CN105405677A - Method for directly preparing graphene-manganese dioxide composite material from graphite and application of graphene-manganese dioxide composite material - Google Patents
Method for directly preparing graphene-manganese dioxide composite material from graphite and application of graphene-manganese dioxide composite material Download PDFInfo
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- CN105405677A CN105405677A CN201510813091.5A CN201510813091A CN105405677A CN 105405677 A CN105405677 A CN 105405677A CN 201510813091 A CN201510813091 A CN 201510813091A CN 105405677 A CN105405677 A CN 105405677A
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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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a method for directly preparing a graphene-manganese dioxide composite material from graphite and an application of the graphene-manganese dioxide composite material. The graphene-manganese dioxide composite material is directly prepared from natural flake graphite by an intercalation-stripping method, and is quickly gathered to form a three-dimensional porous structure by adjusting the pH value; and the graphene-manganese dioxide composite material is finally applied to an electrode of an all-solid supercapacitor. According to the method, preparation of oxidized graphene is not needed; and meanwhile, time-consuming washing, filtering and subsequent sedimentation or in-situ growth of manganese dioxide particles are not needed, so that the technological process is simplified. The prepared graphene is low in oxidation degree and low in defect level; and the conductivity of the composite material is high and can reach above 1.0*10<4>S/m. The three-dimensional structure is formed by adding an acid for induction, so that the effective specific surface area is significantly improved when the conductivity is not affected. Meanwhile, the prepared all-solid supercapacitor shows outstanding electrochemical properties; the specific capacitance can be up to 66mF/cm<2> (138.8F/g); the maximal energy density is 0.21[mu]Wh/cm<2>; the maximal power density is 141.2[mu]W/cm<2>; meanwhile, the specific capacitance can still be reserved above 90% after 1,000 cycles; and the graphene-manganese dioxide composite material shows good cycling stability.
Description
Technical field
The present invention relates to Graphene preparation and applied technical field thereof, particularly a kind of preparation of Graphene-manganese dioxide composite material, pH induction regulating controlling three-dimensional structure build and in the application of all-solid-state supercapacitor.
Background technology
In recent years, ultracapacitor receives increasing concern as a kind of novel energy-storing equipment.Compared with battery, ultracapacitor has higher power density, faster charging rate and good cyclical stability.According to its energy storage mechanism, ultracapacitor can be divided into two classes usually, i.e. double electric layer capacitor and fake capacitance capacitor.Double electric layers supercapacitor uses carbon-based material usually, and as active carbon, carbon nano-tube and Graphene etc., and fake capacitance ultracapacitor uses conducting polymer and transition metal oxide/hydroxide as active material mostly.
Graphene, a kind of by individual layer sp
2the two-dimensional material of hydbridized carbon atoms composition, due to its high theoretical specific surface area (2630m
2g
1), high conductivity (is greater than 1 × 10
4s/m), good chemistry and thermal stability, become the hot research object of ultracapacitor active material, but Graphene is easily reunited, this can greatly reduce the intrinsic high-specific surface area of Graphene, thus limits its use.By the effective ways that Graphene and other Material cladding are head it offs.Current study general is by itself and conducting polymer or transition metal oxide/hydroxide compound, plays the synergy between them, to improve its chemical property.
Manganese dioxide, a kind of typical transition metal oxide, due to its low cost, hypotoxicity, high, the high theoretical ratio capacitance (1370F/g) of natural reserves and good environment compatibility, the electrode material used as ultracapacitor is extremely promising.But because its electrical conductance is poor, the stability that cycle life is short and not good, is faced with no small challenge in actual applications.Therefore be the synergy of both performances, preparing Graphene-manganese dioxide composite material expeditiously to develop high-performance super capacitor is vital key link.
The composite material of excellent performance is no lack of in current Graphene-manganese dioxide research, but usually all need first to prepare graphene oxide preparing in Graphene process, and then its electronation or thermal reduction obtain the graphene oxide that reduces, this needs washing consuming time, the deposition of filtration and follow-up manganese dioxide particle or growth in situ.Process for integrally manufacturing flow process very complicated, the cycle is long, cost is high, is difficult to expansion scale to meet industrial demand.In addition, in redox graphene, still remain some oxygen-containing functional groups, cause degree of oxidation and defect level to increase, conductivity is declined, thus have impact on its chemical property.
Summary of the invention
The object of the present invention is to provide a kind of method directly being prepared Graphene-manganese dioxide composite material by graphite, and demonstrate its application at all-solid-state supercapacitor.
A kind of method directly being prepared Graphene-manganese dioxide composite material by graphite that the present invention proposes, concrete steps are as follows:
(1) added in intercalator by raw graphite and carry out intercalation processing, intercalation process generates manganese dioxide simultaneously, prepares intercalated graphite-manganese dioxide composites; Intercalated graphite-manganese dioxide composites and active material are added to the water, under utilizing Probe Ultrasonic Searching, high speed shear or high-pressure fluid pulverization, process 5 seconds-5 hours, the Graphene that can have been peeled off-manganese dioxide composite material suspension or dispersion liquid; Amount of active mass is 0.01-10 times of raw graphite quality, and water consumption is 1-200 times of raw graphite quality;
(2) pH regulator solution is joined in the Graphene-manganese dioxide composite material suspension or dispersion liquid that step (1) obtains, until the pH value of suspension or dispersion liquid equals 1; After a period of time, there is fluffy aggregation in suspension or dispersion liquid lower floor, namely realizes three-dimensional structure regulation and control, prepare the graphene/manganese dioxide composite material of three-dimensional structure.
In the present invention, raw graphite described in step (1) is any one in native graphite, synthetic graphite or expanded graphite.
In the present invention, intercalator described in step (1) is the combination of one or more and potassium permanganate in sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid or oxalic acid, potassium permanganate consumption is 0.1-10 times of raw graphite quality, and the consumption of acid is the need of control.
In the present invention, active material described in step (1) is one or more combinations in potassium hydroxide, NaOH, lithium hydroxide, sodium carbonate, potash, lithium carbonate, sodium acid carbonate, saleratus, lithium bicarbonate, ammonium hydroxide, tetrabutylammonium or industrial soda.
In the present invention, the pH regulator solution described in step (2) is one or more combinations in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid or oxalic acid.
The application of Graphene-manganese dioxide composite material in the electrode of all-solid-state supercapacitor, is specially: by composite material and solvent.Or composite material is mixed with certain proportion with conductive agent, binding agent and solvent, make uniform sizing material, and be coated on the rear compressing tablet of oven dry on collector, more evenly painting is covered with gel electrolyte, and be assembled into all-solid-state supercapacitor.
In the present invention, after drying, compressing tablet refers under 0.5-5MPa pressure, within the 5min-1h time, by two electrode sheet together, and in cured at room temperature 2-24 hour.Finally be encapsulated, encapsulating material is the one in polyester (PET), polysiloxanes (PDMS), EVA film.
In the present invention, one or more and KOH, KCl, LiCl, Na in acrylic acid (PAA), polyethylene glycol oxide (PEO), polyvinyl alcohol (PVA), the poly-bright e pioic acid methyl ester of methyl (PMMA), polyamideepichlorohydrin (PAE), polyacrylonitrile (PAN), polyvinylidene fluoride (PVdF) and copolymer p VdF-co-HFP, PAN-b-PEG-b-PAN etc.
2sO
4in one or more composition gel electrolytes.
Beneficial effect of the present invention is:
(1) preparation process is without the need to preparing graphene oxide, also without the need to sedimentation or the growth in situ of washing consuming time, filtration and follow-up manganese dioxide particle, greatly simplification of flowsheet, shorten process cycle.
(2) the Graphene degree of oxidation prepared is low, and defect level little (D/G only has 0.13 than minimum), the conductivity of the manganese dioxide composite material of formation is high, reaches as high as 1.0 × 10
4s/m.
(3) three-dimensional structure of acid adding induced synthesis can enlarge markedly effective ratio area while not affecting conductivity.Three-dimensional composite material is prepared into all-solid-state supercapacitor and shows superior chemical property, ratio capacitance reaches as high as 66mF/cm
2(138.8F/g), maximum energy-density 0.21 μ Wh/cm
2and maximum power density 141.2 μ W/cm
2, after 1000 circulations, ratio capacitance still retains more than 90% simultaneously, shows good cyclical stability.
(4) preparation method's technique disclosed by the invention is simply effective, is applicable to very much large-scale industrial and produces, have significant application prospect.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of Graphene-manganese dioxide composite material.
Fig. 2 is the Raman spectrum curve of Graphene-manganese dioxide composite material.
Fig. 3 is the comparison diagram of the Graphene-manganese dioxide composite material added before and after pH regulator solution.
Fig. 4 is the scanning electron microscope (SEM) photograph of the Graphene-manganese dioxide composite material after pH induction adjustment three-dimensional structure.
Fig. 5 is the constant current charge-discharge curve chart that three-dimensional grapheme-manganese dioxide composite material is assembled into ultracapacitor.
Fig. 6 is 1000 discharge and recharge Posterior circle stability test curves that three-dimensional grapheme-manganese dioxide composite material is assembled into ultracapacitor.
Embodiment
The following stated is only the example of technical solution of the present invention, is not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Embodiment 1:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.The ultrasonic probe being 500W by potassium hydroxide solution (potassium hydroxide content 0.1 gram) the middle employing power joining 20 milliliters after this composite filter processes, and obtains the suspension of Graphene-manganese dioxide composites after 5 hours.Fig. 1 i.e. transmission electron microscope picture of composite material for this reason.Demonstrating manganese dioxide particle is evenly distributed on graphene sheet layer, and particle diameter is between 10-20 nanometer.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of concentrated hydrochloric acids to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.What Fig. 3 showed is drip the comparison diagram before and after concentrated hydrochloric acid, it is in the solution dispersed before dropping concentrated hydrochloric acid that a figure shows Graphene-manganese dioxide composites, after b figure shows dropping concentrated hydrochloric acid, Graphene-manganese dioxide composites self-assemble forms the three-dimensional structure of bulk multi-hole.After the scanning electron microscope (SEM) photograph of Fig. 4 intuitively understands and adds concentrated hydrochloric acid, the structure of composite material becomes three-dimensional porous structure, can increase effective ratio area.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PVA/KOH electrolyte, and collector uses nickel foam, and packaging material use PET.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 60 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 0.5MPa.Then at room temperature place 12 hours, make its completion of cure, finally coated with PET, obtain all-solid-state supercapacitor.
The constant current charge-discharge curve of Fig. 5 shows the superperformance of this solid-state super capacitor, and under the current density of 0.5A/g, its ratio capacitance can reach 66mF/cm
2.Fig. 6 demonstrates it and has superior stable circulation performance, and after 1000 discharge and recharges, ratio capacitance still possesses 91.2%.
Embodiment 2:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.Adopt 500W high-speed shearing machine at rotating speed 18 by middle for the industrial soda aqueous solution (industrial soda content 1 gram) joining 100 milliliters after this composite filter, peel off when 000 turn, after 1 hour, obtain the suspension of Graphene-manganese dioxide composites.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of concentrated sulfuric acids to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PEO/KCl electrolyte, and collector uses nickel foam, and packaging material use PDMS film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 5 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 5MPa.Then at room temperature place 24 hours, make its completion of cure, finally coated with PDMS, obtain all-solid-state supercapacitor.Final test result display, the composite material that high speed shear obtains and all-solid-state supercapacitor thereof have the performance similar with device to embodiment 1 resulting materials to the material that ultrasonic stripping obtains with capacitor.
Embodiment 3:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the crystalline flake graphite of 10 grams, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.Adopt 500W high-speed shearing machine at rotating speed 18 by middle for the Lithium carbonate solution (lithium carbonate content 10 grams) joining 200 milliliters after this composite filter, peel off when 000 turn, after 3 hours, obtain the suspension of Graphene-manganese dioxide composites.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of red fuming nitric acid (RFNA)s to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PEO/KCl electrolyte, and collector uses nickel foam, and packaging material use eva film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 30 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 3MPa.Then at room temperature place 24 hours, make its completion of cure, finally coated with eva film, obtain all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment 1 obtains with capacitor.
Embodiment 4:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 10 grams of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.The ultrasonic probe being 500W by solution of potassium carbonate (potash content 10 grams) the middle employing power joining 200 milliliters after this composite filter processes, and obtains the suspension of Graphene-manganese dioxide composites after 3 hours.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of perchloric acid to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PVA/LiCl electrolyte, and collector uses nickel foam, and packaging material use PDMS film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 30 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 3MPa.Then at room temperature place 12 hours, make its completion of cure, finally get up with PDMS film coated, obtain all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment 1 obtains with capacitor.
Embodiment 5:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.By adopt in the sodium carbonate liquor (carbonate content 10 grams) joining 200 milliliters after this composite filter 750W high-pressure fluid pulverizer 25 DEG C, with the above-mentioned mixed liquor of 1.0L/h flow velocity process, obtain the suspension of Graphene-manganese dioxide composites.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of SPAs to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PAN/LiCl electrolyte, and collector uses nickel foam, and packaging material use PET film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 40 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 2MPa.Then at room temperature place 15 hours, make its completion of cure, finally coated by PET film, obtain all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment 1 obtains with capacitor.
Embodiment 6:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the Delanium of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.Adopt 500W high-speed shearing machine at rotating speed 18 by middle for the potassium hydroxide solution (potassium hydroxide content 2 grams) joining 200 milliliters after this composite filter, peel off when 000 turn, after 3 hours, obtain the suspension of Graphene-manganese dioxide composites.(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 10 milliliters of dense formic acid to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PVdF/LiCl electrolyte, and collector uses nickel foam, and packaging material use eva film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 60 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 1MPa.Then at room temperature place 24 hours, make its completion of cure, finally coated with eva film, obtain all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment 1 obtains with capacitor.
Embodiment 7:
(1) slowly joined in 40 milliliters of concentrated sulfuric acids when not stopping stirring in 30 minutes by 1 gram of potassium permanganate, overheated for preventing, said process can carry out in ice-water bath.Then add the pyrolytic graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, obtained intercalated graphite-manganese dioxide composites.By adopt in the sodium hydroxide solution (sodium hydrate content 2 grams) joining 200 milliliters after this composite filter 750W high-pressure fluid pulverizer 25 DEG C, with the above-mentioned mixed liquor of 1.0L/h flow velocity process, obtain the suspension of Graphene-manganese dioxide composites.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 10 milliliters of spirit acids to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) by after three-dimensional grapheme-manganese dioxide composites washing and filtering of obtaining, all-solid-state supercapacitor is assembled into.Gel electrolyte adopts PVdF-co-HFP/LiCl electrolyte, and collector uses nickel foam, and packaging material use PET film.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 30 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 5MPa.Then at room temperature place 5 hours, make its completion of cure, finally coated by PET film, obtain all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment 1 obtains with capacitor.
Embodiment 8:
(1) when not stopping when stirring, the potassium permanganate of 0.4 gram slowly to be joined in 40 milliliters of concentrated sulfuric acids in 30 minutes, overheated for preventing, need carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, namely prepare intercalated graphite-manganese dioxide composites.Carry out Probe Ultrasonic Searching by the lithium hydroxide solution (lithium hydroxide content 2 grams) joining 200 milliliters after this composite filter, the suspension of Graphene-manganese dioxide composites after one hour, can be prepared.Fig. 2 i.e. Raman curve of composite material for this reason, D/G ratio only has 0.13, and illustrate that in this compound, Graphene degree of oxidation is little, conductivity is high, can reach 1.0 × 10
4s/m.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 5 milliliters of concentrated hydrochloric acids to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) all-solid-state supercapacitor is assembled into by after the three-dimensional grapheme obtained-manganese dioxide composites washing and filtering.Gel electrolyte adopts PAN-b-PEG-b-PAN/Na2SO4 electrolyte, and collector uses nickel foam, and packaging material use PET.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 10 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 5MPa.Then at room temperature place 2 hours, make its completion of cure, finally coated with PET, obtained all-solid-state supercapacitor.Final test result display, the composite material obtained and all-solid-state supercapacitor thereof have similar performance to the material that ultrasonic stripping in embodiment (1) obtains with capacitor.
Embodiment 9:
(1) when not stopping when stirring, 2 grams of potassium permanganate slowly to be joined in 40 milliliters of concentrated sulfuric acids in 30 minutes, overheated for preventing, need carry out in ice-water bath.Then add the pyrolytic graphite of 1 gram, stir 3 hours under 35 DEG C of conditions, namely prepare intercalated graphite-manganese dioxide composites.Carry out Probe Ultrasonic Searching by the potassium bicarbonate solution (saleratus content 8 grams) joining 200 milliliters after this composite filter, the suspension of Graphene-manganese dioxide composites after 1 hour, can be prepared.
(2) get the suspension of 40 milliliters of Graphene-manganese dioxide composites, drip 10 milliliters of dense oxalic acid to it, the Graphene-manganese dioxide composites with three-dimensional structure after several minutes, can be obtained.
(3) all-solid-state supercapacitor is assembled into by after the three-dimensional grapheme obtained-manganese dioxide composites washing and filtering.Gel electrolyte adopts PAN/KOH electrolyte, and collector uses nickel foam, and packaging material use PET.First three-dimensional grapheme-manganese dioxide composite material is mixed with the ratio of 80:10:10 with acetylene black and polytetrafluoroethylene, and add a small amount of isopropyl alcohol and make it form uniform sizing material.Then it is evenly coated in nickel foam, dries and compressing tablet.Two electrode slices are kept after a period of time making its tight adhesion together in 30 minutes by the gel electrolyte that then even coating thickness is moderate on electrode slice under the pressure of 1MPa.Then at room temperature place 12 hours, make its completion of cure, finally coated with PET, obtained all-solid-state supercapacitor.
Comparative example 1:
When not stopping when stirring, the potassium permanganate of 1 gram slowly to be joined in 40 milliliters of concentrated sulfuric acids in 30 minutes, overheated for preventing, need carry out in ice-water bath.Then add the crystalline flake graphite of 1 gram, stir 3 hours under 35 DEG C of conditions.Then this mixture is poured in 100 milliliters of frozen water, and then add 10 milliliters of hydrogen peroxide.Carry out Probe Ultrasonic Searching one hour by the potassium hydroxide solution (1 mol/L) joining 200 milliliters after this composite filter after a period of time, prepare the material ining contrast to embodiment 1.
Comparative example 2:
When not stopping when stirring, the potassium permanganate of 0.4 gram slowly to be joined in 40 milliliters of concentrated sulfuric acids in 30 minutes, overheated for preventing, need carry out in ice-water bath.Then add the Delanium of 1 gram, stir 3 hours under 35 DEG C of conditions.Then this mixture is poured in 100 milliliters of frozen water, and then add 10 milliliters of hydrogen peroxide.Carry out Probe Ultrasonic Searching one hour by the potassium hydroxide solution (1 mol/L) joining 200 milliliters after this composite filter after a period of time, prepare the material ining contrast to embodiment 2.
Comparative example 3:
When not stopping when stirring, the potassium permanganate of 2 grams slowly to be joined in 40 milliliters of concentrated sulfuric acids in 30 minutes, overheated for preventing, need carry out in ice-water bath.Then add the pyrolytic graphite of 1 gram, stir 3 hours under 35 DEG C of conditions.Then this mixture is poured in 100 milliliters of frozen water, and then add 10 milliliters of hydrogen peroxide.Carry out Probe Ultrasonic Searching one hour by the potassium hydroxide solution (1 mol/L) joining 200 milliliters after this composite filter after a period of time, prepare the material ining contrast to embodiment 3.
Experimental procedure in above three comparative examples is compared to the step (1) in five embodiments, difference is to add hydrogen peroxide, be used for removing the manganese dioxide particle produced in intercalation process, verify and whether produce synergy between Graphene and manganese dioxide.In three electrode tests, the material chemical property prepared in comparative example is very low, under the current density of 0.5 ampere/gram, only has 56.17 respectively, and 44.67 and 73F/g.Illustrate that Graphene-manganese dioxide composite material prepared by the present invention is under the synergy of the two, chemical property is greatly improved.
Claims (8)
1. directly prepared a method for Graphene-manganese dioxide composite material by graphite, it is characterized in that concrete steps are as follows:
(1) added in intercalator by raw graphite and carry out intercalation processing, intercalation process generates manganese dioxide simultaneously, prepares intercalated graphite-manganese dioxide composites; Intercalated graphite-manganese dioxide composites and active material are added to the water, under utilizing Probe Ultrasonic Searching, high speed shear or high-pressure fluid pulverization, process 5 seconds-5 hours, the Graphene that can have been peeled off-manganese dioxide composite material suspension or dispersion liquid; Amount of active mass is 0.1-10 times of raw graphite quality, and water consumption is 20-200 times of raw graphite quality;
(2) pH regulator solution is joined in the Graphene-manganese dioxide composite material suspension or dispersion liquid that step (1) obtains, until the pH value of suspension or dispersion liquid equals 1; After a period of time, there is fluffy aggregation in suspension or dispersion liquid lower floor, namely realizes three-dimensional structure regulation and control, prepare the graphene/manganese dioxide composite material of three-dimensional structure.
2. a kind of method directly being prepared Graphene-manganese dioxide composite material by graphite according to claim 1, is characterized in that raw graphite described in step (1) is any one in native graphite, synthetic graphite or expanded graphite.
3. a kind of method directly being prepared Graphene-manganese dioxide composite material by graphite according to claim 1, it is characterized in that intercalator described in step (1) is the combination of one or more and potassium permanganate in sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid or oxalic acid, potassium permanganate consumption is 0.1-10 times of raw graphite quality, and the consumption of acid is the need of control.
4. a kind of method directly being prepared Graphene-manganese dioxide composite material by graphite according to claim 1, is characterized in that active material described in step (1) is one or more combinations in potassium hydroxide, NaOH, lithium hydroxide, sodium carbonate, potash, lithium carbonate, sodium acid carbonate, saleratus, lithium bicarbonate, ammonium hydroxide, tetrabutylammonium or industrial soda.
5. a kind of method directly being prepared Graphene-manganese dioxide composite material and ultracapacitor by graphite according to claim 1, is characterized in that the pH regulator solution described in step (2) is one or more combinations in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, formic acid, acetic acid or oxalic acid.
6. the application of Graphene-manganese dioxide composite material in the electrode of all-solid-state supercapacitor that obtain of preparation method as claimed in claim 1, it is characterized in that being specially: by composite material and solvent, or composite material is mixed with certain proportion with conductive agent, binding agent and solvent, make uniform sizing material, and be coated on the rear compressing tablet of oven dry on collector, evenly be coated with again and be covered with gel electrolyte, and be assembled into all-solid-state supercapacitor.
7. application according to claim 6, is characterized in that drying rear compressing tablet refers under 0.5-5MPa pressure, within the 5min-1h time, by two electrode sheet together, and in cured at room temperature 2-24 hour, be finally encapsulated, encapsulating material is the one in PET, PDMS or EVA film.
8. application according to claim 6, is characterized in that described gel electrolyte is one or more and KOH, KCl, LiCl, Na in PAA, PEO, PVA, PMMA, PAE, PAN, PVdF, PVdF-co-HFP or PAN-b-PEG-b-PAN
2sO
4in one or more composition gel electrolytes.
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