CN105523540A - Preparation method of mesoporous carbon sphere material with controllable pore size - Google Patents
Preparation method of mesoporous carbon sphere material with controllable pore size Download PDFInfo
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention discloses a preparation method of a mesoporous carbon sphere material with the controllable pore size. The preparation method comprises steps as follows: Step 1, polyethylene oxide monomethyl ether is dissolved in toluene; Step 2, a bromo-compound is added, and precipitation and drying extraction are performed; Step 3, CuBr and bipyridine (a reaction catalyst) are added; Step 4, oxygen is removed from styrene; Step 5, the pure substance in Step 4 is added to the mixture in Step 3; Step 6, stirring, column passing, precipitation and vacuum drying are performed; Step 7, precursor dopamine is added, purification and calcination are performed, and a product is obtained. The preparation method has the advantages as follows: 1, the method is simple, preparation is performed at the normal temperature, and equipment is easy to operate; 2, required reagents are low-toxic or non-toxic, and the preparation method is environment-friendly; 3, mesoporous spheres with the large and accurately controllable pore size can be prepared with the preparation method; 4, N-doped mesoporous carbon spheres can be used as a high-performance energy storage material to be applied to supercapacitors for the first time.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous material, be specifically related to the preparation method of the controlled mesoporous carbon spheres material of a kind of pore size, and this mesoporous carbon spheres material application in ultracapacitor, belong to nano material preparation and electrochemical energy storage field.
Background technology
Ultracapacitor is a kind of Novel energy storage apparatus between traditional capacitor and rechargeable battery, and its capacity can reach hundreds of to thousands of farad.It is high that ultracapacitor stores the energy force rate ordinary capacitor of electric charge, and have that charge/discharge rates is fast, efficiency is high, environmentally safe, have extended cycle life, use temperature wide ranges, security high.It can as the backup power source of portable instrument equipment, data accumulating storage system and as the energy storage component of electromobile or the startup power supply of diesel locomotive.But the energy density of ultracapacitor is less than secondary cell, in order to ultracapacitor can be applied in the middle of various physical device, the ultracapacitor with high power density and energy density needs exploitation badly.
Mesoporous, particularly large-sized mesoporous, the macromolecular medium transmission of easier realization response.Morphology control is a crucial factor.Spherical morphology, especially particle diameter are less than the ball of 200nm, more and more receive publicity, and provide the short path of medium transmission and reduce viscous effect because spherical.Lot of documents reports and uses spherical carbon material in drug conveying, gene therapy, ultracapacitor, lithium-sulfur cell, the application of the aspects such as carbon dioxide capture.From the prior art, many methods can prepare mesoporous carbon spheres, comprise Stober method, hard template and soft template method.Such as, Lu team (Adv.Mater.2013,25,998) synthesizes the microporous carbon ball of 120 to 800nm particle diameter by direct auto-polymerization and carbonization subsequently.Although have high specific surface area with the carbon ball obtained after KOH etching, the spherical pore obtained is still its aperture of micropore and is less than 2nm.Zhao team (Angew.Chem.Int.Ed.2010,49,7987; Angew.Chem.2010,122,8159) utilize hydrothermal method, synthesize orderly mesoporous carbon spheres with the common assembling of resol and F127.But their aperture is 3nm.Such aperture significantly reduces its practical application.
At present, do soft template by the block polymer (as PS-b-PEO, PIB-b-PEO, PS-b-P4VP and PEO-b-PMMA) by many high molecular and prepare the mesoporous material that aperture is greater than 10nm.But they mostly define film or micron particle in irregular shape.These systems relate to solvent evaporation process and are not suitable for and prepare mesoporous carbon spheres.The application of the mesoporous carbon spheres in large-sized hole can be more extensive.
Doped with heteroatomic carbon nanomaterial, as nitrogen, boron and sulphur, because the characteristic of electron donor(ED)/acceptor has attracted many concerns with the enhancing of the chemical property obtained.The carbon nanomaterial of N doping, as nitrogen-doped carbon nanometer pipe, Graphene and mesoporous carbon, all show excellent electrical property and good hydrogen reduction stability.Therefore, the mesoporous carbon spheres of high aperture size N doping is certain to by reducing the transmission of the evolving path amplified medium.If mesoporous carbon spheres material aperture is too little, because electrolyte ion is difficult to enter wherein, the specific surface area corresponding to these micropores is not contributed to electric capacity.In the middle of the process of discharge and recharge, electrolytic solution can not fully contact, especially organic electrolyte, and it comprises large organic molecule, and under the current density of high loading, electricity storage fully can not be carried out in surface exposed in micropore.Large-sized mesoporous, macromolecular medium transmission more easily realizes, and can strengthen the performance of ultracapacitor.But the aperture of current Mesoporous Spheres is too little, limit actual application.
Prior art is prepared mesoporous carbon spheres material and be there is following technical problem:
1, the mesoporous carbon spheres complex steps utilizing hard template to prepare, program is complicated, and toxic contaminants is strong.
2, current preparation method's severe reaction conditions.
3, the prior art aperture of Mesoporous Spheres of preparing is too little, applies limited.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, the preparation method of the mesoporous carbon spheres material providing a kind of pore size controlled first, aperture can be prepared greatly, and the Mesoporous Spheres of energy fine adjustment pore size.First, PS-b-PEO (polystyrene block polyethylene oxide) block polymer is prepared by ATRP (atom transfer radical polymerization) method, then utilize that Dopamine HCL (DA) and micella are collaborative assemble and through high-temperature roasting after autohemagglutination, achieve the preparation of the mesoporous carbon spheres that N under mild temperature adulterates.As a kind of high-performance energy storage material, be applied on ultracapacitor.
Principle of the present invention is: utilize atom transfer radical polymerization to synthesize a series of PS-b-PEO with different hydrophobic chain length, and utilize block polymer self-assembly principle, these polymkeric substance are assembled into the PS-b-PEO micella with different-grain diameter.Under normal temperature condition, utilize the self-polymeric reaction of Dopamine HCL presoma, the micella that parcel particle diameter differs, obtain and gather Dopamine HCL complex microsphere by PS-b-PEO/, obtain the N doping mesoporous carbon with different pore size by high-temperature roasting.
A first aspect of the present invention, provides the preparation method of the controlled mesoporous carbon spheres material of a kind of pore size, comprises the steps:
Step 1, polyethylene oxide monomethyl ether is dissolved in toluene
Polyethylene oxide monomethyl ether is dissolved in toluene, and component distillation removing is from the water in polyethylene oxide monomethyl ether, and cooling obtains the first solution; Polyethylene oxide monomethyl ether is white powder.
Step 2, adds bromo compound, precipitation, dry extraction
In the first solution, add bromo compound, stirred at ambient temperature reaction is spent the night, the 80%-90% of rotary evaporation removing toluene, then adds ether formation first precipitation; Then the first vacuum-drying of first precipitation is dissolved in water again uses dichloromethane extraction, collects the organic layer extracting and obtain, uses MgSO
4drying, then rotary evaporation in vacuo removing methylene dichloride, obtains initiator.Initiator is denoted as PEO-Br.
Step 3, adds CuBr and bipyridine
First joined in Schlenk bottle by initiator, then join in Schlenk bottle by CuBr and bipyridine, be fully mixed to get the first mixture, the first mixture removes deoxidation under protection of inert gas.
Step 4, vinylbenzene deoxygenation
Vinylbenzene is first crossed through neutral alumina column and is filtered stopper, and the oxygen in recycling drum nitrogen method removing vinylbenzene, obtains vinylbenzene pure substance.
Step 5, joins the vinylbenzene pure substance in step 4 in the mixture of step 3
Vinylbenzene pure substance is joined in Schlenk bottle and be mixed to get the second mixture with the first mixture, second mixture first at room temperature stirs 10 minutes, then under constant temperature oil bath, be heated to 100-120 DEG C and continuous stirring reaction 5-12h, obtain the 3rd mixture.
Step 6, stirs, and crosses post, precipitation, vacuum-drying
3rd mixture adds in tetrahydrofuran solvent and obtains 4 mixture, 4 mixture crosses post through neutral alumina, add excessive methanol again and filter and obtain the second precipitation, the second precipitation with methanol wash column then under 40 DEG C of vacuum conditions dry two days, obtains block polymer again.In 4 mixture, major part is PS-b-PEO block polymer, wherein may contain a small amount of PEO-Br, uses excessive methanol can wash away above-mentioned PEO-Br, obtains pure PS-b-PEO block polymer.
Step 7, adds presoma Dopamine HCL, and purification calcining, obtains product
Block polymer is dissolved in tetrahydrofuran (THF) and obtains the second solution, by ethanol and deionization by volume 1:2 be made into ethanolic soln, ethanolic soln is joined in the second solution, produces micellar aggregates; Joined under agitation by dopamine hydrochloride presoma in the second solution, stirred at ambient temperature 48h is so that the polymerization of Dopamine HCL; Collect product centrifugal purification, final high temperature is calcined, and obtains mesoporous carbon spheres.Mesoporous carbon spheres can be expressed as PDA/PS-b-PEO.
Dopamine HCL presoma can replace with resol.
Preferably, in step 1, the polymerization degree of polyethylene oxide monomethyl ether is 100 ~ 500.
Preferably, in step 1, under 0 DEG C of condition, polyethylene oxide monomethyl ether is dissolved in toluene.
Preferably, in step 2, bromo compound is 2-bromine isobutyl acylbromide.More preferably, 2-bromine isobutyl acylbromide and the amount of substance of polyethylene oxide monomethyl ether are than being 1:(0.1 ~ 1.0).
Preferably, in step 3, CuBr purifies with Glacial acetic acid in advance.
Preferably, in step 3, the mass ratio of CuBr and bipyridine is 1:(2.0 ~ 5.0).
Preferably, in step 3, rare gas element comprises nitrogen, argon gas.
Preferably, in steps of 5, cinnamic consumption is changed with the aperture of fine adjustment mesoporous carbon spheres.
Preferably, in step 7, high-temperature calcination refers to: first in tube furnace, calcine 3h under nitrogen protection atmosphere through 350 DEG C, then per minute heats up 1 DEG C, is incubated 3h after arriving 900 DEG C.
Another aspect of the present invention, additionally provides the application of the controlled Mesoporous Spheres material of a kind of pore size.
Mesoporous Spheres material first Application of the present invention is in three electrode super capacitor system, in a particular embodiment of the present invention, mesoporous carbon spheres is as the electrode materials of ultracapacitor, and the chemical property of mesoporous carbon spheres assesses in the electrochemical workstation of Shanghai Chen Hua Instrument Ltd. production.The H of three-electrode system 1mol/L
2sO
4ionogen carries out constant current charge-discharge measurement.Working electrode is by the powder activated material of mixing quality mark 80%, prepared by the carbon black of massfraction 10% and massfraction 10% PTFE binder.Platinum is used as electrode, and Ag/AgCl electrode is used as reference electrode.Test in different current densities under room temperature, its potential range is 0 ~ 1V (relative to Ag/AgCl electrode).
The invention has the beneficial effects as follows:
1, method is simple, and prepare under normal temperature, equipment is easy to operate;
2, the equal hypotoxicity of required reagent or nontoxicity is a kind of preparation method of environmental protection;
3, preparation method can prepare aperture greatly, and the Mesoporous Spheres of energy fine adjustment pore size;
4, the mesoporous carbon spheres of N doping can be used as a kind of high-performance energy storage material, and first Application is on ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the PS-b-PEO micella transmission electron microscope picture prepared by embodiment 1;
Fig. 2 is PDA/PS-b-PEO transmission electron microscope picture after the roasting by embodiment 2 preparation;
Fig. 3 is PDA/PS-b-PEO scanning electron microscope (SEM) photograph after the roasting by embodiment 2 preparation;
Fig. 4 is the nitrogen adsorption desorption curve of the doped meso-porous carbon ball of N by embodiment 3 preparation;
Fig. 5 is the pore size distribution curve of the doped meso-porous carbon ball of N by embodiment 3 preparation;
Fig. 6 is the nitrogen element X-ray energy spectrum figure of the doped meso-porous carbon ball of N by embodiment 2 preparation;
Fig. 7 is the electric capacity spirogram of the doped meso-porous carbon ball of N by embodiment 4 preparation;
Fig. 8 is the charging and discharging curve of the doped meso-porous carbon ball of N by embodiment 5 preparation;
Fig. 9 is the stable circulation linearity curve of the doped meso-porous carbon ball of N by embodiment 5 preparation.
Embodiment
Elaborate to embodiments of the invention below, following examples are implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
Embodiment 1
In the there-necked flask of a 500mL, the PEO114-OH of the 25.0g polymerization degree of polyethylene oxide monomethyl ether (114 be) is dissolved in the toluene of 100mL.Low pressure component distillation is except anhydrating, and solution is cooled to 0 DEG C.2.47mL2-bromine isobutyl acylbromide is dropwise added by syringe, and stirred at ambient temperature reaction is spent the night.Add ten times of excessive ether and form precipitation.The material vacuum obtained is dry, then uses dichloromethane extraction.Collected organic layer, solvents removed under vacuum, forms pure macromole evocating agent.0.067gCuBr and 0.22g bipyridine joins in Schlenk bottle, and Schlenk bottle vacuumizes, and mend nitrogen, circulation like this removes oxygen several times.Then transferred in macromole evocating agent Schlenk bottle by 8mL vinylbenzene, the dark-brown mixture obtained at room temperature stirs 10 minutes.120 DEG C of reaction 8h are heated under constant temperature oil bath.Add a large amount of THF solvents, cross post, add excessive methanol precipitation, then filtering-depositing uses methanol wash column, final product 40 DEG C of vacuum-dryings two days.Block polymer is dissolved in 2mL tetrahydrofuran (THF), and then, ethanol and the deionized water mixed solution (volume ratio 1:2) of 6mL slowly join in above-mentioned solution, create micellar aggregates.As can be seen from Figure 1, spherical micelle is uniformly dispersed, size uniformity, and particle diameter is about 20nm.
Embodiment 2
In the there-necked flask of a 500mL, the PEO114-OH of 25.0g is dissolved in the toluene of 100mL.Low pressure component distillation is except anhydrating, and solution is cooled to 0 DEG C.2.47mL2-bromo isobutyl acylbromide is dropwise added by syringe, and stirred at ambient temperature reaction is spent the night.Ether sedimentation, raw material drying, dichloromethane extraction.Solvents removed under vacuum.0.067gCuBr and 0.22g bipyridine joins in Schlenk bottle, and the 8mL vinylbenzene of then deoxygenation is transferred in macromole evocating agent Schlenk bottle, and the dark-brown mixture obtained at room temperature stirs 10 minutes.120 DEG C of reaction 8h are heated under constant temperature oil bath.The block polymer that aftertreatment obtains is dissolved in 2mL tetrahydrofuran (THF), and then, ethanol and the deionized water mixed solution (volume ratio 1:2) of 6mL slowly join in above-mentioned solution.Then, the dopamine hydrochloride of 0.124g joins in solution under moderate-speed mixer.After 1h, the NH of 0.3mL
4oH (28wt%) is injected in mixture, and stirred at ambient temperature 48h is so that the polymerization of Dopamine HCL.Collect product, centrifugal purification, then washes away with ethanol and deionized water, and finally, the product of collection was 40 DEG C of dryings two days.The PDA/PS165-b-PEO114 ball polymerization degree of polystyrene (165 be) N in tube furnace produced
2burn 3h at protecting 350 DEG C, last per minute heats up 1 DEG C and arrives 900 DEG C, then is incubated 3h.
As can be seen from Fig. 2 and Fig. 3, after thermal treatment, Electronic Speculum figure obviously presents mesoporous sphere structure.Namely, after Micellar Gel removes, inside Mesoporous Spheres nanoparticle, there is spherical pore.PS-b-PEO as pore former, forms mesoporous carbon spheres in carbonization process.
As can be seen from Figure 6, doped with nitrogen element in mesoporous carbon spheres, pyridine type nitrogen and graphite mould nitrogen all have, and are mainly graphite mould nitrogen.
Embodiment 3
Implementation content is on the basis of embodiment 2, changes cinnamic consumption, is respectively 3mL, 8mL, 15mL, 20mL, 22.5mL, and other condition is constant.
As can be seen from Figure 4, curve all has back stagnant ring, illustrates and is mesoporous material.
As can be seen from Figure 5, all there is distribution in aperture from 20-40nm, and along with the increase of PS chain length, aperture also increases.
Embodiment 4
With the electrode materials of embodiment 3 gained, with the H of 1mol/L in three-electrode system
2sO
4do ionogen.Working electrode is the powder activated material of massfraction 80%, the carbon black of massfraction 10% and the mixing of massfraction 10% PTFE binder, and platinum is used as negative potential, and Ag/AgCl electrode is used as reference electrode.
As can be seen from Figure 7, the performance of MCNS-62 is best.The mesoporous carbon spheres of N doping has the double-layer capacitance behavior of heavy body.
Embodiment 5
Implementation content first half is substantially with embodiment 2, and difference is that cinnamic addition changes 3mL into, obtains PDA/PS62-b-PEO114 carbon ball.With the H of 1mol/L in three-electrode system
2sO
4do ionogen.Working electrode is the powder activated material of massfraction 80%, the carbon black of massfraction 10% and the mixing of massfraction 10% PTFE binder, and platinum is used as negative potential, and Ag/AgCl electrode is used as reference electrode.
As can be seen from Figure 8, constant current charge-discharge test presents trigonometric curve, proves effective ion transport.
As can be seen from Figure 9, in stable circulation linearity curve, under the current density of 10A/g, 10000 charge and discharges circulation still can be stablized.There is fabulous cyclical stability.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a preparation method for the mesoporous carbon spheres material that pore size is controlled, is characterized in that, comprise the steps:
Step 1, polyethylene oxide monomethyl ether is dissolved in toluene, and component distillation removing is from the water in described polyethylene oxide monomethyl ether, and cooling obtains the first solution;
Step 2, adds bromo compound in described first solution, and stirred at ambient temperature reaction is spent the night, and rotary evaporation removes the 80%-90% of described toluene, then adds ether formation first precipitation; Then the first vacuum-drying of described first precipitation is dissolved in water again uses dichloromethane extraction, collects the organic layer extracting and obtain, uses MgSO
4drying, then rotary evaporation in vacuo removes described methylene dichloride, obtains initiator;
Step 3, first joins described initiator in Schlenk bottle, then CuBr and bipyridine is joined in described Schlenk bottle, is fully mixed to get the first mixture, and described first mixture removes deoxidation under protection of inert gas;
Step 4, vinylbenzene is first crossed through neutral alumina column and is filtered stopper, and recycling drum nitrogen method removes the oxygen in described vinylbenzene, obtains vinylbenzene pure substance;
Step 5, described vinylbenzene pure substance is joined in described Schlenk bottle and be mixed to get the second mixture with described first mixture, described second mixture first at room temperature stirs 10 minutes, then under constant temperature oil bath, be heated to 100-120 DEG C and continuous stirring reaction 5-12h, obtain the 3rd mixture;
Step 6, described 3rd mixture adds in tetrahydrofuran solvent and obtains 4 mixture, described 4 mixture crosses post through neutral alumina, add excessive methanol again and filter and obtain the second precipitation, described second precipitation with methanol wash column then under 40 DEG C of vacuum conditions dry two days, obtains block polymer again;
Step 7, described block polymer is dissolved in tetrahydrofuran (THF) and obtains the second solution, by ethanol and deionization by volume 1:2 be made into ethanolic soln, described ethanolic soln is joined in described second solution, produces micellar aggregates; Joined under agitation by dopamine hydrochloride presoma in described second solution, stirred at ambient temperature 48h is so that the polymerization of Dopamine HCL; Collect product centrifugal purification, final high temperature is calcined, and obtains described mesoporous carbon spheres.
2. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 1, the polymerization degree of described polyethylene oxide monomethyl ether is 100 ~ 500.
3. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 1, under 0 DEG C of condition, described polyethylene oxide monomethyl ether is dissolved in described toluene.
4. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 2, described bromo compound is 2-bromine isobutyl acylbromide.
5. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 4 is controlled, is characterized in that, described 2-bromine isobutyl acylbromide is 1:(0.1 ~ 1.0 with the amount of substance ratio of described polyethylene oxide monomethyl ether).
6. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 3, described CuBr purifies with Glacial acetic acid in advance.
7. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 3, the mass ratio of described CuBr and described bipyridine is 1:(2.0 ~ 5.0).
8. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in step 3, described rare gas element comprises nitrogen, argon gas.
9. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled, is characterized in that, in steps of 5, changes described cinnamic consumption with the aperture of mesoporous carbon spheres described in fine adjustment.
10. the preparation method of the mesoporous carbon spheres material that a kind of pore size according to claim 1 is controlled; it is characterized in that, in step 7, described high-temperature calcination refers to: first in tube furnace, calcine 3h under nitrogen protection atmosphere through 350 DEG C; then per minute heats up 1 DEG C, is incubated 3h after arriving 900 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928471A (en) * | 2017-02-07 | 2017-07-07 | 上海交通大学 | A kind of order mesoporous aggregation of Pn 3m Emission in Cubic and preparation method thereof |
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| CN110305634A (en) * | 2019-07-04 | 2019-10-08 | 浙江海洋大学 | A kind of preparation method of carbon ball base composite phase-change material |
| CN110527493A (en) * | 2019-07-04 | 2019-12-03 | 浙江海洋大学 | A kind of preparation method of shaping phase-change material |
| CN114904504A (en) * | 2021-02-06 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Catalyst and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086350A (en) * | 2012-09-20 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon electrode material and preparation method thereof |
| CN104310368A (en) * | 2014-08-11 | 2015-01-28 | 常州大学 | Hollow carbon sphere preparing method |
| US20150232340A1 (en) * | 2013-11-01 | 2015-08-20 | The Board Of Trustees Of The Leland Stanford Junior University | Microporous/Mesoporous Carbon |
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN105236411A (en) * | 2015-10-12 | 2016-01-13 | 湖北朗驰新型材料有限公司 | High-specific surface area nanometer mesoporous silicon carbide hollow ball and preparation method thereof |
| US20160122186A1 (en) * | 2014-07-31 | 2016-05-05 | Fraunhofer Usa, Inc. | Mesoporous carbon material and related methods |
-
2016
- 2016-01-28 CN CN201610061161.0A patent/CN105523540B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086350A (en) * | 2012-09-20 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon electrode material and preparation method thereof |
| US20150232340A1 (en) * | 2013-11-01 | 2015-08-20 | The Board Of Trustees Of The Leland Stanford Junior University | Microporous/Mesoporous Carbon |
| US20160122186A1 (en) * | 2014-07-31 | 2016-05-05 | Fraunhofer Usa, Inc. | Mesoporous carbon material and related methods |
| CN104310368A (en) * | 2014-08-11 | 2015-01-28 | 常州大学 | Hollow carbon sphere preparing method |
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN105236411A (en) * | 2015-10-12 | 2016-01-13 | 湖北朗驰新型材料有限公司 | High-specific surface area nanometer mesoporous silicon carbide hollow ball and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928471A (en) * | 2017-02-07 | 2017-07-07 | 上海交通大学 | A kind of order mesoporous aggregation of Pn 3m Emission in Cubic and preparation method thereof |
| CN109900758A (en) * | 2019-02-22 | 2019-06-18 | 东华大学 | A kind of silver/carbon nanotube composite material and preparation method and application |
| CN110305634A (en) * | 2019-07-04 | 2019-10-08 | 浙江海洋大学 | A kind of preparation method of carbon ball base composite phase-change material |
| CN110527493A (en) * | 2019-07-04 | 2019-12-03 | 浙江海洋大学 | A kind of preparation method of shaping phase-change material |
| CN114904504A (en) * | 2021-02-06 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | Catalyst and preparation method thereof |
| CN114904504B (en) * | 2021-02-06 | 2024-04-26 | 中国科学院青岛生物能源与过程研究所 | Catalyst and preparation method thereof |
| CN114976076A (en) * | 2022-06-07 | 2022-08-30 | 东华大学 | Preparation method of nano high-entropy alloy oxygen reduction electrocatalyst |
| CN117534058A (en) * | 2024-01-04 | 2024-02-09 | 内蒙古大学 | High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof |
| CN117534058B (en) * | 2024-01-04 | 2024-03-29 | 内蒙古大学 | High-specific-surface raspberry-shaped mesoporous carbon ball and preparation method thereof |
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