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 PDF

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CN104183392A
CN104183392A CN201410367910.3A CN201410367910A CN104183392A CN 104183392 A CN104183392 A CN 104183392A CN 201410367910 A CN201410367910 A CN 201410367910A CN 104183392 A CN104183392 A CN 104183392A
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nickel oxide
carbon
source
mesoporous
composite nano
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马立梦
沈绍典
王丽
毛东森
卢冠忠
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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

Abstract

The invention discloses a mesoporous nickel oxide and carbon composite nano-material and a preparation method thereof. The mesoporous nickel oxide and carbon composite nano-material is composed of 1% of oxygen atom, 2.72-3.75% of nickel atom and 96.28-95.25% of carbon atom; the specific surface area of the material is 435.5-800 m2/g, the pore volume of the material is 1.08-1.5 cm3/g, and the aperture of the material is 2.5-12.0nm. The mesoporous nickel oxide and carbon composite nano-material of large specific surface area, pore volume and aperture is prepared by a self-assembly method induced by evaporation by taking a nonionic surfactant as a template and an inorganic nickel salt as a nickel source. The mesoporous nickel oxide and carbon composite nano-material can be used as electrode material for preparing super capacitor. The preparation method is simple, raw materials are simple and easy to obtain, and the method is suitable for large-scale production.

Description

A kind of mesoporous nickel oxide/carbon composite nano-material and preparation method thereof
Technical field
The invention belongs to inorganic material synthetic, the field of preparing electrode material, is specifically related to a kind of mesoporous nickel oxide/carbon composite nano-material and preparation method thereof.
Background technology
Ultracapacitor is as a kind of novel energy-storing system between traditional capacitor and lithium ion battery, its power density is significantly higher than lithium ion battery, energy density is 10 ~ 100 times of traditional capacitor, coefficient of safety is high, charge and discharge circulation life is long, the advantages such as operating temperature range is wide, and economic environmental protection is non-maintaining.Mesoporous material is as a kind of emerging solid porous material, key characters such as not only thering is duct size homogeneous, arrange in order, aperture can regulate continuously among 2 ~ 50nm, but also there is larger pore volume, the feature such as physical absorption or chemical modification and good hydrothermal stability can be carried out in high specific area, surface, duct.Transition metal oxide is owing to having higher theoretical specific capacity, cheap and easily acquisition; become the electrode material of important mistake; but because conductance is low, cyclical stability is poor; its very difficult scale is used; for its these problems, can or improve with material with carbon element is compound by doping.Because the advantages such as the conductance of material with carbon element is high, specific area is large, pliability is good.Simultaneously carbon-coating can improve the monolithic conductive of metal oxide electrode material, and carbon-coating and metal oxide have cooperative effect, can improve specific capacity and speed ratio capacity.
NiO is a kind of 3d transition metal oxide, is a kind of typical directly broad-band gap p-type semiconductor, and energy gap is between 3.6eV ~ 4.0eV under normal circumstances.NiO, owing to having higher theory than electric capacity and good thermal stability, is considered to one of candidate's electrode material of ultracapacitor.But because NiO conductance is lower, limit its application on ultracapacitor, and very good of the conductance of carbon, so both combinations can be improved to the performance of material, simultaneously, nickel oxide/carbon is prepared into there is high-specific surface area, large aperture, the porous nanometer material of macropore volume will be conducive to increase the efficiency of transmission of electronics, thereby improves as the capacitance performance of electric chemical super capacitor.
Fan Zhen etc., to be grown directly upon carbon nano-tube on collector (graphite) as carrier, adopt nickel nitrate high temperature pyrolysis method, successfully synthesize the NiO/CNT/G composite electrode with three-dimensional porous structure.Electrode has represented very high utilance and electrochemistry electrochemical capacitance activity, its potential window reaches 1.7V, height ratio capacity can reach 479 F/g, capacitance behavior that nickel oxide is high and the chemical property of material with carbon element are retained, but be difficult to industrialized carbon nano-tube because this preparation method need to adopt, thereby be unsuitable for large-scale production.(Fan Zhen, Chen Jinhua, Zhang Ping, Liu Bo, spacious Asia and Africa. nickel oxide for ultracapacitor/carbon nano-tube compound electrode investigation of materials [J]. Chinese science and technology paper is online, and 2009.).
It is carbon source that the employings such as Zhang Haijun adopt shitosan, has prepared and has been rich in mesoporous porous carbon materials, and utilized on this basis the complexing of shitosan to metal ion, by having been prepared by the preliminary treatment of shitosan to porous C/NiO composite material.Be that under 0.1A/g, electric capacity reaches 355 F/g in current density, but capacitance reduces under high current density, the specific area of this electrode material has reached 418m 2/ g.(Zhang Haijun, Zhang Jiaogang, former Changzhou, Gao Bo, Sun Kang, Fu Qingbin, Lu Xiangjun, Jiang Jianchun. water soluble chitosan is prepared porous carbon, nickel oxide composite material and electrochemical capacitor performance thereof [J]. Acta PhySico-Chimica Sinica, 2011,27(2), 455-460).
Song Huaihe etc., by carbon nano-tube being flooded in nickel salt ethanolic solution, reduce the processes such as an one-step baking processing of going forward side by side, obtain carbon nano-tube/nickel oxide composite material, and wherein, the mass ratio of carbon nano-tube and nickel oxide is 9:1-2:3.Because carbon nano-tube changes from 120-400 F/g from the different capacitances that make of mass ratio of nickel oxide.Because this this preparation method need to adopt the carbon nano-tube that is difficult to suitability for industrialized production; thereby be unsuitable for large-scale production (Song Huaihe; Xu Jiyong, Chen Xiaohong. a kind of carbon nano-tube/nickel oxide composite material and ultracapacitor thereof: China, CN103560018A[P]. 2014-02-05).
Hu Junqing etc. utilize nickel acetate, urea and polyvinylpyrrolidone to obtain being dissolved in glucose solution and stirring and obtain NiO/C porous electrode material after nickel oxide, this porous and material have high specific area, carbon-coating can improve the monolithic conductive of NiO electrode material simultaneously, and carbon-coating and NiO have cooperative effect, can improve specific capacity and speed ratio capacity.But by the method, step is many and complicated, and hydro-thermal reaction is wayward.(Hu Junqing, Xu Kaibing, Zou Rujia, Li Wenyao, An Lei. the preparation method of the coated nickel oxide NiO/C of a kind of electrode material for super capacitor carbon. China: CN 103219169 A[P]. 2013-07-24).
In sum, the hydro thermal method adopting at present, although the methods such as hard template method have successfully synthesized the compound of the nickel oxide/material with carbon element of various nanostructures, but its building-up process is wayward, and building-up process complexity, it is little that the nickel oxide/carbon composite nano-material finally obtaining has specific area, be unfavorable for the shortcomings such as the migration of electrons/ions, therefore simple in the urgent need to studying a kind of preparation process at present, and the mesoporous nickel oxide/carbon composite nano-material of final gained has bigger serface, the preparation method of high pore volume and wide-aperture mesoporous nickel oxide/carbon composite nano-material.
Summary of the invention
The object of the invention is to the nickel oxide/material with carbon element in order to solve above-mentioned nanostructure compound preparation process exist building-up process wayward, process complexity is difficult to reach a step and obtains the technical problem of end product etc., and a kind of preparation method of mesoporous nickel oxide/carbon composite nano-material is provided.Mesoporous nickel oxide/the carbon composite nano-material obtaining by this preparation method has high-specific surface area, macropore volume and aperture, and production cost is low, simple to operate controlled, be applicable to large-scale production, mesoporous nickel oxide/the carbon composite nano-material of gained can be as making ultracapacitor electrode material used, and the electrode material making has higher specific capacitance.
Technical scheme of the present invention
A kind of preparation method of mesoporous nickel oxide/carbon composite nano-material, using non-ionic surface active agent as template, taking inorganic nickel as nickel source, induce the method for self assembly to prepare one by evaporation and have bigger serface and pore volume and wide-aperture mesoporous nickel oxide/carbon composite nano-material, it specifically comprises the steps:
(1), non-ionic surface active agent, organic high molecular polymer, organosilicon source, inorganic nickel source and solvent are calculated in mass ratio, be non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: the ratio that solvent is 1:1-6:0.1-2:0.2-4:5-30 is mixed, stirs and obtain homogeneous phase solution;
Described non-ionic surface active agent is EO 20pO 70eO 20, EO 106pO 70eO 106, EO 132pO 60eO 132in one or more mixture;
Described organosilicon source is the mixture of one or more compositions in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate, positive silicic acid four butyl esters;
Described organic high molecular polymer be phenolic resins, sucrose, furfural resin, in the mixture of one or more compositions;
Described inorganic nickel source is one or both and above mixture in Nickelous nitrate hexahydrate, six hydration nickel sulfate, nickel chloride;
Described solvent is one or more the mixture in ethanol, water, ethylene glycol;
(2), the homogeneous phase solution obtaining in step (1) is poured in crystallising dish, then crystallising dish is placed in fume hood and controls temperature at 20-60 DEG C, time 24h, and then crystallising dish is placed on to 24h in the air dry oven of 100 DEG C, in crystallising dish, obtain the dry film of organic/inorganic composite;
(3), the dry film of gained organic/inorganic composite in step (2) is scraped from crystallising dish, being placed in nitrogen atmosphere, to control heating rate be 1-3 DEG C/min, be warming up to 600-1000 DEG C and carry out high-temperature roasting 1-3h, then naturally cool to room temperature, obtain mesoporous nickel oxide/carbon/silica composite;
(4), the mesoporous nickel oxide/carbon/silica composite obtaining in step (3) being joined to concentration is in 0.1-2mol/L sodium hydrate aqueous solution; controlling temperature is to stir 5-30min at 20-60 DEG C; and then standing 30min; centrifugation; the precipitate with deionized water of gained is washed until the pH of efflux is neutrality; in air, at 100 DEG C, be dried, can obtain mesoporous nickel oxide/carbon composite nano-material;
Above-mentioned mesoporous nickel oxide/carbon/silica composite and concentration are the consumption of 0.1-2mol/L sodium hydrate aqueous solution, in mesoporous nickel oxide/carbon/silica composite: concentration is that 0.1-2mol/L sodium hydrate aqueous solution is that the ratio of 1g:5-30ml is calculated.
Mesoporous nickel oxide/carbon composite nano-material obtained above, it is the compound of nickel oxide and carbon composition, its element composition is pressed atomic percent and is calculated, wherein the ratio of the ratio 1% of oxygen atom, nickle atom is 2.72-3.75%, the ratio of carbon atom is 96.28-95.25%, and wherein the mass ratio of nickel oxide and carbon is 1:2.5～4.2.
After testing, its specific area is 435.5～800m to the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained 2/ g, pore volume are 1.08～1.5cm 3/ g, its aperture is 2.5～12.0nm.
Mesoporous nickel oxide/the carbon composite nano-material of above-mentioned gained can be used for making ultracapacitor electrode material used.
Beneficial effect of the present invention
The preparation method of a kind of mesoporous nickel oxide/carbon composite nano-material of the present invention, due in preparation process taking non-ionic surface active agent as template, organosilicon source and high molecular polymer be inorganic precursor as organic precursor, inorganic nickel source, induce the method for self assembly to synthesize nickel oxide/carbon/silicon dioxide composite material by evaporation, then further remove silicon dioxide, obtained and had compared with bigger serface and pore volume and wide-aperture nickel oxide/carbon composite nano-material.
Further, the preparation method of a kind of mesoporous nickel oxide/carbon composite nano-material of the present invention, the inorganic nickel presoma quality adding by control in preparation process, can regulate the content of nickel in mesoporous nickel oxide/carbon nano-composite material, thereby obtain the ultracapacitor electrode material used that specific capacitance can arbitrarily change, this is also that other nickel oxide/carbon composite institute is irrealizable at present.
Brief description of the drawings
The little angle XRD figure of the mesoporous nickel oxide/carbon composite nano-material of Fig. 1, embodiment 1 gained;
The wide-angle XRD figure of the mesoporous nickel oxide/carbon composite nano-material of Fig. 2, embodiment 1 gained;
Nitrogen adsorption-desorption curve of the mesoporous vanadium oxide/carbon composite nano-material of Fig. 3, embodiment 1 gained;
The graph of pore diameter distribution of the mesoporous vanadium oxide/carbon composite nano-material of Fig. 4, embodiment 1 gained;
The cyclic voltammogram of the mesoporous nickel oxide/carbon composite nano-material of Fig. 5, embodiment 1 gained.
Specific embodiments
Also come by reference to the accompanying drawings the present invention to conduct further description below by specific embodiment, but protection scope of the present invention is not limited to this.
Described method if no special instructions, is conventional method.Described material if no special instructions, all can buy from open commercial sources.
The instrument that various embodiments of the present invention are used or the model of equipment and manufacturer's information are as follows:
Electronic balance JA203 Shanghai Haikang Electronic Instruments Plant
Muffle furnace DC-B8/11 Beijing original creation Science and Technology Ltd.
Electrochemical workstation CH660D Shanghai Chen Hua instrument company
Electric heating constant-temperature blowing drying box DHG-9070A Shanghai one permanent scientific instrument
Tube furnace, model SL1700 II type Shanghai Sheng Li tester Co., Ltd;
X-ray diffractometer (XRD), PANalytical company of X PERT PRO Holland;
Scanning electron microscopy (SEM), S-3400N HIT;
Full-automatic physical adsorption analysis instrument, Merck & Co., Inc of the ASAP2020 U.S.;
Simultaneous thermal analysis instrument, Nai Chi company of STA-449F3 Germany.
embodiment 1
A preparation method for mesoporous nickel oxide/carbon composite nano-material, specifically comprises the following steps:
(1), the non-ionic surface active agent of 0.6g is scattered in 3g solvent and stirs 5min at 40 DEG C, then add the inorganic nickel of 0.12g source, directly stirring 5min dissolves, add successively again 0.06g organosilicon source and 0.6g organic high molecular polymer, under room temperature, continue to stir 20min to obtaining homogeneous phase solution;
The amount of non-ionic surface active agent, organic high molecular polymer, organosilicon source, inorganic nickel source and solvent used, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: solvent is 1:1:0.1:0.2:5;
Described non-ionic surface active agent is EO 20pO 70eO 20;
Described organosilicon source is positive quanmethyl silicate;
Described organic high molecular polymer is furfural resin;
Described inorganic nickel source is Nickelous nitrate hexahydrate;
Described solvent is ethylene glycol;
(2), the homogeneous phase solution obtaining in step (1) is poured in crystallising dish, then crystallising dish is placed in fume hood and controls temperature at 20 DEG C, time 24h, and then crystallising dish is placed on to 24h in the air dry oven of 100 DEG C, in crystallising dish, obtain the dry film of organic/inorganic composite;
(3), the dry film of gained organic/inorganic composite in step (2) is scraped from crystallising dish, being placed in nitrogen atmosphere, to control heating rate be 1 DEG C/min, be warming up to 600 DEG C and carry out high-temperature roasting 1h, then naturally cool to room temperature, obtain mesoporous nickel oxide/carbon/silica composite;
(4), the mesoporous nickel oxide/carbon/silica composite obtaining in 1g step (3) being joined to 5ml concentration is in 0.1mol/L sodium hydrate aqueous solution; controlling temperature is to stir 15min at 20 DEG C; and then standing 30min; then centrifugal; the precipitate with deionized water of gained is washed until the pH of efflux is neutrality; then control temperature and be 100 DEG C and be dried, can obtain mesoporous nickel oxide/carbon composite nano-material;
Above-mentioned mesoporous nickel oxide/carbon/silica composite and concentration are the consumption of 0.1mol/L sodium hydrate aqueous solution, in mesoporous nickel oxide/carbon/silica composite: concentration is that 0.1mol/L sodium hydrate aqueous solution is that the ratio of 1g:5ml is calculated.
Adopt x-ray diffractometer to measure the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained, the little angle XRD of gained schemes as shown in Figure 1, as can be seen from Figure 1 there is an obvious diffraction maximum at 2 these towers at 1.1 degree places, prove that the mesoporous nickel oxide/carbon composite nano-material of gained has orderly meso-hole structure.
Adopt x-ray diffractometer to carry out structure determination to the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained, the wide-angle XRD of gained schemes as shown in Figure 2, as can be seen from Figure 2, diffraction maximum is sharp-pointed, intensity is large, illustrates that the mesoporous nickel oxide/carbon composite nano-material of gained has mesoporous nickel oxide/carbon composite nano hole material of crystal wall construction.
By energy dispersion x-ray spectrometer (EDS), the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained is analyzed, its element composition is pressed atomic percent and is calculated, wherein the ratio of the ratio 1% of oxygen atom, nickle atom is 2.72%, the ratio of carbon atom is 96.28%, show that mesoporous nickel oxide/carbon composite nano-material is the compound of nickel oxide and carbon, wherein the mass ratio of nickel oxide and carbon is 1:3.56.
Adopt Full-automatic physical adsorption analysis instrument (Merck & Co., Inc of the ASAP2020 U.S.) to measure the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained, its nitrogen adsorption-desorption curve as shown in Figure 3, from Fig. 3, the hysteretic loop in relative pressure 0.65-0.9 left and right can be found out, sample has mesoporous VI type curve, has shown that thus nickel oxide/carbon complex has mesoporous character.
Further, the information gathering from Full-automatic physical adsorption analysis instrument (Merck & Co., Inc of the ASAP2020 U.S.) is analyzed, as shown in Figure 4, as can be seen from Figure 4 pore-size distribution, between 5-25nm, has shown the mesoporous character of the product of gained to its graph of pore diameter distribution thus.
Adopt the specific area of the mesoporous nickel oxide/carbon composite nano-material of automatic physical absorption analyzer to above-mentioned gained to measure, its specific area is 435.5m 2/ g.
Adopt the aperture of the mesoporous nickel oxide/carbon composite nano-material of automatic physical absorption analyzer to above-mentioned gained to measure, its aperture is 12.0 nm.
Adopt the pore volume of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its pore volume is 1.08cm 3/ g.
Mesoporous nickel oxide/carbon composite nano-material obtained above is made to ultracapacitor electrode material used, and its preparation method comprises the steps:
By mesoporous nickel oxide/carbon composite nano-material grind into powder of above-mentioned gained, mix with the ratio that conductive agent acetylene black, polytetrafluoroethylene are 8:1:1 in mass ratio, be coated in uniformly in the nickel foam of accurate weighing, in vacuum drying chamber, control temperature and process 12h at 120 DEG C, at 10MP pressure lower sheeting, be made into work electrode, with reference electrode calomel electrode, to electrode platinum electrode, and the KOH aqueous solution of 6mol/L be electrolyte form three-electrode system, be used for testing chemical property.
The ultracapacitor of above-mentioned gained electrode material used adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation, result as shown in Figure 5, as can be drawn from Figure 5, at 10mVs -1, 20mVs -1, 50mVs -1, 100mVs -1sweep speed under, its specific capacitance is respectively 230F/g, 275F/g, 420F/g, 468F/g.Show that thus mesoporous nickel oxide/carbon composite nano-material prepared by the present invention has higher specific capacitance.
embodiment 2
A preparation method for mesoporous nickel oxide/carbon composite nano-material, specifically comprises the following steps:
(1), the non-ionic surface active agent of 0.6g is scattered in 9g solvent and stirs 5min at 40 DEG C, then add the inorganic nickel of 1.14g source, directly stirring 5min dissolves, add successively again 0.54g organosilicon source and 1.5g organic high molecular polymer, under room temperature, continue to stir 20min to obtaining homogeneous phase solution;
The amount of non-ionic surface active agent, organic high molecular polymer, organosilicon source, inorganic nickel source and solvent used, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: the ratio that solvent is 1:2.5:0.9:1.9:15;
Described non-ionic surface active agent is EO 106pO 70eO 106;
Described organosilicon source is tetraethyl orthosilicate;
Described organic high molecular polymer is sucrose;
Described inorganic nickel source is six hydration nickel sulfate;
Described solvent is ethanol;
(2), the homogeneous phase solution obtaining in step (1) is poured in crystallising dish, then crystallising dish is placed in fume hood and controls temperature at 40 DEG C, time 24h, and then crystallising dish is placed on to 24h in the air dry oven of 100 DEG C, in crystallising dish, obtain the dry film of organic/inorganic composite;
(3), the dry film of gained organic/inorganic composite in step (2) is scraped from crystallising dish, being placed in nitrogen atmosphere, to control heating rate be 2 DEG C/min, be warming up to 800 DEG C and carry out high-temperature roasting 2h, then naturally cool to room temperature, obtain mesoporous nickel oxide/carbon/silica composite;
(4), the mesoporous nickel oxide/carbon/silica composite obtaining in step (3) being joined to concentration is in 1mol/L sodium hydrate aqueous solution; controlling temperature is to stir 15min at 40 DEG C; and then standing 30min; then centrifugal; the precipitate with deionized water of gained is washed until the pH of efflux is neutrality; then control temperature and be 100 DEG C and be dried 24h, can obtain mesoporous nickel oxide/carbon composite nano-material;
Above-mentioned mesoporous nickel oxide/carbon/silica composite and concentration are the consumption of 1mol/L sodium hydrate aqueous solution, in mesoporous nickel oxide/carbon/silica composite: concentration is that 1mol/L sodium hydrate aqueous solution is that the ratio of 1g:15ml is calculated.
By energy dispersion x-ray spectrometer (EDS), the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained is analyzed, its element composition is pressed atomic percent and is calculated, wherein the ratio of the ratio 1% of oxygen atom, nickle atom is 3.12%, the ratio of carbon atom is 95.88%, show that mesoporous nickel oxide/carbon composite nano-material is the compound of nickel oxide and carbon, wherein the mass ratio of nickel oxide and carbon is 1:2.5.
Adopt the specific area of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its specific area is 600 m 2/ g.
Adopt the pore volume of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its pore volume is 1.2cm 3/ g.
Adopt the aperture of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its aperture is 4.8nm.
Mesoporous nickel oxide/carbon composite nano-material obtained above is made to ultracapacitor electrode material used, and its preparation method comprises the steps:
By mesoporous nickel oxide/carbon composite nano-material grind into powder of above-mentioned gained, mix with the ratio that conductive agent acetylene black, polytetrafluoroethylene are 8:1:1 in mass ratio, be coated in uniformly in the nickel foam of accurate weighing, in vacuum drying chamber, control temperature and process 12h at 120 DEG C, at 10MP pressure lower sheeting, be made into work electrode, with reference electrode calomel electrode, to electrode platinum electrode, and the KOH aqueous solution of 6mol/L be electrolyte form three-electrode system, be used for testing chemical property.
The ultracapacitor electrode material used of above-mentioned gained adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation.At 50mVs -1sweep speed under, its specific capacitance is 430.4F/g.
embodiment 3
A preparation method for mesoporous nickel oxide/carbon composite nano-material, specifically comprises the following steps:
(1), the non-ionic surface active agent of 0.6g is scattered in 18g solvent, at 40 DEG C, stir 5min, then add the inorganic nickel of 2.4g source, directly stirring 5min dissolves, add successively again 1.2g organosilicon source and 3.6g organic high molecular polymer, under room temperature, continue to stir 20min to obtaining homogeneous phase solution solution;
The amount of non-ionic surface active agent, organic high molecular polymer, organosilicon source, inorganic nickel source and solvent used, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: solvent is 1:6:2:4:30;
Described non-ionic surface active agent is EO 132pO 60eO 132;
Described organosilicon source is positive silicic acid four butyl esters;
Described organic high molecular polymer is phenolic resins;
Described inorganic nickel source is Nickelous nitrate hexahydrate;
Described solvent is water;
(2), the homogeneous phase solution obtaining in step (1) is poured in crystallising dish, then crystallising dish is placed in fume hood and controls temperature at 60 DEG C, time 24h, and then crystallising dish is placed on to 24h in the air dry oven of 100 DEG C, in crystallising dish, obtain the dry film of organic/inorganic composite;
(3), the dry film of gained organic/inorganic composite in step (2) is scraped from crystallising dish, being placed in nitrogen atmosphere, to control heating rate be 3 DEG C/min, be warming up to 1000 DEG C and carry out high-temperature roasting 3h, then naturally cool to room temperature, obtain mesoporous nickel oxide/carbon/silica composite;
(4), the mesoporous nickel oxide/carbon/silica composite obtaining in 1g step (3) being joined to 30ml concentration is in 2mol/L sodium hydrate aqueous solution; controlling temperature is to stir 15min at 60 DEG C; and then standing 30min; then centrifugal; the precipitate with deionized water of gained is washed until the pH of efflux is neutrality; then control temperature and be 100 DEG C and be dried 24h, can obtain mesoporous nickel oxide/carbon composite nano-material;
Above-mentioned mesoporous nickel oxide/carbon/silica composite and concentration are the consumption of 2mol/L sodium hydrate aqueous solution, in mesoporous nickel oxide/carbon/silica composite: concentration is that 2mol/L sodium hydrate aqueous solution is that the ratio of 1g:30ml is calculated.
By energy dispersion x-ray spectrometer (EDS), the mesoporous nickel oxide/carbon composite nano-material of above-mentioned gained is analyzed, its element composition is pressed atomic percent and is calculated, wherein the ratio of the ratio 1% of oxygen atom, nickle atom is 3.75%, the ratio of carbon atom is 95.25%, show that mesoporous nickel oxide/carbon composite nano-material is the compound of nickel oxide and carbon, wherein the mass ratio of nickel oxide and carbon is 1:4.2.
Adopt the specific area of the mesoporous nickel oxide/carbon composite nano-material of automatic physical absorption analyzer to above-mentioned gained to measure, its specific area is 800m 2/ g.
Adopt the pore volume of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its pore volume is 1.5cm 3/ g.
Adopt the aperture of the mesoporous nickel oxide/carbon composite nano-material of Full-automatic physical adsorption analysis instrument to above-mentioned gained to measure, its aperture is 2.5nm.
Mesoporous nickel oxide/carbon composite nano-material obtained above is made to ultracapacitor electrode material used, and its preparation method comprises the steps:
By mesoporous nickel oxide/carbon composite nano-material grind into powder of above-mentioned gained, mix with the ratio that conductive agent acetylene black, polytetrafluoroethylene are 8:1:1 in mass ratio, be coated in uniformly in the nickel foam of accurate weighing, in vacuum drying chamber, control temperature and process 12h at 120 DEG C, at 10MP pressure lower sheeting, be made into work electrode, with reference electrode calomel electrode, to electrode platinum electrode, and the KOH aqueous solution of 6mol/L be electrolyte form three-electrode system, be used for testing chemical property.
The ultracapacitor electrode material used of above-mentioned gained adopts cyclic voltammetry to measure by Shanghai occasion China CHI660C electrochemical workstation.At 100mVs -1sweep speed under, its specific capacitance is 480.7F/g.
In sum, the preparation method of a kind of mesoporous nickel oxide/carbon composite nano-material of the present invention, adopt the method for evaporation induction self assembly, obtained before this nickel oxide/silicon/carbon dioxide compound, then remove silicon dioxide, thereby the mesoporous nickel oxide/carbon composite nano-material that obtains high-specific surface area and pore volume and aperture, its specific area is 435～800m 2/ g, pore volume are 1.0～1.5cm 3/ g, its aperture is 2.5～12.0nm.
Further, in the mesoporous nickel oxide/carbon composite nano-material due to above-mentioned gained, larger mesoporous aperture and pore volume and bigger serface are conducive to the migration of electrolyte intermediate ion/electronics, thereby have increased the specific capacitance of this composite nano materials.
The above is only giving an example of embodiments of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification; these improve and modification is all considered as protection scope of the present invention, and these can not affect effect of the invention process and practical applicability.

Claims (6)

1. a preparation method for mesoporous nickel oxide/carbon composite nano-material, is characterized in that specifically comprising the steps:
(1), non-ionic surface active agent, organic high molecular polymer, organosilicon source, inorganic nickel source and solvent are calculated in mass ratio, be non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: the ratio that solvent is 1:1-6:0.1-2:0.2-4:5-30 is mixed, stirs and obtain homogeneous phase solution;
Described non-ionic surface active agent is EO 20pO 70eO 20, EO 106pO 70eO 106, EO 132pO 60eO 132in one or more mixture;
Described organosilicon source is the mixture of one or more compositions in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate, positive silicic acid four butyl esters;
Described organic high molecular polymer is the mixture of one or more compositions in phenolic resins, sucrose, furfural resin;
Described inorganic nickel source is Nickelous nitrate hexahydrate, six hydration nickel sulfate, one or both in nickel chloride and above mixture;
Described solvent is one or more the mixture in ethanol, water, ethylene glycol;
(2), the homogeneous phase solution obtaining in step (1) is poured in crystallising dish, and crystallising dish is placed in fume hood and controls temperature at 20-60 DEG C, time 24h, again crystallising dish is taken out to 24h in the air dry oven that is placed on 100 DEG C, in crystallising dish, obtain the dry film of organic/inorganic composite;
(3), the dry film of gained organic/inorganic composite in step (2) is scraped from crystallising dish, being placed in nitrogen atmosphere, to control heating rate be 1-3 DEG C/min, be warming up to 600-1000 DEG C and carry out high-temperature roasting 1～3h, then naturally cool to room temperature, obtain mesoporous nickel oxide/carbon/silica composite;
(4), the mesoporous nickel oxide/carbon/silica composite obtaining in step (3) being joined to concentration is in 0.1-2mol/L sodium hydrate aqueous solution; controlling temperature is to stir 5-30min at 20-60 DEG C; and then standing 30min; centrifugation; the precipitate with deionized water of gained is washed until the pH of efflux is neutrality; in air, at 100 DEG C, be dried, can obtain mesoporous nickel oxide/carbon composite nano-material;
Above-mentioned mesoporous nickel oxide/carbon/silica composite and concentration are the consumption of 0.1-2mol/L sodium hydrate aqueous solution, in mesoporous nickel oxide/carbon/silica composite: concentration is that 0.1-2mol/L sodium hydrate aqueous solution is that the ratio of 1g:5-30ml is calculated.
2. as claimed in claim 1a kind of preparation method of mesoporous nickel oxide/carbon composite nano-material, it is characterized in that the amount of non-ionic surface active agent used in step (1), organic high molecular polymer, organosilicon source, inorganic nickel source and solvent, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: solvent is 1:1:0.1:0.2:5;
Described non-ionic surface active agent is EO 20pO 70eO 20;
Described organosilicon source is positive quanmethyl silicate;
Described organic high molecular polymer is furfural resin;
Described inorganic nickel source is Nickelous nitrate hexahydrate;
Described solvent is ethylene glycol.
3. as claimed in claim 1a kind of preparation method of mesoporous nickel oxide/carbon composite nano-material, it is characterized in that the amount of non-ionic surface active agent used in step (1), organic high molecular polymer, organosilicon source, inorganic nickel source and solvent, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: the ratio that solvent is 1:2.5:0.9:1.9:15;
Described non-ionic surface active agent is EO 106pO 70eO 106;
Described organosilicon source is tetraethyl orthosilicate;
Described organic high molecular polymer is sucrose;
Described inorganic nickel source is six hydration nickel sulfate;
Described solvent is ethanol.
4. as claimed in claim 1a kind of preparation method of mesoporous nickel oxide/carbon composite nano-material, it is characterized in that the amount of non-ionic surface active agent used in step (1), organic high molecular polymer, organosilicon source, inorganic nickel source and solvent, calculate in mass ratio i.e. non-ionic surface active agent: organic high molecular polymer: organosilicon source: inorganic nickel source: solvent is 1:6:2:4:30;
Described non-ionic surface active agent is EO 132pO 60eO 132;
Described organosilicon source is positive silicic acid four butyl esters;
Described organic high molecular polymer is phenolic resins;
Described inorganic nickel source is Nickelous nitrate hexahydrate;
Described solvent is water.
5. the mesoporous nickel oxide/carbon composite nano-material of preparation method's gained as claimed in claim 1, it is characterized in that described mesoporous nickel oxide/carbon composite nano-material is the compound of nickel oxide and carbon composition, its element composition is pressed atomic percent and is calculated, wherein the ratio of the ratio 1% of oxygen atom, nickle atom is 2.72-3.75%, the ratio of carbon atom is 96.28-95.25%, and wherein the mass ratio of nickel oxide and carbon is 1:2.5～4.2;
The specific area of described mesoporous nickel oxide/carbon composite nano-material is 435.5～800m 2/ g, pore volume are 1.08～1.5cm 3/ g, its aperture is 2.5～12.0nm.
6. mesoporous nickel oxide/carbon composite nano-material as claimed in claim 5 is for making ultracapacitor electrode material used.
CN201410367910.3A 2014-07-29 2014-07-29 Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof Pending CN104183392A (en)

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CN114985722A (en) * 2022-07-01 2022-09-02 浙江新和成股份有限公司 Mesoporous nickel powder and preparation method thereof, nickel-phosphorus catalyst system and preparation method of adiponitrile
CN115814798A (en) * 2022-09-21 2023-03-21 宁波九胜创新医药科技有限公司 Supported nano nickel sesquioxide catalyst and preparation method thereof

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CN104569075A (en) * 2015-01-06 2015-04-29 宁夏大学 Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material and preparation method thereof
CN105070520A (en) * 2015-08-11 2015-11-18 上海应用技术学院 Mesoporous iron/ carbon nanocomposite preparation method and application
CN105118684A (en) * 2015-08-11 2015-12-02 上海应用技术学院 Mesoporous cobalt/carbon nano composite material preparation method and use thereof
CN105161311A (en) * 2015-08-11 2015-12-16 上海应用技术学院 Method for preparing titanium nitride/carbon composite materials
CN105152146A (en) * 2015-08-11 2015-12-16 上海应用技术学院 Preparation method of TiN nano-material
CN105161314B (en) * 2015-08-26 2018-09-11 四川天策聚材科技有限公司 Nano-nickel oxide/nickel/graphene composite material and its preparation method and application
CN105161314A (en) * 2015-08-26 2015-12-16 西南石油大学 Nano nickel oxide/nickel/graphene composite material and preparation method and application thereof
CN105702484A (en) * 2016-01-27 2016-06-22 同济大学 A manufacturing method for a NiO/mesoporous carbon nanosphere which is supercapacitor electrode materials
CN105702484B (en) * 2016-01-27 2017-12-26 同济大学 A kind of preparation method of the mesoporous Nano carbon balls of electrode material for super capacitor NiO/
CN106206061A (en) * 2016-07-15 2016-12-07 上海应用技术学院 A kind of preparation method and applications of mesoporous manganese oxide/carbon composite nano-material
CN107221458A (en) * 2017-05-25 2017-09-29 温州大学 Nickel complex is carbon dope nickel oxide combination electrode material of precursor and preparation method thereof
CN114985722A (en) * 2022-07-01 2022-09-02 浙江新和成股份有限公司 Mesoporous nickel powder and preparation method thereof, nickel-phosphorus catalyst system and preparation method of adiponitrile
CN115814798A (en) * 2022-09-21 2023-03-21 宁波九胜创新医药科技有限公司 Supported nano nickel sesquioxide catalyst and preparation method thereof

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