CN102683038A - Solid electrolytic capacitor carbon rubber layer and manufacture method thereof - Google Patents
Solid electrolytic capacitor carbon rubber layer and manufacture method thereof Download PDFInfo
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- CN102683038A CN102683038A CN2012101475954A CN201210147595A CN102683038A CN 102683038 A CN102683038 A CN 102683038A CN 2012101475954 A CN2012101475954 A CN 2012101475954A CN 201210147595 A CN201210147595 A CN 201210147595A CN 102683038 A CN102683038 A CN 102683038A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 137
- 239000003990 capacitor Substances 0.000 title claims abstract description 100
- 239000007787 solid Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 73
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 239000011230 binding agent Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001802 infusion Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002843 nonmetals Chemical class 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000012958 reprocessing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002001 electrolyte material Substances 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052709 silver Inorganic materials 0.000 abstract description 12
- 239000004332 silver Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 93
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- 239000000725 suspension Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 239000007784 solid electrolyte Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 238000006424 Flood reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Chemical compound O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
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- 230000009514 concussion Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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Images
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
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a manufacture method of a solid electrolytic capacitor carbon rubber layer, which comprises the steps of: immersing an electrode needing coating a carbon rubber layer into an emulsion containing a conductive nonmetal, a binding agent and an organic solvent, and curing to obtain the carbon rubber layer, wherein the conductive nonmetal is a graphene material. According to the solid electrolytic capacitor carbon rubber layer manufactured by adopting the manufacture method, the binding force of the carbon rubber layer and a silver paste layer is increased, the content of carbon in the solid electrolytic capacitor carbon rubber layer is reduced but the conduction property of the solid electrolytic capacitor carbon rubber layer is not reduced, the contact resistance is reduced, and the heat resistance is increased, therefore, the solid electrolytic capacitor carbon rubber layer is suitable for massive popularization and application.
Description
Technical field
The present invention relates to a kind of solid electrolytic capacitor carbon paste layer and preparation method thereof; Be specifically related to a kind of solid electrolytic capacitor carbon paste layer and preparation method based on the Graphene derived material; Relating in particular to a kind of is the solid electrolyte capacitor carbon paste layer and preparation method thereof of conductive non-metals with the Graphene derived material, belongs to the solid electrolytic capacitor technical field
Background technology
Electric capacity (Capacitance) is claimed capacitance again, is meant the electric charge reserves under given potential difference, is to characterize the physical quantity that capacitor holds the electric charge ability.Electrical potential difference between the two-plate of capacitor increases by 1 volt of electric capacity that required electric weight is a capacitor.Say that from physics capacitor is a kind of static electric charge storage medium, as being merely able to fill the bucket of depositing electric charge, prerequisite is not have discharge loop, and excludes the self discharge effect of medium electric leakage.
The basic role of capacitor is exactly charge and discharge, and many circuit phenomenons that this basic effect that discharges and recharges extends out make capacitor that all different purposes arranged, and for example in electro-motor, we produce phase shift with it; In photoflash, produce high-octane sparking with it; In circuit, utilize capacitor to cut off direct current, be communicated with the characteristic that exchanges, stops low frequency, be used for being coupled, at a distance from straight, bypass, filtering, tuning, power conversion and control etc. automatically.
Capacitor can be divided into mineral condenser, organic dielectric capacitor and electrolytic capacitor three major types by dielectric difference.Electrolytic capacitor normally by metal forming (aluminium/tantalum) as positive electrode, the insulating oxide of metal forming (aluminium oxide/tantalum pentoxide) is as dielectric.Electrolytic capacitor is divided into tantalum electrolytic capacitor and aluminium electrolytic capacitor with the difference of its positive electrode.The negative electrode of tantalum electrolytic capacitor adopts manganese dioxide usually; And the negative electrode of aluminium electrolytic capacitor is made up of thin paper/film that soaked electrolyte solution (liquid electrolyte) or electrolytic polymer.
Solid electrolyte capacitor is that the employing electroconductive polymer is the electrochemical capacitor of dielectric material.Described conductive polymer material not can with aluminium oxide generation effect, be unlikely to the phenomenon of blasting after the energising; Solid electrolyte capacitor is a solid product simultaneously, does not exist because expanded by heating causes the situation of explosion.As shown in Figure 1
Common solid electrolytic capacitor includes anode part 3 and cathode portion 1, and the central authorities of cathode portion 1 are porousness aluminum metallic foil 4, and the outside of porousness aluminum metallic foil 4 is followed successively by aluminum oxide dielectric layer 5, electroconductive polymer layer 6, carbon paste layer 7, elargol layer 8.The wherein effect of carbon paste layer: preventing on the one hand that elargol layer and polymer from directly contact causes silver-colored the migration to make the rheology of leaking electricity big; Be the contact resistance that reduces elargol layer and polymer as transition zone on the other hand, can also prevent that silver is by the oxidation of the institute of the oxide in the conductive polymer coating.The mixture that the used carbon paste layer of prior art generally adopts graphite and carbon is as conductive non-metals.The defective of said this technology is: on the one hand, because carbon material surface complex structure, interface resistance are bigger, capacity can significantly descend when rate charge-discharge; The carbon of general technology is because quality is loose in addition, and loose in the polymeric layer surface distributed, thereby influences the thickness of solid electrolyte capacitor sheet.Therefore, reducing the carbon content in the carbon paste layer as far as possible, do not reduce simultaneously the electric conductivity of material again, is problem demanding prompt solution in the preparation of present solid electrolyte capacitor carbon paste layer.
Summary of the invention
The carbon content that exists to solid electrolytic capacitor carbon paste layer in the prior art is high; The carbon paste bed thickness; And the reduction carbon content; The bad again problem of carbon paste layer conductivity, the present invention utilizes extremely good conductivity of Graphene and huge specific area, selects for use Graphene to substitute the mixture of graphite of the prior art and carbon.
Graphene (Graphene) is the carbon atomic layer of monatomic thickness, is that carbon atom is with sp
2The thickness that the hydridization carbon atom forms is merely the individual layer two dimensional crystal that is arranged in honeycomb lattice (Honeycomb Crystal Lattice) of the hexaplanar of individual layer atom.The present invention selects for use the Graphene with extremely good conductivity and huge specific area to replace the mixture of graphite and carbon, is used as the conductive non-metals of solid electrolyte capacitor carbon paste layer.
One of the object of the invention is to provide a kind of preparation method of solid electrolytic capacitor carbon paste layer.Said method is the electrode that needs the carbon coated glue-line to be immersed contain in the emulsion of conductive non-metals, binding agent and organic solvent, after solidifying, obtains the carbon paste layer; Said conductive non-metals is a grapheme material; Said conductive non-metals is a Graphene class material.
The preparation method of solid electrolytic capacitor silica gel layer of the present invention adopts infusion process; The emulsion that will contain grapheme material, binding agent and organic solvent is coated on the electrode that needs the carbon coated glue-line; The organic solvent that will be coated on then in the emulsion on the electrode is removed, and solidifies to obtain being coated on the carbon paste layer on the electrode.
Grapheme material has good conductivity, and the present invention adds Graphene in the carbon paste layer, can guarantee under the very low situation of carbon content, still to keep good electrical conductivity.The specific area that grapheme material is big makes that binding agent can deep enough inside, so can be more firm combine with the elargol layer.Compare with the mixture of graphite and carbon, select for use Graphene, can under the prerequisite that obtains same conductivity, reduce the content of carbon, and can increase the adhesion of carbon paste layer and elargol layer as conductive non-metals.
Graphene class material according to the invention is selected from Graphene or Graphene derived material.
Thus, the Graphene class material that those skilled in the art can be known all can be used for the present invention, especially has the grapheme material or the Graphene derived material of the conductivity that big specific area becomes reconciled.So-called Graphene derived material is meant on grapheme material introduces the derived material that group obtains, the derived material that for example obtains after the reaction of Graphene hydrogenation or fluoridize, perhaps the Graphene derived material that combines with polymer to obtain etc.Graphene through with some noble metal nano particles or the composite material that forms with organic conductive macromolecule material etc., performance is very excellent aspect capacitive property.The acquisition of Graphene derived material has had a lot of reports, and those skilled in the art have the ability to obtain, and repeat no more here.
Preferably, Graphene class material of the present invention has three-dimensional structure, and the surface is contained nanometer level microporous in a large number.Further; The Graphene class material of conductivity >=100mS/m; For example conductivity is the Graphene class material of 105mS/m, the Graphene class material of 112mS/m and the Graphene class material of 134mS/m etc.; Perhaps the surface has the Graphene class material of the micropore of aperture in the 2nm-100nm scope, and for example the surface micropore aperture of Graphene class material is 2-4nm, 3-7nm, 4.5-8.8nm and 7-10nm etc., is more suitable for the present invention.
Those skilled in the art can be known can prepare the surface has a large amount of nanometer level microporous grapheme materials or the method for Graphene derived material all to can be used for realizing the present invention, and typical case but non-limiting instance have microwave bulking to handle graphene oxide, utilize strong reductant redox graphene, electrochemical reduction graphene oxide, high-temperature heating treatment graphene oxide etc. such as hydrazine hydrate.There is the method for the grapheme material or the Graphene derived material of a large amount of micrometer grade holes on described preparation surface, and those skilled in the art can and consult related data according to the professional knowledge of grasping and obtain.
Especially preferably can preparing conductivity >=100mS/m and/or surface, a large amount of pore diameter ranges are arranged is that the method for Graphene derived material of the micropore of 2nm-100nm is used for the present invention.For example CN 102070140 A disclose a kind of method for preparing the high-specific surface area grapheme material.
CN 102070140 A disclose a kind of highly basic that utilizes and have handled the method that obtains the high-specific surface area grapheme material; Utilize the reaction at high temperature of highly basic and carbon; The graphene powder that heat treatment or microwave irradiation obtain carries out further chemical treatment, thereby fast, large batch ofly go out the micropore of nanometer scale in the Graphene surface corrosion, greatly improves its specific area; And high-temperature process can further be reduced Graphene, thereby guarantees the high conductivity of resultant material.The grapheme material that CN 102070140 A disclosed methods prepare not only has the structure of three-dimensional, porous, and its specific area is up to 1500m
2/ g-3000m
2/ g, resulting grapheme material also has high conductivity simultaneously.
Preferably, the preparation process that a large amount of nanometer level microporous grapheme materials with three-dimensional structure are contained on said surface is: graphene powder and highly basic reaction with heat treatment or microwave irradiation obtain, pass through reprocessing and prepare.
Particularly, preparation surface is contained a large amount of nanometer level microporous grapheme material steps with three-dimensional structure and comprised: (1) places water with graphite oxide, carries out sonicated, obtains graphite oxide suspension; (2) configuration strong alkali aqueous solution; (3) strong alkali aqueous solution with step (2) joins in the graphite oxide suspension of step (1), stirs, and filters drying; (4) with the resulting solid sintering in the dry back of step (3); (5) solid that step (4) is obtained is washed, is filtered, drying.
Preferably, in said preparation method of graphene, the said ultrasonic time of step (1) is 1-5h, for example 1h, 1.2h, 2h, 2.4h, 3.5h, 4.1h, 4.9h and 5h etc., preferred 2-3h, further preferred 2.5h.Preferably; The concentration of the said graphite oxide of step (1) in water is 0.01-10mg/mL; For example 0.01mg/mL, 0.04mg/mL, 0.13mg/mL, 0.94mg/mL, 1.6mg/mL, 2.34mg/mL, 3.67mg/mL, 4.89mg/mL, 5.2mg/mL, 7.1mg/mL, 9.42mg/mL and 10mg/mL etc.; Preferred 2-5mg/mL, further preferred 4mg/mL.Preferably; The concentration of the said highly basic of step (2) is 0.2-20mol/L; For example 0.2mol/L, 0.4mol/L, 3.1mol/L, 7.6mol/L, 9.9mol/L, 16.1mol/L, 18.7mol/L and 20mol/L etc., preferred 3-15mol/L, further preferred 10mol/L.Preferably, in the step (2), the mass ratio of highly basic and graphite oxide is (1-50): 1, and for example 1:1,5:1,13:1,21:1,39:1,44:1 and 50:1 etc., preferred (5-33): 1.Preferably, the temperature of the said sintering of step (4) is 700-1200 ℃, for example 700 ℃, 705 ℃, 760 ℃, 920 ℃, 1060 ℃, 1137 ℃, 1190 ℃ and 1200 ℃ etc., preferred 750-1180 ℃.
Those skilled in the art should understand; Surface of the present invention is contained a large amount of preparation methods nanometer level microporous and/or that have a grapheme material of three-dimensional structure and is not limited to above-described method, and any Graphene that can prepare composite demand all can be used for the present invention.
The effect of binding agent is to guarantee strong bonded between the Graphene particle among the present invention, and the Stable Carbon glue-line guarantees that simultaneously carbon paste layer and elargol layer can strong bonded.The binding agent with attachment function that those skilled in the art can obtain all can be used for the present invention.Preferably, binding agent according to the invention is the resinae binding agent.
Preferably; 1 kind or at least 2 kinds combination in resinae binding agent preferred epoxy according to the invention, acrylic resin, polymethyl methacrylate and the polyamino resin, said combination is epoxy resin/acrylic resin, epoxy resin/polymethacrylate resin, acrylic resin/polymethacrylate resin/polyamino resin etc. for example.Epoxy resin has that mechanical property is strong, strong adhesion, little, the good stability of cure shrinkage, advantages such as good heat resistance, so preferred epoxy of the present invention.
The effect of organic solvent is that conductive non-metals material and binding agent are uniformly dispersed among the present invention, when guaranteeing that coating needs the electrode slice of coating, and carbon paste layer thickness homogeneous.After electrode carbon coated glue-line finishes, should organic solvent be removed, be convenient to the carbon paste layer is solidified.What therefore those skilled in the art can be known can effectively disperse Graphene and binding agent, and the organic solvent that can after applying completion, effectively remove, all can be used for the present invention.
Preferably; Organic solvent according to the invention is N; 1 kind or at least 2 kinds combination in dinethylformamide, 1-Methyl-2-Pyrrolidone, dimethyl sulfoxide (DMSO), oxolane, propene carbonate, acetone, acetonitrile, pyridine and the chlorobenzene; Said combination is N for example, dinethylformamide/acetonitrile, acetone/acetonitrile, pyridine/chlorobenzene, dimethyl sulfoxide (DMSO)/oxolane, propene carbonate/acetone/acetonitrile etc.N, dinethylformamide are called as " alembroth ", and multiple high polymer such as polyethylene, polyvinyl chloride, polyacrylonitrile, polyamide etc. are had fine solubility.1-Methyl-2-Pyrrolidone also has good dissolubility to polymer, often be used to dissolve polymer solvent and with the medium of polymerization reaction.The preferred N of organic solvent according to the invention, dinethylformamide and/or 1-Methyl-2-Pyrrolidone.
As optimal technical scheme, the method for the invention comprises the steps:
(1) grapheme material, resinae binding agent, organic solvent are mixed processes emulsion;
The electrode that (2) will need the carbon coated glue-line prepares at cathode layer and adopts infusion process to cover carbon paste layer emulsion in the emulsion;
(3) baking and curing is prepared into the carbon paste layer.
In the said mixed emulsion of step (1); All there is relation the time of the stability of the content of grapheme material, resinoid bond and organic solvent and carbon paste layer, adhesion, conductivity, carbon content and preparation; For example grapheme material is many more, and the carbon content of carbon paste layer increases, and conductivity increases; And the stability of the kind of resinoid bond and amount and carbon paste layer and very big relation is arranged with the caking property of elargol layer; Wherein organic solvent is related to the homogeneity and the stability of the dispersion liquid of grapheme material and resinoid bond, thereby has influence on the distributing homogeneity and the adhesion of its carbon paste layer graphene.
Preferably; The mass percent that the said grapheme material of step (1) accounts for mixed emulsion is 0.1-20wt%; For example 0.1wt%, 0.13wt%, 0.87wt%, 1.69wt%, 7.5wt%, 14wt%, 16.3wt%, 18.4wt%, 19.8wt%, 20wt% etc.; Preferred 0.1-10wt%, further preferred 3-10wt%.
The mass percent that the said resinae binding agent of step (1) accounts for mixed emulsion is 25-35wt%, for example 25wt%, 26wt%, 34wt% and 35wt% etc., preferably 30wt%.
The mass percent that the said organic solvent of step (1) accounts for mixed emulsion is 55-74wt%, for example 55wt%, 57wt%, 61wt%, 66wt%, 73wt% and 74wt% etc., preferably 60-65wt%.
Preferably, the said mixing of step (1) does not have specific (special) requirements, and any hybrid mode that those skilled in the art can be known all can realize the present invention, and typical case but non-limiting instance have stirring, concussion, ultrasonic etc.The optional technical scheme of step of the present invention (1) is: after grapheme material, resinae binding agent, organic solvent are mixed, ultrasonicly obtain finely dispersed black suspension.
Preferably, the said baking and curing of step of the present invention (3) is carried out in baking oven, preferably carries out preliminary drying earlier, and elevated temperature continues oven dry then.In order to prevent that in the baking and curing process Graphene is influenced its conductivity by all or part of graphene oxide that is oxidized to, the preferred vacuum drying oven of said baking oven.
Preferably, the temperature of the said preliminary drying of step of the present invention (3) is 60-95 ℃, for example 60 ℃, 63 ℃, 71 ℃, 77 ℃, 86 ℃, 92 ℃, 95 ℃ etc.; The said preliminary drying time is 8-20min, for example 8min, 9min, 15min, 17min, 19min, 20min etc.Preferably, the temperature of said oven dry is 100-200 ℃, for example 100 ℃, 103 ℃, 125 ℃, 136 ℃, 158 ℃, 179 ℃, 182 ℃, 198 ℃, 200 ℃ etc.; Said drying time is 30-120min, for example 30min, 35min, 78min, 106min, 118min, 120min etc.; Further preferably, the temperature of said oven dry is 150-180 ℃, and said drying time is 30-60min.
Two of the object of the invention is to provide a kind of solid electrolytic capacitor carbon paste layer, and said carbon paste layer is prepared by method of the present invention, and the density of said carbon paste layer is 0.05g/cm
3To 1g/cm
3, thickness is 50nm-500 μ m, for example 50nm, 52nm, 60nm, 122nm, 134nm, 158nm, 250nm, 332nm, 430nm, 487nm, 788nm, 1 μ m, 34 μ m, 123 μ m, 289 μ m, 444 μ m, 498 μ m, 500 μ m etc.; Carbon content is 0.1-20%, for example 0.1%, 0.5%, 2%, 4.4%, 7%, 8.9%, 12.2%, 17%, 18.1%, 19.9%, 20% etc.
Three of the object of the invention is to provide a kind of solid electrolytic capacitor.
In theory, a perfect electric capacity, self can not produce any energy loss, but in fact, because make the material of electric capacity resistance is arranged, and the dielectric of electric capacity is lossy, and a variety of causes causes electric capacity become not " perfection ".This loss externally shows as just as a resistance and follows capacitances in series together, is called " equivalent series resistance " so just played individual name, and English name is Equivalent Series Resistance, is abbreviated as ESR.
Can know that thus the ESR of electric capacity and the material of electric capacity have very big relation, solid electrolytic capacitor provided by the present invention contains carbon paste layer of the present invention, and its ESR is 5-20m Ω, for example 5m Ω, 9m Ω, 13m Ω, 18m Ω, 20m Ω etc.
The preparation method of solid electrolytic capacitor according to the invention is: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry, and baking and curing after dipping finishes makes the monolithic solid electrolytic capacitor.
Preferably, the temperature of said baking and curing is 120-180 ℃, for example 120 ℃, 131 ℃, 144 ℃, 153 ℃, 160 ℃, 175 ℃, 179 ℃, 180 ℃ etc., and preferred 150 ℃; Preferably, the time of said baking and curing is 30-120min, for example 30min, 45min, 78min, 95min, 118min, 120min etc., preferably 30-60min.
As optimal technical scheme; The preparation method of solid electrolytic capacitor according to the invention is: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry; Baking 30-60min curing in 150 ℃ of baking ovens made the monolithic solid electrolytic capacitor after dipping finished.
Compared with prior art, the present invention has following beneficial effect:
(1) the solid electrolytic capacitor device carbon paste layer of the present invention's preparation selects for use Graphene to replace the carbon and the graphite of prior art, can satisfy under the prerequisite of conductivity, reduces the content of carbon, thereby reduces the thickness of electrode slice.Carbon paste layer adhesion provided by the invention is strong, has especially improved the adhesion of carbon paste layer and silver slurry layer, has reduced the carbon content in the solid electrolytic capacitor carbon paste layer; But do not reduce the electric conductivity of material; Reduced contact resistance, increased thermal endurance, be fit to large-scale promotion and adopt.
(2) as optimal technical scheme; The present invention is used for substituting carbon and the graphite in the prior art carbon paste layer with the grapheme material of the disclosed preparation porous of CN 102070140 A, three-dimensional structure; Can improve the adhesion of first cathode layer and elargol layer, reduce the carbon content of first cathode layer in the solid electrolyte capacitor, not reduce the electric conductivity of material simultaneously again; Reduce contact resistance, and increase thermal endurance.
(3) preparation method of carbon paste layer provided by the present invention is simple, and is easy to operate, is suitable for large-scale production.And as optimal technical scheme, the preparation method of the grapheme material of porous provided by the invention, three-dimensional structure is also very simple, and is suitable for large-scale industrialization production, so the present invention has boundless market prospects.
(4) electrode slice of solid electrolytic capacitor provided by the invention is under the prerequisite of same conductivity, and thickness is little, on using, bigger usage space can be provided, and has very wide application prospect.
Description of drawings
Fig. 1 is the structural representation of solid electrolytic capacitor.
Fig. 2 is the microstructure sketch map of solid electrolytic capacitor carbon paste layer according to the invention.
Fig. 3 is a laminated solid electrolytic capacitor according to the invention.
Wherein, 1-cathode portion; The 2-insulating barrier; The 3-anode part; 4-porousness aluminum metallic foil; The 5-aluminum oxide dielectric layer; The 6-electroconductive polymer layer; 7-carbon paste layer; 8-elargol layer; The partial enlarged drawing of 9-carbon paste layer according to the invention; 10-monolithic solid electrolytic capacitor.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
A kind of method for preparing solid electrolytic capacitor carbon paste layer comprises following preparation process:
(1) takes by weighing a certain amount of Graphene derived material powder of producing with the said method of patent CN102070140A, place agate mortar, grind evenly; With ground powder, organic solvent N, dinethylformamide (DMF) and epoxy resin of binder are according to mass fraction: Graphene 5%; Binding agent 30%; Organic solvent 65% mixed the stirring back ultrasonic 30 minutes, obtained finely dispersed black suspension;
(2) will need the electrode of carbon coated glue-line in graphene suspension, to adopt infusion process to cover Graphene carbon paste layer;
(3) preliminary drying 10min in 80 ℃ of baking ovens, baking 30-60min solidifies in 150 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 10min in 80 ℃ of baking ovens solidifies 30-60min then in 150 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry; Baking 30-60min curing in 150 ℃ of baking ovens after dipping finishes; Make the monolithic solid electrolytic capacitor; The monolithic solid electrolytic capacitor is repeatedly assembled, be prepared into laminated solid electrolytic capacitor.
A kind of method for preparing solid electrolytic capacitor carbon paste layer comprises following preparation process:
(1) takes by weighing a certain amount of Graphene derived material powder of producing with the said method of patent CN102070140A, place agate mortar, grind evenly; With ground powder, organic solvent 1-Methyl-2-Pyrrolidone and binding agent polymethyl methacrylate according to mass fraction: Graphene 10%; Binding agent 30%; Organic solvent 60% mixed the stirring back ultrasonic 30 minutes, obtained finely dispersed black suspension;
(2) will need the electrode of carbon coated glue-line in graphene suspension, to adopt infusion process to cover Graphene carbon paste layer;
(3) preliminary drying 10min in 80 ℃ of baking ovens, baking 30-60min solidifies in 150 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 10min in 80 ℃ of baking ovens solidifies 30-60min then in 150 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry; Baking 30-60min curing in 150 ℃ of baking ovens after dipping finishes; Make the monolithic solid electrolytic capacitor; The monolithic solid electrolytic capacitor again through repeatedly assembling, is prepared into laminated solid electrolytic capacitor.
A kind of method for preparing solid electrolytic capacitor carbon paste layer comprises following preparation process:
(1) takes by weighing a certain amount of grapheme material powder, place agate mortar, grind evenly; With ground powder, organic solvent dimethyl sulfoxide (DMSO) and binding agent acrylic resin according to mass fraction: Graphene 0.1%; Binding agent 35%; Organic solvent 64.9% mixed the stirring back ultrasonic 30 minutes, obtained finely dispersed black suspension;
(2) will need the electrode of carbon coated glue-line in graphene suspension, to adopt infusion process to cover Graphene carbon paste layer;
(3) preliminary drying 15min in 60 ℃ of baking ovens, baking 100min solidifies in 200 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 10min in 80 ℃ of baking ovens solidifies 30-60min then in 150 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry; Baking 30-60min curing in 150 ℃ of baking ovens after dipping finishes; Make the monolithic solid electrolytic capacitor; The monolithic solid electrolytic capacitor again through repeatedly assembling, is prepared into laminated solid electrolytic capacitor.
The preparation of solid electrolytic capacitor:
(4) will cover in the product immersion silver slurry of Graphene carbon paste layer with infusion process again, and in 180 ℃ of baking ovens, dry by the fire 30min after dipping finishes and solidify, make the monolithic solid electrolytic capacitor.
A kind of method for preparing solid electrolytic capacitor comprises the steps:
At first, a large amount of nanometer level microporous three-dimensional grapheme materials are contained on the preparation surface, comprise the steps:
(1) graphite oxide is placed water (concentration of graphite oxide is 4mg/mL), carry out sonicated, ultrasonic power 200W, ultrasonic time 2.5h obtains graphite oxide suspension; (2) sodium hydrate aqueous solution of configuration 7mol/L; (3) sodium hydrate aqueous solution of step (2) is joined in the graphite oxide suspension of step (1) (guaranteeing that the NaOH and the mass ratio of graphite oxide are 40:1), stir filtration, drying; (4) with the resulting solid in the dry back of step (3) at 1000 ℃ of following sintering; (5) solid that step (4) is obtained is washed, is filtered, drying obtains the surface and contains a large amount of nanometer level microporous three-dimensional grapheme materials.
The method for preparing solid electrolytic capacitor carbon paste layer comprises following preparation process:
(1) takes by weighing a certain amount of above-mentioned surface and contain a large amount of nanometer level microporous three-dimensional grapheme material grapheme material powder, place agate mortar, grind evenly; With ground powder, organic solvent dimethyl sulfoxide (DMSO) and binding agent acrylic resin and epoxy resin (mass ratio 20:3) according to mass fraction: Graphene 20%; Binding agent 25%; Organic solvent 55% mixed the stirring back ultrasonic 40 minutes, obtained finely dispersed black suspension;
(2) will need the electrode of carbon coated glue-line in graphene suspension, to adopt infusion process to cover Graphene carbon paste layer;
(3) preliminary drying 8min in 95 ℃ of baking ovens, baking 120min solidifies in 100 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 8min in 95 ℃ of baking ovens solidifies 120min then in 100 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry, floods the back baking 50min in 120 ℃ of baking ovens that finishes and solidifies, and makes the monolithic solid electrolytic capacitor., the monolithic solid electrolytic capacitor again through repeatedly assembling, is prepared into laminated solid electrolytic capacitor.
A kind of method for preparing solid electrolytic capacitor comprises the steps:
At first, a large amount of nanometer level microporous three-dimensional grapheme materials are contained on the preparation surface, comprise the steps:
(1) graphite oxide is placed water (concentration of graphite oxide is 10mg/mL), carry out sonicated, ultrasonic power 500W, ultrasonic time 5h obtains graphite oxide suspension; (2) sodium hydrate aqueous solution of configuration 10mol/L; (3) sodium hydrate aqueous solution of step (2) is joined in the graphite oxide suspension of step (1) (guaranteeing that the NaOH and the mass ratio of graphite oxide are 30:1), stir filtration, drying; (4) with the resulting solid in the dry back of step (3) at 1200 ℃ of following sintering; (5) solid that step (4) is obtained is washed, is filtered, drying obtains the surface and contains a large amount of nanometer level microporous three-dimensional grapheme materials.
The method for preparing solid electrolytic capacitor carbon paste layer then comprises following preparation process:
(1) takes by weighing a certain amount of grapheme material powder, place agate mortar, grind evenly; With ground powder, organic solvent acetonitrile and acetone (volume ratio 1:1) and binding agent polyamino resin according to mass fraction: Graphene 1%; Binding agent 25%; Organic solvent 74% mixed the stirring back ultrasonic 20 minutes, obtained finely dispersed black suspension;
(2) will need the electrode of carbon coated glue-line in graphene suspension, to adopt infusion process to cover Graphene carbon paste layer;
(3) preliminary drying 18min in 95 ℃ of baking ovens, baking 30min solidifies in 200 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 18min in 95 ℃ of baking ovens solidifies 30min then in 200 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry, floods the back baking 62min in 150 ℃ of baking ovens that finishes and solidifies, and makes the monolithic solid electrolytic capacitor., the monolithic solid electrolytic capacitor again through repeatedly assembling, is prepared into laminated solid electrolytic capacitor.
Comparative Examples
A kind of method for preparing solid electrolytic capacitor carbon paste layer comprises following preparation process:
(1) takes by weighing a certain amount of carbon dust, place agate mortar, grind evenly; With ground powder, organic solvent N, dinethylformamide and epoxy resin of binder are according to mass fraction: carbon dust 5%; Binding agent 30%; Organic solvent 65% mixing and stirring obtains black suspension;
(2) will need the electrode of carbon coated glue-line in the suspension of step (1) gained, to adopt infusion process to cover upward carbon paste layer;
(3) preliminary drying 10min in 80 ℃ of baking ovens, baking 30-60min solidifies in 150 ℃ of baking ovens.
(4) resistivity of test carbon paste layer: on slide, apply the carbon paste tunic of 10mm * 40mm * 25 μ m, preliminary drying 10min in 80 ℃ of baking ovens solidifies 30-60min then in 150 ℃ of baking ovens, the resistance of test 40mm length direction.
(5) preparation solid electrolytic capacitor: the product that will cover Graphene carbon paste layer with infusion process immerses in the silver slurry; Baking 30-60min curing in 150 ℃ of baking ovens after dipping finishes; Make the monolithic solid electrolytic capacitor; The monolithic solid electrolytic capacitor again through repeatedly assembling, is prepared into laminated solid electrolytic capacitor.
Contrast test
Carbon content, thickness, resistance to embodiment 1-embodiment 5 and the prepared solid electrolytic capacitor carbon paste of Comparative Examples layer; And the equivalent series resistance of solid electrolytic capacitor (ESR) detects, and performance test results is as shown in table 1.
The performance of the solid electrolytic capacitor of table 1 solid electrolytic capacitor carbon paste layer and preparation relatively
Can find out according to contrast test; The Graphene of selecting for use provided by the invention is compared with the common solid electrolytic capacitor as the solid electrolytic capacitor of carbon paste layer; The carbon paste layer thickness is little when can guaranteeing carbon content; And resistance is little, and the also more common solid electrolytic capacitor of the ESR of prepared solid electrolytic capacitor is little a lot, and minimum can reach 5m Ω.Especially select for use the surface to contain a large amount of nanometer level microporous three-dimensional grapheme materials as the carbon paste layer; Can reach especially that thickness only has 36 μ m under 20% the carbon content condition; And resistance has only 10 Ω, and the ESR of the solid electrolytic capacitor that this carbon paste layer of usefulness prepares is very little, and 5m Ω is only arranged; Be that prior art is incomparable, have boundless use and market prospects.
Applicant's statement; The above is merely the preferred embodiments of the present invention; Be not limited to the present invention, although the present invention has been carried out detailed explanation, for a person skilled in the art with reference to previous embodiment; It still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a solid electrolytic capacitor carbon paste layer is characterized in that, said method is the electrode that needs the carbon coated glue-line to be immersed contain in the emulsion of conductive non-metals, binding agent and organic solvent, after solidifying, obtains the carbon paste layer; Said conductive non-metals is a Graphene class material.
2. the method for claim 1 is characterized in that, said Graphene class material is selected from Graphene or Graphene derived material;
Preferably, said Graphene class material has three-dimensional structure, and the surface is contained nanometer level microporous in a large number; Preferably, said Graphene class conductivity of electrolyte materials >=100mS/m; Further preferably, the surface of said Graphene class material has the micropore of aperture in the 2nm-100nm scope;
Preferably, the preparation process that a large amount of nanometer level microporous Graphene class materials with three-dimensional structure are contained on said surface is: graphene powder and highly basic reaction with heat treatment or microwave irradiation obtain, pass through reprocessing and prepare.
3. according to claim 1 or claim 2 method; It is characterized in that; Said binding agent is the resinae binding agent, a kind or at least 2 kinds combination in said resinae binding agent preferred epoxy, acrylic resin, polymethyl methacrylate and the polyamino resin, further preferred epoxy;
Preferably; Said organic solvent is N; 1 kind or at least 2 kinds combination in dinethylformamide, 1-Methyl-2-Pyrrolidone, dimethyl sulfoxide (DMSO), oxolane, propene carbonate, acetone, acetonitrile, pyridine and the chlorobenzene; Preferred N, dinethylformamide and/or 1-Methyl-2-Pyrrolidone.
4. like the described method of one of claim 1-3, it is characterized in that said method comprises the steps:
(1) grapheme material, resinae binding agent, organic solvent are mixed processes emulsion;
The electrode that (2) will need the carbon coated glue-line prepares at cathode layer and adopts infusion process to cover carbon paste layer emulsion in the emulsion;
(3) baking and curing is prepared into the carbon paste layer.
5. method as claimed in claim 4 is characterized in that, the mass percent that the said grapheme material of step (1) accounts for mixed emulsion is 0.1-20wt%, preferred 0.1-10wt%, further preferred 3-10wt%.
6. like claim 4 or 5 described methods, it is characterized in that the mass percent that the said resinae binding agent of step (1) accounts for mixed emulsion is 25-35wt%, preferred 30wt%.
7. like the described method of one of claim 4-6, it is characterized in that the mass percent that the said organic solvent of step (1) accounts for mixed emulsion is 55-74wt%, preferred 60-65wt%.
8. like the described method of one of claim 4-7, it is characterized in that the said baking and curing of step (3) is carried out in baking oven, preferably carry out preliminary drying earlier, elevated temperature continues oven dry then; The preferred vacuum drying oven of said baking oven;
Preferably, the temperature of said preliminary drying is 60-95 ℃, and the said preliminary drying time is 8-20min; Preferably, the temperature of said oven dry is 100-200 ℃, and said drying time is 30-120min; Further preferably, the temperature of said oven dry is 150-180 ℃, and said drying time is 30-60min.
9. a solid electrolytic capacitor carbon paste layer is characterized in that, said carbon paste layer is by preparing like the described method of one of claim 1-8, and the density of said carbon paste layer is 0.05g/cm
3To 1g/cm
3, thickness is 50nm-500 μ m, and carbon content is 0.1-20%, and resistance is 10-150 Ω.
10. a solid electrolytic capacitor is characterized in that, said solid electrolytic capacitor contains carbon paste layer as claimed in claim 9, and the equivalent series resistance of said solid electrolytic capacitor is 5-20m Ω.
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| WO2013166928A1 (en) * | 2012-05-11 | 2013-11-14 | 常州第六元素材料科技股份有限公司 | Solid electrolytic capacitor carbon rubber layer and method for manufacturing same |
| CN103833009A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene, its preparation method, electrode slice and supercapacitor |
| CN108010725A (en) * | 2016-10-27 | 2018-05-08 | 株式会社东金 | Solid electrolyte capacitators |
| CN108163848A (en) * | 2017-12-08 | 2018-06-15 | 常州第六元素材料科技股份有限公司 | A kind of graphene particles, preparation method and its equipment |
| CN110942917A (en) * | 2018-09-21 | 2020-03-31 | 钰冠科技股份有限公司 | Capacitor packaging structure, capacitor and polymer composite layer |
| CN110942918A (en) * | 2018-09-21 | 2020-03-31 | 钰冠科技股份有限公司 | Stacked capacitor, manufacturing method thereof and silver colloid layer |
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| CN102683038B (en) * | 2012-05-11 | 2016-06-01 | 常州第六元素材料科技股份有限公司 | A kind of solid electrolytic capacitor rubber layer and preparation method thereof |
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| CN102439670A (en) * | 2009-05-21 | 2012-05-02 | 凯米特电子公司 | Solid electrolytic capacitors with improved reliability |
| CN101941693A (en) * | 2010-08-25 | 2011-01-12 | 北京理工大学 | Graphene aerogel and preparation method thereof |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
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| WO2013166928A1 (en) * | 2012-05-11 | 2013-11-14 | 常州第六元素材料科技股份有限公司 | Solid electrolytic capacitor carbon rubber layer and method for manufacturing same |
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| CN110942917A (en) * | 2018-09-21 | 2020-03-31 | 钰冠科技股份有限公司 | Capacitor packaging structure, capacitor and polymer composite layer |
| CN110942918A (en) * | 2018-09-21 | 2020-03-31 | 钰冠科技股份有限公司 | Stacked capacitor, manufacturing method thereof and silver colloid layer |
| CN110942918B (en) * | 2018-09-21 | 2022-08-12 | 钰冠科技股份有限公司 | Stacked capacitor, manufacturing method thereof and silver colloid layer |
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