CN103258653A - Vanadium oxide and carbon composite material with hierarchical pore structure and preparation method thereof - Google Patents
Vanadium oxide and carbon composite material with hierarchical pore structure and preparation method thereof Download PDFInfo
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- CN103258653A CN103258653A CN2013101286834A CN201310128683A CN103258653A CN 103258653 A CN103258653 A CN 103258653A CN 2013101286834 A CN2013101286834 A CN 2013101286834A CN 201310128683 A CN201310128683 A CN 201310128683A CN 103258653 A CN103258653 A CN 103258653A
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- carbon composite
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- barium oxide
- mesoporous
- hydrochloric acid
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title abstract 4
- 239000002149 hierarchical pore Substances 0.000 title abstract 4
- 229910001935 vanadium oxide Inorganic materials 0.000 title abstract 4
- 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
- 239000000463 material Substances 0.000 claims abstract description 13
- 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 9
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 78
- 229920001400 block copolymer Polymers 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003990 capacitor Substances 0.000 claims description 7
- 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- HJIYJLZFNBHCAN-UHFFFAOYSA-N [V].[C] Chemical compound [V].[C] HJIYJLZFNBHCAN-UHFFFAOYSA-N 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 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
- 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
- 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
- 238000007654 immersion Methods 0.000 description 1
- 238000001802 infusion Methods 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
- 238000004519 manufacturing process Methods 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
- 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
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to vanadium oxide and carbon composite material with a hierarchical pore structure and a preparation method of the vanadium oxide and carbon composite material with the hierarchical pore structure. The vanadium-carbon ratio of the material is 0.4-1.5, the material is of the hierarchical pore structure and provided with macropores and mesopores, the diameters of the macropores are 0.2-1.5 micrometers, the diameters of the mesoporous are 15-50 nanometers and 2.6-5.4 nanometers, and the specific surface areas of the material are 105.0-413.8 square meter per gram. The preparation method includes the following steps: mixing hydrochloric acid, segmented copolymers, ethanol, phenolic resin and ammonium metavanadate, and obtaining the material through thermal polymerization and carbonization after volatilization induced self-assembly. The composite material can be used as supercapacitor electrode material. Researches in cyclic voltammetry and continuous current charge and discharge of a three-electrode system show that capacitive performance of a vanadium oxide and carbon composite material electrode is improved obviously compared with capacitive performance of an electrode made of mesoporous carbon. The preparation method is simple, low in requirement for devices, good in operability, and low in cost.
Description
Technical field
The present invention relates to the electrode material for super capacitor field, be specially a kind of barium oxide with hierarchical porous structure and carbon composite and preparation method thereof.
Background technology
The world today, resource and the energy is shortage day by day, and the traditional energy nervous situation that supply falls short of demand and serious environmental problem day by day make that large-scale developing and utilizing of new forms of energy is imperative.New forms of energy such as the solar energy of at present tool prospect, wind energy, tidal energy, because the unsteadiness of the intermittence of its generating and electric energy output, urgent need has the memory device of high-energy-density, high power density, big specific energy, in order to storage and stable, discharge electric energy constantly.In novel environment friendly power vehicle field, the transient high-current demand when also being badly in need of this type of energy storage device and satisfying it and start climbing, but and the high-power energy that produces during the quick storage automobile brake.Novel energy-storing device ultracapacitor arises at the historic moment, and the development of it and automobile with novel power is closely related, is vitals indispensable in the renewable new energy field, is the key of new forms of energy industry.It is on the low side that but the bottleneck of present ultracapacitor is still energy density, and the current problem that needs to be resolved hurrily is how significantly to improve the energy density of ultracapacitor.
Ultracapacitor mainly is the active carbon porous electrode that adopts based on the electric double layer energy storage at present, but its specific area practical efficiency is low.And metal oxide containing precious metals has the performance of pseudo-capacitance, and than electric capacity height, but this type of material specific area is less, unstable properties, and also expensive, limited its commercialization.Therefore, paid close attention to based on the advanced composite material (ACM) of cheap transition metal oxide.
Barium oxide is because characteristics such as it has valence state and stoichiometry changes greatly, layer structure, high power capacity, just be used as anode material for lithium-ion batteries as far back as 1976 and study, but just come into one's own in recent years used as the research of electrode material for super capacitor.Barium oxide is followed highly reversible redox reaction in charge and discharge process, produce very big fake capacitance, and than capacitance height, but its large current density electrical characteristics and cycle performance are relatively poor.Since 2009, successively reported with vanadic oxide and active carbon to be the research of negative pole assembling hybrid super capacitor and asymmetric ultracapacitor both at home and abroad, and the research of immersion process for preparing vanadic oxide and mesoporous carbon composite electrode material.Yet infusion process easily causes the object particle aggregation, cause the basis material duct to stop up, and barium oxide content is on the low side, can not effectively bring into play its fake capacitance advantage.In addition, the fusing point of barium oxide is lower and active higher, and high temperature such as chemical gaseous phase injection are handled and are easy to cause structure to cave in and phase transition.
Up to the present, the Shang Weijian barium oxide that adopts volatilization to induce self-assembly method directly to obtain having hierarchical porous structure is reported as the pertinent literature of electrode material for super capacitor with carbon composite.
Summary of the invention
The purpose of this invention is to provide a kind of barium oxide with hierarchical porous structure and carbon composite and preparation method thereof, 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 vanadium and carbon mass ratio are 0.4 ~ 1.5 in this material, material has hierarchical porous structure, has macropore and mesoporous simultaneously, big hole dimension is at 0.2 ~ 1.5 μ m, mesoporous size is at 15 ~ 50 nm and 2.6 ~ 5.4 nm, and specific area is 105.0 ~ 413.8 m
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 self assembly is induced in volatilization, obtain having hierarchical porous structure through thermal polymerization and charing again, have macropore and mesoporous barium oxide and carbon composite simultaneously, wherein used block copolymer is EO
100PO
70EO
100, wherein EO is oxirane, PO is expoxy propane.
The preparation of barium oxide of the present invention and carbon composite may further comprise the steps:
(1) hydrochloric acid, block copolymer, ethanol, phenolic resins ethanolic solution are pressed mass ratio=1.0: 1.6: 8.0: 5.0, mix with ammonium metavanadate;
(2) mixture is transferred in the flat bottom evaporating dishes,double, self assembly is induced in volatilization at room temperature, again through 100 ℃ of thermal polymerizations and under nitrogen atmosphere, be warming up to 700 ℃ the insulation charings, namely obtain having hierarchical porous structure, have macropore and mesoporous barium oxide and carbon composite simultaneously;
Wherein, in the step (1), used hydrochloric acid is 0.2 mol/L hydrochloric acid solution; Used block copolymer is poly-oxireme-poly-propylene oxide-poly-oxireme class triblock copolymer, and molecular formula is EO
100PO
70EO
100, EO is oxirane, PO is expoxy propane; The ethanolic solution of described phenolic resins is 20 wt% phenolic resins ethanolic solutions; The mass ratio of described ammonium metavanadate inventory and hydrochloric acid consumption is 0.5 ~ 2.0.
100 ℃ of hot polymerizations merge insulation 24 h in above-mentioned preparation method's step (2); Be warming up to 700 ℃ of insulation charing 3 h under nitrogen protection, it is 1 ~ 2 ℃/min that charing is warming up to 700 ℃ speed.
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, are suitable as electrode material for super capacitor.Barium oxide and the carbon composite of the present invention's preparation studies show that at cyclic voltammetry and the constant current charge-discharge of three-electrode system, with only use mesoporous carbon and compare as electrode, the capacitive property of barium oxide and C-C composite electrode obviously improves, and stability better.
Preparation technology of the present invention is simple, and is low for equipment requirements, and operability is good, and is with low cost, for ultracapacitor provides new direction with the exploitation of novel electrode material.
Description of drawings
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, this method is mixed hydrochloric acid, block copolymer, ethanol, phenolic resins and vanadium source, induce self assembly by volatilization after, obtain barium oxide and carbon composite through thermal polymerization and charing.This method technology is simple, low for equipment requirements, and operability is good, and prepared barium oxide and carbon composite have hierarchical porous structure, is a kind of ultracapacitor novel electrode material.Exemplifying the present invention of embodiment is below further specified.
Embodiment 1
An embodiment preferred among barium oxide and the carbon composite preparation method comprises the steps:
Be that the ethanolic solution of 20 wt% phenolic resins mixes with 1.5 g ammonium metavanadates with 1.0 g hydrochloric acid solutions (0.2 mol/L), 1.6 g block copolymer F127,8.0 g ethanol, 5.0 g concentration, stir 2 h at 40 ℃.Mixture is transferred in the flat bottom evaporating dishes,double, under 25 ℃ of room temperatures, make the ethanol volatilization, form the dark-brown film behind about 8 h, this film is put into 100 ℃ of baking oven hot polymerizations merge insulation 24 h, heating rate with 1 ℃/min is warming up to 700 ℃ of charings under nitrogen atmosphere again, naturally cool to room temperature after being incubated 3 h, obtain barium oxide and carbon composite.
The XRD collection of illustrative plates of product is seen Fig. 1, as seen from the figure, has V in the composite material
2O
3And VO
2Two kinds of thing phases.The SEM image is seen Fig. 2, illustrates to have the macropore that is of a size of 0.4 ~ 1.3 μ m in the composite material.The TEM image is seen Fig. 3, shows to exist in the composite material to be of a size of the mesoporous of 20 ~ 50 nm.The pore-size distribution of this material as shown in Figure 4, its aperture concentrates on 2.6 ~ 5.0 nm as we know from the figure.By Fig. 2, Fig. 3 and Fig. 4 analysis as can be known, composite material has hierarchical porous structure.The specific area of product is 105.0 m
2/ g.
The ptfe emulsion of embodiment 1 sample and 10 wt% is mixed the back compressing tablet by the 9:1 mass ratio, in 80 ℃ of vacuumizes, under the pressure of 10 MPa, this material is pressed on the nickel foam again, make 11 cm
2Electrode.As reference electrode, the platinum electrode conduct is to electrode, at 1 mol/L KNO with saturated calomel electrode
3Form the standard three-electrode system in the electrolyte.Fig. 5 is presented at the cyclic voltammetry curve under the 2 mV/s sweep speeds, is the class rectangle.When current density was 0.1 A/g, the discharge of combination electrode material was 171.0 F/g than electric capacity.
An embodiment among barium oxide and the 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, ethanol is volatilized form the navy blue film behind about 8 h, after 100 ℃ of hot polymerizations merge insulation 24 h, heating rate with 2 ℃/min is warming up to 700 ℃ of charings under nitrogen atmosphere again, naturally cools to room temperature after being incubated 3 h, obtains barium oxide and carbon composite.SEM, TEM and pore-size distribution test shows, product has macropore, meso-hole structure, and macropore is of a size of 0.4 ~ 1.5 μ m, mesoporous 3.5 ~ 5.4 nm that are of a size of.There is V in XRD analysis test shows gained material
2O
3And VO
2Two kinds of thing phases.The specific area of composite material is 413.8 m
2/ g is 115.7 F/g than electric capacity.
An embodiment among barium oxide and the 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, ethanol is volatilized form the brownish black film behind about 8 h, after 100 ℃ of hot polymerizations merge insulation 24 h, heating rate with 1.5 ℃/min is warming up to 700 ℃ of charings under nitrogen atmosphere again, be incubated naturally cool to room temperature behind 3 h after, obtain barium oxide and carbon composite.SEM, TEM and pore-size distribution test shows, product has macropore, meso-hole structure, and macropore is of a size of 0.2 ~ 0.8 μ m, mesoporous 2.8 ~ 4.6 nm that are of a size of.There is V in XRD analysis test shows gained material
2O
3And VO
2Two kinds of thing phases.The specific area of composite material is 198.2 m
2/ g is 143.1 F/g than electric capacity.
Claims (6)
1. a barium oxide and carbon composite, it is characterized in that: vanadium and carbon mass ratio are 0.4 ~ 1.5 in this material, has hierarchical porous structure, has macropore and mesoporous simultaneously, big hole dimension is at 0.2 ~ 1.5 μ m, mesoporous size is at 15 ~ 50 nm and 2.6 ~ 5.4 nm, and specific area is 105.0 ~ 413.8 m
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 hydrochloric acid, block copolymer, ethanol, phenolic resins and ammonium metavanadate to mix, after self assembly is induced in volatilization, obtain having hierarchical porous structure through thermal polymerization and charing again, have macropore and mesoporous barium oxide and carbon composite simultaneously, wherein used block copolymer is EO
100PO
70EO
100, wherein EO is oxirane, PO is expoxy propane.
3. the preparation method of barium oxide according to claim 2 and carbon composite is characterized in that, preparation may further comprise the steps:
(1) hydrochloric acid, block copolymer, ethanol, phenolic resins ethanolic solution are pressed mass ratio=1.0: 1.6: 8.0: 5.0, mix with ammonium metavanadate;
(2) mixture is transferred in the flat bottom evaporating dishes,double, self assembly is induced in volatilization at room temperature, again through 100 ℃ of thermal polymerizations and under nitrogen atmosphere, be warming up to 700 ℃ the insulation charings, namely obtain having hierarchical porous structure, have macropore and mesoporous barium oxide and carbon composite simultaneously;
Wherein, in the step (1), used hydrochloric acid is 0.2 mol/L hydrochloric acid solution; Used block copolymer formula is EO
100PO
70EO
100, EO is oxirane, PO is expoxy propane; The ethanolic solution of described phenolic resins is 20 wt% phenolic resins ethanolic solutions; The mass ratio of described ammonium metavanadate inventory and hydrochloric acid consumption is 0.5 ~ 2.0.
4. the preparation method of barium oxide according to claim 3 and carbon composite is characterized in that: 100 ℃ of hot polymerizations merging insulation 24 h in the described step (2).
5. the preparation method of barium oxide according to claim 3 and carbon composite is characterized in that: be warming up to 700 ℃ of insulation charing 3 h in the described step (2) under nitrogen protection, it is 1 ~ 2 ℃/min that charing is warming up to 700 ℃ speed.
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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112233911A (en) * | 2020-10-16 | 2021-01-15 | 成都先进金属材料产业技术研究院有限公司 | 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN112233911A (en) * | 2020-10-16 | 2021-01-15 | 成都先进金属材料产业技术研究院有限公司 | Vanadium dioxide nano carbon fiber composite material and preparation method and application thereof |
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| CN103258653B (en) | 2015-12-02 |
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