CN102810403B - A kind of solid electrolyte capacitor sheet and preparation method thereof - Google Patents
A kind of solid electrolyte capacitor sheet and preparation method thereof Download PDFInfo
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- CN102810403B CN102810403B CN201110144746.6A CN201110144746A CN102810403B CN 102810403 B CN102810403 B CN 102810403B CN 201110144746 A CN201110144746 A CN 201110144746A CN 102810403 B CN102810403 B CN 102810403B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 60
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 59
- 239000004411 aluminium Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 29
- 239000002322 conducting polymer Substances 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 2
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 39
- 239000005030 aluminium foil Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000007743 anodising Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 229920000867 polyelectrolyte Polymers 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009490 roller compaction Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to electrode for capacitors field, it discloses a kind of solid electrolyte capacitor sheet and preparation method thereof; This solid electrolyte capacitor chip architecture is aluminium/alundum (Al2O3)-barium titanate/Graphene-conducting polymer. Solid electrolyte capacitor sheet provided by the invention, replaces traditional conductive polyelectrolyte material with Graphene, makes it have good stability and uniformity; And this electrode slice preparation technology is simple, with low cost, be applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of electrode slice, relate in particular to a kind of solid electrolyte capacitor sheet and systemPreparation Method.
Background technology
It is organic that solid capacitor is mainly divided into the organic molecule such as manganese dioxide, TCNQ and PEDOT etc.Macromolecular solid bulk capacitor. In electrochemical capacitor, traditional alminium electrolytic condenser by be using electrolyte asDielectric material, this capacitor is not broken away from because of physical characteristic and expanded by heating, occurs the danger of leakageDanger phenomenon, allows aluminium electrolutic capacitor face the unprecedented pressure of work and challenge; In addition, conventional aluminum electricitySeparate electric capacity and adopt manganese dioxide as cathode material, except easily there is the danger of burning due to voltage problemOutside danger, more because environmental issue makes future market significantly limited.
Organic semiconductor TCNQ is a kind of cyanide, easily volatilizes hypertoxic dicyanogen in the time of high temperature,Therefore, also just limited TCNQ application. Macromolecule product PEDOT is as the solid of cathode materialCapacitor, its production cost is high, has also just limited the application of PEDOT.
Summary of the invention
The object of the present invention is to provide a kind of security performance good, nontoxic, and the low solid of production costElectrolytic capacitor sheet
Technical scheme of the present invention is as follows:
A kind of solid electrolyte capacitor sheet, its structure be aluminium/alundum (Al2O3)-barium titanate/Graphene-Conducting polymer, the electrical conductivity of this solid electrolyte capacitor sheet is 2500～10000s/m; Wherein,Conducting polymer comprises aniline monomer, 3,4-ethylene dioxythiophene monomer or pyrrole monomer.
Another object of the present invention is to provide the preparation method of solid electrolyte capacitor sheet, its stepRapid as follows:
S1, aluminium foil or aluminium net are immersed and filled in the container of suspension of Barium Titanate nano-powder, thenUnder vacuum, in 500-700 DEG C of heat treatment 0.5-12h, obtain applying aluminium foil or the aluminium net of barium titanate;
S2, by water-soluble graphene oxide solution, subsequently toward add in the aqueous solution conducting polymer (as,Conducting polymer comprises aniline monomer, 3,4-ethylene dioxythiophene monomer or pyrrole monomer), make electrolysisLiquid; Wherein, in electrolyte, the molar concentration of graphene oxide is 1～3mol/L;
The aluminium foil of S3, coating barium titanate that step S1 is made or aluminium net are as electrode inserting step S2In the electrolyte making, and on electrode, pass to the DC current of 1～10mA, be 1～24h conduction time,Obtain aluminium/barium titanate/graphene oxide-conducting polymer electrode slice;
S4, aluminium/barium titanate/graphene oxide-conducting polymer electrode slice that step S3 is made are placed in veryIn empty atmosphere, at 80～300 DEG C, toast 2～24h, make aluminium/barium titanate/Graphene-conducting polymer electrodeSheet;
S5, employing anodizing, the aluminium/barium titanate/Graphene-conducting polymer obtaining at step S4On electrode slice, by DC voltage, after being 0.5～2h conduction time, aluminum oxidation makes alundum (Al2O3),The structure of attaining the Way is the described solid electrolytic capacitor of aluminium/alundum (Al2O3)-barium titanate/Graphene-conducting polymerDevice electrode slice; Wherein, the magnitude of voltage of described DC voltage is solid electrolytic capacitor load voltage value135～200%, the voltage that the about every volt of the thickness of alundum (Al2O3) forms is 1.2～1.5nm.
In above-mentioned preparation method, in step S2, described graphite oxide adopts following step to make:
S21, the mass ratio graphite powder of 2: 1: 1, potassium peroxydisulfate, phosphorus pentoxide are added in the concentrated sulfuric acid,Stir, cooling, filtration subsequently, and wash screening to neutral, dry, for subsequent use;
S22, dried step S21 screening is added in the concentrated sulfuric acid of 0 DEG C, add subsequently permanganic acidPotassium, stirs; Then add successively the hydrogen peroxide solution that deionized water and mass concentration are 30%, stirBe mixed into mixed solution; Wherein, the quality of potassium permanganate is 3 times of graphite powder quality;
The mixed solution of S23, filtration step S22, and the salt acid elution that is 10% by mass concentration, take outFilter, dry screening, finally obtain graphene oxide.
Solid electrolyte capacitor sheet provided by the invention, replaces traditional conductive polymer with GrapheneSub-electrolyte, Graphene and conductive polymer meet the high conduction performance that combines grapheme materialWith flexibility and the self-healing performance of conducting polymer, both are compound, can well improve the stable of productProperty and uniformity; And this electrode slice preparation technology is simple, with low cost, be applicable to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the SEM of aluminium/alundum (Al2O3)-barium titanate/Graphene of the present invention-conducting polymer electrode sliceFigure; Wherein, surface sweeping Electronic Speculum model: FESEM, HitachiS-4300; Accelerating potential: 10-15KV;
Fig. 2 is the cross section of aluminium/alundum (Al2O3)-barium titanate/Graphene of the present invention-conducting polymer electrode sliceSEM figure; Wherein, surface sweeping Electronic Speculum model: FESEM, HitachiS-4300; Accelerating potential: 10-15KV;
Fig. 3 is the preparation of aluminium/alundum (Al2O3)-barium titanate/Graphene of the present invention-conducting polymer electrode sliceProcess chart.
Detailed description of the invention
A kind of solid electrolyte capacitor sheet provided by the invention, as illustrated in fig. 1 and 2, its structureFor aluminium/alundum (Al2O3)-barium titanate/Graphene-conducting polymer, this solid electrolyte capacitor sheetElectrical conductivity is 2500～10000s/m; Wherein, conducting polymer comprises aniline monomer, 3,4-enedioxyThiophene monomer or pyrrole monomer.
The preparation method of above-mentioned solid electrolyte capacitor sheet provided by the invention, its step is as follows:
S1, aluminium foil or aluminium net are immersed and filled in the container of suspension of Barium Titanate nano-powder, thenUnder vacuum, in the many 0.5～12h of 500-700 DEG C of heat treatment, obtain applying aluminium foil or the aluminium net of barium titanate;
S2, by water-soluble graphene oxide solution, subsequently toward add in the aqueous solution conducting polymer (as,Conducting polymer comprises aniline monomer, 3,4-ethylene dioxythiophene monomer or pyrrole monomer), make electrolysisLiquid; Wherein, in electrolyte, the molar concentration of graphene oxide is 1～3mol/L;
The aluminium foil of S3, coating barium titanate that step S1 is made or aluminium net are as electrode inserting step S2In the electrolyte making, and on electrode, pass to the DC current of 1～10mA, be 1～24h conduction time,Obtain aluminium/barium titanate/graphene oxide-conducting polymer electrode slice;
S4, aluminium/barium titanate/graphene oxide-conducting polymer electrode slice that step S3 is made are placed in veryIn empty atmosphere, at 80～300 DEG C, toast 2～24h, make aluminium/barium titanate/Graphene-conducting polymer electrodeSheet;
S5, employing anodizing, the aluminium/barium titanate/Graphene-conducting polymer obtaining at step S4On electrode slice, by DC voltage, after being 0.5～2h conduction time, aluminium direct oxidation makes three oxidations twoAluminium, the described solid electrolytic that the structure of attaining the Way is aluminium/alundum (Al2O3)-barium titanate/Graphene-conducting polymerCapacitor electrode slice; Wherein, the magnitude of voltage of described DC voltage is solid electrolytic capacitor rated voltage135～200% of value, the voltage that the about every volt of the thickness of alundum (Al2O3) forms is 1.2～1.5nm.
In above-mentioned preparation method, in step S2, described graphite oxide adopts following step to make:
S21, the mass ratio graphite powder of 2: 1: 1, potassium peroxydisulfate, phosphorus pentoxide are added to 80 DEG C denseIn sulfuric acid, stir, more than cooling 6h, filter subsequently, and wash screening to neutral, dry, for subsequent use;
S22, dried step S21 screening is added in the concentrated sulfuric acid of 0 DEG C, add subsequently permanganic acidPotassium, stirs; Then add successively the hydrogen peroxide solution that deionized water and mass concentration are 30%, stirBe mixed into mixed solution; Wherein, the quality of potassium permanganate is 3 times of graphite powder quality;
The mixed solution of S23, filtration step S22, and the salt acid elution that is 10% by mass concentration, take outFilter, vacuum drying screening 48h at 60 DEG C, finally obtain graphene oxide.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The preparation method of solid electrolyte capacitor sheet is as follows:
(1) graphite oxide: the 50 order graphite powders that are 99.5% by 20g purity, 10g potassium peroxydisulfate and10g phosphorus pentoxide adds in the concentrated sulfuric acid of 80 DEG C, stirs, and more than cooling 6h, washing extremelyNeutrality, dry; Dried sample is added in 0 DEG C, the concentrated sulfuric acid of 230mL, then add 60gPotassium permanganate, the temperature of mixture remains on below 20 DEG C, then in the oil bath of 35 DEG C, keeps 2hAfter, slowly add 920mL deionized water; After 15min, then add successively 2.8L deionized waterWith the hydrogen peroxide that 50mL mass concentration is 30%, mixture color becomes glassy yellow afterwards, takes out while hotFilter, then with the hydrochloric acid that 5L concentration is 10% wash, suction filtration, at 60 DEG C of vacuum drying 48hObtain graphite oxide;
(2) aluminium foil is immersed and filled in the container of suspension of Barium Titanate nano-powder, then vacuum atmosphereUnder enclosing, 500 DEG C of heat treatment 0.5h, obtain applying the aluminium foil of barium titanate;
(3) graphene oxide (1) being prepared is dissolved in the container that fills water, then addsEnter aniline monomer, the graphene oxide electrolyte that formation molar concentration is 1mol/L;
(4) aluminium foil of the coating barium titanate (2) being made inserts as electrode the electrolysis that (3) makeIn liquid, and on electrode, pass to the DC current of 1mA, be 1h conduction time, obtain aluminium/barium titanate/Graphene-aniline monomer electrode slice;
(5) aluminium/barium titanate/graphene oxide-aniline monomer electrode slice (4) being made is placed in vacuum atmosphereEnclose, toast 12h at 120 DEG C, make aluminium/barium titanate/Graphene-aniline monomer electrode slice;
(6) aluminium/barium titanate/Graphene-aniline monomer electrode slice (5) being obtained carries out roller compaction processing;
(7) aluminium/barium titanate/Graphene through the compaction treatment-aniline monomer electrode slice (6) being obtained is logicalCross DC voltage, this voltage is 135% of final capacitor rated voltage, and be 0.5h conduction time; CompleteAfter, obtaining structure is the described solid electrolytic electricity of aluminium/alundum (Al2O3)-barium titanate/Graphene-aniline monomerContainer electrode sheet, and the electrical conductivity of this electrode slice is 2500s/m; Wherein, the thickness of alundum (Al2O3) is largeAbout 720nm.
Embodiment 2
The preparation method of solid electrolyte capacitor sheet is as follows:
(1) graphite oxide: the 50 order graphite powders that are 99.5% by 20g purity, 10g potassium peroxydisulfate and10g phosphorus pentoxide adds in the concentrated sulfuric acid of 80 DEG C, stirs, and more than cooling 6h, washing extremelyNeutrality, dry; Dried sample is added in 0 DEG C, the concentrated sulfuric acid of 230mL, then add 60gPotassium permanganate, the temperature of mixture remains on below 20 DEG C, then in the oil bath of 35 DEG C, keeps 2hAfter, slowly add 920mL deionized water; After 15min, then add successively 2.8L deionized waterWith the hydrogen peroxide that 50mL mass concentration is 30%, mixture color becomes glassy yellow afterwards, takes out while hotFilter, then with the hydrochloric acid that 5L concentration is 10% wash, suction filtration, at 60 DEG C of vacuum drying 48hObtain graphite oxide;
(2) aluminium foil is immersed and filled in the container of suspension of Barium Titanate nano-powder, then vacuum atmosphereUnder enclosing, 550 DEG C of heat treatment 2h, obtain applying the aluminium net of barium titanate;
(3) graphene oxide (1) being prepared is dissolved in the container that fills water, then addsEnter 3,4-ethylene dioxythiophene monomer, the graphene oxide electrolyte that formation molar concentration is 1.5mol/L;
(4) the aluminium net of the coating barium titanate (2) being made inserts as electrode the electrolysis that (3) makeIn liquid, and on electrode, pass to the DC current of 1mA, be 24h conduction time, obtains aluminium/barium titanate/ Graphene-3,4-ethylene dioxythiophene monomer electrode slice;
(5) aluminium/barium titanate/graphene oxide-3,4-ethylene dioxythiophene monomer electrode (4) being madeSheet is placed at vacuum, 300 DEG C and toasts 24h, makes aluminium/barium titanate/Graphene-3,4-enedioxyThiophene monomer electrode slice;
(6) aluminium/barium titanate/Graphene-3,4-ethylene dioxythiophene monomer electrode slice (5) being obtained entersThe processing of row roller compaction;
(7) aluminium/barium titanate/Graphene-3,4-ethylene dioxythiophene through compaction treatment (6) being obtainedMonomer electrode slice is by DC voltage, and this voltage is 150% of final capacitor rated voltage, when energisingBetween be 1h; After complete, obtaining structure is aluminium/alundum (Al2O3)-barium titanate/Graphene-3,4-enedioxy thiopheneThe described solid electrolyte capacitor sheet of thiophene monomer, and the electrical conductivity of this electrode slice is 3200s/m; ItsIn, the thickness of alundum (Al2O3) is greatly about 800nm.
Embodiment 3
The preparation method of solid electrolyte capacitor sheet is as follows:
(1) graphite oxide: the 50 order graphite powders that are 99.5% by 20g purity, 10g potassium peroxydisulfate and10g phosphorus pentoxide adds in the concentrated sulfuric acid of 80 DEG C, stirs, and more than cooling 6h, washing extremelyNeutrality, dry; Dried sample is added in 0 DEG C, the concentrated sulfuric acid of 230mL, then add 60gPotassium permanganate, the temperature of mixture remains on below 20 DEG C, then in the oil bath of 35 DEG C, keeps 2hAfter, slowly add 920mL deionized water; After 15min, then add successively 2.8L deionized waterWith the hydrogen peroxide that 50mL mass concentration is 30%, mixture color becomes glassy yellow afterwards, takes out while hotFilter, then with the hydrochloric acid that 5L concentration is 10% wash, suction filtration, at 60 DEG C of vacuum drying 48hObtain graphite oxide;
(2) aluminium foil is immersed and filled in the container of suspension of Barium Titanate nano-powder, then vacuum atmosphereUnder enclosing, 500 DEG C of heat treatment 12h, obtain applying the aluminium foil of barium titanate;
(3) graphene oxide (1) being prepared is dissolved in the container that fills water, then addsEnter pyrrole monomer, the graphene oxide electrolyte that formation molar concentration is 3mol/L;
(4) aluminium foil of the coating barium titanate (2) being made inserts as electrode the electrolysis that (3) makeIn liquid, and on electrode, pass to the DC current of 10mA, be 1h conduction time, obtains aluminium/barium titanate/ Graphene-pyrrole monomer electrode slice;
(5) aluminium/barium titanate/graphene oxide-pyrrole monomer electrode slice (4) being made is placed in vacuum atmosphereEnclose, toast 2h at 80 DEG C, make aluminium/barium titanate/Graphene-pyrrole monomer electrode slice; ;
(6) aluminium/barium titanate/Graphene-pyrrole monomer electrode slice (5) being obtained carries out roller compaction processing;
(7) aluminium/barium titanate/Graphene through the compaction treatment-pyrrole monomer electrode slice (6) being obtained is logicalCross DC voltage, this voltage is 180% of final capacitor rated voltage, and be 1.5h conduction time; CompleteAfter, obtaining structure is the described solid electrolytic electricity of aluminium/alundum (Al2O3)-barium titanate/Graphene-pyrrole monomerContainer electrode sheet, and the electrical conductivity of this electrode slice is 7500s/m; Wherein, the thickness of alundum (Al2O3) is largeAbout 830nm.
Embodiment 4
The preparation method of solid electrolyte capacitor sheet is as follows:
(1) graphite oxide: the 50 order graphite powders that are 99.5% by 20g purity, 10g potassium peroxydisulfate and10g phosphorus pentoxide adds in the concentrated sulfuric acid of 80 DEG C, stirs, and more than cooling 6h, washing extremelyNeutrality, dry; Dried sample is added in 0 DEG C, the concentrated sulfuric acid of 230mL, then add 60gPotassium permanganate, the temperature of mixture remains on below 20 DEG C, then in the oil bath of 35 DEG C, keeps 2hAfter, slowly add 920mL deionized water; After 15min, then add successively 2.8L deionized waterWith the hydrogen peroxide that 50mL mass concentration is 30%, mixture color becomes glassy yellow afterwards, takes out while hotFilter, then with the hydrochloric acid that 5L concentration is 10% wash, suction filtration, at 60 DEG C of vacuum drying 48hObtain graphite oxide;
(2) aluminium foil is immersed and filled in the container of suspension of Barium Titanate nano-powder, then vacuum atmosphereUnder enclosing, 500 DEG C of heat treatment 24h, obtain applying the aluminium foil of barium titanate;
(3) graphene oxide (1) being prepared is dissolved in the container that fills water, then addsEnter 3,4-ethylene dioxythiophene monomer, the graphene oxide electrolyte that formation molar concentration is 2mol/L;
(4) aluminium foil of the coating barium titanate (2) being made inserts as electrode the electrolysis that (3) makeIn liquid, and on electrode, pass to the DC current of 2mA, be 5h conduction time, obtain aluminium/barium titanate/Graphene-3,4-ethylene dioxythiophene monomer electrode slice;
(5) aluminium/barium titanate/graphene oxide-3,4-ethylene dioxythiophene monomer electrode (4) being madeSheet is placed at vacuum, 300 DEG C and toasts 12h, makes aluminium/barium titanate/Graphene-3,4-enedioxyThiophene monomer electrode slice;
(6) aluminium/barium titanate/Graphene-3,4-ethylene dioxythiophene monomer electrode slice (5) being obtained entersThe processing of row roller compaction;
(7) aluminium/barium titanate/Graphene-3,4-ethylene dioxythiophene through compaction treatment (6) being obtainedMonomer electrode slice is by DC voltage, and this voltage is 200% of final capacitor rated voltage, when energisingBetween be 2h; After complete, obtaining structure is aluminium/alundum (Al2O3)-barium titanate/Graphene-3,4-enedioxy thiopheneThe described solid electrolyte capacitor sheet of thiophene monomer, and the electrical conductivity of this electrode slice is 10000s/m;Wherein, the thickness of alundum (Al2O3) is greatly about 900nm. .
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can notTherefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be withClaims are as the criterion.
Claims (7)
1. a preparation method for solid electrolyte capacitor sheet, is characterized in that, comprises following stepRapid:
S1, aluminium foil or aluminium net are immersed and filled in the container of suspension of Barium Titanate nano-powder, thenUnder vacuum, in 500-700 DEG C of heat treatment 0.5-12h, obtain applying aluminium foil or the aluminium net of barium titanate;
S2, by water-soluble graphene oxide solution, in the aqueous solution, add conducting polymer subsequently,Make electrolyte;
The aluminium foil of S3, coating barium titanate that step S1 is made or aluminium net are as electrode inserting step S2In the electrolyte making, and on electrode, pass to the DC current of 1～10mA, be 1～24h conduction time,Obtain aluminium/barium titanate/graphene oxide-conducting polymer electrode slice;
S4, aluminium/barium titanate/graphene oxide-conducting polymer electrode slice that step S3 is made are placed in veryIn empty atmosphere, at 80～300 DEG C, toast 2～24h, make aluminium/barium titanate/Graphene-conducting polymer electrodeSheet;
S5, employing anodizing, the aluminium/barium titanate/Graphene-conducting polymer obtaining at step S4On electrode slice, by DC voltage, after being 0.5～2h conduction time, making structure is aluminium/alundum (Al2O3)The described solid electrolyte capacitor sheet of-barium titanate/Graphene-conducting polymer; Wherein, described straightThe magnitude of voltage of stream voltage is 135～200% of solid electrolytic capacitor load voltage value.
2. preparation method according to claim 1, is characterized in that, in step S2, described inGraphite oxide adopts following step to make:
S21, the graphite powder of mass ratio 2:1:1, potassium peroxydisulfate, phosphorus pentoxide are added in the concentrated sulfuric acid,Stir, cooling, filtration subsequently, and wash screening to neutral, dry, for subsequent use;
S22, dried step S21 screening is added in the concentrated sulfuric acid of 0 DEG C, add subsequently permanganic acidPotassium, stirs; Then add successively the hydrogen peroxide solution that deionized water and mass concentration are 30%, stirBe mixed into mixed solution;
The mixed solution of S23, filtration step S22, and the salt acid elution that is 10% by mass concentration, take outFilter, dry screening, finally obtain graphene oxide.
3. preparation method according to claim 2, is characterized in that, in step S22, and Gao MengThe quality of acid potassium is 3 times of graphite powder quality.
4. preparation method according to claim 2, is characterized in that, in step S22, described inThe volume number of hydrogen peroxide is 50ml.
5. preparation method according to claim 1, is characterized in that, the described electricity of step S2Separate in liquid, the molar concentration of described graphene oxide is 1～3mol/L.
6. preparation method according to claim 1, is characterized in that, in step S2, described inConducting polymer comprises aniline monomer, 3,4-ethylene dioxythiophene monomer or pyrrole monomer.
7. according to the arbitrary described preparation method of claim 1 to 6, it is characterized in that described solidThe electrical conductivity of electrolytic capacitor sheet is 2500～10000s/m.
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