CN111009425B - Low-noise breakdown-resistant supercapacitor - Google Patents

Low-noise breakdown-resistant supercapacitor Download PDF

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CN111009425B
CN111009425B CN201911269979.1A CN201911269979A CN111009425B CN 111009425 B CN111009425 B CN 111009425B CN 201911269979 A CN201911269979 A CN 201911269979A CN 111009425 B CN111009425 B CN 111009425B
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electrode
diaphragm
nitrogen
ceramic
raw materials
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CN111009425A (en
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杜嘉杰
魏蓉晖
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Dong Jia Electronics Chenzhou Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a low-noise breakdown-resistant supercapacitor, which comprises a shell and at least one capacitor unit connected in series, wherein the capacitor unit comprises: the electrode comprises a first electrode, a second electrode and a diaphragm arranged between the first electrode and the second electrode, wherein the first electrode and the second electrode respectively comprise a current collector and an electrode material formed on the current collector, the diaphragm is polypropylene-cellulose paper doped with ceramic micro powder, and the ceramic micro powder is Er-Nb-doped BiFeO3‑BaTiO3The shell of the capacitor is wrapped with the heat-conducting sound-absorbing cotton, so that noise generated during working is low, the heat dissipation performance of the capacitor is not affected, and breakdown caused by overheating is avoided; the diaphragm paper modified by the rare earth doped BFBT ceramic has higher breakdown field intensity and more uniform diaphragm electrical property.

Description

Low-noise breakdown-resistant supercapacitor
Technical Field
The invention relates to the technical field of super capacitors, in particular to a low-noise breakdown-resistant super capacitor.
Background
The super capacitor is a novel component for storing energy through an interface double layer formed between an electrode and an electrolyte, is also called as an electric double layer capacitor, is a novel energy storage device between a traditional capacitor and a rechargeable battery, has the characteristics of quick charge and discharge and high cycle service life, is widely applied in the field of energy storage, and is easy to generate heat and noise during working.
The electrodes, electrolyte and separator have a decisive influence on the performance of the supercapacitor, and the separator is less studied than the electrodes and electrolyte. The diaphragm of the super capacitor is positioned between two electrodes and is soaked in electrolyte together with the electrodes, the isolation effect is achieved in the repeated charging and discharging process, short circuit caused by contact between the two electrodes is prevented, the current diaphragm material mainly comprises polypropylene diaphragm paper and a battery diaphragm, and the problems of poor affinity to the electrolyte, low strength and breakdown intolerance exist.
Disclosure of Invention
In view of the above problems, the present invention provides a low noise breakdown resistant supercapacitor.
The purpose of the invention is realized by adopting the following technical scheme:
a low-noise breakdown-resistant super capacitor comprises a shell and at least one capacitor connected in seriesThe capacitor unit comprises a first electrode, a second electrode and a diaphragm arranged between the first electrode and the second electrode, the first electrode, the second electrode and the diaphragm are arranged in electrolyte, the first electrode and the second electrode respectively comprise a current collector and an electrode material formed on the current collector, the diaphragm is polypropylene-cellulose paper doped with ceramic micro powder, and the ceramic micro powder is Er and Nb doped BiFeO3-BaTiO3The shell of the capacitor is wrapped with heat-conducting sound-absorbing cotton;
preferably, the current collector is graphite or Al or Ni or Cu or Mg or Ti or Pt or Al2O3Or NiO or CuO or MgO or TiO2；
Preferably, the preparation method of the separator comprises the following steps:
s1 preparation of ceramic micropowder
Barium titanate, barium carbonate, titanium dioxide, bismuth oxide and ferric oxide are used as raw materials according to the proportion of 0.6BiFeO3-0.4BaTiO3Weighing raw materials, putting the raw materials into a ball milling tank, taking zirconia balls as a ball milling medium, absolute ethyl alcohol as a medium and triolein as a dispersing agent, wherein the ball-material ratio is 4:1-5:1, carrying out ball milling for 4-12h by using a planetary ball mill to obtain a dispersion suspension, drying the suspension, carrying out heat treatment for 4h at 600 ℃, adding a doping raw material, taking erbium trioxide and niobium pentoxide as raw materials, and mixing ErNbO according to a proportion4Weighing the raw materials, wherein the doping proportion is not higher than 1%, performing ball milling for 4-6h again, sintering at the temperature of 1000 ℃ and 1100 ℃ and preserving heat for 3h, cooling and then crushing to obtain ceramic micro powder with the particle size of below 5 mu m;
s2 preparation of diaphragm
50-65 parts of polypropylene fiber and 35-50 parts of cellulose fiber by weight are put into a beater, are added with water for defibering, the percentage concentration of the fiber is controlled to be 0.2-0.5%, polyacrylamide with the volume concentration of 1% is added, the mixture is beaten until the mixture is completely dispersed, 30-45 parts of ceramic micro powder by weight are added, the mixture is uniformly mixed, and the diaphragm is prepared by wet papermaking and cutting;
preferably, the purity contents of the raw materials of barium titanate, barium carbonate, titanium dioxide, bismuth oxide, ferric oxide, erbium trioxide and niobium pentoxide are all more than 99%;
preferably, the fiber length of the polypropylene fiber is 1-10mm, the titer is 0.2-0.6detx, and the fiber length of the cellulose fiber is 1-10 mm;
preferably, the diaphragm also comprises a ceramic coating, and the preparation method comprises the steps of dispersing 1-1.5 parts by weight of ceramic micro powder in polyvinyl alcohol to obtain a coating liquid, coating the coating liquid on the diaphragm, and performing calendaring treatment to obtain the diaphragm comprising the ceramic coating;
preferably, the electrode material of at least one electrode is a carbonized graphene grafted composite PMMA material;
further preferably, the carbonized graphene grafted composite PMMA material is a carbonized nitrogen-doped graphene grafted composite PMMA material;
preferably, the preparation of the carbonized nitrogen-doped graphene grafted composite PMMA material comprises the following steps:
s1, nitrogen-doped graphene
Ultrasonically dispersing graphene oxide in absolute ethyl alcohol, wherein the material-liquid ratio is 0.6-1g/L, adding urea with the mass of 1% of that of a solution system as a nitrogen source, continuing ultrasonic treatment to uniformly disperse the solution system, putting the solution system into a hydrothermal reaction kettle for hydrothermal reaction for 6-12h at the reaction temperature of 150 ℃ and 200 ℃, centrifugally separating out a product after self-cooling, washing the product with absolute ethyl alcohol and distilled water in sequence, drying the product in vacuum and crushing the product for later use;
s2 graphene grafted composite PMMA
Dispersing the nitrogen-doped graphene prepared by S1 in dimethylformamide, adding methyl methacrylate with the mass of 20-50 times of the nitrogen-doped graphene according to the feed-liquid ratio of 0.8-1g/L, uniformly mixing, adding benzoyl peroxide with the mass of 0.2-0.3 time of the nitrogen-doped graphene, stirring at the rotating speed of not higher than 100rpm, heating to react for 12-16h at 80 ℃, removing a heat source, self-cooling the system, adding absolute ethyl alcohol with the volume twice of the solution, uniformly stirring, centrifugally separating and precipitating, sequentially washing with absolute ethyl alcohol and distilled water, and vacuum drying;
s3, carbonization
And (3) carbonizing the product prepared by the S2 in an atmosphere furnace, heating to 300 ℃ at a heating rate of 10-20 ℃/min under a flowing nitrogen protection atmosphere, heating to 700 ℃ at a heating rate of 5-10 ℃/min, mixing 2-5% of carbon dioxide and 5-10% of water vapor into the atmosphere, preserving heat for 2h, and cooling to obtain the carbonized nitrogen-doped graphene grafted composite PMMA material.
The invention has the beneficial effects that:
(1) the sound cotton is inhaled through the shell parcel heat conduction at the condenser for the noise that the during operation produced is little, does not produce the noise even, does not influence the heat dispersion of condenser itself simultaneously, can avoid overheated emergence to puncture.
(2) The method combines the fibrous polypropylene with the cellulose fiber on the basis of the original polypropylene film, and the wet paper making method can not only conveniently control the film thickness, but also cause higher and more uniform porosity due to the staggered and overlapped fibers and play a role in mechanical reinforcement; the cellulose fiber not only contributes to reinforcement, but also improves the liquid absorption and retention of the diaphragm material due to abundant functional groups; ceramic micro powder is added into the diaphragm paper as a reinforcing filler, so that the diaphragm material has good tensile strength, and meanwhile, the insulativity, the dielectricity and the chemical stability are improved, and the diaphragm material has good isolation performance; the rare earth Nb and Er are doped with oxides, so that the chemical structure of the BFBT ceramic is changed, the intrinsic impedance of the BFBT ceramic is improved, higher breakdown field intensity and more uniform electrical property of the diaphragm are obtained, and the working voltage of the super capacitor is improved, thereby improving the energy density.
(3) The graphene is a promising electrode material due to good conductivity and high theoretical specific capacitance, but the graphene sheet layer is easy to generate pi-pi stacking, the specific surface area of the graphene sheet layer can be obviously reduced, the rapid transmission of electrolyte is influenced, the energy storage potential of the electrolyte is difficult to fully exert, the application takes the nitrogen-doped graphene as a template, polymethyl methacrylate is grown on the surface of the graphene as a carbon source, and then the carbon source is carbonized and loaded on graphene, meanwhile, high-temperature steam causes a pore expanding effect on the carbon-loaded graphene, further causes an open pore structure, obtains a carbon material with high specific surface area and electric conductivity, the composite material has good wettability in a water system and an ionic liquid, has good circulation stability, and can effectively improve the charge transmission and the extraction and injection of ions when being used as an electrode material of a super capacitor, thereby effectively improving the performance of the super capacitor.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
The super capacitor comprises a shell and at least one capacitor unit connected in series, wherein the capacitor unit comprises a first electrode, a second electrode and a diaphragm arranged between the first electrode and the second electrode, the first electrode, the second electrode and the diaphragm are arranged in electrolyte, the first electrode and the second electrode respectively comprise a current collector and an electrode material formed on the current collector, the diaphragm is polypropylene-cellulose paper doped with ceramic micropowder, and the ceramic micropowder is Er and Nb doped BiFeO3-BaTiO3The shell of the capacitor is wrapped with heat-conducting sound-absorbing cotton; the current collector is a graphite carbon rod, foamed nickel or platinum;
the preparation method of the diaphragm comprises the following steps:
s1 preparation of ceramic micropowder
Barium titanate, barium carbonate, titanium dioxide, bismuth oxide and ferric oxide are used as raw materials according to the proportion of 0.6BiFeO3-0.4BaTiO3Weighing raw materials, putting the raw materials into a ball milling tank, taking zirconia balls as a ball milling medium, taking absolute ethyl alcohol as a medium, taking glycerol trioleate as a dispersing agent, mixing the raw materials in a ball-material ratio of 4:1, ball-milling the raw materials for 5 to 6 hours by using a planetary ball mill to obtain a dispersion suspension, drying the suspension, carrying out heat treatment at the temperature of 600 ℃ for 4 hours, adding a doping raw material, taking erbium trioxide and niobium pentoxide as raw materials, and mixing the raw materials according to a proportion ErNbO4Weighing raw materials with a doping ratio of 0.8%, ball-milling for 4-5h again, sintering at 1050 ℃ and keeping the temperature for 3h, cooling and then crushing to obtain ceramic micro powder with a particle size of below 5 mu m;
s2 preparation of diaphragm
60 parts by weight of polypropylene fiber and 40 parts by weight of cellulose fiber are put into a beater and are defibered by adding water, the percentage concentration of the fiber is controlled to be 0.2-0.5%, polyacrylamide with the volume concentration of 1% is added, the mixture is beaten until the mixture is completely dispersed, 35 parts by weight of ceramic micro powder are added, the mixture is uniformly mixed, and the diaphragm is prepared by wet papermaking and cutting;
the purity contents of the raw materials of barium titanate, barium carbonate, titanium dioxide, bismuth oxide, ferric oxide, erbium trioxide and niobium pentoxide are all more than 99%;
the fiber length of the polypropylene fiber is 1-10mm, the titer is 0.2-0.6detx, and the fiber length of the cellulose fiber is 1-10 mm.
The average pore diameter of the diaphragm of the embodiment is 0.17-0.18 μm, the porosity is 67%, and the liquid absorption rate is 546%.
Example 2
The super capacitor comprises a shell and at least one capacitor unit connected in series, wherein the capacitor unit comprises a first electrode, a second electrode and a diaphragm arranged between the first electrode and the second electrode, the first electrode, the second electrode and the diaphragm are arranged in electrolyte, the first electrode and the second electrode respectively comprise a current collector and an electrode material formed on the current collector, the diaphragm is polypropylene-cellulose paper doped with ceramic micropowder, and the ceramic micropowder is Er and Nb doped BiFeO3-BaTiO3The shell of the capacitor is wrapped with heat-conducting sound-absorbing cotton; the current collector is a graphite carbon rod, foamed nickel or platinum;
the preparation method of the diaphragm comprises the following steps:
s1 preparation of ceramic micropowder
Barium titanate, barium carbonate, titanium dioxide, bismuth oxide and ferric oxide are used as raw materials according to the proportion of 0.6BiFeO3-0.4BaTiO3Weighing raw materials, putting the raw materials into a ball milling tank, taking zirconia balls as a ball milling medium, taking absolute ethyl alcohol as a medium, taking glycerol trioleate as a dispersing agent, mixing the raw materials in a ball-material ratio of 4:1, ball-milling the raw materials for 5 to 6 hours by using a planetary ball mill to obtain a dispersion suspension, drying the suspension, carrying out heat treatment at the temperature of 600 ℃ for 4 hours, adding a doping raw material, taking erbium trioxide and niobium pentoxide as raw materials, and mixing the raw materials according to a proportion ErNbO4Weighing raw materials with a doping ratio of 0.8%, ball-milling for 4-5h again, sintering at 1050 ℃ and keeping the temperature for 3h, cooling and then crushing to obtain ceramic micro powder with a particle size of below 5 mu m;
s2 preparation of diaphragm
60 parts by weight of polypropylene fiber and 40 parts by weight of cellulose fiber are put into a beater, are defibered by adding water, the percentage concentration of the fiber is controlled to be 0.2-0.5%, polyacrylamide with the volume concentration of 1% is added, the mixture is beaten until the mixture is completely dispersed, 35 parts by weight of ceramic micro powder is added, the mixture is uniformly mixed, wet papermaking and cutting are carried out to obtain the diaphragm, then a ceramic coating is coated, 1-1.5 parts by weight of ceramic micro powder is taken to be dispersed in polyvinyl alcohol to obtain a coating liquid, the coating liquid is coated on the diaphragm, and the diaphragm containing the ceramic coating is obtained by calendaring treatment;
the purity contents of the raw materials of barium titanate, barium carbonate, titanium dioxide, bismuth oxide, ferric oxide, erbium trioxide and niobium pentoxide are all more than 99%;
the fiber length of the polypropylene fiber is 1-10mm, the titer is 0.2-0.6detx, and the fiber length of the cellulose fiber is 1-10 mm;
the electrode material is prepared from the following components in percentage by weight: conductive carbon black: the electrolyte is prepared from 85 weight percent to 5 weight percent to 10 weight percent of tetraethylammonium tetrafluoroborate.
The average pore diameter of the diaphragm of the embodiment is 0.16-0.17 μm, the porosity is 70%, the liquid absorption rate is 572%, the working voltage is 3V, the specific capacitance is 290F/g, and the power density can reach 0.07 Wh/g.
Example 3
On the basis of embodiment 2, the electrode material of the electrode is a carbonized nitrogen-doped graphene grafted composite PMMA material;
the preparation method of the carbonized nitrogen-doped graphene grafted composite PMMA material comprises the following steps:
s1, nitrogen-doped graphene
Ultrasonically dispersing graphene oxide in absolute ethyl alcohol, wherein the material-liquid ratio is 0.7g/L, adding urea with the mass of 1% of that of a solution system as a nitrogen source, continuing ultrasonic treatment to uniformly disperse the solution system, performing hydrothermal reaction in a hydrothermal reaction kettle for 8 hours at the reaction temperature of 150 ℃ and 200 ℃, centrifugally separating out a product after self-cooling, sequentially washing with absolute ethyl alcohol and distilled water, and crushing for later use after vacuum drying;
s2 graphene grafted composite PMMA
Dispersing the nitrogen-doped graphene prepared by S1 in dimethylformamide, wherein the material-liquid ratio is 0.8-1g/L, adding methyl methacrylate with the mass 35 times that of the nitrogen-doped graphene, uniformly mixing, adding benzoyl peroxide with the mass 0.2-0.3 time that of the nitrogen-doped graphene, stirring at the rotating speed of not higher than 100rpm, heating and reacting at 80 ℃ for 12h, removing a heat source, self-cooling the system, adding absolute ethyl alcohol with the volume twice that of the solution, uniformly stirring, centrifugally separating and precipitating, washing with absolute ethyl alcohol and distilled water in sequence, and vacuum drying;
s3, carbonization
And (3) carbonizing the product prepared in the step (S2) in an atmosphere furnace, heating to 300 ℃ at a heating rate of 10-20 ℃/min under a flowing nitrogen protection atmosphere, heating to 700 ℃ at a heating rate of 5-10 ℃/min, mixing 5% of carbon dioxide and 8% of water vapor into the atmosphere, preserving heat for 2h, and cooling to obtain the carbonized nitrogen-doped graphene grafted composite PMMA material.
The electrode material and a binder LA132 are subjected to ultrasonic dispersion in ethanol-water to form uniform slurry, the slurry is uniformly coated on a current collector, the thickness of the slurry is 10 micrometers, the electrolyte is tetraethylammonium tetrafluoroborate, the working voltage of the electrolyte can reach 50V, the specific capacitance can reach 497F/g, and the power density can reach 0.26 Wh/g.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. The utility model provides a low noise is resisted and is broken through ultracapacitor system, its characterized in that includes shell, at least one capacitor cell of series connection, the capacitor cell includes first electrode, second electrode and sets up the diaphragm between first electrode and the second electrode, first electrode, second electrode and diaphragm setting are in electrolyte, first electrode and second electrode include respectively the mass flow body and are formed electrode material on the mass flow body, the diaphragm is mixed for ceramic miropowder and is beaten the electrode material on the mass flow bodyThe mixed polypropylene-cellulose paper is characterized in that the ceramic micro powder is Er and Nb doped BiFeO3-BaTiO3The shell of the capacitor is wrapped with heat-conducting sound-absorbing cotton;
the preparation method of the diaphragm comprises the following steps:
50-65 parts of polypropylene fiber and 35-50 parts of cellulose fiber by weight are put into a beater, are added with water for defibering, the percentage concentration of the fiber is controlled to be 0.2-0.5%, polyacrylamide with the volume concentration of 1% is added, the mixture is beaten until the mixture is completely dispersed, 30-45 parts of ceramic micro powder by weight are added, the mixture is uniformly mixed, and the diaphragm is prepared by wet papermaking and cutting;
wherein the fiber length of the polypropylene fiber is 1-10mm, the titer is 0.2-0.6detx, and the fiber length of the cellulose fiber is 1-10 mm.
2. The low-noise breakdown-resistant supercapacitor according to claim 1, wherein the current collector is graphite or Al or Ni or Cu or Mg or Ti or Pt.
3. The low-noise breakdown-resistant supercapacitor according to claim 1, wherein the preparation method of the ceramic micropowder comprises the following steps:
barium titanate, barium carbonate, titanium dioxide, bismuth oxide and ferric oxide are used as raw materials according to the proportion of 0.6BiFeO3-0.4BaTiO3Weighing raw materials, putting the raw materials into a ball milling tank, taking zirconia balls as a ball milling medium, absolute ethyl alcohol as a medium and triolein as a dispersing agent, wherein the ball-material ratio is 4:1-5:1, carrying out ball milling for 4-12h by using a planetary ball mill to obtain a dispersion suspension, drying, and carrying out heat treatment for 4h at 600 ℃; adding doping raw materials, taking erbium trioxide and niobium pentoxide as raw materials according to the proportion ErNbO4Weighing the raw materials, wherein the doping proportion is not higher than 1%, performing ball milling for 4-6h, sintering at the temperature of 1000 ℃ and 1100 ℃ for 3h, cooling, and crushing to obtain ceramic micropowder with the particle size of below 5 mu m.
4. The low-noise breakdown-resistant supercapacitor according to claim 3, wherein the purity contents of the raw materials of barium titanate, barium carbonate, titanium dioxide, bismuth oxide and iron oxide are all more than 99%.
5. The low-noise breakdown-resistant supercapacitor according to claim 1, wherein the separator further comprises a ceramic coating, and the preparation method comprises the steps of dispersing 1-1.5 parts by weight of ceramic micropowder in polyvinyl alcohol to obtain a coating solution, coating the coating solution on the separator, and performing calendaring treatment to obtain the separator comprising the ceramic coating.
6. The low-noise breakdown-resistant supercapacitor according to claim 1, wherein the electrode material of at least one electrode is a carbonized graphene grafted composite PMMA material.
7. The low-noise breakdown-resistant supercapacitor according to claim 6, wherein the carbonized graphene grafted composite PMMA material is a carbonized nitrogen-doped graphene grafted composite PMMA material.
8. The low-noise breakdown-resistant supercapacitor according to claim 7, wherein the preparation of the carbonized nitrogen-doped graphene grafted composite PMMA material comprises the following steps:
s1, nitrogen-doped graphene
Ultrasonically dispersing graphene oxide in absolute ethyl alcohol, wherein the material-liquid ratio is 0.6-1g/L, adding urea with the mass of 1% of that of a solution system as a nitrogen source, continuing ultrasonic treatment to uniformly disperse the solution system, putting the solution system into a hydrothermal reaction kettle for hydrothermal reaction for 6-12h at the reaction temperature of 150 ℃ and 200 ℃, centrifugally separating out a product after self-cooling, washing the product with absolute ethyl alcohol and distilled water in sequence, drying the product in vacuum and crushing the product for later use;
s2 graphene grafted composite PMMA
Dispersing the nitrogen-doped graphene prepared by S1 in dimethylformamide, adding methyl methacrylate with the mass of 20-50 times of the nitrogen-doped graphene according to the feed-liquid ratio of 0.8-1g/L, uniformly mixing, adding benzoyl peroxide with the mass of 0.2-0.3 time of the nitrogen-doped graphene, stirring at the rotating speed of not higher than 100rpm, heating to react for 12-16h at 80 ℃, removing a heat source, self-cooling the system, adding absolute ethyl alcohol with the volume twice of the solution, uniformly stirring, centrifugally separating and precipitating, sequentially washing with absolute ethyl alcohol and distilled water, and vacuum drying;
s3, carbonization
And (3) carbonizing the product prepared by the S2 in an atmosphere furnace, heating to 300 ℃ at a heating rate of 10-20 ℃/min under a flowing nitrogen protection atmosphere, heating to 700 ℃ at a heating rate of 5-10 ℃/min, mixing 2-5% of carbon dioxide and 5-10% of water vapor into the atmosphere, preserving heat for 2h, and cooling to obtain the carbonized nitrogen-doped graphene grafted composite PMMA material.
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JP6349021B1 (en) * 2016-10-17 2018-06-27 三菱製紙株式会社 Electrochemical element separator and electrochemical element including the same
CN109065813A (en) * 2018-08-07 2018-12-21 长沙理工大学 Lithium ion battery diaphragm with thermal closing function, preparation method and application

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Denomination of invention: A Low Noise Anti breakdown Supercapacitor

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