CN112357959A - Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material - Google Patents
Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material Download PDFInfo
- Publication number
- CN112357959A CN112357959A CN202011115822.6A CN202011115822A CN112357959A CN 112357959 A CN112357959 A CN 112357959A CN 202011115822 A CN202011115822 A CN 202011115822A CN 112357959 A CN112357959 A CN 112357959A
- Authority
- CN
- China
- Prior art keywords
- graphite
- vanadium dioxide
- nano vanadium
- reticular
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 84
- 239000010439 graphite Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 35
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007772 electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002861 polymer material Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a preparation method of a nano vanadium dioxide/reticular graphite-based composite electrode material, which comprises the following steps: a. expansion and activation of graphite; b. compounding expanded graphite and nano vanadium dioxide: uniformly mixing the graphite treated in the step a with absolute ethyl alcohol and nano vanadium dioxide; carrying out ultrasonic treatment at the ultrasonic frequency of 15-35 khz, then filtering, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain composite graphite; c. uniformly mixing foamed nickel and composite graphite, adding a high polymer material, uniformly mixing, extruding, granulating, pressing into a required shape, soaking with sulfuric acid with the concentration of 15-30%, washing and drying. The invention uses graphite with good conductivity but low price as a matrix material, and the porous electrode material is prepared by expanding the graphite, introducing active groups, combining the active groups with the nano vanadium dioxide and compounding the active groups with a high polymer material. The method of the invention is novel, short, low in cost and easy to control.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to a preparation method of a nano vanadium dioxide/reticular graphite-based composite electrode material.
Background
The supercapacitor is an energy storage device with high efficiency, practicality and environmental protection, and has the advantages of high power density, convenient control, high conversion efficiency, wide working temperature range, no pollution and the like. With the improvement of the technology, the production cost is gradually reduced and is applied to the energy storage field more and more, and the energy storage battery can be replaced by a storage battery on many occasions in the future. At present, the super capacitor is expensive and cannot be used for large-scale power energy storage. Therefore, reducing the production cost is an essential step for the further development of super capacitors and the replacement of storage batteries in the future.
The super capacitor is composed of electrode materials, electrolyte, a diaphragm, a collector and the like, each part has great influence on the super capacitor, and the electrode materials play a decisive role in the performance of the super capacitor. Common electrode materials of the super capacitor include carbon materials, metal oxide materials, conductive polymer materials and composite materials. Carbon materials are widely used as electrode materials for supercapacitors because of their low cost and various existing forms, but since they store energy only by means of an electric double layer, there is a limit in performance, and thus electrode development and research of metal oxide materials have been emerging. The metal oxide material is different from a carbon material electrode in an electric double layer capacitor for storing energy, and when the capacitor is charged and discharged, reversible oxidation-reduction reaction occurs at the interface of the metal oxide and a solution, so that higher specific capacity is obtained. The material electrode has larger specific capacity, but is expensive, and is not beneficial to the development of the super capacitor. The composite material is a composite material which uses a carbon material as a matrix and a metal oxide as an active substance to carry out a nano-composite technology to improve the charge utilization rate and is the main direction of the future development and research of the electrode material of the supercapacitor.
Although the composite electrode material of the supercapacitor with the carbon material as the matrix and the metal oxide as the active material can obtain larger specific capacity, the application of the composite electrode material in the field of energy storage is severely limited due to the fact that the used carbon materials such as carbon fibers, carbon nanotubes, graphene and the like are not cheap.
Disclosure of Invention
The invention aims to solve the technical problem of reducing the electrode cost of the super capacitor.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the nano vanadium dioxide/reticular graphite-based composite electrode material comprises the following steps:
a. expansion and activation of graphite;
b. compounding expanded graphite and nano vanadium dioxide: uniformly mixing the graphite treated in the step a with absolute ethyl alcohol and nano vanadium dioxide; carrying out ultrasonic treatment at the ultrasonic frequency of 15-35 khz, then filtering, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain composite graphite;
c. preparing a porous composite material: uniformly mixing foamed nickel and composite graphite, adding a high polymer material, uniformly mixing, extruding, granulating, pressing into a required shape, soaking with sulfuric acid with the concentration of 15-30%, washing and drying.
In the step b of the method, the volume ratio of the graphite to the absolute ethyl alcohol is 1: 1-3, and the mass ratio of the graphite to the nano vanadium dioxide is 5-15: 100.
In the step b of the method, the ultrasonic treatment time is 15-30 minutes.
In the step c of the method, the mass ratio of the foamed nickel to the composite graphite is 1: 1-4; the mass ratio of the high polymer material to the composite graphite to the foam nickel is 1-3: 1.
In the step c, the nickel foam is obtained by selecting commercially available nickel foam with the pore diameter of 0.1-10 mm, the porosity of 80-98% and the through-hole rate ≧ 90%, pulverizing, and screening to obtain the nickel foam with the particle diameter of 0.5-2 mm.
In step c of the method, the polymer material is PP or PE or a mixture of PP and PE.
In the step c of the method, the sulfuric acid is soaked for 24-72 hours, and the drying temperature is 50-80 ℃.
In step c of the method, after the required shape is pressed, the surface is polished and then the surface is soaked by sulfuric acid.
In the step a of the method, the expansion of the graphite is carried out by adopting the following treatment mode:
selecting crystalline flake graphite with the mesh number of 50-100 microns, and weighing the crystalline flake graphite, concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and vanadium pentoxide according to the mass ratio of 100: 25-50: 1-5: 25-50: 1-3;
putting the flake graphite into concentrated sulfuric acid, adding potassium permanganate, adding vanadium pentoxide after the potassium permanganate is finished, and slowly stirring for 10-20 minutes;
adding hydrogen peroxide under the condition of slow stirring, and reacting for 2-5 minutes after dropwise adding;
heating to 50-70 ℃, and reacting for 30-50 minutes under slow stirring;
after the reaction is finished, cooling to room temperature and cleaning.
Further, in the step a, the activation of graphite adopts the following treatment mode: and (3) feeding the cleaned graphite into vacuum heating equipment, starting vacuum and heating, controlling the temperature to be 800-950 ℃, introducing steam to react with the graphite, calcining for 15-30 minutes, and cooling to room temperature.
The vacuum heating equipment provided by the invention is equipment capable of performing vacuum pumping treatment and heating materials, and can meet the use requirements of the vacuum heating equipment. The vacuum heating equipment can be directly selected from a vacuum tube furnace. As can be understood by those skilled in the art, the invention opens the vacuum, and the impurity gas in the equipment is pumped out completely by introducing nitrogen gas instead of making the equipment in a vacuum state.
The invention has the beneficial effects that: the invention uses graphite with good conductivity but low price as a matrix material, and the porous electrode material is prepared by expanding the graphite, introducing active groups, combining the active groups with the nano vanadium dioxide and compounding the active groups with a high polymer material. The method of the invention is novel, short, low in cost and easy to control.
The product of the invention has relatively low price. Because the graphite with low price is used as the main conductive matrix material, compared with other materials such as fiber, carbon nano tube and graphene, the price of the graphite is low, the cost of the electrode of the super capacitor can be effectively reduced, and the market-oriented and large-scale production of the super capacitor is promoted.
The invention has the advantages of short production flow, simple process, controllable active substance quantity, product porosity and thickness. Compared with other composite electrodes containing vanadium dioxide, the method is simple, the flow is short, the amount of the added nano vanadium dioxide and the amount of the graphite can be adjusted according to requirements, and the gap and the thickness of the product can be controlled by adjusting the content and the grain size of the high polymer material and the foamed nickel.
Detailed Description
The present invention can be specifically carried out in the following manner.
The preparation method of the nano vanadium dioxide/reticular graphite-based composite electrode material comprises the following steps:
a. expansion and activation of graphite;
b. compounding expanded graphite and nano vanadium dioxide: uniformly mixing the graphite treated in the step a with absolute ethyl alcohol and nano vanadium dioxide; carrying out ultrasonic treatment at the ultrasonic frequency of 15-35 khz, then filtering, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain composite graphite;
c. preparing a porous composite material: uniformly mixing foamed nickel and composite graphite, adding a high polymer material, uniformly mixing, extruding, granulating, pressing into a required shape, soaking with sulfuric acid with the concentration of 15-30%, washing and drying.
In order to better compound the expanded graphite and the nano vanadium dioxide and save raw materials and energy, the method preferably comprises the step b, wherein the volume ratio of the graphite to the absolute ethyl alcohol is 1: 1-3, and the mass ratio of the graphite to the nano vanadium dioxide is 5-15: 100. The ultrasonic treatment time is 15-30 minutes.
In order to control the utilization rate of raw materials in the preparation process of the porous composite material, improve the pore-forming effect and save the cost, the mass ratio of the foam nickel to the composite graphite is preferably 1: 1-4 in the step c; the mass ratio of the high polymer material to the composite graphite to the foam nickel is 1-3: 1. Preferably, the foamed nickel is obtained by selecting commercially available foamed nickel with the pore diameter of 0.1-10 mm, the porosity of 80-98% and the through-hole rate of not less than 90%, crushing and screening the crushed foamed nickel with the particle diameter of 0.5-2 mm. Preferably, the high polymer material is PP or PE or a mixture of PP and PE. Preferably, the sulfuric acid is soaked for 24-72 hours, and the drying temperature is 50-80 ℃. Preferably pressing into a required shape, polishing the surface, and soaking in sulfuric acid.
In order to achieve better graphite expansion effect and activation effect, the graphite is preferably expanded in the step a by adopting the following treatment mode:
selecting crystalline flake graphite with the mesh number of 50-100 microns, and weighing the crystalline flake graphite, concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and vanadium pentoxide according to the mass ratio of 100: 25-50: 1-5: 25-50: 1-3;
putting the flake graphite into concentrated sulfuric acid, adding potassium permanganate, adding vanadium pentoxide after the potassium permanganate is finished, and slowly stirring for 10-20 minutes;
adding hydrogen peroxide under the condition of slow stirring, and reacting for 2-5 minutes after dropwise adding;
heating to 50-70 ℃, and reacting for 30-50 minutes under slow stirring;
after the reaction is finished, cooling to room temperature and cleaning.
Further preferably, the activation of graphite is carried out by the following treatment: and (3) feeding the cleaned graphite into vacuum heating equipment, starting vacuum and heating, controlling the temperature to be 800-950 ℃, introducing steam to react with the graphite, calcining for 15-30 minutes, and cooling to room temperature.
The present invention and effects will be further described below by way of examples, but the scope of the present invention is not limited to the examples.
Example 1
The graphite for standby treatment according to the method of the invention and absolute ethyl alcohol are mixed according to the volume ratio of 1:1, uniformly mixing nano vanadium dioxide and treated graphite according to the mass ratio of 5 percent, carrying out ultrasonic treatment for 20 minutes at the ultrasonic frequency of 15khz, then carrying out suction filtration, washing for 3 times by using absolute ethyl alcohol, drying, grinding into powder, uniformly mixing with foamed nickel with the pore diameter of 0.5mm, the porosity of 80 percent and the through-hole rate of 90 percent in the size of 0.2mm according to the mass ratio of 3:1, uniformly mixing with PP according to the mass ratio of 1:3, extruding and granulating on a double screw, pressing into a product with the required thickness of 1mm on a press, grinding the surfaces of two sides on a grinding wheel, soaking in dilute sulfuric acid with the concentration of 15 percent for 72 hours, washing and drying, and assembling the electrode of the super capacitor with the specific capacitance of 0.201F-cm-2At a charge-discharge current density of 15 mA/cm-2Then, the specific capacitance after 2000 cycles was 89.4% of the initial value.
Example 2
The graphite for standby treatment according to the method of the invention and absolute ethyl alcohol are mixed according to the volume ratio of 1:2, mixing the nano vanadium dioxide and the treated graphite uniformly according to the mass ratio of 10 percent, carrying out ultrasonic treatment for 20 minutes at the ultrasonic frequency of 20khz, then carrying out suction filtration, washing for 3 times by using absolute ethyl alcohol, drying, grinding into powder, mixing the powder with foamed nickel with the aperture of 5mm, the porosity of 90 percent and the through-hole rate of 92 percent being 1.5mm uniformly according to the mass ratio of 2:1, mixing the powder with PP uniformly according to the mass ratio of 1:2, extruding and granulating on a double screw rod, pressing the mixture into a product with the required thickness of 1.5mm on a press, grinding the surfaces of two sides on a grinding wheel, soaking the product in dilute sulfuric acid with the concentration of 20 percent for 48 hours, washing and drying, and assembling the electrode of the supercapacitor with the specific capacitance of 1.5mm0.214F·cm-2At a charge-discharge current density of 20 mA/cm-2Then, the specific capacitance after 2000 cycles was 89.3% of the initial value.
Example 3
The graphite for standby treatment according to the method of the invention and absolute ethyl alcohol are mixed according to the volume ratio of 1:2, uniformly mixing nano vanadium dioxide and the treated graphite according to the mass ratio of 15 percent, carrying out ultrasonic treatment for 15 minutes at the ultrasonic frequency of 25khz, then carrying out suction filtration, washing for 3 times by using absolute ethyl alcohol, drying, grinding into powder, uniformly mixing with foamed nickel with the aperture of 8mm, the porosity of 92 percent and the through-hole rate of 94 percent being 2mm according to the mass ratio of 1:1, uniformly mixing with PP according to the mass ratio of 1:1, extruding and granulating on a double screw, pressing into a product with the required thickness of 2mm on a press, grinding the two surfaces on a grinding wheel, soaking in dilute sulfuric acid with the concentration of 20 percent for 24 hours, washing, drying and assembling to obtain the super capacitor electrode with the specific capacitance of 0.211F-cm-2At a charge-discharge current density of 25 mA/cm-2Then, the specific capacitance after 2000 cycles was 88.9% of the initial value.
Claims (10)
1. The preparation method of the nano vanadium dioxide/reticular graphite-based composite electrode material is characterized by comprising the following steps:
a. expansion and activation of graphite;
b. compounding expanded graphite and nano vanadium dioxide: uniformly mixing the graphite treated in the step a with absolute ethyl alcohol and nano vanadium dioxide; carrying out ultrasonic treatment at the ultrasonic frequency of 15-35 khz, then filtering, washing with absolute ethyl alcohol, drying, and grinding into powder to obtain composite graphite;
c. preparing a porous composite material: uniformly mixing foamed nickel and composite graphite, adding a high polymer material, uniformly mixing, extruding, granulating, pressing into a required shape, soaking with sulfuric acid with the concentration of 15-30%, washing and drying.
2. The preparation method of the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, characterized in that: in the step b, the volume ratio of the graphite to the absolute ethyl alcohol is 1: 1-3, and the mass ratio of the graphite to the nano vanadium dioxide is 5-15: 100.
3. The preparation method of the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, characterized in that: in the step b, the ultrasonic treatment time is 15-30 minutes.
4. The method for preparing the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein the method comprises the following steps: in the step c, the mass ratio of the foamed nickel to the composite graphite is 1: 1-4; the mass ratio of the high polymer material to the composite graphite to the foam nickel is 1-3: 1.
5. The method for preparing the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein the method comprises the following steps: in the step c, the foamed nickel is obtained by selecting commercially available foamed nickel with the pore diameter of 0.1-10 mm, the porosity of 80-98% and the through-hole rate not less than 90%, crushing, and screening to obtain the foamed nickel with the particle diameter of 0.5-2 mm.
6. The method for preparing the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein the method comprises the following steps: in the step c, the high polymer material is PP or PE or a mixture of PP and PE.
7. The method for preparing the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein the method comprises the following steps: in the step c, the sulfuric acid is soaked for 24-72 hours, and the drying temperature is 50-80 ℃.
8. The method for preparing the nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein the method comprises the following steps: in step c, pressing into a required shape, polishing the surface, and soaking in sulfuric acid.
9. The method for preparing nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 1, 2 or 3, wherein in the step a, the graphite is expanded by adopting the following treatment method:
selecting crystalline flake graphite with the mesh number of 50-100 microns, and weighing the crystalline flake graphite, concentrated sulfuric acid, potassium permanganate, hydrogen peroxide and vanadium pentoxide according to the mass ratio of 100: 25-50: 1-5: 25-50: 1-3;
putting the flake graphite into concentrated sulfuric acid, adding potassium permanganate, adding vanadium pentoxide after the potassium permanganate is finished, and slowly stirring for 10-20 minutes;
adding hydrogen peroxide under the condition of slow stirring, and reacting for 2-5 minutes after dropwise adding;
heating to 50-70 ℃, and reacting for 30-50 minutes under slow stirring;
after the reaction is finished, cooling to room temperature and cleaning.
10. The method for preparing nano vanadium dioxide/reticular graphite-based composite electrode material according to claim 9, wherein in the step a, the activation of graphite is carried out by adopting the following treatment modes: and (3) feeding the cleaned graphite into vacuum heating equipment, starting vacuum and heating, controlling the temperature to be 800-950 ℃, introducing steam to react with the graphite, calcining for 15-30 minutes, and cooling to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115822.6A CN112357959B (en) | 2020-10-19 | 2020-10-19 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115822.6A CN112357959B (en) | 2020-10-19 | 2020-10-19 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112357959A true CN112357959A (en) | 2021-02-12 |
| CN112357959B CN112357959B (en) | 2022-07-29 |
Family
ID=74506821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011115822.6A Active CN112357959B (en) | 2020-10-19 | 2020-10-19 | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112357959B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101335349A (en) * | 2008-08-06 | 2008-12-31 | 攀钢集团研究院有限公司 | Combination electrode for all vanadium redox flow battery and preparation thereof |
| CN103046072A (en) * | 2012-12-31 | 2013-04-17 | 黑龙江大学 | Mn/Nano-G|foam-Ni/Pd combination electrode and preparation method thereof |
| CN103066312A (en) * | 2012-12-21 | 2013-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for electrolyte used for vanadium flow cell |
| CN103700810A (en) * | 2013-12-27 | 2014-04-02 | 安徽亿诺新能源有限责任公司 | Preparation technology of negative electrode of lithium secondary battery |
| CN104916854A (en) * | 2015-06-11 | 2015-09-16 | 中银（宁波）电池有限公司 | Alkaline zinc-manganese battery for improving high-power/current pulse discharge performance |
| JP2016015264A (en) * | 2014-07-02 | 2016-01-28 | 冨士色素株式会社 | Composition, electrode with porous layer including the same, and metal air secondary battery having the same |
| CN105355927A (en) * | 2015-11-28 | 2016-02-24 | 成都九十度工业产品设计有限公司 | VO2/S-AC nickel foam air cathode |
| US20170062143A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Production process for a supercapacitor having a high volumetric energy density |
| US20170062869A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Rechargeable lithium batteries having an ultra-high volumetric energy density and required production process |
| US20170103856A1 (en) * | 2015-10-13 | 2017-04-13 | Aruna Zhamu | Continuous process for producing electrodes for supercapacitors having high energy densities |
| CN109473649A (en) * | 2018-11-07 | 2019-03-15 | 哈尔滨理工大学 | A kind of sodium-ion battery composite negative pole material and preparation method thereof |
| WO2019135827A1 (en) * | 2018-01-02 | 2019-07-11 | Nanotek Instruments, Inc. | Anode particulates or cathode particulates for alkali metal batteries |
| US20190372100A1 (en) * | 2018-06-01 | 2019-12-05 | Nanotek Instruments, Inc. | Method of producing multi-level graphene-protected cathode active material particles for battery applications |
| US20200168899A1 (en) * | 2018-11-26 | 2020-05-28 | Nanotek Instruments, Inc. | Graphite protected anode active material particles for lithium batteries |
| CN111640921A (en) * | 2020-05-22 | 2020-09-08 | 大连海事大学 | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery |
-
2020
- 2020-10-19 CN CN202011115822.6A patent/CN112357959B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101335349A (en) * | 2008-08-06 | 2008-12-31 | 攀钢集团研究院有限公司 | Combination electrode for all vanadium redox flow battery and preparation thereof |
| CN103066312A (en) * | 2012-12-21 | 2013-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for electrolyte used for vanadium flow cell |
| CN103046072A (en) * | 2012-12-31 | 2013-04-17 | 黑龙江大学 | Mn/Nano-G|foam-Ni/Pd combination electrode and preparation method thereof |
| CN103700810A (en) * | 2013-12-27 | 2014-04-02 | 安徽亿诺新能源有限责任公司 | Preparation technology of negative electrode of lithium secondary battery |
| JP2016015264A (en) * | 2014-07-02 | 2016-01-28 | 冨士色素株式会社 | Composition, electrode with porous layer including the same, and metal air secondary battery having the same |
| CN104916854A (en) * | 2015-06-11 | 2015-09-16 | 中银（宁波）电池有限公司 | Alkaline zinc-manganese battery for improving high-power/current pulse discharge performance |
| US20170062869A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Rechargeable lithium batteries having an ultra-high volumetric energy density and required production process |
| US20170062143A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Production process for a supercapacitor having a high volumetric energy density |
| US20170103856A1 (en) * | 2015-10-13 | 2017-04-13 | Aruna Zhamu | Continuous process for producing electrodes for supercapacitors having high energy densities |
| CN105355927A (en) * | 2015-11-28 | 2016-02-24 | 成都九十度工业产品设计有限公司 | VO2/S-AC nickel foam air cathode |
| WO2019135827A1 (en) * | 2018-01-02 | 2019-07-11 | Nanotek Instruments, Inc. | Anode particulates or cathode particulates for alkali metal batteries |
| US20190372100A1 (en) * | 2018-06-01 | 2019-12-05 | Nanotek Instruments, Inc. | Method of producing multi-level graphene-protected cathode active material particles for battery applications |
| CN109473649A (en) * | 2018-11-07 | 2019-03-15 | 哈尔滨理工大学 | A kind of sodium-ion battery composite negative pole material and preparation method thereof |
| US20200168899A1 (en) * | 2018-11-26 | 2020-05-28 | Nanotek Instruments, Inc. | Graphite protected anode active material particles for lithium batteries |
| CN111640921A (en) * | 2020-05-22 | 2020-09-08 | 大连海事大学 | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery |
Non-Patent Citations (4)
| Title |
|---|
| NDIAYE, NM ET AL.: "High-performance asymmetric supercapacitor based on vanadium dioxide/activated expanded graphite composite and carbon-vanadium oxynitride nanostructures", 《ELECTROCHIMICA ACTA》 * |
| 刘波等: "化学沉淀过程对VO2前驱体粒径的影响及其水热晶化的研究", 《钢铁钒钛》 * |
| 张海啸: "全钒液流储能电池电极材料的设计制备与性能研究", 《中国优秀硕士学位论文全文数据库》 * |
| 牛厂磊: "钒基锂离子电池正极材料的制备及电化学性能研究", 《中国博士学位论文全文数据库》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112357959B (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| WO2021027100A1 (en) | Nitrogen-doped porous carbon material, preparation method therefor and use thereof | |
| CN103871756B (en) | A kind of preparation method of sub-micron porous charcoal ball | |
| CN112467067B (en) | Three-dimensional porous silicon-carbon material prepared by purifying photovoltaic silicon mud and preparation method thereof | |
| CN111320173B (en) | Preparation method of modified activated carbon material for capacitor | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN104617280A (en) | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof | |
| CN111807345A (en) | Silicon-carbon composite material, preparation method thereof, lithium battery negative electrode material and lithium battery | |
| JP2023169201A (en) | Activated carbon for power storage device electrode | |
| CN111422865A (en) | Nitrogen-containing carbon material for supercapacitor and preparation method and application thereof | |
| CN116914123B (en) | High-stability layered positive electrode material of battery for vehicle and preparation method thereof | |
| CN112357959B (en) | Preparation method of nano vanadium dioxide/reticular graphite-based composite electrode material | |
| CN108155022B (en) | Preparation method of lithium ion capacitor using microcrystalline graphite material | |
| CN114628631B (en) | Preparation method of high-capacity alkali metal-carbon fluoride secondary battery | |
| CN113130905A (en) | Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof | |
| CN109961966B (en) | Preparation method of porous carbon/ferroferric oxide composite electrode material of peanut shell | |
| CN113044839A (en) | Preparation method and application of hierarchical porous carbon material | |
| CN111847526A (en) | High-capacity super capacitor | |
| CN112038111B (en) | Method for preparing supercapacitor by using rare earth/3D (three-dimensional) hierarchical porous carbon composite material | |
| CN112233909B (en) | Zinc oxide-nano vanadium dioxide doped porous carbon composite electrode material and preparation method thereof | |
| CN113096964B (en) | Electrode preparation method for realizing adhesive fibrosis based on expansion micro stress | |
| CN107895657A (en) | A kind of preparation method of lithium-ion capacitor using spherical microcrystalline graphite material | |
| CN111987298B (en) | Method for compounding lithium battery silicon carbon by using homogenizer and lithium battery silicon carbon cathode | |
| CN113880085A (en) | Preparation method of biomass activated carbon for supercapacitor and supercapacitor | |
| CN116514099A (en) | Preparation method and application of high-performance bamboo charcoal nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 1509, xiangdao Avenue, Chengxiang Town, Qingbaijiang District, Chengdu, Sichuan 610000 (rooms a1301-1311 and 1319, 13th floor, block a, railway port building) Applicant after: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Address before: 610306 Chengdu City, Chengdu, Sichuan, China (Sichuan) free trade test zone, Chengdu City, Qingbaijiang District, xiangdao Boulevard, Chengxiang Town, No. 1509 (room 13, A District, railway port mansion), room 1319 Applicant before: CHENGDU ADVANCED METAL MATERIAL INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20210212 Assignee: SICHUAN PAN YAN TECHNOLOGY Co.,Ltd. Assignor: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Contract record no.: X2024980003062 Denomination of invention: Preparation method of nano vanadium dioxide/network graphite based composite electrode material Granted publication date: 20220729 License type: Exclusive License Record date: 20240322 |