CN105552318A - Graphene catalyst - Google Patents

Graphene catalyst Download PDF

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CN105552318A
CN105552318A CN201510903543.9A CN201510903543A CN105552318A CN 105552318 A CN105552318 A CN 105552318A CN 201510903543 A CN201510903543 A CN 201510903543A CN 105552318 A CN105552318 A CN 105552318A
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catalyst
solution
adds
barrier film
reaction
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宋宏婷
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a graphene catalyst, and belongs to the field of a catalyst. The graphene catalyst is prepared through three steps, and the step 1 includes: weighing a part of gamma-mercaptopropyltrimethoxy silane, taking a proper amount of absolute ethanol as a solvent, performing uniform mixing, adding phenyltriethoxysilane to the obtained solution according to a mole ratio of gamma-mercaptopropyltrimethoxy silane to phenyltriethoxysilane being 1:1, performing uniform mixing, adding tetraethylammonium hydroxide to the obtained solution according to a mole ratio of gamma-mercaptopropyltrimethoxy silane to tetraethylammonium hydroxide being 1:1.2, performing heating and a reflux reaction for 48h, naturally cooling the reaction to room temperature, evaporating the solvent out through a rotary evaporator to obtain a lime-milk-shaped product, washing the product with a mixed solvent of tetrahydrofuran and methanol, and performing freeze-drying to obtain diamino-POSS. The graphene catalyst can be applied to a lithium polymer battery, and can effectively improve capacity and a working platform of the battery.

Description

Graphen catalyst
Technical field
The present invention relates to a kind of catalyst, particularly graphen catalyst.
Background technology
After trial-produceing successfully change into formula lead acid accumulator from Pu Lai get in 1859, chemical power source enters people's bud.In the evolution of more than 100 years, the chemical power source of new range constantly occurs, the performance of chemical power source is constantly improved.Particularly after World War II, the development of chemical power source is rapider.Created Cd-Ni battery afterwards, the eighties in 20th century creates MH-Ni battery, through the exploration of nearly 20 years, finally lithium ion battery and lithium polymer battery is developed in early 1990s, their development has also been arrived by the commercial stage, and at present, lithium ion battery comes into one's own with its high specific energy density and long service life, rapidly, lithium polymer battery is also given priority in the countries and regions such as the U.S., Japan and Taiwan in development.Lithium polymer battery development is swift and violent, progressively replaces cadmium nickel and Ni-H cell, and the research and development that employing polymer makes electrode and electrolyte are particularly noticeable.But, ionic conductivity and the mechanical strength of current lithium polymer battery are poor, manufacturing process is complicated, battery volume is comparatively large, and battery capacity is inadequate, because positive active material and negative electrode active material easily come off, after long-time use ionic conductivity and electrochemical stability poor, isolation film strength and stability also can change along with the use of battery, and be easy to cause lithium polymer battery aging after a long time use, the life-span of discharge and recharge is very restricted.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, provides one to be applied in lithium polymer battery, effectively improves the capacity of battery and the graphen catalyst of workbench.
The technical solution used in the present invention is as follows:
Graphen catalyst of the present invention, is prepared from by following steps:
Step one: take a γ-mercaptopropyl trimethoxysilane, get appropriate absolute ethyl alcohol as solvent, stir, according to γ-mercaptopropyl trimethoxysilane: phenyl triethoxysilane mol ratio 1:1 adds phenyl triethoxysilane in solution, after stirring, according to γ-mercaptopropyl trimethoxysilane: tetraethyl ammonium hydroxide mol ratio 1:1.2 adds tetraethyl ammonium hydroxide in solution, heating reflux reaction 48h, naturally cool to normal temperature, by Rotary Evaporators, solvent is steamed, obtain lime milky product, by the mixed solution washed product of oxolane and methyl alcohol, under vacuum condition, freeze-drying obtains diamine POSS,
Step 2: take a graphite powder, under the condition of ice bath, add the appropriate concentrated sulfuric acid as solvent, stir, control reaction temperature lower than under the condition of 20 DEG C, according to graphite powder: sodium nitrate: potassium permanganate mass ratio 1:0.5:3 slowly adds sodium nitrate and potassium permanganate in solution, stir 10min; Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid: deionized water volume ratio 1:0.2 adds deionized water in solution, be warming up to 98 DEG C, stir 30min, again according to the concentrated sulfuric acid: deionized water volume ratio 1:0.5 adds deionized water, stop reaction, according to graphite powder: hydrogen peroxide mol ratio 1:0.2 adds the hydrogen peroxide of 5% in solution, centrifugal while hot, respectively with appropriate 5% watery hydrochloric acid and distilled water washing, obtained graphene oxide;
Step 3: take a graphene oxide ultrasonic wave and be scattered in appropriate absolute ethyl alcohol, after stirring, according to graphene oxide: diamine POSS mol ratio 1:12 adds diamine POSS in solution, according to graphene oxide: cyclopentadienyl titanium dichloride mol ratio 1:0.5 adds cyclopentadienyl titanium dichloride in solution, after stirring at room temperature 30min, solution is transferred in reactor, pass into argon gas as protection hermetic seal, at 210 DEG C of reaction 36h, stop reaction, after product is filtered, wash with distilled water, be freeze-drying under the condition of 0.98 again in vacuum degree, obtain oligomeric cagelike silsesquioxane-Graphene.
Graphen catalyst of the present invention, the application of described catalyst in lithium polymer battery.
Owing to have employed technique scheme, electrode adds this appropriate catalyst, can in wider temperature range, the capacity of battery and workbench be made to be improved, particularly when low temperature and heavy-current discharge, thus effectively avoid Li ion to form oxide at electrode passivation, extend the useful life of battery, the catalyst that the present invention uses can ensure that battery all can normally work in the scope of-50 ~ 60 DEG C.
Graphen catalyst of the present invention, described lithium polymer battery comprises the positive plate and negative plate of being located at battery case inside, is provided with barrier film between described positive plate and negative plate; Be provided with positive pole overlay film and anode catalytic net between described positive plate and barrier film successively, described positive pole overlay film is overlying on the surface of positive plate, and described anode catalytic net is overlying on the surface of barrier film; Be provided with negative pole catalysis net and negative pole overlay film between described barrier film and negative plate successively, described negative pole catalysis net is overlying on the surface of barrier film, and described negative pole overlay film is overlying on the surface of negative plate; The thickness of described anode catalytic net is 10 μm, the load of described anode catalytic net has anode catalyst, described anode catalyst is Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer, and the bearing capacity of the online anode catalyst of described anode catalytic is 0.38mg/cm 2; The thickness of described negative pole catalysis net is 10 μm, and the load of described negative pole catalysis net has cathode catalyst, and described cathode catalyst is oligomeric cagelike silsesquioxane-Graphene, and on described negative pole catalysis net, the bearing capacity of cathode catalyst is 0.71mg/cm 2.
Owing to have employed technique scheme, lithium battery is in the process of discharge and recharge, due to overload, passivation is forming oxide on electrode in meeting, thus causing the decline of battery capacity, the efficiency for charge-discharge of electrode reduces, at positive plate and negative plate surface coating, effectively can improve the affinity between electrode and barrier film, increase ionic conducting property, reduce the generation of oxide, thus the useful life of the battery extended.
Graphen catalyst of the present invention, described positive plate is nanometer Rh-graphene combination electrode, and the thickness of described positive plate is 40 μm; Described negative plate is nano Co 2snO 4poly-sulfonic acid naphthalene electrode, the thickness of described negative plate is 50 μm; The described positive plate ratio capacitance that discharges when electric current is 1A/g is 576.3F/g, and the described negative plate ratio capacitance that discharges when electric current is 1A/g is 817.6F/g.
Owing to have employed technique scheme, positive plate material is microstructure, Rh is that porous side's laminated structure is attached to and graphene nanometer sheet is conducive to increase rhodium and electrolytical contact area, improve the utilance of active material, Graphene also contributes to the conductivity improving material simultaneously, improve the battery performance of positive plate, thus improve the operating efficiency of battery.
Graphen catalyst of the present invention, described barrier film is polymer-LiClO 4-Li 4ti 5o 12composite electrolyte, described polymer is polystyrene-ethylene pyrrolidones-styrene triblock copolymer, and the thickness of described barrier film is 40 μm; Described barrier film surface is covered with coat, and described coat is Kynoar-hexafluoropropylene, and the thickness of described coat is 100nm.
Owing to have employed technique scheme, polystyrene-ethylene pyrrolidones-styrene triblock copolymer, as matrix, has stronger polarity, and containing easily forming the group of hydrogen bond, in conjunction with some Small molecular, the conduction efficiency of lithium ion can be improved, ion conductor Li 4ti 5o 12nano particle add the degree of crystallinity reducing polymer, improve the conductivity of polymer dielectric, add at stream subnumber order in polymer, thus improve the operating efficiency of battery; Polystyrene-ethylene pyrrolidones-styrene triblock copolymer has good elasticity, lighter weight simultaneously, and from microcosmic, its molecular structure presents stable network structure, and apparent activation energy is larger.After coating, the hot strength of barrier film strengthens, and increases the adsorption capacity of electronics, and shrinkage reduces, and venting capability slightly reduces, and internal resistance significantly reduces, thus the phenomenon reducing inside battery heating produces, and adds the safety and stability performance of battery.
Graphen catalyst of the present invention, described battery case is made up of soft plastic, and described soft plastic comprises dimethicone 18.5%, talcum powder 7.8%, TPR33%, zinc stearate 2.2%, white carbon 10.2%, boric acid 1.2%, deca-BDE 9.5%, antioxidant 168 is 0.25%, erucyl amide 3.3%, organic siliconresin 14.05%.
Owing to have employed technique scheme, adopt flexiplast when inside battery goes wrong, can to embody timely, show as bulging and can not explode, the material character that the present invention adopts is stablized, ageing-resistant, life cycle is long, improves fail safe and the stability of battery.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
1, prepare and be applied in lithium polymer battery, effectively improve the capacity of battery and the graphen catalyst of workbench, can effectively avoid Li ion to form oxide at electrode passivation, extend the useful life of battery.
2, internal resistance significantly reduces, thus the phenomenon reducing inside battery heating produces, and when inside battery goes wrong, embodies timely, shows as bulging and can not explode, add the safety and stability performance of battery.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation of lithium polymer battery;
Fig. 2 is the SEM figure of positive plate;
Fig. 3 is the SEM figure of negative plate;
Fig. 4 is the SEM figure of polystyrene-ethylene pyrrolidones-styrene triblock copolymer.
Mark in figure: 1 is positive plate, and 2 is negative plate, and 3 is anode catalytic net, and 4 is negative pole catalysis net, and 5 is barrier film, and 6 is battery case, and 7 is positive pole overlay film, and 8 is negative pole overlay film.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
In order to make the object of invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Graphen catalyst, oligomeric cagelike silsesquioxane-Graphene is prepared from by following steps,
Step one: take a γ-mercaptopropyl trimethoxysilane, get appropriate absolute ethyl alcohol as solvent, stir, according to γ-mercaptopropyl trimethoxysilane: phenyl triethoxysilane mol ratio 1:1 adds phenyl triethoxysilane in solution, after stirring, according to γ-mercaptopropyl trimethoxysilane: tetraethyl ammonium hydroxide mol ratio 1:1.2 adds tetraethyl ammonium hydroxide in solution, heating reflux reaction 48h, naturally cool to normal temperature, by Rotary Evaporators, solvent is steamed, obtain lime milky product, by the mixed solution washed product of oxolane and methyl alcohol, under vacuum condition, freeze-drying obtains diamine POSS,
Step 2: take a graphite powder, under the condition of ice bath, add the appropriate concentrated sulfuric acid as solvent, stir, control reaction temperature lower than under the condition of 20 DEG C, according to graphite powder: sodium nitrate: potassium permanganate mass ratio 1:0.5:3 slowly adds sodium nitrate and potassium permanganate in solution, stir 10min; Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid: deionized water volume ratio 1:0.2 adds deionized water in solution, be warming up to 98 DEG C, stir 30min, again according to the concentrated sulfuric acid: deionized water volume ratio 1:0.5 adds deionized water, stop reaction, according to graphite powder: hydrogen peroxide mol ratio 1:0.2 adds the hydrogen peroxide of 5% in solution, centrifugal while hot, respectively with appropriate 5% watery hydrochloric acid and distilled water washing, obtained graphene oxide;
Step 3: take a graphene oxide ultrasonic wave and be scattered in appropriate absolute ethyl alcohol, after stirring, according to graphene oxide: diamine POSS mol ratio 1:12 adds diamine POSS in solution, according to graphene oxide: cyclopentadienyl titanium dichloride mol ratio 1:0.5 adds cyclopentadienyl titanium dichloride in solution, after stirring at room temperature 30min, solution is transferred in reactor, pass into argon gas as protection hermetic seal, at 210 DEG C of reaction 36h, stop reaction, after product is filtered, wash with distilled water, be freeze-drying under the condition of 0.98 again in vacuum degree, obtain oligomeric cagelike silsesquioxane-Graphene.
Embodiment 2
As shown in Figure 1, a kind of polymer battery, comprises the positive plate 1 and negative plate 2 of being located at battery case 6 inside, is provided with barrier film 5 between positive plate 1 and negative plate 2; Be provided with positive pole overlay film 7 and anode catalytic net 3 between positive plate 1 and barrier film 5 successively, positive pole overlay film 7 is overlying on the surface of positive plate 1, and anode catalytic net 3 is overlying on the surface of barrier film 5; Negative pole catalysis net 4 and negative pole overlay film 8 is provided with successively between barrier film 5 and negative plate 2, negative pole catalysis net 4 is overlying on the surface of barrier film 5, negative pole overlay film 8 is overlying on the surface of negative plate 2, and positive pole overlay film 7 connects with anode catalytic net 3, and negative pole overlay film 8 connects with negative pole catalysis net 4.
Positive plate 1 is nanometer Rh-graphene combination electrode, and the thickness of positive plate 1 is 40 μm; Negative plate 2 is nano Co 2snO 4poly-sulfonic acid naphthalene electrode, the thickness of negative plate 2 is 50 μm; Positive plate 1 ratio capacitance that discharges when electric current is 1A/g is 576.3F/g, and negative plate 2 ratio capacitance that discharges when electric current is 1A/g is 817.6F/g.
The thickness of anode catalytic net 3 is 10 μm, and anode catalytic net 3 load has anode catalyst, and anode catalyst is Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer, and on anode catalytic net 3, the bearing capacity of anode catalyst is 0.38mg/cm 2; The thickness of negative pole catalysis net 4 is 10 μm, and negative pole catalysis net 4 load has cathode catalyst, and cathode catalyst is oligomeric cagelike silsesquioxane-Graphene, and on negative pole catalysis net 4, the bearing capacity of cathode catalyst is 0.71mg/cm 2.
Barrier film 5 is polymer-LiClO 4-Li 4ti 5o 12composite electrolyte, polymer is polystyrene-ethylene pyrrolidones-styrene triblock copolymer, and the thickness of barrier film 5 is 40 μm.Barrier film 5 surface is covered with coat, and coat is Kynoar-hexafluoropropylene, and the thickness of coat is 100nm.
Positive pole overlay film 6 is cell nafion proton membrane, and negative pole overlay film 7 is silicon dioxide, and the thickness of positive pole overlay film 6 is 300nm, the thickness 300nm of negative pole overlay film 7.
Battery case 6 is made up of soft plastic, and soft plastic comprises dimethicone 18.5%, talcum powder 7.8%, TPR33%, zinc stearate 2.2%, white carbon 10.2%, boric acid 1.2%, deca-BDE 9.5%, antioxidant 168 is 0.25%, erucyl amide 3.3%, organic siliconresin 14.05%.
Embodiment 3
As shown in Figure 2, nanometer Rh-graphene combination electrode is prepared from by following steps,
Step one: take a graphite powder, under the condition of ice bath, add the appropriate concentrated sulfuric acid as solvent, stir, control reaction temperature lower than under the condition of 20 DEG C, according to graphite powder: sodium nitrate: potassium permanganate mass ratio 1:0.5:3 slowly adds sodium nitrate and potassium permanganate in solution, stir 10min; Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid: deionized water volume ratio 1:0.2 adds deionized water in solution, be warming up to 98 DEG C, stir 30min, again according to the concentrated sulfuric acid: deionized water volume ratio 1:0.5 adds deionized water, stop reaction, according to graphite powder: hydrogen peroxide mol ratio 1:0.2 adds the hydrogen peroxide of 5% in solution, centrifugal while hot, respectively with appropriate 5% watery hydrochloric acid and distilled water washing, obtained graphene oxide;
Step 2: take a Rh(Ac) 3, get proper amount of methanol as solvent, stirring at normal temperature is dissolved, under condition of ice bath, according to rhodium acetate: lithium hydroxide mol ratio 1:1.2 adds LiOHH in solution 2the methanol solution of O, control reaction temperature 0 DEG C and stir 8h, according to rhodium acetate in solution: n-hexane mol ratio 1:20 adds n-hexane in solution, continue to stir 1h, filter, precipitation washs 3 times with distilled water and absolute methanol respectively, is scattered in by product in ethanol, is mixed with the Rh(OH that concentration is 13.7mg/mL) 3alcohol dispersion liquid;
Step 3: take a graphene oxide ultrasonic wave and be scattered in appropriate absolute ethyl alcohol, according to graphene oxide: rhodium hydroxide: urea mol ratio 1:1:0.5 adds the urea-ethanolic solution of alcohol dispersion liquid that concentration is 13.7mg/mL rhodium hydroxide and 5mol/L in solution, after stirring at room temperature 30min, solution is transferred in reactor, pass into argon gas as protection hermetic seal, at 160 DEG C of reaction 24h, stop reaction, after product is filtered, wash with distilled water, be freeze-drying under the condition of 0.98 again in vacuum degree, again product is put into reactor, pass into argon gas and under the condition of 300 DEG C, heat 5.5h as after protection hermetic seal, obtain nanometer Rh-graphene combination electrode.
Embodiment 4
As shown in Figure 3, nano Co 2snO 4poly-sulfonic acid naphthalene electrode is prepared from by following steps,
Step one: take a SnCl 4, get appropriate amount of deionized water as solvent, stirring and dissolving, according to stannic chloride: cobalt chloride mol ratio 1:2 adds CoCl in solution 2according to stannic chloride: NaOH mol ratio 1:10 adds the aqueous solution of NaOH in solution, stirring at normal temperature 10min, is placed in reactor by solution, passes into nitrogen: oxygen 15:1 passes into the mist of nitrogen and oxygen, sealing, under the condition of 240 DEG C, react 30h, naturally cool to room temperature, use deionized water and absolute ethanol washing respectively, be freeze-drying under the condition of 0.98 in vacuum degree, obtain Co 2snO 4powder;
Step 2: take a Co 2snO 4powder, by cobaltous stannate: hydrochloric acid mol ratio 1:15 adds the hydrochloric acid solution of 2mol/L as solvent, stirring and dissolving, according to cobaltous stannate: sulfonic acid naphthalene: potassium peroxydisulfate mol ratio 1:20:5 adds sulfonic acid naphthalene and potassium peroxydisulfate in solution, after ultrasonic wave dispersion 30min, 5min is reacted under power 2000W microwave condition, filter, getting filter residue and use distilled water and absolute ethanol washing filtrate in neutral respectively, is under the condition of 0.98 in vacuum degree, air drying 24h, obtains nano Co 2snO 4poly-sulfonic acid naphthalene.
Embodiment 5
Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer is prepared from by following steps,
Step one: take a 1,2-dicyano-1,2-bis-(2 ', 4 ', 5 '-trimethyl-3 '-thiophene) ethene, get appropriate n-amyl alcohol to dissolve as stirring solvent, according to 1,2-dicyano-1,2-bis-(2 ', 4 ', 5 '-trimethyl-3 '-thiophene) ethene: chromic acetate mol ratio 1:2 adds six water and chromic acetate in solution, adds appropriate DBU catalyst, heating reflux reaction 20h, naturally cool to normal temperature, by Rotary Evaporators, solvent is steamed, obtain Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin polymer;
Step 2: take a Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin polymer, get q. s. methylene chloride and make solvent, ultrasonic wave dispersion 30min, under 5 atmospheric pressure, puts into reactor under the condition of 150 DEG C and heats 5h, naturally cool to normal temperature, filter, spending deionized water, is under the condition of 0.98 in vacuum degree, air drying 24h, obtains Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer.
Embodiment 6
As shown in Figure 4, polymer-LiClO 4-Li 4ti 5o 12composite electrolyte is prepared from by following steps,
Step one: take a styrene, getting appropriate cyclohexane give is solvent, stirring and dissolving, according to styrene: tert-butyl lithium mol ratio 1:1.2 adds tert-butyl lithium in solution, after stirring, put into reactor, be heated to 80 DEG C, reaction 1h, 20 DEG C are cooled to after reaction, according to styrene: vinylpyrrolidone mol ratio 1:1 adds vinylpyrrolidone in solution, stir in backward reactor and pass into nitrogen as protection gas, after being warming up to 240 DEG C of reaction 3h, be cooled to 20 DEG C, again according to vinylpyrrolidone: styrene mol ratio 1:1 adds styrene in solution, stir in backward reactor and pass into nitrogen as protection gas, be warming up to 240 DEG C of reaction 3h, add absolute methanol cessation reaction, solution is poured in absolute ethyl alcohol and precipitates, after filtration, dry under vacuum condition, obtained polystyrene-ethylene pyrrolidones-styrene triblock copolymer,
Step 2: take a LiOH, according to lithium hydroxide: lithium hydroxide solid mixes with titanium dioxide solids by titanium dioxide mol ratio 1:1, be placed in Muffle furnace and be warming up to 800 DEG C and carry out high temperature solid state reaction, after complete reaction, naturally cool taking-up, ball milling sub-sieve obtains Li 4ti 5o 12nano particle;
Step 3: take a polystyrene-ethylene pyrrolidones-styrene triblock copolymer, gets appropriate acetonitrile as solvent, according to polystyrene-ethylene pyrrolidones-styrene triblock copolymer: LiClO after stirring 4mol ratio 20:1 adds LiClO in solution 4, according to LiClO after stirring 4: Li 4ti 5o 12mol ratio 1:1 adds Li in solution 4ti 5o 12nano particle, stirs and obtains white viscous liquid, mucus poured in Teflon mould, freeze-drying under vacuum condition, obtain polymer-LiClO 4-Li 4ti 5o 12composite electrolyte.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. graphen catalyst, is characterized in that being prepared from by following steps:
Step one: take a γ-mercaptopropyl trimethoxysilane, get appropriate absolute ethyl alcohol as solvent, stir, according to γ-mercaptopropyl trimethoxysilane: phenyl triethoxysilane mol ratio 1:1 adds phenyl triethoxysilane in solution, after stirring, according to γ-mercaptopropyl trimethoxysilane: tetraethyl ammonium hydroxide mol ratio 1:1.2 adds tetraethyl ammonium hydroxide in solution, heating reflux reaction 48h, naturally cool to normal temperature, by Rotary Evaporators, solvent is steamed, obtain lime milky product, by the mixed solution washed product of oxolane and methyl alcohol, under vacuum condition, freeze-drying obtains diamine POSS,
Step 2: take a graphite powder, under the condition of ice bath, add the appropriate concentrated sulfuric acid as solvent, stir, control reaction temperature lower than under the condition of 20 DEG C, according to graphite powder: sodium nitrate: potassium permanganate mass ratio 1:0.5:3 slowly adds sodium nitrate and potassium permanganate in solution, stir 10min; Temperature is risen to 35 DEG C, stirring reaction 3h, according to the concentrated sulfuric acid: deionized water volume ratio 1:0.2 adds deionized water in solution, be warming up to 98 DEG C, stir 30min, again according to the concentrated sulfuric acid: deionized water volume ratio 1:0.5 adds deionized water, stop reaction, according to graphite powder: hydrogen peroxide mol ratio 1:0.2 adds the hydrogen peroxide of 5% in solution, centrifugal while hot, respectively with appropriate 5% watery hydrochloric acid and distilled water washing, obtained graphene oxide;
Step 3: take a graphene oxide ultrasonic wave and be scattered in appropriate absolute ethyl alcohol, after stirring, according to graphene oxide: diamine POSS mol ratio 1:12 adds diamine POSS in solution, according to graphene oxide: cyclopentadienyl titanium dichloride mol ratio 1:0.5 adds cyclopentadienyl titanium dichloride in solution, after stirring at room temperature 30min, solution is transferred in reactor, pass into argon gas as protection hermetic seal, at 210 DEG C of reaction 36h, stop reaction, after product is filtered, wash with distilled water, be freeze-drying under the condition of 0.98 again in vacuum degree, obtain oligomeric cagelike silsesquioxane-Graphene.
2. graphen catalyst as claimed in claim 1, is characterized in that: the application of described catalyst in lithium polymer battery.
3. graphen catalyst as claimed in claim 2, it is characterized in that: described lithium polymer battery comprises is located at the inner positive plate (1) of battery case (6) and negative plate (2), is provided with barrier film (5) between described positive plate (1) and negative plate (2); Be provided with positive pole overlay film (7) and anode catalytic net (3) between described positive plate (1) and barrier film (5) successively, described positive pole overlay film (7) is overlying on the surface of positive plate (1), and described anode catalytic net (3) is overlying on the surface of barrier film (5); Be provided with negative pole catalysis net (4) and negative pole overlay film (8) between described barrier film (5) and negative plate (2) successively, described negative pole catalysis net (4) is overlying on the surface of barrier film (5), and described negative pole overlay film (8) is overlying on the surface of negative plate (2); The thickness of described anode catalytic net (3) is 10 μm, the load of described anode catalytic net (3) has anode catalyst, described anode catalyst is Cr-di-thiofuran ethylene base tetraazatetradecane porphyrin two dimension conjugated polymer, and the bearing capacity of the upper anode catalyst of described anode catalytic net (3) is 0.38mg/cm 2; The thickness of described negative pole catalysis net (4) is 10 μm, the load of described negative pole catalysis net (4) has cathode catalyst, described cathode catalyst is oligomeric cagelike silsesquioxane-Graphene, and the bearing capacity of the upper cathode catalyst of described negative pole catalysis net (4) is 0.71mg/cm 2.
4. graphen catalyst as claimed in claim 3, it is characterized in that: described positive plate (1) is nanometer Rh-graphene combination electrode, the thickness of described positive plate (1) is 40 μm; Described negative plate (2) is nano Co 2snO 4poly-sulfonic acid naphthalene electrode, the thickness of described negative plate (2) is 50 μm; Described positive plate (1) ratio capacitance that discharges when electric current is 1A/g is 576.3F/g, and described negative plate (2) ratio capacitance that discharges when electric current is 1A/g is 817.6F/g.
5. graphen catalyst as claimed in claim 4, is characterized in that: described barrier film (5) is polymer-LiClO 4-Li 4ti 5o 12composite electrolyte, described polymer is polystyrene-ethylene pyrrolidones-styrene triblock copolymer, and the thickness of described barrier film (5) is 40 μm; Described barrier film (5) surface is covered with coat, and described coat is Kynoar-hexafluoropropylene, and the thickness of described coat is 100nm.
6. the graphen catalyst as described in claim 4 or 5, it is characterized in that: described battery case (6) is made up of soft plastic, and described soft plastic comprises dimethicone 18.5%, talcum powder 7.8%, TPR33%, zinc stearate 2.2%, white carbon 10.2%, boric acid 1.2%, deca-BDE 9.5%, antioxidant 168 is 0.25%, erucyl amide 3.3%, organic siliconresin 14.05%.
CN201510903543.9A 2015-12-09 2015-12-09 Graphene catalyst Pending CN105552318A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784654A (en) * 2016-11-28 2017-05-31 荆门市格林美新材料有限公司 A kind of preparation method of graphene coated cobalt acid lithium material
CN107394259A (en) * 2017-09-07 2017-11-24 南京汉尔斯生物科技有限公司 Graphen catalyst applied to the ionic conductivity for improving lithium polymer battery
CN107585802A (en) * 2017-10-13 2018-01-16 南京旭羽睿材料科技有限公司 A kind of graphene composite material applied to Industrial Waste Water Treatments
CN114335495A (en) * 2021-12-28 2022-04-12 南昌航空大学 Method for preparing silicon-carbon negative electrode material by using waste graphite of lithium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120010337A1 (en) * 2010-07-08 2012-01-12 Xerox Corporation Method For Treating A Carbon Allotrope
CN102731809A (en) * 2012-06-04 2012-10-17 西北工业大学 Preparation method of atomic oxygen-resistant polyimide hybrid films containing POSS (polyhedral oligomeric silsesquioxanes) structures
CN104356413A (en) * 2014-11-11 2015-02-18 西北工业大学 Preparation method of anti-atomic oxygen polyimide hybrid films containing octamer cage-shaped silsesquioxane structures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120010337A1 (en) * 2010-07-08 2012-01-12 Xerox Corporation Method For Treating A Carbon Allotrope
CN102731809A (en) * 2012-06-04 2012-10-17 西北工业大学 Preparation method of atomic oxygen-resistant polyimide hybrid films containing POSS (polyhedral oligomeric silsesquioxanes) structures
CN104356413A (en) * 2014-11-11 2015-02-18 西北工业大学 Preparation method of anti-atomic oxygen polyimide hybrid films containing octamer cage-shaped silsesquioxane structures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUHUA XUE ET AL: "Functionalization of Graphene Oxide with Polyhedral Oligomeric Silsesquioxane (POSS) for Multifunctional Applications", 《THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784654A (en) * 2016-11-28 2017-05-31 荆门市格林美新材料有限公司 A kind of preparation method of graphene coated cobalt acid lithium material
CN107394259A (en) * 2017-09-07 2017-11-24 南京汉尔斯生物科技有限公司 Graphen catalyst applied to the ionic conductivity for improving lithium polymer battery
CN107585802A (en) * 2017-10-13 2018-01-16 南京旭羽睿材料科技有限公司 A kind of graphene composite material applied to Industrial Waste Water Treatments
CN114335495A (en) * 2021-12-28 2022-04-12 南昌航空大学 Method for preparing silicon-carbon negative electrode material by using waste graphite of lithium ion battery

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