CN104900418A - Electrode material of super capacitor, preparation method and application of electrode material - Google Patents
Electrode material of super capacitor, preparation method and application of electrode material Download PDFInfo
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- 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
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- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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 belongs to the electrode material technical field and relates to an electrode material of a super capacitor with high specific volumetric capacity, a preparation method and application of the electrode material; grapheme and metallic oxide nano-particles are composited so as to form the electrode material of the super capacitor, a large number of holes being distributed in the surface of the graphite; and the density of the composite material is greater than that 1/gcm3. Compared with the prior art, the density of the composite material is high; since a large number of holes are formed in the surface of the graphite in the composite material, even if the electrode material is under a high-density state, electrolyte and the metallic oxide can fully contact with each other, and are subjected to an electrochemical reaction, and fast diffusion paths can be provided for ions in the electrolyte, and therefore, the electrode material can have high specific volumetric capacity and favorable charging and discharging performance.
Description
Technical field
The present invention relates to the technical field of electrode material, particularly a kind of electrode material of ultracapacitor and preparation method, application.
Background technology
Ultracapacitor, as one of most important energy storing device, has power density high, the significant advantage had extended cycle life, but its energy density is low.The ultracapacitor that exploitation high-energy-density has high power density concurrently is focus and the difficult point of current capacitor industry.The electrode material of exploitation high power capacity is the key of preparation high-energy density super capacitor.
Graphene is due to the two-dimensional nanostructure of its uniqueness, high surface area, excellent chemical stability, wide electrochemical window, remarkable electricity and thermal property, and be easily processed into the excellent properties such as fexible film, be considered to a kind of desirable electrode material for super capacitor.Graphene is mainly through forming electric double layer energy storage at electrode/electrolyte interface, and its theoretical ratio capacitance is at 550F/g.Comparatively speaking, the transition metal oxide electrode material based on redox reaction energy storage has higher theoretical capacity, such as, and MnO
2ratio capacitance reaches 1370F/g, but the poor electric conductivity of the transition metal oxide of these high power capacity, thus limit quick storage and the release of energy.The Graphene compound of transition metal oxide and high conductivity is expected the defect overcoming one-component, obtains high power capacity electrode material for super capacitor.
The performance of electrode of super capacitor commonly uses specific discharge capacity evaluation, but obtain more and more thinner along with many portable design of electronic products, volume is more and more less, space for depositing energy storage device is extremely limited, therefore uses volume and capacity ratio (electricity stored in unit volume space) to evaluate super capacitor material performance and just becomes particularly important.From formula Q=Cg × p (Q: the electricity that unit volume stores, Cg: specific discharge capacity, p: the density of electrode) known, want to obtain high-volume and capacity ratio, need the density improving electrode, but this can cause the utilized surface area of electrode reduce and electrolyte intermediate ion diffusion velocity in the electrodes slack-off, finally cause the specific capacity of device and power density to diminish.For current graphene/metal oxide electrode material, due to the two-dimentional lamellar structure of Graphene, its tightly packed electrolyte that will limit in the material fully contacts with metal oxide, and hinder electrolyte intermediate ion fast transferring in whole electrode material, cause the capacity of device and charge-discharge performance not good.
Summary of the invention
The object of the invention is the electrode material providing a kind of ultracapacitor, to solve existing graphene/metal oxide electrode material, due to the two-dimentional lamellar structure of Graphene, its tightly packed electrolyte that will limit in the material fully contacts with metal oxide, and hinder electrolyte intermediate ion fast transferring in whole electrode material, cause the capacity of device and charge-discharge performance not good, and the technical matters that volume and capacity ratio is not high.
Another object of the present invention is to provide the preparation method of the electrode material of above-mentioned ultracapacitor, to solve existing graphene/metal oxide electrode material, due to the two-dimentional lamellar structure of Graphene, its tightly packed electrolyte that will limit in the material fully contacts with metal oxide, and hinder electrolyte intermediate ion fast transferring in whole electrode material, cause the capacity of device and charge-discharge performance not good, and the technical matters that volume and capacity ratio is not high.
Another object of the present invention is to provide the electrode material of above-mentioned ultracapacitor preparing the application in ultracapacitor.
The object of the invention is realized by following technical scheme:
An electrode material for ultracapacitor, comprise porous graphene/metal oxide nanoparticles composite material, the density of described composite material is greater than 1g/cm
3.
Preferably, the density of described composite material is 1.1-3g/cm
3.
Preferably, described composite material comprises porous graphene and metal oxide nanoparticles, and the content of described porous graphene is 0.1wt%-70wt%.
Preferably, described composite material comprises porous graphene, metal oxide nanoparticles and adhesive.
Preferably, described metal oxide nanoparticles is selected from MnO
2nano particle, Ni (OH)
2nano particle, NiO nano particle, RuO
2nano particle, TiO
2nano particle or CuO nano particle wherein one or more.
The preparation method of the electrode material of above-mentioned ultracapacitor, comprises the following steps:
A. porous graphene/metal oxide nanoparticles composite material is prepared;
B. by the compacting under press of described composite material, the pressure of described press is 1-200Mpa, obtains density and is greater than 1g/cm
3electrode material.
Preferably, described step a comprises further:
A1. make graphenic surface form hole with etching agent and obtain porous graphene;
A2. porous graphene and metal oxide nanoparticles compound are obtained porous graphene/metal oxide nanoparticles composite material.
Preferably, described step a comprises further:
A1. Graphene and metal oxide nanoparticles are compounded to form graphene/metal oxide nano particle composite material;
A2. again the Graphene in described graphene/metal oxide nano particle composite material is etched into porous graphene and obtains porous graphene/metal oxide nanoparticles composite material.
Preferably, described step a comprises further:
Porous graphene and metal oxide nanoparticles compound are obtained porous graphene/metal oxide nanoparticles composite material.
Preferably, described step a comprises further:
In the dispersion of porous graphene, with slaine or organo-metallic compound for precursor, obtain corresponding metal oxide nanoparticles by thermal decomposition or hydrolysis and obtain porous graphene/metal oxide nanoparticles composite material with described porous graphene compound, this complex method can avoid metal oxide nanoparticles to reunite.
Preferably, adhesive is added described composite material before being also included in compacting in described step b and the step of mixing.Adding adhesive can make combination between combination electrode material particle more firm, and is easy to combine closely with the metal collector such as Copper Foil.
Preferably, described composite steps comprises:
By metal oxide nanoparticles and Graphene or porous graphene mechanical mixture.
The electrode material of above-mentioned ultracapacitor is preparing the application in ultracapacitor.
Described porous graphene can etch Graphene by a kind of in the etching agents such as oxygen, carbon dioxide, potassium hydroxide, hydrogen peroxide, potassium permanganate, nitric acid or their mixture and obtain.
Metal oxide nanoparticles can by its precursor, and as manganese chloride, manganese nitrate, potassium permanganate, titanate esters, titanium tetrachloride, titanium trichloride, nickel oxalate, nickel acetate, cobalt nitrate and ammonium hexa-fluorotitanate etc. generate through thermal decomposition or hydrolysis.
Compared with prior art, the present invention has following beneficial effect:
1, the porous graphene of electrode material of the present invention is owing to having a large amount of holes, electrolyte can fully be contacted with metal oxide, metal oxide materials can be made full use of for electrochemical reaction, and provide rapid diffusion passage for electrolyte intermediate ion, electrode material is made to have high volume capacity and have high power density, and have preferably charge-discharge performance, and the density of electrode material is high.
2, electrode material of the present invention is compounded to form by porous graphene and metal oxide, all penetrating to electrolyte in all directions, electrode material refers to the ion in electrolyte not by the obstruction of graphene film Rotating fields in all directions to electrolyte is all penetrating, both also can contact to participate in electrochemical reaction through the hole of graphenic surface with metal oxide in the space between graphene sheet layer, thus improve capacity and the charge-discharge performance of ultracapacitor.
3, the porous graphene in electrode material of the present invention can improve the electric conductivity of electrode, particularly due to hole that porous graphene surface distributed is a large amount of, electrolyte intermediate ion can by the diffusion of hole fast in whole electrode and transmission and with metal oxide generation electrochemical reaction, thus significantly improve quality and the volume and capacity ratio of ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of porous graphene/metal oxide nano composite material;
Fig. 2 is the transmission electron microscope photo of porous graphene prepared by embodiment 1.
Embodiment
Further specific descriptions will be done to the present invention below by specific embodiment.
In high density porous graphene/metal oxide nano combination electrode material provided by the invention, as shown in Figure 1, the surface distributed of porous graphene has a large amount of holes, this hole is that electrolyte provides guarantee with fully contacting of metal oxide, and provides rapid diffusion passage for electrolyte ion.This porous graphene can prepare by the method for etchant, and etching agent can select oxygen, carbon dioxide, potassium hydroxide, hydrogen peroxide, potassium permanganate, nitric acid etc., preferred potassium hydroxide and hydrogen peroxide.
When the present invention prepares porous graphene/metal oxide nano combination electrode material, first Graphene can be etched into porous graphene, again with metal oxide nanoparticles compound, also first Graphene and metal oxide compound can be etched into porous graphene Graphene again.
In order to improve the density of electrode material, the present invention under high pressure suppresses electrode material and obtains highdensity electrode material, and the density of electrode material is at least greater than 1g/cm
3, pressure is 1-200Mpa.
In order to prepare porous graphene/metal oxide nano combination electrode material, first can prepare (or purchase obtains) metal oxide nanoparticles, again with porous graphene mechanical mixture, prepare nano composite material, wherein the content of porous graphene in porous graphene/metal oxide nano combination electrode material is 0.1wt%-70wt%.In order to avoid metal oxide nanoparticles is reunited, also can in the dispersion of porous graphene, with slaine or organo-metallic compound for precursor, obtain corresponding metal oxide nanoparticles by thermal decomposition or hydrolysis and with porous graphene compound.These slaines and organic metal organic compound modal be manganese chloride, manganese nitrate, potassium permanganate, titanate esters, titanium tetrachloride, titanium trichloride, nickel oxalate, nickel acetate and cobalt nitrate etc.
The nanometer combined electrode material that the present invention prepares, can be used for water be solvent electrolyte in, or with carbonic ester etc. in the organic electrolyte of solvent, also may be used for polymer such as polyvinyl alcohol is in electrolytical solid electrolyte.
Be below specific embodiment:
But the preparation of following examples porous graphite used, metal oxide nanoparticles oneself, also can buy and obtain.
Embodiment 1
First synthesize graphite oxide: get 1g native graphite, add 0.75g NaNO
3the concentrated sulfuric acid with 70ml, is stirred to dissolve, and is then placed in ice-water bath, after slowly adding 5g potassium permanganate, is warming up to room temperature, slowly adds deionized water and be about 200ml after continuing to stir 3h.After temperature is down to room temperature, under 4000 revs/min centrifugal three times, collecting precipitation thing, load in bag filter, dialysis is except the impurity such as disacidify and salt in deionized water, obtains graphite oxide.
The synthesis of porous graphene: get the above-mentioned graphite oxide 100mg prepared, be dispersed in 50ml deionized water, add the hydrogen peroxide that 10ml concentration is 0.3%, be placed in water heating kettle, take out after reacting 8h at 180 DEG C, by washed with de-ionized water, obtain porous graphene, the transmission electron microscope photo of porous graphene as shown in Figure 2.
The preparation of porous graphene/metal oxide nanoparticles composite material: get the above-mentioned porous graphene 10mg prepared and be dispersed in 50mlN-methyl pyrrole promise alkane ketone, after ultrasonic 20 minutes, add the MnO of 0.1g
2nano particle, after ultrasonic 10 minutes, mechanical agitation 1h mixes, centrifugal, collecting precipitation thing, dries, obtains porous graphene/MnO
2nano particle composite material.
Porous graphene/the MnO prepared
2add polytetrafluoroethyl-ne aqueous solution (adhesive) in nano particle composite material, be mixed into paste, then under 150MP, be pressed into film with press, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.Electrolyte is the H of 1M
2sO
4solution, electrode material is close to electrically conductive graphite sheet surface, and centre barrier film separates two electrodes.Electrode test result is: quality electric capacity is 457F/g, and electrode material density is 1.64g/cm
3, volumetric capacitance is 750F/cm
3.Also adhesive can not be added in the preparation process of above-mentioned electrode material.
Embodiment 2
Graphite oxide is according to the method preparation in embodiment 1.Getting the graphite oxide 20mg prepared is dispersed in 150ml water, after ultrasonic 20 minutes, adds the MnO of 0.1g
2nano particle, after ultrasonic 10 minutes, mechanical agitation 1h mixes, centrifugal, collecting precipitation thing, dries, obtains nano composite material.100mg nano composite material is immersed in 50ml deionized water, adds the hydrogen peroxide that 10ml concentration is 0.3%, be placed in water heating kettle, take out after reacting 8h at 180 DEG C, by washed with de-ionized water, obtain porous graphene/MnO
2nano particle composite material, the content of porous graphene is 0.3wt%.Porous graphene/the MnO prepared
2add polytetrafluoroethyl-ne aqueous solution (adhesive) in nano particle composite material, be mixed into paste, then under 100MP, be pressed into film, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.Electrolyte is the H of 1M
2sO
4solution, electrode material is close to electrically conductive graphite sheet surface, and centre barrier film separates two electrodes.Electrode test result is: quality electric capacity is 498F/g, and electrode material density is 1.67g/cm
3, volumetric capacitance is 830F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
Embodiment 3
Graphite oxide and porous graphene are prepared, when preparing porous graphene/metal oxide nanoparticles composite material, with Ni (OH) according to the method in embodiment 1
2nano particle replaces MnO
2, prepare porous graphene/Ni (OH) nano particle composite material, the content of porous graphene is 0.1wt%.
The Kynoar (being dissolved in N-methyl pyrrole promise alkane ketone) of 1% is added in porous graphene/Ni (OH) nano particle composite material prepared, Kynoar is as adhesive, be mixed into paste, then under 50MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 110 DEG C, for electro-chemical test.Electrolyte is the KOH solution of 1M, and Ag/AgCl is reference electrode, and electrode material is close to stainless steel substrates surface as work electrode.Electrode test result is: quality electric capacity is 436F/g, and electrode material density is 1.43g/cm
3, volumetric capacitance is 625F/cm
3(sweep speed 1mV/s).Also adhesive can not be added in the preparation process of electrode material.
Embodiment 4
Graphite oxide and porous graphene, according to method preparation in embodiment 1, when preparing porous graphene/metal oxide nanoparticles composite material, replace the Ni (OH) of one-component by NiO and Ni (OH) mix nanoparticles
2, the mass ratio of NiO and Ni (OH) is 1:10, prepares porous graphene/NiO nano particle/Ni (OH) nano particle composite material, and the content of porous graphene is 70wt%.
The polytetrafluoroethyl-ne aqueous solution of 1% is added in the porous graphene prepared/NiO nano particle/Ni (OH) nano particle composite material, polytetrafluoroethyl-ne aqueous solution is as adhesive, be mixed into paste, then under 50MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 110 DEG C, for electro-chemical test.Electrolyte is the KOH solution of 1M, and Ag/AgCl is reference electrode, and electrode material is close to stainless steel substrates surface as work electrode.Electrode test result is: quality electric capacity is 345F/g, and electrode material density is 1.5g/cm
3, volumetric capacitance is 520F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
Embodiment 5
Graphite oxide and porous graphene, according to method preparation in embodiment 1, when preparing porous graphene/metal oxide nanoparticles composite material, use RuO
2replace MnO
2, prepare porous graphene/RuO
2nano particle composite material, the content of porous graphene is 10wt%.
Porous graphene/the RuO prepared
2add the polytetrafluoroethyl-ne aqueous solution of 1% in nano particle composite material, polytetrafluoroethyl-ne aqueous solution, as adhesive, is mixed into paste, then under 200MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.Electrolyte is the H of 1M
2sO
4solution, saturated calomel electrode is reference electrode, and electrode material is close on electrically conductive graphite sheet as work electrode.Electrode test result is: quality electric capacity is 415F/g, and electrode material density is 1.74g/cm
3, volumetric capacitance is 725F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
Embodiment 6
In-situ chemical synthetic method prepares porous graphene/metal oxide nanoparticles composite material.Graphite oxide and porous graphene are according to method preparation in embodiment 1.Porous graphene ultrasonic disperse is in the DMF solvent of 20ml (porous graphene is about 0.2mg/ml), add the nickel acetate aqueous solution of 2ml0.2M, react 1h at 80 DEG C after, at 180 DEG C, react 12h further, prepare porous graphene/Ni (OH)
2nano particle composite material.
Porous graphene/the Ni (OH) prepared
2add the polytetrafluoroethyl-ne aqueous solution of 1% in nano particle composite material, polytetrafluoroethyl-ne aqueous solution, as adhesive, is mixed into paste, then under 1MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.Electrolyte is the KOH solution of 1M, and Ag/AgCl is reference electrode, and electrode material is close to stainless steel substrates surface as work electrode, and electrode material density is 1.32g/cm
3.Electrode test result is: quality electric capacity is 650F/g, and volumetric capacitance is 860F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
Embodiment 7
Graphite oxide and porous graphene are according to method preparation in embodiment 1.25mg porous graphene ultrasonic disperse, in the deionized water of 600ml, adds potassium permanganate, and the solubility of potassium permanganate is 0.5mM, collect reactant after at room temperature stirring 1h, at 80 DEG C, within 24 hours, dry, further 350 times bakings, obtain porous graphene/MnO
2nano particle composite material.Porous graphene/the MnO prepared
2add the polytetrafluoroethyl-ne aqueous solution of 1% in nano particle composite material, polytetrafluoroethyl-ne aqueous solution, as adhesive, is mixed into paste, then under 200MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.Electrolyte is the H of 1M
2sO
4solution, electrode material is close to electrically conductive graphite sheet surface, and centre barrier film separates two electrodes.Electrode test result is: quality electric capacity is 478F/g, and electrode material density is 1.57g/cm
3, volumetric capacitance is 750F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
Embodiment 8
Graphite oxide and porous graphene, according to method preparation in embodiment 1, during preparation nano composite material, use RuO
2replace MnO
2, prepare porous graphene/RuO
2nano particle composite material, the content of porous graphene is 5wt%.
Do not need adhesive, directly under 200Mpa, the nanometer combined electrode material prepared is pressed together on graphite sheet, and cut into 1/4 inch as electrode, dry at 120 DEG C, for electro-chemical test.Electrolyte is the H of 1M
2sO
4solution, saturated calomel electrode is reference electrode.Electrode test result is: quality electric capacity is 427F/g, and electrode material density is 3g/cm
3, volumetric capacitance is 1281F/cm
3.
Embodiment 9
Graphite oxide and porous graphene, according to method preparation in embodiment 1, when preparing porous graphene/metal oxide nanoparticles composite material, replace MnO with NiO
2, prepare porous graphene/NiO nano particle composite material, the content of porous graphene is 70wt%.
The polytetrafluoroethyl-ne aqueous solution of 1% is added in the porous graphene prepared/NiO nano particle composite material, polytetrafluoroethyl-ne aqueous solution is as adhesive, be mixed into paste, then under 1MP, film is pressed into, cut into the electrode of 1/4 inch, dry at 120 DEG C, for electro-chemical test.For electro-chemical test.Electrolyte is the KOH solution of 1M, and Ag/AgCl is reference electrode, and electrode material is close to stainless steel substrates surface as work electrode.Electrode test result is: quality electric capacity is 470F/g, and electrode material density is 1.1g/cm
3, volumetric capacitance is 470F/cm
3.Also adhesive can not be added in the preparation process of electrode material.
The porous graphene of electrode material of the present invention is owing to having a large amount of holes, even if make electrode material under high-density state, electrolyte and metal oxide also can fully contact, metal oxide materials can be made full use of for electrochemical reaction, and provide rapid diffusion passage for electrolyte intermediate ion, make electrode material have high volume capacity and have high power density.
Electrode material of the present invention is compounded to form by porous graphene and metal oxide, all penetrating to electrolyte in all directions, electrode material refers to the ion in electrolyte not by the obstruction of graphene film Rotating fields in all directions to electrolyte is all penetrating, both also can contact to participate in electrochemical reaction through the hole of graphenic surface with metal oxide in the space between graphene sheet layer, thus improve capacity and the charge-discharge performance of ultracapacitor.
The density of electrode material of the present invention is high, the hole that Graphene in electrode material is a large amount of because surface has, even if under making electrode material be in high-density state, electrolyte and metal oxide also can fully contact generation electrochemical reaction, and provide rapid diffusion passage for electrolyte intermediate ion, make electrode material have high-volume and capacity ratio and preferably charge-discharge performance.
Porous graphene in electrode material of the present invention can improve the electric conductivity of electrode, particularly due to hole that porous graphene surface distributed is a large amount of, electrolyte intermediate ion can by the diffusion of hole fast in whole electrode and transmission and with metal oxide generation electrochemical reaction, thus significantly improve quality and the volume and capacity ratio of ultracapacitor.
Be only several specific embodiments of the application above, but the application is not limited thereto, the changes that any person skilled in the art can think of, all should drops in the protection range of the application.
Claims (13)
1. an electrode material for ultracapacitor, is characterized in that, comprise porous graphene/metal oxide nanoparticles composite material, the density of described composite material is greater than 1g/cm
3.
2. the electrode material of ultracapacitor as claimed in claim 1, it is characterized in that, the density of described composite material is 1.1-3g/cm
3.
3. the electrode material of ultracapacitor as claimed in claim 1 or 2, it is characterized in that, described composite material comprises porous graphene and metal oxide nanoparticles, and the content of described porous graphene is 0.1wt%-70wt%.
4. the electrode material of ultracapacitor as claimed in claim 1 or 2, it is characterized in that, described composite material comprises porous graphene, metal oxide nanoparticles and adhesive.
5. the electrode material of the ultracapacitor as described in claim 3 or 4, is characterized in that, described metal oxide nanoparticles is selected from MnO
2nano particle, Ni (OH)
2nano particle, NiO nano particle, RuO
2nano particle, TiO
2nano particle or CuO nano particle wherein one or more.
6. the preparation method of the electrode material of the ultracapacitor in claim 1-5 described in any one, is characterized in that, comprises the following steps:
A. porous graphene/metal oxide nanoparticles composite material is prepared;
B. by the compacting under press of described composite material, the pressure of described press is 1-200Mpa, obtains density and is greater than 1g/cm
3electrode material.
7. the preparation method of the electrode material of ultracapacitor as claimed in claim 6, it is characterized in that, described step a comprises further:
A1. make graphenic surface form hole with etching agent and obtain porous graphene;
A2. porous graphene and metal oxide nanoparticles compound are obtained porous graphene/metal oxide nanoparticles composite material.
8. the preparation method of the electrode material of ultracapacitor as claimed in claim 6, it is characterized in that, described step a comprises further:
A1. Graphene and metal oxide nanoparticles are compounded to form graphene/metal oxide nano particle composite material;
A2. again the Graphene in described graphene/metal oxide nano particle composite material is etched into porous graphene and obtains porous graphene/metal oxide nanoparticles composite material.
9. the preparation method of the electrode material of ultracapacitor as claimed in claim 6, it is characterized in that, described step a comprises further:
Porous graphene and metal oxide nanoparticles compound are obtained porous graphene/metal oxide nanoparticles composite material.
10. the preparation method of the electrode material of ultracapacitor as claimed in claim 6, it is characterized in that, described step a comprises further:
In the dispersion of porous graphene, with slaine or organo-metallic compound for precursor, obtain corresponding metal oxide nanoparticles by thermal decomposition or hydrolysis and obtain porous graphene/metal oxide nanoparticles composite material with described porous graphene compound.
The preparation method of the electrode material of 11. ultracapacitors as claimed in claim 6, is characterized in that, adhesive is added described composite material and the step of mixing in described step b before being also included in compacting.
12. as the preparation method of the electrode material of the ultracapacitor in claim 7-9 as described in any one, and it is characterized in that, described composite steps comprises:
By metal oxide nanoparticles and Graphene or porous graphene mechanical mixture.
The electrode material of the ultracapacitor in 13. claim 1-5 described in any one is preparing the application in ultracapacitor.
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| CN105390298A (en) * | 2015-12-11 | 2016-03-09 | 中航锂电（洛阳）有限公司 | Lithium ion capacitor negative unit, cell and lithium ion capacitor |
| CN106298285A (en) * | 2016-09-26 | 2017-01-04 | 安徽师范大学 | A kind of nickel hydroxide@manganese dioxide nucleocapsid heterogeneous structural nano chip arrays material of growth, preparation method and applications on carbon cloth |
| CN109148162A (en) * | 2018-10-08 | 2019-01-04 | 中车青岛四方车辆研究所有限公司 | A kind of TiO for supercapacitor2With CuO composite porous material and preparation method thereof |
| CN109950457A (en) * | 2017-12-21 | 2019-06-28 | 北京金羽新能科技有限公司 | A kind of water system ion energy storage device |
| CN113496823A (en) * | 2020-03-18 | 2021-10-12 | 天津理工大学 | Symmetric hybrid supercapacitor and application thereof |
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| CN103137957A (en) * | 2013-02-27 | 2013-06-05 | 中国石油大学(北京) | Porous graphene-metal oxide composite material and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105390298A (en) * | 2015-12-11 | 2016-03-09 | 中航锂电（洛阳）有限公司 | Lithium ion capacitor negative unit, cell and lithium ion capacitor |
| CN106298285A (en) * | 2016-09-26 | 2017-01-04 | 安徽师范大学 | A kind of nickel hydroxide@manganese dioxide nucleocapsid heterogeneous structural nano chip arrays material of growth, preparation method and applications on carbon cloth |
| CN109950457A (en) * | 2017-12-21 | 2019-06-28 | 北京金羽新能科技有限公司 | A kind of water system ion energy storage device |
| CN109148162A (en) * | 2018-10-08 | 2019-01-04 | 中车青岛四方车辆研究所有限公司 | A kind of TiO for supercapacitor2With CuO composite porous material and preparation method thereof |
| CN113496823A (en) * | 2020-03-18 | 2021-10-12 | 天津理工大学 | Symmetric hybrid supercapacitor and application thereof |
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