CN103258653B - There is the barium oxide and carbon composite and preparation method thereof of hierarchical porous structure - Google Patents
There is the barium oxide and carbon composite and preparation method thereof of hierarchical porous structure Download PDFInfo
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- CN103258653B CN103258653B CN201310128683.4A CN201310128683A CN103258653B CN 103258653 B CN103258653 B CN 103258653B CN 201310128683 A CN201310128683 A CN 201310128683A CN 103258653 B CN103258653 B CN 103258653B
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- barium oxide
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- 229920001400 block copolymer Polymers 0.000 claims abstract description 11
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 11
- 239000005011 phenolic resin Substances 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 238000000802 evaporation-induced self-assembly Methods 0.000 claims abstract description 7
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000009413 insulation Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000011160 research Methods 0.000 abstract description 5
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of barium oxide and carbon composite and preparation method thereof with hierarchical porous structure.In this material, vanadium and carbon mass ratio are 0.4 ~ 1.5, have hierarchical porous structure, and have macropore and mesoporous, macropore size is at 0.2 ~ 1.5 μm, and mesopore size is at 15 ~ 50nm and 2.6 ~ 5.4nm, and specific area is 105.0 ~ 413.8m simultaneously
2/ g.Its preparation method is mixed hydrochloric acid, block copolymer, ethanol, phenolic resins and ammonium metavanadate, after evaporation induced self-assembly, then through thermal polymerization and carbonize and get final product.This composite material can be used as electrode material for super capacitor, in the cyclic voltammetry of three-electrode system and constant current charge-discharge research display, and only use mesoporous carbon as compared with electrode, the capacitive property of barium oxide and C-C composite electrode significantly improves.Preparation technology of the present invention is simple, and low for equipment requirements, operability is good, with low cost.
Description
Technical field
The present invention relates to electrode material for super capacitor field, be specially a kind of barium oxide and carbon composite and preparation method thereof with hierarchical porous structure.
Background technology
The world today, resource and the energy are day by day short, the traditional energy nervous situation that supply falls short of demand and day by day serious environmental problem, make large-scale developing and utilizing of new forms of energy imperative.The new forms of energy such as solar energy, wind energy, tidal energy of current most prospect, due to the unsteadiness that intermittence and the electric energy of its generating export, be badly in need of the memory device with high-energy-density, high power density, large specific energy, in order to store and to stablize, discharge electric energy constantly.In novel environment friendly power vehicle field, be also badly in need of this type of energy storage device to meet transient high-current demand when it starts climbing, and can quick storage automobile brake time the high-power energy that produces.Novel energy-storing device ultracapacitor arises at the historic moment, and the development of it and automobile with novel power is closely related, and being vitals indispensable in renewable new energy field, is the key of New Energy Industry.But it is on the low side that the bottleneck of current ultracapacitor is still energy density, and current problem urgently to be resolved hurrily how significantly to improve the energy density of ultracapacitor.
Current ultracapacitor mainly adopts the active carbon porous electrode based on electric double layer energy storage, but its specific area practical efficiency is low.And metal oxide containing precious metals, have the performance of pseudo-capacitance, ratio capacitance is high, but this type of material specific surface area is less, unstable properties, and expensive, limits its commercialization.Therefore, the advanced composite material (ACM) based on cheap transition metal oxide is paid close attention to.
Barium oxide due to its have valence state and stoichiometry change greatly, the feature such as layer structure, high power capacity, just be used as anode material for lithium-ion batteries as far back as 1976 to be studied, but just come into one's own in recent years used as the research of electrode material for super capacitor.Barium oxide is with the redox reaction of high reversible in charge and discharge process, and produce very large fake capacitance, ratio capacitance value is high, but its large current density electrical characteristics and cycle performance poor.Since 2009, it has been reported at home and abroad that with vanadic oxide and active carbon be the research that negative pole assembles hybrid super capacitor and asymmetric super-capacitor, and infusion process prepares the research of vanadic oxide and mesoporous carbon composite electrode material.But infusion process easily causes guest particles to assemble, cause basis material duct to block, and barium oxide content is on the low side, effectively can not plays its fake capacitance advantage.In addition, the high-temperature process such as the fusing point of barium oxide is lower and activity is higher, chemical gaseous phase injection are easy to cause structure collapses and phase transition.
Up to the present, there is not yet and adopt evaporation induced self-assembly method directly to obtain having the barium oxide of hierarchical porous structure and carbon composite is reported as the pertinent literature of electrode material for super capacitor.
Summary of the invention
The object of this invention is to provide a kind of barium oxide and carbon composite and preparation method thereof with hierarchical porous structure, this composite material is as the electrode material of ultracapacitor.
Realize the technical scheme that the object of the invention adopts: a kind of barium oxide and carbon composite, it is characterized in that in this material, vanadium and carbon mass ratio are 0.4 ~ 1.5, material has hierarchical porous structure, there is macropore and mesoporous simultaneously, macropore size is at 0.2 ~ 1.5 μm, mesopore size is at 15 ~ 50nm and 2.6 ~ 5.4nm, and specific area is 105.0 ~ 413.8m
2/ g.
The preparation method of a kind of barium oxide of the present invention and carbon composite, hydrochloric acid, block copolymer, ethanol, phenolic resins and ammonium metavanadate are mixed, after evaporation induced self-assembly, obtain that there is hierarchical porous structure through thermal polymerization and charing again, have macropore and mesoporous barium oxide and carbon composite, wherein block copolymer used is EO simultaneously
100pO
70eO
100, wherein EO is oxirane, and PO is expoxy propane.
The preparation of barium oxide of the present invention and carbon composite comprises the following steps:
(1) by hydrochloric acid, block copolymer, ethanol, phenolic resins ethanolic solution in mass ratio=1.0:1.6:8.0:5.0, mix with ammonium metavanadate;
(2) mixture is transferred in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, again through 100 DEG C of thermal polymerizations be warming up to 700 DEG C of insulation charings in a nitrogen atmosphere, must obtain that there is hierarchical porous structure, there is macropore and mesoporous barium oxide and carbon composite simultaneously;
Wherein, in step (1), hydrochloric acid used is 0.2mol/L hydrochloric acid solution; Block copolymer used is Pluronic F-127-polycyclic oxypropylene-Pluronic F-127 class triblock copolymer, and molecular formula is EO
100pO
70eO
100, EO is oxirane, and PO is expoxy propane; The ethanolic solution of described phenolic resins is 20wt% phenolic resins ethanolic solution; Described ammonium metavanadate inventory and the mass ratio of hydrochloric acid consumption are 0.5 ~ 2.0.
In above-mentioned preparation method's step (2), 100 DEG C of hot polymerizations merge insulation 24h; Be warming up to 700 DEG C of insulation charing 3h under nitrogen protection, carbonizing the speed being warming up to 700 DEG C is 1 ~ 2 DEG C/min.
Barium oxide of the present invention and carbon composite can be used as electrode material for super capacitor.
Barium oxide of the present invention and carbon composite have hierarchical porous structure, are conducive to electronics and transmit quickly and efficiently, be suitable as electrode material for super capacitor.Barium oxide prepared by the present invention and carbon composite show in the cyclic voltammetry of three-electrode system and constant current charge-discharge research, with only use mesoporous carbon as compared with electrode, the capacitive property of barium oxide and C-C composite electrode significantly improves, and stability is better.
Preparation technology of the present invention is simple, and low for equipment requirements, operability is good, with low cost, and the exploitation for ultracapacitor new electrode materials provides new direction.
Accompanying drawing explanation
Fig. 1 is the barium oxide of embodiment 1 preparation and the XRD collection of illustrative plates of carbon composite;
Fig. 2 is the barium oxide of embodiment 1 preparation and the SEM image of carbon composite;
Fig. 3 is the barium oxide of embodiment 1 preparation and the TEM image of carbon composite;
Fig. 4 is the barium oxide of embodiment 1 preparation and the graph of pore diameter distribution of carbon composite;
Fig. 5 is the barium oxide of embodiment 1 preparation and the cyclic voltammetry curve of carbon composite electrode material.
Embodiment
The invention provides the preparation method of a kind of barium oxide and carbon composite, the method, by hydrochloric acid, block copolymer, ethanol, phenolic resins and the mixing of vanadium source, after evaporation induced self-assembly, obtains barium oxide and carbon composite through thermal polymerization and charing.The method technique is simple, and low for equipment requirements, operability is good, and prepared barium oxide and carbon composite have hierarchical porous structure, is a kind of ultracapacitor new electrode materials.Exemplify embodiment to be below further described the present invention.
Embodiment 1
A preferred embodiment in barium oxide and carbon composite preparation method, comprises the steps:
Be that the ethanolic solution of 20wt% phenolic resins mixes with 1.5g ammonium metavanadate by 1.0g hydrochloric acid solution (0.2mol/L), 1.6g block copolymer F127,8.0g ethanol, 5.0g concentration, stir 2h at 40 DEG C.Mixture is transferred in flat bottom evaporating dishes,double, at room temperature 25 DEG C, ethanol is volatilized, dark-brown film is formed after about 8h, this film is put into 100 DEG C of baking oven hot polymerizations and merge insulation 24h, 700 DEG C of charings are warming up in a nitrogen atmosphere again with the heating rate of 1 DEG C/min, naturally cool to room temperature after insulation 3h, obtain barium oxide and carbon composite.
Fig. 1 is shown in by the XRD collection of illustrative plates of product, as seen from the figure, there is V in composite material
2o
3and VO
2two kinds of thing phases.SEM image is shown in Fig. 2, and the macropore existing in composite material and be of a size of 0.4 ~ 1.3 μm is described.TEM image is shown in Fig. 3, shows to exist in composite material to be of a size of the mesoporous of 20 ~ 50nm.As shown in Figure 4, its aperture concentrates on 2.6 ~ 5.0nm to the pore-size distribution of this material as we know from the figure.Analyzed from Fig. 2, Fig. 3 and Fig. 4, composite material has hierarchical porous structure.The specific area of product is 105.0m
2/ g.
Embodiment 1 sample is mixed rear compressing tablet with the ptfe emulsion of 10wt% by 9:1 mass ratio, in 80 DEG C of vacuumizes, then under the pressure of 10MPa, this material is pressed in nickel foam, makes 1 × 1cm
2electrode.Using saturated calomel electrode as reference electrode, platinum electrode as to electrode, at 1mol/LKNO
3standard three-electrode system is formed in electrolyte.Fig. 5 is presented at the cyclic voltammetry curve under 2mV/s sweep speed, in class rectangle.When current density is 0.1A/g, the electric discharge ratio capacitance of combination electrode material is 171.0F/g.
Embodiment 2
An embodiment in barium oxide and carbon composite preparation method, step is with embodiment 1, difference is that the inventory of ammonium metavanadate and hydrochloric acid consumption mass ratio are 0.5, at room temperature 25 DEG C, make ethanol volatilize after about 8h form navy blue film, after 100 DEG C of hot polymerizations merge insulation 24h, be warming up to 700 DEG C of charings with the heating rate of 2 DEG C/min in a nitrogen atmosphere again, naturally cool to room temperature after insulation 3h, obtain barium oxide and carbon composite.SEM, TEM and pore-size distribution test show, product has macropore, meso-hole structure, and macropore size is 0.4 ~ 1.5 μm, and mesopore size is 3.5 ~ 5.4nm.XRD analysis test shows that resulting materials exists V
2o
3and VO
2two kinds of thing phases.The specific area of composite material is 413.8m
2/ g, ratio capacitance is 115.7F/g.
Embodiment 3
An embodiment in barium oxide and carbon composite preparation method, step is with embodiment 1, difference is that the inventory of ammonium metavanadate and hydrochloric acid consumption mass ratio are 2.0, at room temperature 25 DEG C, make ethanol volatilize after about 8h form brownish black film, merge after insulation 24h through 100 DEG C of hot polymerizations, be warming up to 700 DEG C of charings with the heating rate of 1.5 DEG C/min in a nitrogen atmosphere again, after naturally cooling to room temperature after insulation 3h, obtain barium oxide and carbon composite.SEM, TEM and pore-size distribution test show, product has macropore, meso-hole structure, and macropore size is 0.2 ~ 0.8 μm, and mesopore size is 2.8 ~ 4.6nm.XRD analysis test shows that resulting materials exists V
2o
3and VO
2two kinds of thing phases.The specific area of composite material is 198.2m
2/ g, ratio capacitance is 143.1F/g.
Claims (6)
1. barium oxide and a carbon composite, is characterized in that: in this material, vanadium and carbon mass ratio are 0.4 ~ 1.5, have hierarchical porous structure, there is macropore and mesoporous simultaneously, macropore size is at 0.2 ~ 1.5 μm, and mesopore size is at 15 ~ 50nm and 2.6 ~ 5.4nm, and specific area is 105.0 ~ 413.8m
2/ g.
2. the preparation method of a kind of barium oxide as claimed in claim 1 and carbon composite, it is characterized in that: adopt the mixing of hydrochloric acid, block copolymer, ethanol, phenolic resins and ammonium metavanadate, after evaporation induced self-assembly, obtain that there is hierarchical porous structure through thermal polymerization and charing again, have macropore and mesoporous barium oxide and carbon composite, wherein block copolymer used is EO simultaneously
100pO
70eO
100, wherein EO is oxirane, and PO is expoxy propane.
3. the preparation method of barium oxide according to claim 2 and carbon composite, is characterized in that, preparation comprises the following steps:
(1) by hydrochloric acid, block copolymer, ethanol, phenolic resins ethanolic solution in mass ratio=1.0:1.6:8.0:5.0, mix with ammonium metavanadate;
(2) mixture is transferred in flat bottom evaporating dishes,double, at room temperature evaporation induced self-assembly, again through 100 DEG C of thermal polymerizations be warming up to 700 DEG C of insulation charings in a nitrogen atmosphere, must obtain that there is hierarchical porous structure, there is macropore and mesoporous barium oxide and carbon composite simultaneously;
Wherein, in step (1), hydrochloric acid used is 0.2mol/L hydrochloric acid solution; Block copolymer formula used is EO
100pO
70eO
100, EO is oxirane, and PO is expoxy propane; The ethanolic solution of described phenolic resins is 20wt% phenolic resins ethanolic solution; Described ammonium metavanadate inventory and the mass ratio of hydrochloric acid consumption are 0.5 ~ 2.0.
4. the preparation method of barium oxide according to claim 3 and carbon composite, is characterized in that: in described step (2), 100 DEG C of hot polymerizations merge insulation 24h.
5. the preparation method of barium oxide according to claim 3 and carbon composite, is characterized in that: be warming up to 700 DEG C of insulation charing 3h in described step (2) under nitrogen protection, carbonizing the speed being warming up to 700 DEG C is 1 ~ 2 DEG C/min.
6. the application of barium oxide according to claim 1 and carbon composite, is characterized in that: be used as electrode material for super capacitor.
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| CN104867689A (en) * | 2015-04-02 | 2015-08-26 | 安徽江威精密制造有限公司 | Waste PVC based electrode material with high energy storage capacity and preparation method thereof |
| CN104851599A (en) * | 2015-04-02 | 2015-08-19 | 安徽江威精密制造有限公司 | Composite electrode material with high cycle performance stability and preparation method thereof |
| CN112233911B (en) * | 2020-10-16 | 2022-07-15 | 成都先进金属材料产业技术研究院股份有限公司 | Vanadium dioxide nano carbon fiber composite material and preparation method and application thereof |
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| WO2008118422A1 (en) * | 2007-03-26 | 2008-10-02 | The Trustees Of Columbia University In The City Of New York | Metal oxide nanocrystals: preparation and uses |
| CN101572191A (en) * | 2009-06-05 | 2009-11-04 | 武汉理工大学 | V2O5-ordered mesoporous carbon composite material and preparation method thereof |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008118422A1 (en) * | 2007-03-26 | 2008-10-02 | The Trustees Of Columbia University In The City Of New York | Metal oxide nanocrystals: preparation and uses |
| CN101572191A (en) * | 2009-06-05 | 2009-11-04 | 武汉理工大学 | V2O5-ordered mesoporous carbon composite material and preparation method thereof |
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| Title |
|---|
| Ordered Mesoporous Carbon Composite Films Containing Cobalt Oxide and Vanadia for Electrochemical Applications;Mingzhi Dai等;《American Chemical Society》;20110510;2869-2878页 * |
| Ordered Mesoporous Carbon/MoO2 Nanocomposites as Stable Supercapacitor Electrodes;Yuanyuan Zhou等;《ECS Electrochemistry Letters》;20120717;A17-A20页 * |
| Synthesis of ordered mesoporous carbon materials and their catalytic performance in dehydrogenation of propane to propylene;Lei Liu等;《Catalysis Today》;20110803;35-41页 * |
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Effective date of registration: 20240122 Address after: 572024 Building 9, UFIDA Industrial Park, yazhouwan science and Technology City, Yazhou District, Sanya City, Hainan Province Patentee after: Sanya science and Education Innovation Park Wuhan University of Technology Country or region after: China Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: WUHAN University OF TECHNOLOGY Country or region before: China |