CN106531460B - A kind of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, preparation method and applications - Google Patents
A kind of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, preparation method and applications.Nonionic surfactant, inorganic nickel source, inorganic manganese source, organic silicon source and organic high molecular polymer are mixed, stirred by the present invention in organic solvent first, form homogeneous phase solution;Then it is crosslinked in an oven, obtains membranoid substance;Membranoid substance is calcined again, obtains nickel oxide/manganese oxide/SiO2/ C composite mesoporous thing, silica finally is removed with neutralizing treatment, mesoporous nickel oxide/manganese oxide/carbon nano-composite material is prepared;Its specific surface area is 130~350m2/ g, pore volume are 0.28~0.75cm3/ g, aperture are 2.3~5.2nm.The preparation method of the present invention is simple, is adapted to large-scale production.The nano composite material of the present invention can use the electrode material made used in ultracapacitor, and under 0.5A/g current density, capacitance can reach 480F/g.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, it particularly relates to a kind of mesoporous nickel oxide/manganese oxide/carbon
Nano composite material, preparation method and applications.
Background technology
21 century facing mankind energy crisis and environmental pollution this two it is big important the problem of, therefore the exploitation of clean energy resource
Have far-reaching significance with research.Wherein, all kinds of automobiles account for 40% of consumption of petroleum or so, and global atmosphere pollution 42% comes from
The discharge of vehicular traffic.Country has put into effect many policies and has encouraged everybody to buy new-energy automobile, and countries in the world are to developing electronic vapour
Car is paid much attention to, and development electric car also is classified as into important development direction in China's 863 Program.Electrokinetic cell as onboard power
Research, turn into power vehicle development main bottleneck.Current driving force battery is mainly Ni-H cell, lithium ion battery and fuel
Battery.Ultracapacitor is of great interest as new energy storage device.The exploitation of electrode material is to perplex expert very
A big problem.Conventional electrode material mainly has carbon material, transition metal oxide and conducting polymer.Due to metal oxygen
Compound is significantly larger than the two point layer capacitance of carbon material in pseudo capacitance caused by Cathode/Solution Interface reaction, therefore draws
The interest of many researchers is played.
Nano structural material has special electronics, optics and magnetic property, gets more and more people's extensive concerning.Oversubscription submodule
Plate, such as surfactant and block polymer, frequently as " soft template " be used for synthesizing different compositions nano structural material (including
Silica, metal, metal oxide, metal phosphate and organic silicic acid compound).
Simple transition metal and transition metal oxide are because have higher theoretical capacity, therefore widely closed
Note, is great potential battery material of new generation.Wherein the oxide of nickel has higher theoretical specific capacity, cheap and environment
The advantages that friendly, receive more research.
Nickel oxide, or nickel oxide has been prepared with the compound of other materials by a variety of methods at present, but
It is or few people makes the mesoporous bimetallic oxide i.e. composite of nickel oxide/manganese oxide, then applies in electrochemistry
On example, this bimetal composite oxide have synergy, it is possible to improve the performance of ultracapacitor.Meanwhile with
It is preceding prepare nickel oxide process it is comparatively comparatively laborious such as higher by requirement of the mechanical lapping to apparatus, pass through water
Solution method preparation process is less susceptible to control etc., and comparatively the specific surface area for the material being synthesized is not very
Height,
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides one kind to have high-crystallinity, compared with Large ratio surface
Long-pending mesoporous nickel oxide/manganese oxide/carbon nano-composite material, preparation method and applications.Present invention process is simple, easily control
System, mesoporous nickel oxide/manganese oxide/carbon nano-composite material of acquisition can use as electrode material, and chemical property is good.
In the present invention, we use nonionic surfactant, inorganic nickel source, inorganic manganese source, organic silicon source and organic high score
Sub- polymer is acted synergistically by organic and inorganic in organic solvent, and at a certain temperature further to high molecular polymer
It is crosslinked, obtains membranoid substance;Membranoid substance is calcined under an inert atmosphere again, obtains nickel oxide/manganese oxide/SiO2/ C's is mesoporous
Compound, silica finally is removed with neutralizing treatment, mesoporous nickel oxide/manganese oxide/carbon nano-composite material is prepared, so as to
Avoid the hydrolysis of nickel source and manganese source in aqueous.Present invention obtains the mesoporous bimetallic oxide of bigger serface.
Technical scheme is specifically described as follows.
The present invention provides a kind of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, and its specific surface area is 130~
350m2/ g, pore volume are 0.28~0.75cm3/ g, aperture are 2.3~5.2nm.Preferably, specific surface area is 200~250m2/ g,
Pore volume is 0.40~0.60cm3/ g, aperture are 3.5~4.5nm.
The present invention also provides a kind of preparation method of above-mentioned mesoporous nickel oxide/manganese oxide/carbon nano-composite material, specifically
Step is as follows:
(1) nonionic surfactant, inorganic nickel source, inorganic manganese source, organic silicon source and organic high molecular polymer are existed
In solvent, it is sufficiently stirred under the water-bath of 35~45 DEG C of temperature, forms homogeneous phase solution;Then by homogeneous phase solution in 35~45 DEG C of temperature
15~30h is placed in the baking oven of degree, then places 15~30h in the baking oven of 85~110 DEG C of temperature and is crosslinked, is obtained membranaceous
Thing;Wherein:Nonionic surfactant, solvent, inorganic nickel source, inorganic manganese source, organic silicon source and organic high molecular polymer
Mass ratio is 1:(10~40):(0.5~5):(0.5~5):(0.2~2):(2~6);
(2) gained membranoid substance in step (1) is scraped from reaction vessel, is placed in inert atmosphere and is calcined, that is, be situated between
Hole nickel oxide/manganese oxide/carbon/silica composite;
(3) the mesoporous nickel oxide/manganese oxide/carbon/silica composite obtained in step (2) is added to sodium hydroxide
In solution, stir, stand at a temperature of 20~60 DEG C, centrifugation, the precipitation of gained is washed with deionized water, dried, and is obtained
Mesoporous nickel oxide manganese oxide/carbon composite nano-material.
In the present invention, in step (1), nonionic surfactant is selected from EO20PO70EO20、EO106PO70EO106Or
EO132PO60EO132In one or more;Described organic high molecular polymer is selected from phenolic resin, sucrose or furfural tree
One or more in fat.
In the present invention, in step (1), described organic silicon source is selected from tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid
One or more in orthocarbonate or the butyl ester of positive silicic acid four;Described inorganic nickel source is selected from nickel nitrate, nickel sulfate or nickel chloride
One or more;One or more of the described inorganic manganese source in potassium permanganate, manganese nitrate aqueous solution or manganese sulfate.
In the present invention, in step (1), the one kind of described solvent in ethanol, water, formic acid, ether or ethylene glycol
It is or several.
In the present invention, in step (2), the heating schedule of roasting is as follows:With 1~3 DEG C/min heating rate, it is warming up to
600~1000 DEG C of progress 1~3h of high-temperature roasting, then naturally cool to room temperature.
In the present invention, in step (3), sodium hydroxide solution is 0.1~2mol/L.
In the present invention, in step (3), mesoporous nickel oxide/manganese oxide/carbon/silica composite and sodium hydroxide are water-soluble
The mass volume ratio of liquid is 1:5~1:30g/ml.
Further, the present invention also provides a kind of above-mentioned mesoporous nickel oxide/manganese oxide/carbon nano-composite material and made
The purposes in electrode material used in ultracapacitor.
The present invention due in preparation process using nonionic surfactant as template, organic silicon source and organic polymer
Polymer is that organic precursor, inorganic nickel source and inorganic manganese source are inorganic precursor, is closed by the method for evaporation-induced self-assembly
Into mesoporous nickel oxide/manganese oxide/silicon dioxide composite material is gone out, silica is then further removed, is obtained with larger
Specific surface area and pore volume and nickel oxide/manganese oxide/carbon composite nano-material of large aperture.Added in preparation process by control
The inorganic nickel source and the difference of inorganic manganese source ratio entered, can adjust nickel in mesoporous nickel oxide/manganese oxide/carbon nano-composite material
With the content ratio of manganese, so as to obtain the electrode material used in the ultracapacitor that specific capacitance can arbitrarily change, this is also mesh
Preceding other double metallic composite materials institute is irrealizable.Mesoporous nickel oxide/the manganese oxide obtained by the preparation method of the present invention/
Carbon nano-composite material has the characteristics of high-crystallinity, bigger serface, homogeneous aperture.
The present invention compares with prior art, and its technological progress is significant.The beneficial effects of the present invention are:Present invention solution
Bimetallic material of the prior art of having determined is used as the unstability of electrode material, and in building-up process, condition is difficult to control,
Process complexity is extremely difficult to a step and obtains the technical problem of final product.The mesoporous oxidation obtained by the preparation method of the present invention
Nickel/manganese oxide/carbon nano-composite material can make the electrode material used in the ultracapacitor with higher specific capacitance, and
It is simple to operate controllable and production cost is low, it is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is the wide-angle XRD of mesoporous nickel oxide/manganese oxide/carbon nano-composite material prepared by the present invention.
Fig. 2 is the nitrogen adsorption desorption figure of mesoporous nickel oxide/manganese oxide/carbon nano-composite material prepared by the present invention.
Fig. 3 is the graph of pore diameter distribution of mesoporous nickel oxide/manganese oxide/carbon nano-composite material prepared by the present invention.
Fig. 4 is the constant current charge-discharge figure of mesoporous nickel oxide/manganese oxide/carbon nano-composite material prepared by the present invention.
Embodiment
The present invention is further described below by way of specific embodiment and with reference to accompanying drawing, but the protection of the present invention
Scope not limited to this.
Methods described is unless otherwise instructed.It is conventional method.The material unless otherwise instructed, can be from open business
Approach can buy.
The model and manufacturer's information of instrument or equipment used in various embodiments of the present invention are as follows:
Tube furnace, the types of model SL1700 II, manufacturer:Shanghai Sheng Li testers Co., Ltd;
X-ray diffractometer (XRD), PANalytical company of X PERT PRO Holland;
SEM (SEM), S-3400N HITs;
Full-automatic physical Sorption Analyzer, Merck & Co., Inc of the ASAP2020 U.S.;
Synchronous solving, Nai Chi companies of STA-449F3 Germany.
Embodiment 1
A kind of preparation method of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, specifically includes following steps:
(1), at 40 DEG C, 0.6g nonionic surfactants is dissolved in 12.0g solvents, then sequentially add 0.9g
Inorganic nickel source, the inorganic manganese sources of 0.9g and the organic silicon sources of 0.6g, the polymerization of 2.4g organic polymers is added after dissolving complete 10min
Thing, it is sufficiently stirred to form homogeneous phase solution under 40 DEG C of water-baths, is then poured into surface plate, 24h is placed in 40 DEG C of baking ovens, then
Place 24h in 100 DEG C of baking ovens to be crosslinked, so as to obtain the dry film of transparent organic/inorganic composite;
Above-mentioned nonionic surfactant used, solvent, inorganic nickel source, inorganic manganese source, organic silicon source, organic polymer
The amount of polymer, is calculated in mass ratio, nonionic surfactant:Solvent:Inorganic nickel source:Inorganic manganese source:Organic silicon source:It is organic
High molecular polymer is 1:20:1.5:1.5:1:4;
Described nonionic surfactant is EO20PO70EO20;
Described organic silicon source is positive quanmethyl silicate;
Described organic high molecular polymer is furfural resin;
Described inorganic nickel source is nickel nitrate solution;
Described inorganic manganese source is manganese nitrate aqueous solution;
Described solvent is ethylene glycol.
(2), the dry film of gained organic/inorganic composite in step (1) is scraped from crystallising dish, is placed in nitrogen atmosphere
Middle to control heating rate be 1 DEG C/min, is warming up to 600 DEG C of progress high-temperature roasting 2h, then naturally cools to room temperature, that is, be situated between
Hole nickel oxide/manganese oxide/carbon/silica composite;
(3), the mesoporous nickel oxide/manganese oxide/carbon/silica composite obtained in step (3) is added to concentration and is
In 0.5mol/L sodium hydrate aqueous solutions, it is to stir 15min at 40 DEG C to control temperature, then stands 30min again, is then centrifuged for,
The precipitation of gained with deionized water carries out washing until the pH of efflux is neutral, then control temperature to be 100 DEG C and is dried,
It can obtain mesoporous nickel oxide/manganese oxide/carbon nano-composite material.
Above-mentioned mesoporous nickel oxide/manganese oxide/carbon/silica composite and concentration are 0.5mol/L sodium hydrate aqueous solutions
Dosage, by mesoporous nickel oxide/manganese oxide/carbon/silica composite:Concentration is that 0.5mol/L sodium hydrate aqueous solutions are
1g:20ml ratio calculates.
Using x-ray powder diffraction instrument (PANalytical X ' Pert diffractometer) to above-mentioned steps (3)
High-crystallinity, the mesoporous nickel oxide/manganese oxide/carbon nano-composite material of bigger serface of final gained are measured, gained
Wide-angle XRD spectrum as shown in figure 1, from figure 1 it appears that the mesoporous nickel oxide of the high-crystallinity of gained, bigger serface/
Manganese oxide/carbon nano-composite material has obvious diffraction maximum, and it is nano combined to be indicated above mesoporous nickel oxide/manganese oxide/carbon
The crystallization degree of material is very high.
Using specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010adsorption
Analyzer), according to nitrogen adsorption-desorption method (Dong W, Sun Y, Lee C W, et al.Journal of the
American Chemical Society,2007,129(45):13894-13904.) to the mesoporous oxygen obtained by above-mentioned steps (3)
Change nickel/manganese oxide/carbon nano-composite material to be measured, nitrogen adsorption-desorption result of gained is as shown in figure 3, can from Fig. 3
Stagnant ring is obviously returned to find out that curve has, the mesoporous nickel oxide/manganese oxide/carbon nanometer for being indicated above being prepared is answered
Condensation material is mesoporous material, and has big specific surface area.Its specific surface area is 150m2/ g, pore volume 0.25cm3/ g, aperture are
4.8nm。
Mesoporous nickel oxide/manganese oxide/carbon nano-composite material obtained above is made to the electrode used in ultracapacitor
Material, its preparation method comprise the following steps:
By mesoporous nickel oxide/manganese oxide/carbon nano-composite material grind into powder of above-mentioned gained, with conductive agent acetylene
Black, polytetrafluoroethylene (PTFE) is 8 in mass ratio:1:1 ratio mixing, is uniformly coated in the nickel foam of precise, is done in vacuum
Control temperature to handle 12h at 120 DEG C in dry case, in 10MPa pressure lower sheetings, working electrode is fabricated to, with reference electrode Ag/
AgCl, three-electrode system is formed for electrolyte to the KOH aqueous solution of electrode platinum electrode, and 2mol/L, for testing electrochemistry
Energy.
Electrode material used in the ultracapacitor of above-mentioned gained is used by Shanghai Chen Hua CHI660C electrochemical workstations
Transverse electric stream discharge and recharge is measured.As a result as shown in figure 4, as can be drawn from Figure 4, the constant current charge-discharge curve of electrode material
Show good triangular waveform, it was demonstrated that material has a good chemical property.Enter under 0.5A/g current density
Row measure, its specific capacitance is respectively 480F/g.Above-mentioned data result indicates mesoporous nickel oxide/oxidation prepared by the present invention
Manganese/carbon composite nano-material has higher specific capacitance.
Embodiment 2
A kind of preparation method of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, specifically includes following steps:
(1), at 40 DEG C, 0.6g nonionic surfactants is dissolved in 6.0g solvents, then sequentially add 0.6g
Inorganic nickel source, the inorganic manganese sources of 0.3g and the organic silicon sources of 0.12g, the polymerization of 1.2g organic polymers is added after dissolving complete 10min
Thing, it is sufficiently stirred to form homogeneous phase solution under 40 DEG C of water-baths, is then poured into surface plate, 24h is placed in 40 DEG C of baking ovens, then
Place 24h in 100 DEG C of baking ovens to be crosslinked, so as to obtain the dry film of transparent organic/inorganic composite;
Above-mentioned nonionic surfactant used, solvent, inorganic nickel source, inorganic manganese source, organic silicon source, organic polymer
The amount of polymer, is calculated in mass ratio, nonionic surfactant:Solvent:Inorganic nickel source:Inorganic manganese source:Organic silicon source:It is organic
High molecular polymer is 1:10:1.0:0.5:0.2:2;
Described nonionic surfactant is EO106PO70EO106;
Described organic silicon source is tetraethyl orthosilicate;
Described organic high molecular polymer is sucrose;
Described inorganic nickel source is nickel chloride solution;
Described inorganic manganese source is potassium permanganate;
Described solvent is ethanol.
(2), the dry film of gained organic/inorganic composite in step (1) is scraped from crystallising dish, is placed in nitrogen atmosphere
Middle to control heating rate be 2 DEG C/min, is warming up to 800 DEG C of progress high-temperature roasting 1h, then naturally cools to room temperature, that is, be situated between
Hole nickel oxide/manganese oxide/carbon/silica composite;
(3), the mesoporous nickel oxide/manganese oxide/carbon/silica composite obtained in step (3) is added to concentration and is
In 0.2mol/L sodium hydrate aqueous solutions, it is to stir 10min at 20 DEG C to control temperature, then stands 30min again, is then centrifuged for,
The precipitation of gained with deionized water carries out washing until the pH of efflux is neutral, then control temperature to be 100 DEG C and is dried,
It can obtain mesoporous nickel oxide/manganese oxide/carbon nano-composite material.
Above-mentioned mesoporous nickel oxide/manganese oxide/carbon/silica composite and concentration are 0.2mol/L sodium hydrate aqueous solutions
Dosage, by mesoporous nickel oxide/manganese oxide/carbon/silica composite:Concentration is that 0.2mol/L sodium hydrate aqueous solutions are
1g:10ml ratio calculates.
Using specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010adsorption
Analyzer), according to nitrogen adsorption-desorption method (Dong W, Sun Y, Lee C W, et al.Journal of the
American Chemical Society,2007,129(45):13894-13904.) to the mesoporous oxygen obtained by above-mentioned steps (3)
Change nickel/manganese oxide/carbon nano-composite material to be measured, its specific surface area is 350m2/ g, pore volume 0.75cm3/ g, aperture are
2.3nm。
Mesoporous nickel oxide/manganese oxide/carbon nano-composite material obtained above is made to the electrode used in ultracapacitor
Material, its preparation method comprise the following steps:
By mesoporous nickel oxide/manganese oxide/carbon nano-composite material grind into powder of above-mentioned gained, with conductive agent acetylene
Black, polytetrafluoroethylene (PTFE) is 8 in mass ratio:1:1 ratio mixing, is uniformly coated in the nickel foam of precise, is done in vacuum
Control temperature to handle 12h at 120 DEG C in dry case, in 10MPa pressure lower sheetings, working electrode is fabricated to, with reference electrode Ag/
AgCl, three-electrode system is formed for electrolyte to the KOH aqueous solution of electrode platinum electrode, and 1mol/L, for testing electrochemistry
Energy.
Electrode material used in the ultracapacitor of above-mentioned gained is used by Shanghai Chen Hua CHI660C electrochemical workstations
Transverse electric stream discharge and recharge is measured, and the capacitance for as a result obtaining electrode is 350F/g under 0.5A/g current density.
Embodiment 3
A kind of preparation method of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, specifically includes following steps:
(1), at 40 DEG C, 0.6g nonionic surfactants are dissolved in 24.0g solvents, then sequentially add 3g's
The inorganic manganese source of inorganic nickel source, 9g and the organic silicon sources of 1.2g, 3.6g organic high molecular polymers are added after dissolving complete 10min,
It is sufficiently stirred to form homogeneous phase solution under 40 DEG C of water-baths, is then poured into surface plate, 24h is placed in 40 DEG C of baking ovens, then 100
Place 24h in DEG C baking oven to be crosslinked, so as to obtain the dry film of transparent organic/inorganic composite;
Above-mentioned nonionic surfactant used, solvent, inorganic nickel source, inorganic manganese source, organic silicon source, organic polymer
The amount of polymer, is calculated in mass ratio, nonionic surfactant:Solvent:Inorganic nickel source:Inorganic manganese source:Organic silicon source and have
The mass ratio of machine high molecular polymer is 1:40:5:15:2:6.
Described nonionic surfactant is EO132PO60EO132;
Described organic silicon source is the positive butyl ester of silicic acid four;
Described organic high molecular polymer is phenolic resin;
Described inorganic nickel source is nickel nitrate solution;
Described inorganic manganese source is manganese sulfate;
Described solvent is water.
(2), the dry film of gained organic/inorganic composite in step (1) is scraped from crystallising dish, is placed in nitrogen atmosphere
Middle to control heating rate be 3 DEG C/min, is warming up to 1000 DEG C of progress high-temperature roasting 3h, then naturally cools to room temperature, that is, obtain
Mesoporous nickel oxide/manganese oxide/carbon/silica composite;
(3), the mesoporous nickel oxide/manganese oxide/carbon/silica composite obtained in step (3) is added to concentration and is
In 2mol/L sodium hydrate aqueous solutions, it is to stir 30min at 60 DEG C to control temperature, then stands 30min again, is then centrifuged for, institute
Precipitation with deionized water carry out washing until the pH of efflux is neutral, then control temperature to be 100 DEG C and is dried, i.e.,
It can obtain mesoporous nickel oxide/manganese oxide/carbon nano-composite material.
Above-mentioned mesoporous nickel oxide/manganese oxide/carbon/silica composite and concentration are 2mol/L sodium hydrate aqueous solutions
Dosage, by mesoporous nickel oxide/manganese oxide/carbon/silica composite:Concentration is that 2mol/L sodium hydrate aqueous solutions are 1g:
30ml ratio calculates.
Using specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010adsorption
Analyzer), according to nitrogen adsorption-desorption method (Dong W, Sun Y, Lee C W, et al.Journal of the
American Chemical Society,2007,129(45):13894-13904.) to the mesoporous oxygen obtained by above-mentioned steps (3)
Change nickel/manganese oxide/carbon nano-composite material to be measured, its specific surface area is 298m2/ g, pore volume 0.49cm3/g, aperture is
3.9nm。
Mesoporous nickel oxide/manganese oxide/carbon nano-composite material obtained above is made to the electrode used in ultracapacitor
Material, its preparation method comprise the following steps:
By mesoporous nickel oxide/manganese oxide/carbon nano-composite material grind into powder of above-mentioned gained, with conductive agent acetylene
Black, polytetrafluoroethylene (PTFE) is 8 in mass ratio:1:1 ratio mixing, is uniformly coated in the nickel foam of precise, is done in vacuum
Control temperature to handle 12h at 120 DEG C in dry case, in 10MPa pressure lower sheetings, working electrode is fabricated to, with reference electrode Ag/
AgCl, three-electrode system is formed for electrolyte to the KOH aqueous solution of electrode platinum electrode, and 6mol/L, for testing electrochemistry
Energy.
Electrode material used in the ultracapacitor of above-mentioned gained is used by Shanghai Chen Hua CHI660C electrochemical workstations
Constant current charge-discharge is measured, and the capacitance for as a result obtaining electrode is 480F/g under 0.5A/g current density.
Claims (7)
1. a kind of preparation method of mesoporous nickel oxide/manganese oxide/carbon nano-composite material, it is characterised in that its specific surface area is
130~350m2/ g, pore volume are 0.28~0.75cm3/ g, aperture are 2.3~5.2nm, are comprised the following steps that:
(1) by nonionic surfactant, inorganic nickel source, inorganic manganese source, organic silicon source and organic high molecular polymer in solvent
In, it is sufficiently stirred under the water-bath of 35~45 DEG C of temperature, forms homogeneous phase solution;Then by homogeneous phase solution in 35~45 DEG C of temperature
15~30h is placed in baking oven, then places 15~30h in the baking oven of 85~110 DEG C of temperature and is crosslinked, obtains membranoid substance;Its
In:Nonionic surfactant, solvent, inorganic nickel source, inorganic manganese source, the mass ratio of organic silicon source and organic high molecular polymer
For 1:(10~40):(0.5~5):(0.5~5):(0.2~2):(2~6);
(2) gained membranoid substance in step (1) is scraped from reaction vessel, is placed in inert atmosphere and is calcined, that is, obtain mesoporous oxygen
Change nickel/manganese oxide/carbon/silica composite;
(3) the mesoporous nickel oxide/manganese oxide/carbon/silica composite obtained in step (2) is added to sodium hydroxide solution
In, at a temperature of 20~60 DEG C under stir, stand, centrifuge, the precipitation of gained is washed with deionized water, dried, and is situated between
Hole nickel oxide manganese oxide/carbon nano-composite material.
2. preparation method according to claim 1, it is characterised in that in step (1), nonionic surfactant is selected from
EO20PO70EO20、EO106PO70EO106Or EO132PO60EO132In one or more;Described organic high molecular polymer
One or more in phenolic resin, sucrose or furfural resin.
3. preparation method according to claim 1, it is characterised in that in step (1), described organic silicon source is selected from positive silicon
One or more in sour tetra-ethyl ester, positive quanmethyl silicate, positive silicic acid orthocarbonate or the butyl ester of positive silicic acid four;Described is inorganic
Nickel source is selected from the one or more of nickel nitrate, nickel sulfate or nickel chloride;Described inorganic manganese source is selected from potassium permanganate, manganese nitrate water
One or more in solution or manganese sulfate.
4. preparation method according to claim 1, it is characterised in that in step (1), described solvent be selected from ethanol, water,
One or more in formic acid, ether or ethylene glycol.
5. preparation method according to claim 1, it is characterised in that in step (2), the heating schedule of roasting is as follows:With 1
~3 DEG C/min heating rate, 600~1000 DEG C of progress 1~3h of high-temperature roasting are warming up to, then naturally cool to room temperature.
6. preparation method according to claim 1, it is characterised in that in step (3), sodium hydroxide solution be 0.1~
2mol/L。
7. preparation method according to claim 1, it is characterised in that in step (3), mesoporous nickel oxide/manganese oxide/carbon/
The mass volume ratio of silica composite and sodium hydrate aqueous solution is 1:5~1:30g/ml.
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