CN106241884A - A kind of preparation method and applications of mesoporous iron oxide nano material - Google Patents
A kind of preparation method and applications of mesoporous iron oxide nano material Download PDFInfo
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- CN106241884A CN106241884A CN201610560014.8A CN201610560014A CN106241884A CN 106241884 A CN106241884 A CN 106241884A CN 201610560014 A CN201610560014 A CN 201610560014A CN 106241884 A CN106241884 A CN 106241884A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/46—Metal oxides
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Abstract
The present invention relates to the preparation method of a kind of mesoporous iron oxide nano material, nonionic surfactant is dissolved in organic solvent, it is sequentially added into inorganic source of iron and organosilicon source, high molecular polymer is added after dissolving completely, under water-bath, stirring forms homogeneous phase solution, is then poured in a reaction vessel, cross-links in an oven, the transparent membranoid substance obtained is carried out roasting under an inert atmosphere, obtains ferrum/SiO2The composite mesoporous thing of/C, then removes carbon at Muffle kiln roasting, obtains ferrum oxide/SiO2Complex, then remove silicon dioxide through further neutralizing treatment, filter, wash, after drying, i.e. obtain mesoporous iron oxide nano material；The present invention is compared with the existing technology, preparation method is simple, is suitable for large-scale production, solves the method complex process preparing mesoporous iron oxide nano material in prior art, the mesoporous iron oxide nano material specific surface area obtained is low, uses the technical problem of instability as electrode material.
Description
[technical field]
The invention belongs to field of inorganic nano material, the preparation method of a kind of mesoporous iron oxide nano material
And application.
[background technology]
Due in recent ten years, walkie electronic apparatus product, and the developing rapidly of electric automobile, all it is greatly promoted
The development of new energy technology.Ultracapacitor is a kind of green energy-storing dress with series of advantages such as high power long-lives
Put, have great importance for solving the problems such as the energy shortage that faces of the world and environmental pollution.Therefore exploitation has high energy
The electrode material of the storage of amount is the task that current one is urgent.Ultracapacitor is broadly divided into double electric layers supercapacitor,
Pseudo capacitance ultracapacitor, hybrid super capacitor three kinds, owing to metal-oxide reacts at Cathode/Solution Interface
Produced pseudo capacitance is significantly larger than the electric double layer capacitance of material with carbon element, therefore causes the interest of many researcheres.
Simple transition metal and transition metal oxide, because having higher theoretical capacity, therefore suffer from closing widely
Note, is i.e. to have potential a new generation battery material.Wherein the oxide of ferrum has higher theoretical specific capacity, cheap and environment
The advantages such as close friend, receive more research.
High-temperature solid phase reaction method is used to be prepared for α-Fe2O3/ C composite.Detailed process is: commercialization α-Fe2O3With sugarcane
Sugar is ratio ball milling mix homogeneously in ball mill of 10:1 in mass ratio, then by mixture in tube furnace at dynamic argon
Protect and roasting 12h at 800 DEG C, after equitemperature is reduced to room temperature naturally, after the mixture after roasting is taken out from tube furnace
In mortar, grind 1h, i.e. obtain α-Fe2O3/ C composite.α-Fe without carbon cladding2O3Initial charge capacity is up to
1163.8mAh/g, but its stable circulation performance is very poor, and after circulation in 50 weeks, charging capacity is 501.3mAh/g, capability retention
It is only 43.1%.Although the α-Fe through carbon cladding2O3/ C composite initial charge capacity only has 700.1mAh/g, but charges
Capacity promotes steadily along with cycle-index, and after circulation in 50 weeks, charging capacity reaches 935.3mAh/g.The above results shows, carbon is coated with
α-Fe can be increased substantially2O3Cycle performance.Here the material prepared with the addition of carbon compared to simple ferrum oxide, increases
Added the stability of material, but synthesis be not mesoporous material, therefore specific surface area be not very big (Wu Chao. iron-based aoxidizes
The preparation of thing and electrode interface performance study [D]. Jiangsu: China Mining University, 2014.).
Shuhua Yang waited simple hydro-thermal reaction to coordinate after roasting process dixie cup obtained porous α-
Fe2O3/ graphene nanometer composite, specific surface area is 95.9m2/ g, aperture 0.29nm, this testing of materials transverse electric stream discharge and recharge exists
The when that current intensity being 3A/g, capacitance is 343.7F/g.Circulate 50000 times current intensity is 10A/g when, electric capacity
Conservation rate is 95.8%, it was demonstrated that this material has good stability.And Litao Kang etc. are prepared also with hydrothermal method
Obtain Fe2O3The composite nano materials of/carbon, but apply as electrode material in electrochemistry, it is the feelings of 1A/g in electric current density
Under condition, capacitance is only 139.7F/g.
Sang Xiankui etc. utilize the nano-cellulose of carboxylated modification to be masterplate, and concrete operations are the nanometers in carboxylated modification
Cellulose dispersion liquid adds iron salt solutions, regulates pH with ammonia, treat that the iron ion absorption in iron salt is formed on nanofiber
After complex, dehydration, calcination, products therefrom is the mesoporous nano ferrum oxide of uniform pore diameter, good dispersion.By this side
Mesoporous iron oxide prepared by method should belong to hard template method group and prepare, and the aperture of material prepared by this method is non-adjustable, and (Mulberry shows
Certain herbaceous plants with big flowers, Liu Xinliang, Qin Chengrong, Dai Yi, Gao Cong, Zhang Yixia, Huang Linjuan. the preparation method of a kind of mesoporous nano ferrum oxide: China,
CN104341009A[P].2015-02-11)
In sum, the most prepare ferrum oxide with the complex of material with carbon element by multiple method, but also
It is not manufactured separately and obtains mesoporous iron oxide material as capacitor electrode material, or few people make mesoporous iron material.
The process preparing ferrum oxide before and is the most comparatively laborious, such as higher to the requirement of apparatus by mechanical lapping,
It is less susceptible to control etc. by method for hydrolysis preparation process, and the aperture of the mesoporous material synthesized is non-adjustable.Therefore we
Have studied synthetic method a kind of simple to operate, that be easily controlled, can be synthesized and there is high-crystallinity, Jie of large hole volume
Hole ferrum oxide composite nano materials, and it is applied in electrochemistry.
[summary of the invention]
Present invention aim to solve above-mentioned deficiency and the preparation side of a kind of mesoporous iron oxide nano material is provided
Method, preparation method is simple, is suitable for large-scale production, solves the method work preparing mesoporous iron oxide nano material in prior art
Skill is complicated, it is thus achieved that mesoporous iron oxide nano material specific surface area low, uses unstable technical problem as electrode material.
Design the preparation method of a kind of mesoporous iron oxide nano material for achieving the above object, comprise the following steps:
1) at 35-45 DEG C, nonionic surfactant is dissolved in organic solvent, be then sequentially added into inorganic source of iron and
Organosilicon source, adds organic high molecular polymer after dissolving completely, is sufficiently stirred under 30-40 DEG C of water-bath, forms homogeneous phase solution,
It is then poured in a reaction vessel, 35-45 DEG C of baking oven is placed 12-30h, in 90-110 DEG C of baking oven, then places 15-30h
Cross-link, obtain transparent membranoid substance；
2) by step 1) the transparent membranoid substance of gained scrapes from reaction vessel, and it is placed in nitrogen atmosphere control and heats up speed
Rate is 1-3 DEG C/min, is warming up to 600-900 DEG C and carries out high-temperature roasting 1-3h, then naturally cools to room temperature, i.e. obtain mesoporous
Ferrum/carbon/silica composite；
3) by step 2) the mesoporous ferrum/carbon/silica composite of gained is placed in Muffle furnace, is 400-500 in temperature
Carry out roasting 9-15h between DEG C, obtain mesoporous iron oxide/silica composite；
4) by step 3) to join concentration be 0.5-2mol/L hydroxide for the mesoporous iron oxide/silica composite of gained
In sodium water solution, control to stir 5-30min at temperature is 30-50 DEG C, then stand 20-50min, be then centrifuged for, the precipitation of gained
Wash with deionized water, until the pH of effluent is neutral, then controls temperature and be 80-110 DEG C and be dried, i.e. obtain
Mesoporous iron oxide nano material.
Further, step 1) in, described nonionic surfactant, organic solvent, inorganic source of iron, organosilicon source, have
The mass ratio of machine high molecular polymer is 1:10-40:1-5:0.5-2:2-6.
Further, step 1) in, described nonionic surfactant is EO20PO70EO20、EO106PO70EO106、
EO132PO60EO132In one or more mixture；Described organosilicon source be tetraethyl orthosilicate, positive quanmethyl silicate,
One or more mixture in positive silicic acid orthocarbonate, positive silicic acid four butyl ester；Described organic high molecular polymer is phenolic aldehyde
One or more mixture in resin, sucrose, furfural resin；Described inorganic source of iron is Fe(NO3)39H2O, seven hydrations
One or more mixture in iron sulfate, four water ferrous chlorides；Described organic solvent be ethanol, water, formic acid, ether,
One or more mixture in ethylene glycol.
Further, step 4) in, mesoporous iron oxide/silica composite and concentration are 0.5-2mol/L sodium hydroxide
The consumption of aqueous solution, by mesoporous iron oxide/silica composite: concentration be 0.5-2mol/L sodium hydrate aqueous solution be 1g:
The ratio of 5-30ml calculates.
Further, step 1) in, nonionic surfactant, organic solvent, inorganic source of iron, organosilicon source, You Jigao
The mass ratio of Molecularly Imprinted Polymer is 1:20:1.5:1:4, and described nonionic surfactant is EO20PO70EO20, described organosilicon
Source is positive quanmethyl silicate, and described organic high molecular polymer is furfural resin, and described inorganic source of iron is seven ferric sulfate hydrates, institute
Stating organic solvent is ethylene glycol.
Further, step 1) in, nonionic surfactant, organic solvent, inorganic source of iron, organosilicon source, You Jigao
The mass ratio of Molecularly Imprinted Polymer is 1:10:1:0.5:2, and described nonionic surfactant is EO106PO70EO106, described organosilicon
Source is tetraethyl orthosilicate, and described organic high molecular polymer is sucrose, and described inorganic source of iron is Fe(NO3)39H2O, described in have
Machine solvent is ethanol.
Further, step 1) in, nonionic surfactant, organic solvent, inorganic source of iron, organosilicon source, You Jigao
The mass ratio of Molecularly Imprinted Polymer is 1:40:5:2:6, and described nonionic surfactant is EO132PO60EO132, described organosilicon source
For positive silicic acid four butyl ester, described organic high molecular polymer is phenolic resin, and described inorganic source of iron is four water ferrous chlorides, described
Organic solvent is water.
Further, step 4) in, the specific surface area of obtained mesoporous iron oxide nano material is 67-134m2/ g, hole
Hold for 0.23-0.89cm3/ g, aperture is 18.1-34.2nm.
Present invention also offers a kind of mesoporous iron oxide nano material obtained according to above-mentioned preparation method for making
The application of the electrode material used by ultracapacitor.
Further, mesoporous iron oxide nano material obtained above is made the electrode material used by ultracapacitor,
Its preparation method comprises the steps: mesoporous iron oxide nano material grind into powder, with conductive agent acetylene black, polytetrafluoroethyl-ne
Alkene is the ratio mixing of 8:1:1 in mass ratio, is coated in uniformly in the nickel foam of precise, controls temperature in vacuum drying oven
Degree processes 12h at 120 DEG C, at 10MP pressure lower sheeting, is fabricated to working electrode, with reference electrode Ag/AgCl, to electrode platinum
Electrode, and the KOH aqueous solution of 1mol/L be electrolyte constitute three-electrode system, be used for test chemical property.
The present invention compared with the existing technology, due in preparation process with nonionic surfactant as template, organic
Silicon source and high molecular polymer be organic precursor, inorganic source of iron be inorganic precursor, by the method for evaporation-induced self-assembly
Synthesize ferrum oxide/carbon/silicon dioxide composite material, remove carbon afterwards, remove silicon dioxide the most further, thus obtain
There is large specific surface area and pore volume and wide-aperture iron oxide nano material, and preparation method is simple, be suitable for extensive
Producing, the mesoporous iron oxide nano material obtained by this preparation method has the feature of high-crystallinity, bigger serface, solves
Mesoporous iron oxide of the prior art is used as the unstability of electrode material, and in building-up process, condition is wayward, mistake
Journey complexity is extremely difficult to a step and obtains the technical problems such as end product；Additionally, pass through the mesoporous of the preparation method acquisition of the present invention
Ferrum/carbon composite nano-material can make the electrode material used by the ultracapacitor with higher specific capacitance, and produces
Low cost, simple to operate controlled, it is suitable for large-scale production.
[accompanying drawing explanation]
Fig. 1 is the Radix Rumicis XRD figure of mesoporous iron oxide nano material prepared by the present invention；
Fig. 2 is the nitrogen adsorption desorption figure of mesoporous iron oxide nano material prepared by the present invention；
Fig. 3 is the graph of pore diameter distribution of mesoporous iron oxide nano material prepared by the present invention；
Fig. 4 is the transverse electric stream charge and discharge electrograph of mesoporous iron oxide nano material prepared by the present invention.
[detailed description of the invention]
Below by way of concrete specific embodiment and combine accompanying drawing the present invention is conducted further description, but the present invention
Protection domain is not limited to this.
Described method is if no special instructions.It is conventional method；Described material if no special instructions, all can be from open business
Approach can buy.
Instrument used by various embodiments of the present invention or the model of equipment and manufacturer's information are as follows:
Tube furnace, model SL1700 II type, manufacturer: Shanghai Sheng Li test instrunment company limited；
X-ray diffractometer (XRD), PANalytical company of X PERT PRO Holland；
Scanning electron microscope (SEM), S-3400N HIT；
Full-automatic physical Sorption Analyzer, Merck & Co., Inc of the ASAP2020 U.S.；
Synchronous solving, Nai Chi company of STA-449F3 Germany.
Embodiment 1
The preparation method of a kind of mesoporous iron oxide nano material, specifically includes following steps:
(1) at 40 DEG C, 0.6g surfactant is dissolved in 12.0g organic solvent, is then sequentially added into 0.9g's
Source of iron and 0.6g silicon source, add 2.4g organic high molecular polymer after dissolving complete 10min, be sufficiently stirred for shape under 40 DEG C of water-baths
Become homogeneous phase solution, be then poured in surface plate, 40 DEG C of baking ovens are placed 24h, in 100 DEG C of baking ovens, then place 24h carry out
Crosslinking, thus obtain transparent membranoid substance；
Above-mentioned surfactant used, solvent, source of iron, silicon source, the amount of organic high molecular polymer, count in mass ratio
Calculate, surfactant: solvent: titanium source: silicon source: mass percent concentration be the phenolic resin ethanol solution of 20% be 1:20:
1.5:1:4；
Described nonionic surfactant is EO20PO70EO20；
Described organosilicon source is positive quanmethyl silicate；
Described organic high molecular polymer is furfural resin；
Described inorganic source of iron is seven ferric sulfate hydrates；
Described solvent is ethylene glycol.
(2) dry film of gained organic/inorganic composite in step (1) is scraped from crystallizing dish, be placed in nitrogen atmosphere
Middle control heating rate is 1 DEG C/min, is warming up to 800 DEG C and carries out high-temperature roasting 2h, then naturally cools to room temperature, be i.e. situated between
Kong Tie/carbon/silica composite；
(3) complex of the mesoporous ferrum/silicon/carbon dioxide obtained in step (2) is placed in Muffle furnace, in temperature is
Carry out roasting 12h between 450 DEG C, obtain the complex of ferrum oxide/silicon dioxide.
(4) mesoporous iron oxide/silica composite obtained in step (3) being joined concentration is 1mol/L hydroxide
In sodium water solution, control temperature be 40 DEG C stirring 15min, stand 20min the most again, be then centrifuged for, the precipitation of gained spend from
Sub-water carries out washing until the pH of effluent is neutrality, then controls temperature and is 100 DEG C and is dried, i.e. can get mesoporous oxidation
Ferrum nano material；Wherein, mesoporous iron oxide/silica composite and use that concentration is 0.5mol/L sodium hydrate aqueous solution
Amount, by mesoporous iron oxide/silica composite: concentration be 0.5mol/L sodium hydrate aqueous solution be based on the ratio of 1g:20ml
Calculate.
Use x-ray powder diffraction instrument (PANalytical X ' Pert diffractometer) to above-mentioned steps (3)
The whole high-crystallinity of gained, the mesoporous iron oxide nano material of bigger serface are measured, little angle the XRD figure spectrum such as figure of gained
Shown in 1, from figure 1 it appears that the mesoporous iron oxide nano material of the high-crystallinity of gained, bigger serface is in 1 ° of 2 this tower
There is an obvious diffraction maximum left and right, has been indicated above mesoporous iron oxide nano material and has had good order.
Use specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010 adsorption
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.) Jie to above-mentioned above-mentioned steps (3) gained
Hole iron oxide nano material is measured, and the nitrogen adsorption of gained-desorption result is as it is shown on figure 3, as can be seen from Figure 3 curve
Having and obviously return stagnant ring, the iron oxide nano material being indicated above preparing is mesoporous material, and has big
Specific surface area.Its specific surface area is 89m2/ g, pore volume is 0.43cm3/ g, aperture is 21.5nm.
Mesoporous iron oxide nano material obtained above is made the electrode material used by ultracapacitor, its preparation method
Comprise the steps: mesoporous iron oxide nano material grind into powder, with conductive agent acetylene black, politef in mass ratio
Ratio for 8:1:1 mixes, and is coated in uniformly in the nickel foam of precise, controls temperature at 120 DEG C in vacuum drying oven
Lower process 12h, at 10MP pressure lower sheeting, is fabricated to working electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and
The KOH aqueous solution of 1mol/L is that electrolyte constitutes three-electrode system, is used for testing chemical property.
Electrode material used by the ultracapacitor of above-mentioned gained is used by Shanghai occasion China CHI660C electrochemical workstation
Transverse electric stream discharge and recharge is measured.Result as shown in Figure 4, as can be drawn from Figure 4, at 0.2A/g, 0.5A/g, 1A/g, 2A/g
Electric current density under be measured, its specific capacitance is respectively 37F/g, 32F/g, 27F/g, 21F/g.
Embodiment 2
The preparation method of a kind of mesoporous iron oxide nano material, specifically includes following steps:
(1) at 35 DEG C, 0.6g surfactant is dissolved in 6.0g organic solvent, is then sequentially added into the ferrum of 0.6g
Source and 0.3g silicon source, add 1.2g organic high molecular polymer after dissolving complete 10min, is sufficiently stirred for being formed under 30 DEG C of water-baths
Homogeneous phase solution, is then poured in surface plate, places 12h in 45 DEG C of baking ovens, then places 15h in 110 DEG C of baking ovens and hands over
Connection, thus obtain transparent membranoid substance；
Above-mentioned surfactant used, solvent, source of iron, silicon source, the amount of organic high molecular polymer, count in mass ratio
Calculate, surfactant: solvent: titanium source: silicon source: mass percent concentration be the phenolic resin ethanol solution of 20% be 1:10:1:
0.5:2；
Described nonionic surfactant is EO106PO70EO106；
Described organosilicon source is tetraethyl orthosilicate；
Described organic high molecular polymer is sucrose；
Described inorganic source of iron is Fe(NO3)39H2O；
Described solvent is ethanol.
(2) dry film of gained organic/inorganic composite in step (1) is scraped from crystallizing dish, be placed in nitrogen atmosphere
Middle control heating rate is 2 DEG C/min, is warming up to 600 DEG C and carries out high-temperature roasting 1h, then naturally cools to room temperature, be i.e. situated between
Kong Tie/carbon/silica composite；
(3) complex of the mesoporous ferrum/silicon/carbon dioxide obtained in step (2) is placed in Muffle furnace, in temperature is
Carry out roasting 15h between 400 DEG C, obtain the complex of ferrum oxide/silicon dioxide；
(4) mesoporous iron oxide/silica composite obtained in step (3) being joined concentration is 0.5mol/L hydrogen-oxygen
Changing in sodium water solution, controlling temperature is stirring 30min at 30 DEG C, stands 50min the most again, is then centrifuged for, and the precipitation of gained is used
Deionized water carries out washing until the pH of effluent is neutrality, then controls temperature and is 110 DEG C and is dried, i.e. can get mesoporous
Iron oxide nano material；Wherein, mesoporous iron oxide/silica nano material and concentration are 0.2mol/L sodium hydrate aqueous solution
Consumption, by mesoporous iron oxide/silica nano material: concentration be 0.2mol/L sodium hydrate aqueous solution be the ratio of 1g:5ml
Example calculates.
Use specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010 adsorption
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.) Jie to above-mentioned above-mentioned steps (3) gained
Hole iron oxide nano material is measured, and its specific surface area is 67m2/ g, pore volume is 0.23cm3/ g, aperture is 18.1nm.
Mesoporous iron oxide nano material obtained above is made the electrode material used by ultracapacitor, its preparation method
Comprise the steps: mesoporous iron oxide nano material grind into powder, with conductive agent acetylene black, politef in mass ratio
Ratio for 8:1:1 mixes, and is coated in uniformly in the nickel foam of precise, controls temperature at 120 DEG C in vacuum drying oven
Lower process 12h, at 10MP pressure lower sheeting, is fabricated to working electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and
The KOH aqueous solution of 1mol/L is that electrolyte constitutes three-electrode system, is used for testing chemical property.
Electrode material used by the ultracapacitor of above-mentioned gained is used by Shanghai occasion China CHI660C electrochemical workstation
Transverse electric stream discharge and recharge is measured, and result obtains the capacitance of electrode under the electric current density of 0.2A/g for 23F/g.
Embodiment 3
The preparation method of a kind of mesoporous iron oxide nano material, specifically includes following steps:
(1) at 45 DEG C, 0.6g surfactant is dissolved in 24.0g organic solvent, is then sequentially added into the ferrum of 3g
Source and 1.2g silicon source, add 3.6g organic high molecular polymer after dissolving complete 10min, is sufficiently stirred for being formed under 40 DEG C of water-baths
Homogeneous phase solution, is then poured in surface plate, places 30h in 35 DEG C of baking ovens, then places 30h in 90 DEG C of baking ovens and hands over
Connection, thus obtain transparent membranoid substance；
Above-mentioned surfactant used, solvent, source of iron, silicon source, the amount of organic high molecular polymer, count in mass ratio
Calculate, surfactant: solvent: titanium source: silicon source: mass percent concentration be the phenolic resin ethanol solution of 20% be 1:40:5:
2:6；
Described nonionic surfactant is EO132PO60EO132；
Described organosilicon source is positive silicic acid four butyl ester；
Described organic high molecular polymer is phenolic resin；
Described inorganic source of iron is four water ferrous chlorides；
Described solvent is water.
(2) dry film of gained organic/inorganic composite in step (1) is scraped from crystallizing dish, be placed in nitrogen atmosphere
Middle control heating rate is 3 DEG C/min, is warming up to 900 DEG C and carries out high-temperature roasting 3h, then naturally cools to room temperature, be i.e. situated between
Kong Tie/carbon/silica composite；
(3) complex of the mesoporous ferrum/silicon/carbon dioxide obtained in step (2) is placed in Muffle furnace, in temperature is
Carry out roasting 9h between 500 DEG C, obtain the complex of ferrum oxide/silicon dioxide；
(4) mesoporous iron oxide/silica composite obtained in step (3) being joined concentration is 2mol/L hydroxide
In sodium water solution, control temperature be at 50 DEG C stirring 5min, stand 30min the most again, be then centrifuged for, the precipitation of gained spend from
Sub-water carries out washing until the pH of effluent is neutrality, then controls temperature and is 80 DEG C and is dried, i.e. can get mesoporous oxidation
Ferrum nano material；Wherein, mesoporous iron oxide/silica nano material and use that concentration is 2mol/L sodium hydrate aqueous solution
Amount, by mesoporous iron oxide/silica nano material: concentration be 2mol/L sodium hydrate aqueous solution be based on the ratio of 1g:30ml
Calculate.
Use specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2010 adsorption
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.) Jie to above-mentioned above-mentioned steps (3) gained
Kong Tie/carbon nano-composite material is measured, and its specific surface area is 134m2/ g, pore volume is 0.89cm3/g, and aperture is 34.2nm.
Mesoporous iron oxide nano material obtained above is made the electrode material used by ultracapacitor, its preparation method
Comprise the steps: mesoporous iron oxide nano material grind into powder, with conductive agent acetylene black, politef in mass ratio
Ratio for 8:1:1 mixes, and is coated in uniformly in the nickel foam of precise, controls temperature at 120 DEG C in vacuum drying oven
Lower process 12h, at 10MP pressure lower sheeting, is fabricated to working electrode, with reference electrode Ag/AgCl, to electrode platinum electrode, and
The KOH aqueous solution of 1mol/L is that electrolyte constitutes three-electrode system, is used for testing chemical property.
Electrode material used by the ultracapacitor of above-mentioned gained is used by Shanghai occasion China CHI660C electrochemical workstation
Transverse electric stream discharge and recharge is measured, and result obtains the capacitance of electrode under the electric current density of 0.2A/g for 67F/g.
Preparation method of the present invention, is not limited to above-mentioned specific embodiment, its step 1) in, nonionic surfactant
Can be EO20PO70EO20、EO106PO70EO106、EO132PO60EO132In one or more mixture；Organosilicon source is just
One or more mixture in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate, positive silicic acid four butyl ester；Have
Machine high molecular polymer is one or more mixture in phenolic resin, sucrose, furfural resin；Inorganic source of iron is nine water
Close one or more mixture in ferric nitrate, seven ferric sulfate hydrates, four water ferrous chlorides；Organic solvent be ethanol, water,
One or more mixture in formic acid, ether, ethylene glycol.Step 4) in, obtained mesoporous iron oxide nano material
Specific surface area be 67-134m2/ g, pore volume is 0.23-0.89cm3/ g, aperture is 18.1-34.2nm.
The present invention is not limited by above-mentioned embodiment, other any spirit without departing from the present invention and principle
Lower made change, modify, substitute, combine, simplify, all should be the substitute mode of equivalence, be included in the protection model of the present invention
Within enclosing.
Claims (10)
1. the preparation method of a mesoporous iron oxide nano material, it is characterised in that comprise the following steps:
1) at 35-45 DEG C, nonionic surfactant is dissolved in organic solvent, is then sequentially added into inorganic source of iron and organic
Silicon source, adds organic high molecular polymer after dissolving completely, is sufficiently stirred under 30-40 DEG C of water-bath, forms homogeneous phase solution, subsequently
Pour in a reaction vessel, 35-45 DEG C of baking oven is placed 12-30h, in 90-110 DEG C of baking oven, then place 15-30h carry out
Crosslinking, obtains transparent membranoid substance；
2) by step 1) the transparent membranoid substance of gained scrapes from reaction vessel, and being placed in nitrogen atmosphere control heating rate is
1-3 DEG C/min, be warming up to 600-900 DEG C and carry out high-temperature roasting 1-3h, then naturally cool to room temperature, i.e. obtain mesoporous ferrum/carbon/
Silica composite；
3) by step 2) the mesoporous ferrum/carbon/silica composite of gained is placed in Muffle furnace, temperature be 400-500 DEG C it
Between carry out roasting 9-15h, obtain mesoporous iron oxide/silica composite；
4) by step 3) to join concentration be 0.5-2mol/L sodium hydroxide water for the mesoporous iron oxide/silica composite of gained
In solution, controlling to stir 5-30min at temperature is 30-50 DEG C, then stand 20-50min, be then centrifuged for, the precipitation of gained spends
Ionized water washs, until the pH of effluent is neutral, then controls temperature and is 80-110 DEG C and is dried, i.e. obtain mesoporous
Iron oxide nano material.
2. preparation method as claimed in claim 1, it is characterised in that: step 1) in, described nonionic surfactant, organic
Solvent, inorganic source of iron, organosilicon source, the mass ratio of organic high molecular polymer are 1:10-40:1-5:0.5-2:2-6.
3. preparation method as claimed in claim 2, it is characterised in that: step 1) in, described nonionic surfactant is
EO20PO70EO20、EO106PO70EO106、EO132PO60EO132In one or more mixture；Described organosilicon source is just
One or more mixture in tetraethyl orthosilicate, positive quanmethyl silicate, positive silicic acid orthocarbonate, positive silicic acid four butyl ester；Institute
Stating organic high molecular polymer is one or more mixture in phenolic resin, sucrose, furfural resin；Described inorganic iron
Source is one or more mixture in Fe(NO3)39H2O, seven ferric sulfate hydrates, four water ferrous chlorides；Described organic molten
Agent is one or more mixture in ethanol, water, formic acid, ether, ethylene glycol.
4. preparation method as claimed in claim 3, it is characterised in that: step 4) in, mesoporous iron oxide/silica composite
With the consumption that concentration is 0.5-2mol/L sodium hydrate aqueous solution, by mesoporous iron oxide/silica composite: concentration is 0.5-
2mol/L sodium hydrate aqueous solution is that the ratio of 1g:5-30ml calculates.
5. preparation method as claimed in claim 1, it is characterised in that: step 1) in, nonionic surfactant, You Jirong
Agent, inorganic source of iron, organosilicon source, the mass ratio of organic high molecular polymer are 1:20:1.5:1:4, and described non-ionic surface is lived
Property agent is EO20PO70EO20, described organosilicon source is positive quanmethyl silicate, and described organic high molecular polymer is furfural resin, institute
Stating inorganic source of iron is seven ferric sulfate hydrates, and described organic solvent is ethylene glycol.
6. preparation method as claimed in claim 1, it is characterised in that: step 1) in, nonionic surfactant, You Jirong
Agent, inorganic source of iron, organosilicon source, the mass ratio of organic high molecular polymer are 1:10:1:0.5:2, and described non-ionic surface is lived
Property agent is EO106PO70EO106, described organosilicon source is tetraethyl orthosilicate, and described organic high molecular polymer is sucrose, described
Inorganic source of iron is Fe(NO3)39H2O,
Described organic solvent is ethanol.
7. preparation method as claimed in claim 1, it is characterised in that: step 1) in, nonionic surfactant, You Jirong
Agent, inorganic source of iron, organosilicon source, the mass ratio of organic high molecular polymer are 1:40:5:2:6, described non-ionic surface active
Agent is EO132PO60EO132, described organosilicon source is positive silicic acid four butyl ester, and described organic high molecular polymer is phenolic resin, institute
Stating inorganic source of iron is four water ferrous chlorides, and described organic solvent is water.
8. preparation method as claimed in claim 1, it is characterised in that: step 4) in, obtained mesoporous iron oxide nanometer material
The specific surface area of material is 67-134m2/ g, pore volume is 0.23-0.89cm3/ g, aperture is 18.1-34.2nm.
9. the mesoporous iron oxide nano material that a preparation method according to any one of claim 1 to 8 obtains with
Application in the electrode material made used by ultracapacitor.
Apply the most as claimed in claim 9, it is characterised in that mesoporous iron oxide nano material obtained above is made super
Level electrode material used by capacitor, its preparation method comprises the steps: mesoporous iron oxide nano material grind into powder,
Mix for the ratio of 8:1:1 in mass ratio with conductive agent acetylene black, politef, be coated in the nickel foam of precise uniformly
On, vacuum drying oven controls temperature at 120 DEG C, processes 12h, at 10MP pressure lower sheeting, be fabricated to working electrode, with
Reference electrode Ag/AgCl, to electrode platinum electrode, and the KOH aqueous solution of 1mol/L is that electrolyte constitutes three-electrode system, is used for surveying
Examination chemical property.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981376A (en) * | 2017-04-07 | 2017-07-25 | 深圳市佩成科技有限责任公司 | Electrode of super capacitor preparation method |
| CN109817928A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/iron oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580240A (en) * | 2009-06-11 | 2009-11-18 | 南京理工大学 | Method for preparing iron-carrying ordered mesoporous carbon materials |
| CN103301809A (en) * | 2013-07-01 | 2013-09-18 | 湖南大学 | Magnetic carrier iron ordered mesoporous carbon, preparation method and application thereof |
| CN103395818A (en) * | 2013-07-16 | 2013-11-20 | 上海应用技术学院 | Mesoporous cerium oxide nano-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 |
-
2016
- 2016-07-15 CN CN201610560014.8A patent/CN106241884A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580240A (en) * | 2009-06-11 | 2009-11-18 | 南京理工大学 | Method for preparing iron-carrying ordered mesoporous carbon materials |
| CN103301809A (en) * | 2013-07-01 | 2013-09-18 | 湖南大学 | Magnetic carrier iron ordered mesoporous carbon, preparation method and application thereof |
| CN103395818A (en) * | 2013-07-16 | 2013-11-20 | 上海应用技术学院 | Mesoporous cerium oxide nano-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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981376A (en) * | 2017-04-07 | 2017-07-25 | 深圳市佩成科技有限责任公司 | Electrode of super capacitor preparation method |
| CN109817928A (en) * | 2019-01-25 | 2019-05-28 | 安徽师范大学 | A kind of helical form silica/iron oxide composite nano materials and preparation method thereof and the application in lithium ion battery |
| CN109817928B (en) * | 2019-01-25 | 2020-11-03 | 安徽师范大学 | Spiral silicon dioxide/iron oxide composite nano material, preparation method thereof and application thereof in lithium ion battery |
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