制备方法。 The invention belongs to the field of inorganic material synthesis and preparation of electrode materials, and in particular relates to a mesoporous nickel oxide/carbon composite nanometer material and a preparation method thereof.
背景技术 Background technique
超级电容器作为一种介于传统电容器和锂离子电池之间的新型储能体系，其功率密度显著高于锂离子电池，能量密度是传统电容器的10~100倍,安全系数高，充放电循环寿命长，工作温度范围宽，经济环保免维护等优点。介孔材料作为一种新兴的固体多孔材料，不仅具有孔道大小均一、排列有序、孔径可以在2~50nm内连续调节等重要特征，而且还具有较大的孔容、高的比表面积、孔道表面可进行物理吸附或化学修饰及较好的水热稳定性等特点。过度金属氧化物由于具有较高的理论比容量、价格低廉且易获得，成为重要过的电极材料，但是由于导电率低、循环稳定性差，使其很难规模化运用，针对它的这些问题，可以通过掺杂或与碳材料复合进行改进。因为碳材料的导电率高、比表面积大、柔韧性好等优点。同时碳层可以提高金属氧化物电极材料的整体导电性，而且碳层和金属氧化物具有协同效应，可以提高比容量和速率比容量。 As a new type of energy storage system between traditional capacitors and lithium-ion batteries, supercapacitors have significantly higher power density than lithium-ion batteries, and energy density is 10 to 100 times that of traditional capacitors. Long, wide operating temperature range, economical, environmentally friendly and maintenance-free. As an emerging solid porous material, mesoporous materials not only have important characteristics such as uniform pore size, orderly arrangement, and continuous adjustment of pore diameter within 2-50nm, but also have large pore volume, high specific surface area, and pore size. The surface can be physically adsorbed or chemically modified and has good hydrothermal stability. Transition metal oxides have become important electrode materials due to their high theoretical specific capacity, low price and easy availability. However, due to their low conductivity and poor cycle stability, it is difficult to use them on a large scale. For these problems, It can be improved by doping or compounding with carbon materials. Because of the advantages of high electrical conductivity, large specific surface area, and good flexibility of carbon materials. At the same time, the carbon layer can improve the overall conductivity of the metal oxide electrode material, and the carbon layer and the metal oxide have a synergistic effect, which can increase the specific capacity and rate specific capacity.
NiO是一种3d 过渡金属氧化物，是一种典型的直接宽带隙p型半导体，通常情况下禁带宽度在 3.6eV~4.0eV之间。NiO由于具有较高的理论比电容以及较好的热稳定性，被认为是超级电容器的候选电极材料之一。但是由于NiO导电率比较低，限制了其在超级电容器上的应用，而碳的导电率非常的好，所以把两者结合可以提高材料的性能，同时，将氧化镍/碳制备成具有高比表面积、大孔径，大孔体积的多孔纳米材料将有利于增加电子的传输效率，从而提高作为电化学超级电容器的电容量性能。 NiO is a 3d transition metal oxide and a typical direct wide bandgap p-type semiconductor, usually with a bandgap between 3.6eV and 4.0eV. NiO is considered to be one of the candidate electrode materials for supercapacitors due to its high theoretical specific capacitance and good thermal stability. However, due to the relatively low conductivity of NiO, its application in supercapacitors is limited, and the conductivity of carbon is very good, so the combination of the two can improve the performance of the material. Porous nanomaterials with large surface area, large pore diameter, and large pore volume will help to increase the electron transmission efficiency, thereby improving the capacitance performance as an electrochemical supercapacitor.
樊桢等以直接生长在集流体（石墨）上的碳纳米管为载体，采用硝酸镍高温热解方法，成功合成了具有三维多孔结构的NiO/CNT/G复合物电极。电极展现了非常高的利用率和电化学超电容活性，其电位窗口达到1.7V，最高比容量可以达到479 F/g，保留了氧化镍高的电容行为和碳材料的电化学性能，但是由于这种制备方法需要采用难以工业化的碳纳米管，因而不适于规模生产。（樊桢，陈金华，张炳，刘博，旷亚非.超级电容器用氧化镍/碳纳米管复合物电极材料研究[J].中国科技论文在线，2009.）。 Using carbon nanotubes grown directly on the current collector (graphite) as a carrier, Fan Zhen et al. successfully synthesized a NiO/CNT/G composite electrode with a three-dimensional porous structure by using a high-temperature pyrolysis method of nickel nitrate. The electrode exhibits a very high utilization rate and electrochemical supercapacitive activity, its potential window reaches 1.7V, and the highest specific capacity can reach 479 F/g, retaining the high capacitive behavior of nickel oxide and the electrochemical performance of carbon materials, but due to This preparation method requires the use of carbon nanotubes, which are difficult to industrialize, and thus is not suitable for large-scale production. (Fan Zhen, Chen Jinhua, Zhang Bing, Liu Bo, Kuang Yafei. Research on nickel oxide/carbon nanotube composite electrode materials for supercapacitors [J]. China Science and Technology Papers Online, 2009.).
张海军等采用采用壳聚糖为碳源，制备了富含介孔的多孔碳材料，并在此基础上利用壳聚糖对金属离子的络合作用，通过对壳聚糖的预处理制备了多孔C/NiO复合材料。在电流密度为0.1A/g下电容达355 F/g,但是在大电流密度下电容量降低，该电极材料的比表面积达到了418m2/g。（张海军，张校刚，原长洲，高 博，孙 康，傅清宾，卢向军，蒋剑春.水溶性壳聚糖制备多孔碳，氧化镍复合材料及其电化学电容行为[J].物理化学学报，2011,27（2），455-460）。 Zhang Haijun et al. used chitosan as a carbon source to prepare a porous carbon material rich in mesoporous carbon, and on this basis, the complexation of chitosan to metal ions was used to prepare a porous carbon material by pretreatment of chitosan. C/NiO composites. The capacitance reaches 355 F/g at a current density of 0.1A/g, but the capacitance decreases at a high current density, and the specific surface area of the electrode material reaches 418m 2 /g. (Zhang Haijun, Zhang Xiaogang, Yuan Changzhou, Gao Bo, Sun Kang, Fu Qingbin, Lu Xiangjun, Jiang Jianchun. Preparation of porous carbon and nickel oxide composites from water-soluble chitosan and their electrochemical capacitive behavior[J]. Acta Physicochemical Sinica, 2011, 27(2), 455-460).
宋怀河等通过将碳纳米管在镍盐乙醇溶液中浸渍，进行还原并进一步焙烧处理等过程，得到碳纳米管/氧化镍复合材料，其中，碳纳米管与氧化镍的质量比为9:1-2:3。由于碳纳米管与氧化镍的质量比不同使电容量从120-400 F/g变化。由于该这种制备方法需要采用难以工业化生产的碳纳米管，因而不适于规模化生产（宋怀河，徐继勇，陈晓红.一种碳纳米管 /氧化镍复合材料及其超级电容器:中国，CN103560018A[P]. 2014-02-05）。 Song Huaihe et al. obtained carbon nanotube/nickel oxide composite materials by impregnating carbon nanotubes in nickel salt ethanol solution, reducing them and further roasting them. The mass ratio of carbon nanotubes to nickel oxide was 9:1- 2:3. Due to the difference in the mass ratio of carbon nanotubes to nickel oxide, the capacitance varies from 120-400 F/g. Because this preparation method needs to adopt carbon nanotubes that are difficult to industrialized production, it is not suitable for large-scale production (Song Huaihe, Xu Jiyong, Chen Xiaohong. A kind of carbon nanotube/nickel oxide composite material and supercapacitor thereof: China, CN103560018A[P] . 2014-02-05).
胡俊青等利用乙酸镍、尿素和聚乙烯吡咯烷酮得到氧化镍之后溶于葡萄糖溶液中搅拌得到NiO/C多孔电极材料，这种多孔和材料具有高的比表面积，同时碳层可以提高NiO电极材料的整体导电性，而且碳层和NiO具有协同效应，可以提高比容量和速率比容量。但是用此方法，步骤多且复杂，而且水热反应不易控制。（胡俊青，徐开兵，邹儒佳，李文尧，安磊.一种超级电容器电极材料碳包覆氧化镍NiO/C的制备方法.中国：CN 103219169 A[P]. 2013-07-24）。 Hu Junqing et al. used nickel acetate, urea and polyvinylpyrrolidone to obtain nickel oxide, then dissolved it in glucose solution and stirred to obtain NiO/C porous electrode material. Conductivity, and the carbon layer and NiO have a synergistic effect, which can improve the specific capacity and rate specific capacity. But with this method, there are many and complicated steps, and the hydrothermal reaction is not easy to control. (Hu Junqing, Xu Kaibing, Zou Rujia, Li Wenyao, An Lei. A preparation method of carbon-coated nickel oxide NiO/C as an electrode material for supercapacitors. China: CN 103219169 A[P]. 2013-07-24).
综上所述，目前采用的水热法，硬模板法等方法虽然成功合成出了各种纳米结构的氧化镍/碳材料的复合物，但是其合成过程不易控制，且合成过程复杂，最终得到的氧化镍/碳复合纳米材料具有比表面积小，不利于电子/离子的迁移等缺点，因此目前迫切需要研究一种制备过程简单，且最终所得的介孔氧化镍/碳复合纳米材料具有大比表面积、高孔体积以及大孔径的介孔氧化镍/碳复合纳米材料的制备方法。 In summary, although the hydrothermal method, hard template method and other methods currently used have successfully synthesized various nanostructured nickel oxide/carbon composites, the synthesis process is not easy to control, and the synthesis process is complicated. The nickel oxide/carbon composite nanomaterial has the disadvantages of small specific surface area, which is not conducive to the migration of electrons/ions. Therefore, there is an urgent need to study a simple preparation process, and the final mesoporous nickel oxide/carbon composite nanomaterial has a large specificity. A method for preparing mesoporous nickel oxide/carbon composite nanomaterials with surface area, high pore volume and large pore size.
发明内容 Contents of the invention
本发明的目的在于为了解决上述的纳米结构的氧化镍/碳材料的复合物制备过程存在的合成过程不易控制，过程复杂很难达到一步得到最终产物等的技术问题，而提供一种介孔氧化镍/碳复合纳米材料的制备方法。通过该制备方法获得的介孔氧化镍/碳复合纳米材料具有高比表面积、大孔体积和孔径，而且生产成本低，操作简单可控，适合大规模生产，所得的介孔氧化镍/碳复合纳米材料可以用作制作超级电容器所用的电极材料，制得的电极材料具有较高的比电容量。 The purpose of the present invention is to provide a kind of mesoporous oxidation in order to solve the technical problems that the synthesis process of the above-mentioned nanostructured nickel oxide/carbon material composite preparation process is difficult to control, and the process is complicated and difficult to obtain the final product in one step. Preparation method of nickel/carbon composite nanomaterial. The mesoporous nickel oxide/carbon composite nanomaterial obtained by this preparation method has high specific surface area, large pore volume and pore size, and low production cost, simple and controllable operation, and is suitable for large-scale production. The obtained mesoporous nickel oxide/carbon composite Nanomaterials can be used as electrode materials for making supercapacitors, and the prepared electrode materials have high specific capacitance.
本发明的技术方案 Technical scheme of the present invention
一种介孔氧化镍/碳复合纳米材料的制备方法，即以非离子表面活性剂作为模板剂、以无机镍盐为镍源，通过蒸发诱导自组装的方法制备出一种具有大比表面积和孔体积以及大孔径的介孔氧化镍/碳复合纳米材料，其具体包括如下步骤： A method for preparing a mesoporous nickel oxide/carbon composite nanomaterial, that is, using a nonionic surfactant as a template and using an inorganic nickel salt as a nickel source to prepare a material with a large specific surface area and A mesoporous nickel oxide/carbon composite nanomaterial with a pore volume and a large pore size, which specifically includes the following steps:
（1）、将非离子表面活性剂、有机高分子聚合物、有机硅源、无机镍源和溶剂按质量比计算，即非离子表面活性剂：有机高分子聚合物：有机硅源：无机镍源：溶剂为1:1-6:0.1-2:0.2-4:5-30的比例进行混合，搅拌均匀得到均相溶液； (1) Calculate the nonionic surfactant, organic high molecular polymer, organic silicon source, inorganic nickel source and solvent according to the mass ratio, that is, nonionic surfactant: organic high molecular polymer: organic silicon source: inorganic nickel Source: The solvent is mixed in a ratio of 1:1-6:0.1-2:0.2-4:5-30, and stirred evenly to obtain a homogeneous solution;
所述的非离子表面活性剂为EO20PO70EO20、EO106PO70EO106、EO132PO60EO132中的一种或两种以上的混合物； The nonionic surfactant is one or a mixture of two or more of EO 20 PO 70 EO 20 , EO 106 PO 70 EO 106 , EO 132 PO 60 EO 132 ;
所述的有机硅源为正硅酸四乙酯、正硅酸四甲酯、正硅酸四丙酯、正硅酸四丁酯中的一种或两种以上组成的混合物； The organosilicon source is one or a mixture of two or more of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate;
所述的有机高分子聚合物为酚醛树脂、蔗糖、糠醛树脂、中的一种或两种以上组成的混合物； The organic macromolecular polymer is one or a mixture of two or more of phenolic resin, sucrose, and furfural resin;
所述的无机镍源为六水合硝酸镍、六水合硫酸镍、氯化镍中一种或两种及以上混合物； The inorganic nickel source is one or a mixture of two or more of nickel nitrate hexahydrate, nickel sulfate hexahydrate, and nickel chloride;
所述的溶剂为乙醇、水、乙二醇中的一种或两种以上的混合物； Described solvent is one or the mixture of two or more in ethanol, water, ethylene glycol;
（2）、将步骤(1)中得到的均相溶液倒入结晶皿中，然后将结晶皿放在通风橱中控制温度在20-60℃，时间24h，然后再将结晶皿放在100℃的鼓风干燥箱中24h，在结晶皿中得到有机/无机复合物的干燥薄膜； (2) Pour the homogeneous solution obtained in step (1) into a crystallization dish, then place the crystallization dish in a fume hood to control the temperature at 20-60°C for 24 hours, and then place the crystallization dish at 100°C 24h in the blower drying oven, obtain the dry film of organic/inorganic compound in the crystallization dish;
（3）、将步骤（2）中所得有机/无机复合物的干燥薄膜从结晶皿刮下，置于氮气氛围中控制升温速率为1-3℃/min，升温至600-1000℃进行高温焙烧1-3h，然后自然冷却至室温，即得到介孔氧化镍/碳/二氧化硅复合物； (3) Scrape off the dry film of the organic/inorganic compound obtained in step (2) from the crystallization dish, place it in a nitrogen atmosphere, control the heating rate to 1-3°C/min, and heat up to 600-1000°C for high-temperature roasting 1-3h, then naturally cooled to room temperature to obtain a mesoporous nickel oxide/carbon/silicon dioxide composite;
（4）、将步骤（3）中得到的介孔氧化镍/碳/二氧化硅复合物加入到浓度为0.1-2mol/L氢氧化钠水溶液中，控制温度为20-60℃下搅拌5-30min，然后再静置30min，离心分离，所得的沉淀用去离子水进行洗涤直至流出液的pH为中性，空气中100℃下进行干燥，即可得到介孔氧化镍/碳复合纳米材料; (4) Add the mesoporous nickel oxide/carbon/silicon dioxide composite obtained in step (3) into an aqueous sodium hydroxide solution with a concentration of 0.1-2mol/L, and stir at a temperature of 20-60°C for 5- 30min, then stand still for 30min, centrifuge, the precipitate obtained is washed with deionized water until the pH of the effluent is neutral, and dried at 100°C in the air to obtain the mesoporous nickel oxide/carbon composite nanomaterial;
上述介孔氧化镍/碳/二氧化硅复合物和浓度为0.1-2mol/L氢氧化钠水溶液的用量，按介孔氧化镍/碳/二氧化硅复合物：浓度为0.1-2mol/L氢氧化钠水溶液为1g:5-30ml的比例计算。 The amount of the above-mentioned mesoporous nickel oxide/carbon/silicon dioxide compound and the concentration of 0.1-2mol/L sodium hydroxide aqueous solution, according to the mesoporous nickel oxide/carbon/silicon dioxide compound: the concentration is 0.1-2mol/L hydrogen Sodium oxide aqueous solution is calculated at the ratio of 1g:5-30ml.
上述得到的介孔氧化镍/碳复合纳米材料，是氧化镍与碳组成的复合物，其元素组成按原子百分比计算，其中氧原子的比例1%、镍原子的比例为2.72-3.75%，碳原子的比例为96.28-95.25%，其中氧化镍与碳的质量比为1:2.5～4.2。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above is a compound composed of nickel oxide and carbon, and its element composition is calculated by atomic percentage, wherein the proportion of oxygen atoms is 1%, the proportion of nickel atoms is 2.72-3.75%, carbon The atomic ratio is 96.28-95.25%, and the mass ratio of nickel oxide to carbon is 1:2.5-4.2.
上述所得介孔氧化镍/碳复合纳米材料经检测，其比表面积为435.5～800m2/g、孔体积为1.08～1.5cm3/g，其孔径为2.5～12.0nm。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above has been tested and found to have a specific surface area of 435.5-800m 2 /g, a pore volume of 1.08-1.5cm 3 /g, and a pore diameter of 2.5-12.0nm.
上述所得的介孔氧化镍/碳复合纳米材料可用于制作超级电容器所用的电极材料。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above can be used to make electrode materials for supercapacitors.
本发明的有益效果 Beneficial effects of the present invention
本发明一种介孔氧化镍/碳复合纳米材料的制备方法，由于在制备过程中以非离子表面活性剂为模板剂、有机硅源和高分子聚合物为有机前驱体、无机镍源为无机前驱体，通过蒸发诱导自组装的方法合成出氧化镍/碳/二氧化硅复合材料，然后进一步除去二氧化硅，获得了具有较大比表面积和孔体积以及大孔径的氧化镍/碳复合纳米材料。 The preparation method of a kind of mesoporous nickel oxide/carbon composite nano material of the present invention, because in the preparation process, use non-ionic surfactant as template agent, organosilicon source and macromolecular polymer as organic precursor, inorganic nickel source as inorganic Precursors, nickel oxide/carbon/silicon dioxide composites were synthesized by evaporation-induced self-assembly, and then the silicon dioxide was further removed to obtain nickel oxide/carbon composite nanoparticles with large specific surface area, pore volume and large pore size. Material.
进一步，本发明一种介孔氧化镍/碳复合纳米材料的制备方法，制备过程中通过控制加入的无机镍前驱体质量，可以调节介孔氧化镍/碳纳米复合材料中镍的含量，从而获得比电容量可以随意改变的超级电容器所用的电极材料，这也是目前其他氧化镍/碳复合材料所不能实现的。 Further, the present invention provides a method for preparing a mesoporous nickel oxide/carbon composite nanomaterial. During the preparation process, by controlling the quality of the inorganic nickel precursor added, the content of nickel in the mesoporous nickel oxide/carbon nanocomposite material can be adjusted, thereby obtaining It is an electrode material for supercapacitors whose specific capacitance can be changed at will, which cannot be realized by other nickel oxide/carbon composite materials at present.
附图说明 Description of drawings
图1、实施例1所得的介孔氧化镍/碳复合纳米材料的小角XRD图； The small-angle XRD pattern of the mesoporous nickel oxide/carbon composite nanomaterial of Fig. 1, embodiment 1 gained;
图2、实施例1所得的介孔氧化镍/碳复合纳米材料的广角XRD图； The wide-angle XRD pattern of the mesoporous nickel oxide/carbon composite nanomaterial of Fig. 2, embodiment 1 gained;
图3、实施例1所得的介孔氧化钒/碳复合纳米材料的氮气吸附-脱附曲线； Fig. 3, the nitrogen adsorption-desorption curve of the mesoporous vanadium oxide/carbon composite nanomaterial obtained in Example 1;
图4、实施例1所得的介孔氧化钒/碳复合纳米材料的孔径分布图； Fig. 4, the pore size distribution figure of the mesoporous vanadium oxide/carbon composite nanomaterial obtained in embodiment 1;
图5、实施例1所得的介孔氧化镍/碳复合纳米材料的循环伏安图。 Fig. 5, the cyclic voltammogram of the mesoporous nickel oxide/carbon composite nanomaterial obtained in Example 1.
具体实施方案 specific implementation plan
下面通过具体实施例并结合附图来对本发明进行进一步的描述，但本发明的保护范围不限于此。 The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings, but the protection scope of the present invention is not limited thereto.
所述方法如无特别说明，均为常规方法。所述材料如无特别说明，均能从公开商业途径买得到。 The methods are conventional methods unless otherwise specified. The materials can be purchased from open commercial channels unless otherwise specified.
本发明各实施例所用的仪器或设备的型号及生产厂家信息如下： The model and manufacturer's information of instrument or equipment used in each embodiment of the present invention are as follows:
电子天平 JA203 上海海康电子仪器厂 Electronic Balance JA203 Shanghai Haikang Electronic Instrument Factory
马弗炉 DC－B8/11 北京独创科技有限公司 Muffle Furnace DC－B8/11 Beijing Unique Technology Co., Ltd.
电化学工作站 CH660D 上海辰华仪器公司 Electrochemical Workstation CH660D Shanghai Chenhua Instrument Co., Ltd.
电热恒温鼓风干燥箱 DHG－9070A 上海一恒科学仪器 Electric constant temperature blast drying oven DHG-9070A Shanghai Yiheng Scientific Instruments
管式炉，型号SL1700 Ⅱ型 上海升利测试仪器有限公司； Tube furnace, model SL1700 Type II Shanghai Shengli Testing Instrument Co., Ltd.;
X-射线衍射仪(XRD)，X PERT PRO 荷兰帕纳科公司； X-ray diffractometer (XRD), X PERT PRO Netherland PANalytical company;
扫描电子显微镜(SEM)，S-3400N 日本日立公司； Scanning electron microscope (SEM), S-3400N Hitachi, Japan;
全自动物理吸附分析仪，ASAP2020 美国麦克公司； Fully automatic physical adsorption analyzer, ASAP2020 American Mike Company;
同步热分析仪，STA-449F3 德国耐驰公司。 Synchronous Thermal Analyzer, STA-449F3, Netzsch, Germany.
实施例1Example 1
一种介孔氧化镍/碳复合纳米材料的制备方法，具体包括以下步骤： A method for preparing a mesoporous nickel oxide/carbon composite nanomaterial, specifically comprising the following steps:
（1）、将0.6g的非离子表面活性剂分散于3g溶剂中在40℃下搅拌5min，然后加入0.12g无机镍源，直接搅拌5min溶解，再依次加入0.06g有机硅源和0.6g有机高分子聚合物，室温下继续搅拌20min至获得均相溶液； (1) Disperse 0.6g of non-ionic surfactant in 3g of solvent and stir at 40°C for 5min, then add 0.12g of inorganic nickel source, stir directly for 5min to dissolve, then add 0.06g of organic silicon source and 0.6g of organic High molecular polymer, continue stirring at room temperature for 20 minutes until a homogeneous solution is obtained;
所用的非离子表面活性剂、有机高分子聚合物、有机硅源、无机镍源和溶剂的量，按质量比计算，即非离子表面活性剂：有机高分子聚合物：有机硅源：无机镍源：溶剂为1:1:0.1:0.2:5； The amount of nonionic surfactant, organic high molecular polymer, organic silicon source, inorganic nickel source and solvent used is calculated by mass ratio, that is, nonionic surfactant: organic high molecular polymer: organic silicon source: inorganic nickel Source: solvent is 1:1:0.1:0.2:5;
所述的非离子表面活性剂为EO20PO70EO20； Described nonionic surfactant is EO 20 PO 70 EO 20 ;
所述的有机硅源为正硅酸四甲酯； Described organosilicon source is tetramethyl orthosilicate;
所述的有机高分子聚合物为糠醛树脂； Described organic polymer is furfural resin;
所述的无机镍源为六水合硝酸镍; Described inorganic nickel source is nickel nitrate hexahydrate;
所述的溶剂为乙二醇； Described solvent is ethylene glycol;
（2）、将步骤(1)中得到的均相溶液倒入结晶皿中，然后将结晶皿放在通风橱中控制温度在20℃，时间24h，然后再将结晶皿放在100℃的鼓风干燥箱中24h，在结晶皿中得到有机/无机复合物的干燥薄膜； (2) Pour the homogeneous solution obtained in step (1) into a crystallization dish, then place the crystallization dish in a fume hood to control the temperature at 20°C for 24 hours, and then place the crystallization dish in a drum at 100°C 24h in the air drying oven to obtain a dry film of the organic/inorganic compound in the crystallization dish;
（3）、将步骤（2）中所得有机/无机复合物的干燥薄膜从结晶皿刮下，置于氮气氛围中控制升温速率为1℃/min，升温至600℃进行高温焙烧1h，然后自然冷却至室温，即得到介孔氧化镍/碳/二氧化硅复合物； (3) Scrape off the dry film of the organic/inorganic compound obtained in step (2) from the crystallization dish, place it in a nitrogen atmosphere, control the heating rate to 1°C/min, raise the temperature to 600°C for high-temperature roasting for 1 hour, and then naturally Cool to room temperature to obtain the mesoporous nickel oxide/carbon/silicon dioxide composite;
（4）、将1g步骤（3）中得到的介孔氧化镍/碳/二氧化硅复合物加入到5ml浓度为0.1mol/L氢氧化钠水溶液中，控制温度为20℃下搅拌15min，然后再静置30min，然后离心，所得的沉淀用去离子水进行洗涤直至流出液的pH为中性，然后控制温度为100℃进行干燥，即可得到介孔氧化镍/碳复合纳米材料; (4) Add 1 g of the mesoporous nickel oxide/carbon/silicon dioxide composite obtained in step (3) to 5 ml of 0.1 mol/L sodium hydroxide aqueous solution, stir at 20°C for 15 min, and then Let it stand for another 30 minutes, then centrifuge, wash the obtained precipitate with deionized water until the pH of the effluent is neutral, then control the temperature to 100°C for drying, and then obtain the mesoporous nickel oxide/carbon composite nanomaterial;
上述介孔氧化镍/碳/二氧化硅复合物和浓度为0.1mol/L氢氧化钠水溶液的用量，按介孔氧化镍/碳/二氧化硅复合物：浓度为0.1mol/L氢氧化钠水溶液为1g:5ml的比例计算。 The above-mentioned mesoporous nickel oxide/carbon/silicon dioxide compound and the concentration are the consumption of 0.1mol/L sodium hydroxide aqueous solution, according to the mesoporous nickel oxide/carbon/silicon dioxide compound: the concentration is 0.1mol/L sodium hydroxide The aqueous solution is calculated at the ratio of 1g:5ml.
采用X-射线衍射仪对上述所得的介孔氧化镍/碳复合纳米材料进行测定，所得的小角XRD图如图1所示，从图1中可以看出在2斯塔在1.1度处有一个明显的衍射峰，证明所得的介孔氧化镍/碳复合纳米材料具有有序的介孔结构。 Adopt X-ray diffractometer to measure the above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterial, the small-angle XRD figure of gained is as shown in Figure 1, as can be seen from Figure 1 there is a Obvious diffraction peaks prove that the obtained mesoporous nickel oxide/carbon composite nanomaterial has an ordered mesoporous structure.
采用X-射线衍射仪对上述所得的介孔氧化镍/碳复合纳米材料进行结构测定，所得的广角XRD图如图2所示，从图2中可以看出，衍射峰尖锐，强度大，说明所得的介孔氧化镍/碳复合纳米材料具有晶体墙结构的介孔氧化镍/碳复合纳米孔材料。 Adopt X-ray diffractometer to carry out structure measurement to the above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterial, the wide-angle XRD pattern of gained is as shown in Figure 2, as can be seen from Figure 2, the diffraction peak is sharp, and intensity is big, illustrates The obtained mesoporous nickel oxide/carbon composite nanomaterial has a crystal wall structure and is a mesoporous nickel oxide/carbon composite nanoporous material.
通过能量色散X射线光谱仪（EDS）对上述所得的介孔氧化镍/碳复合纳米材料进行分析，其元素组成按原子百分比计算，其中氧原子的比例1%、镍原子的比例为2.72%，碳原子的比例为96.28%，表明介孔氧化镍/碳复合纳米材料是氧化镍与碳的复合物，其中氧化镍与碳的质量比为1:3.56。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above was analyzed by energy dispersive X-ray spectrometer (EDS). The atomic ratio is 96.28%, indicating that the mesoporous nickel oxide/carbon composite nanomaterial is a composite of nickel oxide and carbon, where the mass ratio of nickel oxide to carbon is 1:3.56.
采用全自动物理吸附分析仪(ASAP2020 美国麦克公司)对上述所得的介孔氧化镍/碳复合纳米材料进行测定，其氮气吸附-脱附曲线如图3所示，从图3中相对压力0.65-0.9左右一个滞回环可以看出，样品具有介孔VI型曲线，由此表明了氧化镍/碳复合物具有介孔性质。 Adopt full-automatic physical adsorption analyzer (ASAP2020 U.S. Mike company) to measure the mesoporous nickel oxide/carbon composite nanomaterial of above-mentioned gained, its nitrogen adsorption-desorption curve is as shown in Figure 3, from Figure 3 relative pressure 0.65- A hysteresis loop around 0.9 shows that the sample has a mesoporous VI curve, which indicates that the nickel oxide/carbon composite has mesoporous properties.
进一步，从全自动物理吸附分析仪(ASAP2020 美国麦克公司)采集的信息进行分析，其孔径分布图如图4所示，从图4中可以看出孔径分布在5-25nm之间，由此表明了所得的产品的介孔性质。 Further, the information collected from the automatic physical adsorption analyzer (ASAP2020 American Mike Company) is analyzed, and its pore size distribution diagram is shown in Figure 4. From Figure 4, it can be seen that the pore size distribution is between 5-25nm, which shows that The mesoporous properties of the resulting products were investigated.
采用自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的比表面积进行测定，其比表面积为435.5m2/g。 The specific surface area of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by an automatic physical adsorption analyzer, and the specific surface area was 435.5 m 2 /g.
采用自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔径进行测定，其孔径为12.0 nm。 The pore diameter of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by an automatic physical adsorption analyzer, and the pore diameter was 12.0 nm.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔体积进行测定，其孔体积为1.08cm3/g。 The pore volume of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the pore volume was 1.08 cm 3 /g.
将上述得到的介孔氧化镍/碳复合纳米材料制成超级电容器所用的电极材料，其制备方法包括如下步骤： The above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterial is made into an electrode material for a supercapacitor, and its preparation method comprises the following steps:
将上述所得的介孔氧化镍/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MP压力下压片，制作成工作电极，以参比电极甘汞电极，对电极铂电极，和6mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous nickel oxide/carbon composite nanomaterial obtained above into powder, mix it with conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on accurately weighed foamed nickel Above, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MP, and make it into a working electrode, using the reference electrode calomel electrode, the counter electrode platinum electrode, and 6mol/L KOH aqueous solution as the electrolysis A three-electrode system was formed to test the electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定，结果如图5所示，从图5中可以得出，在10mVs-1、20mVs-1、50mVs-1、100mVs-1的扫描速率下，其比电容量分别为230F/g、275F/g、420F/g、468F/g。由此表明了本发明制备的介孔氧化镍/碳复合纳米材料具有较高的比电容量。 The electrode materials used in the supercapacitor obtained above were measured by Shanghai Chenhua CHI660C electrochemical workstation using cyclic voltammetry. The results are shown in Figure 5. -1 and 100mVs -1 scan rates, the specific capacitances are 230F/g, 275F/g, 420F/g, 468F/g respectively. This shows that the mesoporous nickel oxide/carbon composite nanomaterial prepared by the present invention has a higher specific capacitance.
实施例2Example 2
一种介孔氧化镍/碳复合纳米材料的制备方法，具体包括以下步骤： A method for preparing a mesoporous nickel oxide/carbon composite nanomaterial, specifically comprising the following steps:
（1）、将0.6g的非离子表面活性剂分散于9g溶剂中在40℃下搅拌5min，然后加入1.14g无机镍源，直接搅拌5min溶解，再依次加入0.54g有机硅源和1.5g有机高分子聚合物，室温下继续搅拌20min至获得均相溶液； (1) Disperse 0.6g of nonionic surfactant in 9g of solvent and stir at 40°C for 5min, then add 1.14g of inorganic nickel source, stir directly for 5min to dissolve, then add 0.54g of organic silicon source and 1.5g of organic High molecular polymer, continue stirring at room temperature for 20 minutes until a homogeneous solution is obtained;
所用的非离子表面活性剂、有机高分子聚合物、有机硅源、无机镍源和溶剂的量，按质量比计算，即非离子表面活性剂：有机高分子聚合物：有机硅源：无机镍源：溶剂为1:2.5:0.9:1.9:15的比例； The amount of nonionic surfactant, organic high molecular polymer, organic silicon source, inorganic nickel source and solvent used is calculated by mass ratio, that is, nonionic surfactant: organic high molecular polymer: organic silicon source: inorganic nickel Source: solvent in a ratio of 1:2.5:0.9:1.9:15;
所述的非离子表面活性剂为EO106PO70EO106； Described nonionic surfactant is EO 106 PO 70 EO 106 ;
所述的有机硅源为正硅酸四乙酯； Described organosilicon source is tetraethyl orthosilicate;
所述的有机高分子聚合物为蔗糖； The organic polymer is sucrose;
所述的无机镍源为六水合硫酸镍； Described inorganic nickel source is nickel sulfate hexahydrate;
所述的溶剂为乙醇； Described solvent is ethanol;
（2）、将步骤(1)中得到的均相溶液倒入结晶皿中，然后将结晶皿放在通风橱中控制温度在40℃，时间24h，然后再将结晶皿放在100℃的鼓风干燥箱中24h，在结晶皿中得到有机/无机复合物的干燥薄膜； (2) Pour the homogeneous solution obtained in step (1) into a crystallization dish, then place the crystallization dish in a fume hood to control the temperature at 40°C for 24 hours, and then place the crystallization dish in a drum at 100°C 24h in the air drying oven to obtain a dry film of the organic/inorganic compound in the crystallization dish;
（3）、将步骤（2）中所得有机/无机复合物的干燥薄膜从结晶皿刮下，置于氮气氛围中控制升温速率为2℃/min，升温至800℃进行高温焙烧2h，然后自然冷却至室温，即得到介孔氧化镍/碳/二氧化硅复合物； (3) Scrape off the dry film of the organic/inorganic composite obtained in step (2) from the crystallization dish, place it in a nitrogen atmosphere to control the heating rate at 2°C/min, raise the temperature to 800°C for high-temperature roasting for 2 hours, and then naturally Cool to room temperature to obtain the mesoporous nickel oxide/carbon/silicon dioxide composite;
（4）、将步骤（3）中得到的介孔氧化镍/碳/二氧化硅复合物加入到浓度为1mol/L氢氧化钠水溶液中，控制温度为40℃下搅拌15min，然后再静置30min，然后离心，所得的沉淀用去离子水进行洗涤直至流出液的pH为中性，然后控制温度为100℃进行干燥24h，即可得到介孔氧化镍/碳复合纳米材料; (4) Add the mesoporous nickel oxide/carbon/silicon dioxide composite obtained in step (3) into an aqueous solution of sodium hydroxide with a concentration of 1mol/L, stir at a temperature of 40°C for 15 minutes, and then let it stand 30min, then centrifuged, the resulting precipitate was washed with deionized water until the pH of the effluent was neutral, and then the temperature was controlled at 100°C to dry for 24h to obtain the mesoporous nickel oxide/carbon composite nanomaterial;
上述介孔氧化镍/碳/二氧化硅复合物和浓度为1mol/L氢氧化钠水溶液的用量，按介孔氧化镍/碳/二氧化硅复合物：浓度为1mol/L氢氧化钠水溶液为1g:15ml的比例计算。 Above-mentioned mesoporous nickel oxide/carbon/silicon dioxide compound and concentration are the consumption of 1mol/L sodium hydroxide aqueous solution, press mesoporous nickel oxide/carbon/silicon dioxide compound: concentration is 1mol/L sodium hydroxide aqueous solution is 1g:15ml ratio calculation.
通过能量色散X射线光谱仪（EDS）对上述所得的介孔氧化镍/碳复合纳米材料进行分析，其元素组成按原子百分比计算，其中氧原子的比例1%、镍原子的比例为3.12%，碳原子的比例为95.88%，表明介孔氧化镍/碳复合纳米材料是氧化镍与碳的复合物，其中氧化镍与碳的质量比为1:2.5。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above was analyzed by energy dispersive X-ray spectrometer (EDS). The atomic ratio is 95.88%, indicating that the mesoporous nickel oxide/carbon composite nanomaterial is a composite of nickel oxide and carbon, where the mass ratio of nickel oxide to carbon is 1:2.5.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的比表面积进行测定，其比表面积为600 m2/g。 The specific surface area of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the specific surface area was 600 m 2 /g.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔体积进行测定，其孔体积为1.2cm3/g。 The pore volume of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the pore volume was 1.2 cm 3 /g.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔径进行测定，其孔径为4.8nm。 The pore diameter of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the pore diameter was 4.8 nm.
将上述得到的介孔氧化镍/碳复合纳米材料制成超级电容器所用的电极材料，其制备方法包括如下步骤： The above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterial is made into an electrode material for a supercapacitor, and its preparation method comprises the following steps:
将上述所得的介孔氧化镍/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MP压力下压片，制作成工作电极，以参比电极甘汞电极，对电极铂电极，和6mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous nickel oxide/carbon composite nanomaterial obtained above into powder, mix it with conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on accurately weighed foamed nickel Above, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MP, and make it into a working electrode, using the reference electrode calomel electrode, the counter electrode platinum electrode, and 6mol/L KOH aqueous solution as the electrolysis A three-electrode system was formed to test the electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定。在50mVs-1的扫描速率下，其比电容量为430.4F/g。 The electrode materials used in the supercapacitor obtained above were measured by Shanghai Chenhua CHI660C electrochemical workstation by cyclic voltammetry. At a scan rate of 50mVs -1 , its specific capacitance is 430.4F/g.
实施例3Example 3
一种介孔氧化镍/碳复合纳米材料的制备方法，具体包括以下步骤： A method for preparing a mesoporous nickel oxide/carbon composite nanomaterial, specifically comprising the following steps:
（1）、将0.6g的非离子表面活性剂分散于18g溶剂中，在40℃下搅拌5min，然后加入2.4g无机镍源，直接搅拌5min溶解，再依次加入1.2g有机硅源和3.6g有机高分子聚合物，室温下继续搅拌20min至获得均相溶液溶液； (1) Disperse 0.6g of nonionic surfactant in 18g of solvent, stir at 40°C for 5min, then add 2.4g of inorganic nickel source, stir for 5min to dissolve, then add 1.2g of organic silicon source and 3.6g of Organic macromolecular polymer, continue to stir at room temperature for 20 minutes until a homogeneous solution is obtained;
所用的非离子表面活性剂、有机高分子聚合物、有机硅源、无机镍源和溶剂的量，按质量比计算，即非离子表面活性剂：有机高分子聚合物：有机硅源：无机镍源：溶剂为1:6: 2:4:30； The amount of nonionic surfactant, organic high molecular polymer, organic silicon source, inorganic nickel source and solvent used is calculated by mass ratio, that is, nonionic surfactant: organic high molecular polymer: organic silicon source: inorganic nickel Source: solvent is 1:6:2:4:30;
所述的非离子表面活性剂为EO132PO60EO132； Described nonionic surfactant is EO 132 PO 60 EO 132 ;
所述的有机硅源为正硅酸四丁酯； Described organosilicon source is tetrabutyl orthosilicate;
所述的有机高分子聚合物为酚醛树脂； Described organic macromolecular polymer is phenolic resin;
所述的无机镍源为六水合硝酸镍； Described inorganic nickel source is nickel nitrate hexahydrate;
所述的溶剂为水； Described solvent is water;
（2）、将步骤(1)中得到的均相溶液倒入结晶皿中，然后将结晶皿放在通风橱中控制温度在60℃，时间24h，然后再将结晶皿放在100℃的鼓风干燥箱中24h，在结晶皿中得到有机/无机复合物的干燥薄膜； (2) Pour the homogeneous solution obtained in step (1) into a crystallization dish, then place the crystallization dish in a fume hood to control the temperature at 60°C for 24 hours, and then place the crystallization dish in a drum at 100°C 24h in the air drying oven to obtain a dry film of the organic/inorganic compound in the crystallization dish;
（3）、将步骤（2）中所得有机/无机复合物的干燥薄膜从结晶皿刮下，置于氮气氛围中控制升温速率为3℃/min，升温至1000℃进行高温焙烧3h，然后自然冷却至室温，即得到介孔氧化镍/碳/二氧化硅复合物； (3) Scrape off the dry film of the organic/inorganic composite obtained in step (2) from the crystallization dish, place it in a nitrogen atmosphere, control the heating rate to 3°C/min, raise the temperature to 1000°C for high-temperature roasting for 3 hours, and then naturally Cool to room temperature to obtain the mesoporous nickel oxide/carbon/silicon dioxide composite;
（4）、将1g步骤（3）中得到的介孔氧化镍/碳/二氧化硅复合物加入到30ml浓度为2mol/L氢氧化钠水溶液中，控制温度为60℃下搅拌15min，然后再静置30min，然后离心，所得的沉淀用去离子水进行洗涤直至流出液的pH为中性，然后控制温度为100℃进行干燥24h，即可得到介孔氧化镍/碳复合纳米材料; (4) Add 1 g of the mesoporous nickel oxide/carbon/silicon dioxide composite obtained in step (3) to 30 ml of 2 mol/L sodium hydroxide aqueous solution, stir at 60°C for 15 min, and then Stand still for 30 minutes, then centrifuge, wash the obtained precipitate with deionized water until the pH of the effluent is neutral, and then control the temperature to 100 ° C for 24 hours to dry to obtain the mesoporous nickel oxide/carbon composite nanomaterial;
上述介孔氧化镍/碳/二氧化硅复合物和浓度为2mol/L氢氧化钠水溶液的用量，按介孔氧化镍/碳/二氧化硅复合物：浓度为2mol/L氢氧化钠水溶液为1g: 30ml的比例计算。 Above-mentioned mesoporous nickel oxide/carbon/silicon dioxide compound and concentration are the consumption of 2mol/L sodium hydroxide aqueous solution, press mesoporous nickel oxide/carbon/silicon dioxide compound: concentration is 2mol/L sodium hydroxide aqueous solution is 1g: 30ml ratio calculation.
通过能量色散X射线光谱仪（EDS）对上述所得的介孔氧化镍/碳复合纳米材料进行分析，其元素组成按原子百分比计算，其中氧原子的比例1%、镍原子的比例为3.75%，碳原子的比例为95.25%，表明介孔氧化镍/碳复合纳米材料是氧化镍与碳的复合物，其中氧化镍与碳的质量比为1:4.2。 The mesoporous nickel oxide/carbon composite nanomaterial obtained above was analyzed by energy dispersive X-ray spectrometer (EDS). The atomic ratio is 95.25%, indicating that the mesoporous nickel oxide/carbon composite nanomaterial is a composite of nickel oxide and carbon, where the mass ratio of nickel oxide to carbon is 1:4.2.
采用自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的比表面积进行测定，其比表面积为800m2/g。 The specific surface area of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by an automatic physical adsorption analyzer, and the specific surface area was 800 m 2 /g.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔体积进行测定，其孔体积为1.5cm3/g。 The pore volume of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the pore volume was 1.5 cm 3 /g.
采用全自动物理吸附分析仪对上述所得的介孔氧化镍/碳复合纳米材料的孔径进行测定，其孔径为2.5nm。 The pore diameter of the mesoporous nickel oxide/carbon composite nanomaterial obtained above was measured by a fully automatic physical adsorption analyzer, and the pore diameter was 2.5 nm.
将上述得到的介孔氧化镍/碳复合纳米材料制成超级电容器所用的电极材料，其制备方法包括如下步骤： The above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterial is made into an electrode material for a supercapacitor, and its preparation method comprises the following steps:
将上述所得的介孔氧化镍/碳复合纳米材料研磨成粉末，与导电剂乙炔黑、聚四氟乙烯按质量比为8:1:1的比例混合，均匀的涂在准确称量的泡沫镍上，在真空干燥箱中控制温度在120℃下处理12h，在10MP压力下压片，制作成工作电极，以参比电极甘汞电极，对电极铂电极，和6mol/L的KOH水溶液为电解液构成三电极体系，用来测试电化学性能。 Grind the mesoporous nickel oxide/carbon composite nanomaterial obtained above into powder, mix it with conductive agent acetylene black and polytetrafluoroethylene in a mass ratio of 8:1:1, and evenly coat it on accurately weighed foamed nickel Above, control the temperature in a vacuum drying oven at 120°C for 12 hours, press the tablet under a pressure of 10MP, and make it into a working electrode, using the reference electrode calomel electrode, the counter electrode platinum electrode, and 6mol/L KOH aqueous solution as the electrolysis A three-electrode system was formed to test the electrochemical performance.
上述所得的超级电容器所用的电极材料通过上海辰华CHI660C电化学工作站采用循环伏安法进行测定。在100mVs-1的扫描速率下，其比电容量为480.7F/g。 The electrode materials used in the supercapacitor obtained above were measured by Shanghai Chenhua CHI660C electrochemical workstation by cyclic voltammetry. At a scan rate of 100mVs -1 , its specific capacitance is 480.7F/g.
综上所述，本发明的一种介孔氧化镍/碳复合纳米材料的制备方法，采用蒸发诱导自组装的方法，先是获得了氧化镍/二氧化硅/碳复合物，然后除去二氧化硅，从而获得高比表面积和孔体积以及孔径的介孔氧化镍/碳复合纳米材料，其比表面积为435～800m2/g、孔体积为1.0～1.5cm3/g，其孔径为2.5～12.0nm。 In summary, the preparation method of a mesoporous nickel oxide/carbon composite nanomaterial of the present invention adopts the method of evaporation-induced self-assembly, first obtains the nickel oxide/silicon dioxide/carbon composite, and then removes the silicon dioxide , so as to obtain mesoporous nickel oxide /carbon composite nanomaterials with high specific surface area, pore volume and pore diameter. nm.
进一步，由于上述所得的介孔氧化镍/碳复合纳米材料中较大的介孔孔径和孔体积以及大比表面积有利于电解液中离子/电子的迁移，从而增加了该复合纳米材料的比电容量。 Further, due to the large mesoporous pore size and pore volume and large specific surface area in the above-mentioned obtained mesoporous nickel oxide/carbon composite nanomaterials are conducive to the migration of ions/electrons in the electrolyte, thereby increasing the specific electric capacity of the composite nanomaterials. capacity.
以上所述仅是本发明的实施方式的举例，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型均视为本发明的保护范围，这些都不会影响本发明实施的效果和专利的实用性。 The foregoing is only an example of the embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the technical principles of the present invention. Variations are regarded as the scope of protection of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent.
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