CN104599866A - Hybrid electrolytic capacitor and manufacturing method thereof - Google Patents
Hybrid electrolytic capacitor and manufacturing method thereof Download PDFInfo
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- CN104599866A CN104599866A CN201310523507.0A CN201310523507A CN104599866A CN 104599866 A CN104599866 A CN 104599866A CN 201310523507 A CN201310523507 A CN 201310523507A CN 104599866 A CN104599866 A CN 104599866A
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Abstract
The invention relates to a hybrid electrolytic capacitor composed of a positive electrode, a negative electrode, a membrane, and an electrolyte. The positive electrode is connected with an electrolytic capacitor positive plate which is composed of valve metal or niobium monoxide and an oxide of valve metal or an oxide of niobium monoxide covering the surface of valve metal or niobium monoxide. The negative electrode is connected with a super capacitor negative plate which is composed of a negative current collector and a negative active layer covering the surface of the negative current collector and containing negative active materials. The super capacitor negative active materials include at least one among a conductive polymer, a lithium compound, grapheme, activated carbon, nanocarbon, carbon gel, carbon fiber, soft carbon, hard carbon and graphite or at least one among a lithium-doped conductive polymer, a lithium compound, grapheme, activated carbon, nanocarbon, carbon gel, carbon fiber, soft carbon, hard carbon and graphite. The hybrid electrolytic capacitor of the invention has the advantages of high energy density, low cost, and simple manufacture process.
Description
Technical field
The present invention relates to a kind of mixed type electrolytic capacitor and preparation method thereof.
Background technology
Electrolytic capacitor has fast charging and discharging characteristic, is widely used in consumer electronics, communication, automotive electronics, aviation military field.But electronic product is towards the trend development of miniaturization, this just requires that the volume of electrolytic capacitor is also less, and improves the energy density of electrolytic capacitor, can effectively reduce the volume of electrolytic capacitor, meet the requirement of small size better.Mixed type electrolytic capacitor is the super capacitor anode sheet adopting Fabrication of High Specific Capacitance, substitutes the negative plate in traditional electrolyte capacitors, substantially reduces the volume of negative plate; Under the prerequisite of same volume and quality, the volume of positive plate is increased, thus improves capacity.E=1/2CV again
2, wherein E is energy, and C is capacity, and V is rated voltage, and the capacity of mixed type electrolytic capacitor significantly improves compared with the electrolytic capacitor of same volume and quality, and corresponding energy density also significantly improves.And existing mixed type electrolytic capacitor generally adopts noble metal as electrode of super capacitor active material, cost is too high.
Summary of the invention
The present invention is directed to above-mentioned prior art Problems existing and make improvement, namely technical problem to be solved by this invention is to provide and a kind ofly has high-energy-density, low cost, mixed type electrolytic capacitor that preparation technology is simple and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme one of the present invention is: a kind of mixed type electrolytic capacitor, by positive pole, negative pole, barrier film and electrolyte composition, described positive pole connects electrolytic capacitor positive plate, described electrolytic capacitor positive plate is by valve metal or columbium monoxide and be covered in the corresponding oxide of valve metal of valve metal or columbium monoxide surface or the oxide of columbium monoxide is formed, described negative pole connects super capacitor anode sheet, described super capacitor anode sheet is by negative current collector and be covered in the negative electrode active layer that negative pole currect collecting surface comprises negative active core-shell material and form, described super capacitor anode active material is conducting polymer, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite or the conducting polymer of elements doped lithium, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite.
Further, described valve metal is any one in aluminium, tantalum, niobium, titanium, zirconium.
Further, described electrolytic capacitor positive plate surface is also coated with solid-state conductive layer, and the material of described solid-state conductive layer comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.
Further, conducting polymer in described super capacitor anode active material is polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, polypyridine and derivative thereof, gathers at least one in benzene and its derivative, poly quinoline and derivative thereof, and described lithium compound is at least one in cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickel cobalt manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium titanate, lithium nickelate, lithium vanadate, ferric metasilicate lithium.
Further, described electrolyte is liquid electrolyte or solid electrolyte, described liquid electrolyte is at least one in aqueous electrolyte, organic system electrolyte, il electrolyte, and described solid electrolyte is at least one in inorganic solid electrolyte, gel solid state electrolyte, organic solid-state electrolyte.
Further, described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
In order to solve the problems of the technologies described above, technical scheme two of the present invention is: a kind of manufacture method of mixed type electrolytic capacitor, carries out according to the following steps:
(1) preparation of electrolytic capacitor positive plate: at valve metal or the oxide of the corresponding valve metal of columbium monoxide surface coverage one deck or the oxide of columbium monoxide, make electrolytic capacitor positive plate;
(2) connection of positive pole: the valve metal of electrolytic capacitor positive plate or columbium monoxide are connected with positive pole;
(3) preparation of super capacitor anode sheet: cover at super capacitor anode collection liquid surface the negative electrode active layer that at least one deck comprises negative active core-shell material, make super capacitor anode sheet;
(4) connection of negative pole: the negative current collector of super capacitor anode sheet is connected with negative pole;
(5) encapsulate: between electrolytic capacitor positive plate and super capacitor anode sheet, arrange barrier film, add electrolyte, many group pole pieces are assembled at least one mode in series, parallel and are packaged into mixed type electrolytic capacitor.
Further, in step (1), also cover at least one deck solid-state conductive layer on electrolytic capacitor positive plate surface, the material of described solid-state conductive layer comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.
Further, described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
Compared with prior art, the present invention has following beneficial effect: this mixed type electrolytic capacitor has high-energy-density, low cost, the simple advantage of preparation technology.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described in detail.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention 1.
Fig. 2 is the structural representation of the embodiment of the present invention 2.
In figure: 1-valve metal or columbium monoxide, the oxide of 2-valve metal or the oxide of columbium monoxide, 3-solid-state conductive layer, 4-electrolytic capacitor positive plate, 5-super capacitor anode collector, 6-super capacitor anode active layer, 7-super capacitor anode sheet, 8-barrier film, 9-electrolyte, 10-positive pole, 11-negative pole.
Embodiment
As shown in Figure 1 and 2, a kind of mixed type electrolytic capacitor, by positive pole 10, negative pole 11, barrier film 8 and electrolyte 9 form, described positive pole 10 connects electrochemical capacitor positive plate 4, described electrolytic capacitor positive plate 4 is by valve metal or columbium monoxide 1 and be covered in the corresponding oxide of valve metal of valve metal or columbium monoxide 1 surface or the oxide 2 of columbium monoxide is formed, described negative pole 11 connects super capacitor anode sheet 7, described super capacitor anode sheet 7 is by super capacitor anode collector 5 and be covered in the super capacitor anode active layer 6 that negative current collector 5 surface comprises negative active core-shell material and form, described super capacitor anode active material is conducting polymer, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite or the conducting polymer of elements doped lithium, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite.
The present invention is at negative current collector 5 surface coverage super capacitor anode active layer 6 by coating, spraying, dipping, printing, printing, chemical reaction, electrochemical reaction, thermal response or sputtering sedimentation mode.Described super capacitor anode collector 5 is the paper tinsel of at least one in aluminium, copper, nickel, tantalum, titanium, lead, stainless steel, carbon, graphite, conducting polymer or Graphene, net or block.
In the present invention, described ultracapacitor is any one in double electric layer capacitor, electrochemical capacitor, pseudocapacitors, lithium-ion capacitor.
In the present invention, described valve metal is any one in aluminium, tantalum, niobium, titanium, zirconium.The oxide of its surface coverage is that the oxide 2(of the oxide of corresponding valve metal or columbium monoxide is as niobium pentaoxide).Such as: valve metal is aluminium foil, the oxide on its surface is alundum (Al2O3); Valve metal is tantalum block, and the oxide on its surface is tantalum pentoxide.
In the present invention, the oxide of described valve metal or oxide 2 surface of columbium monoxide can also be coated with solid-state conductive layer 3, and the material of described solid-state conductive layer 3 comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.The present invention is by coating, spraying, dipping, printing, printing, chemical reaction, electrochemical reaction, thermal response or the sputtering sedimentation mode oxide at valve metal or the oxide 2 surface coverage solid-state conductive layer 3 of columbium monoxide.
In the present invention, the conducting polymer in described super capacitor anode active material is polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, polypyridine and derivative thereof, gathers at least one in benzene and its derivative, poly quinoline and derivative thereof.Described lithium compound is at least one in cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickel cobalt manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium titanate, lithium nickelate, lithium vanadate, ferric metasilicate lithium.
In the present invention, described electrolyte 9 is liquid electrolyte or solid electrolyte, described liquid electrolyte is at least one in aqueous electrolyte, organic system electrolyte, il electrolyte, and described solid electrolyte is at least one in inorganic solid electrolyte, gel solid state electrolyte, organic solid-state electrolyte.
In the present invention, described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
In the present invention, the manufacture method of this hybrid capacitors, carry out according to the following steps:
(1) preparation of electrolytic capacitor positive plate 4: at valve metal or the oxide of the corresponding valve metal of columbium monoxide 1 surface coverage one deck or the oxide 2 of columbium monoxide, make electrolytic capacitor positive plate 4;
(2) connection of positive pole 10: the valve metal of electrolytic capacitor positive plate 4 or columbium monoxide 1 are connected with positive pole 10;
(3) preparation of super capacitor anode sheet 7: super capacitor anode collector 5 surface coverage at least one deck comprise the negative electrode active layer 6 of negative active core-shell material, make super capacitor anode sheet 7;
(4) connection of negative pole 11: the negative current collector 5 of super capacitor anode sheet 7 is connected with negative pole 11;
(5) encapsulate: between electrolytic capacitor positive plate 4 and super capacitor anode sheet 7, arrange barrier film 8, add electrolyte 9, many group pole pieces are assembled at least one mode in series, parallel and are packaged into mixed type electrolytic capacitor.
In step (1), can also cover at least one deck solid-state conductive layer 3 on electrolytic capacitor positive plate 4 surface, the material of described solid-state conductive layer comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.
In step (5), described barrier film 8 can prevent positive plate from directly contacting and short circuit with negative plate, but allows the conduction of ion.Described barrier film 8 is at least one in polyethene microporous membrane, microporous polypropylene membrane, polyvinylidene fluoride microporous film, polypropylene-polyethylene composite membrane, inorganic ceramic membrane, paper barrier film, nonwoven fabrics barrier film.
In the present invention, described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
In the present invention, the electrode slice of described mixed type electrolytic capacitor inside with the mode such as lamination, winding be assembled into sheet, square, button, cylindric in any one, also can be assembled into irregularly shaped.
In the present invention, mixed type electrolytic capacitor is the super capacitor anode sheet adopting Fabrication of High Specific Capacitance, substitutes the negative plate in traditional electrolyte capacitors, substantially reduces the volume of negative plate; Under the prerequisite of same volume and quality, the volume of positive plate is increased, thus improves capacity.E=1/2CV again
2, wherein E is energy, and C is capacity, and V is rated voltage, therefore the capacity of mixed type electrolytic capacitor of the present invention significantly improves compared with the electrolytic capacitor of same volume and quality, and its energy density also significantly improves.
embodiment 1:as shown in Figure 1, wherein, the valve metal 1 of electrolytic capacitor positive plate 4 is corrosive aluminum foil, and the valve metal oxides 2 of surface coverage is alundum (Al2O3), is made into electrolytic capacitor positive plate 4; Surface also covers the solid-state conductive layer 3 comprising conduction Polyglycolic acid fibre; The valve metal 1 of electrolytic capacitor positive plate 4 is connected with positive pole 10.Wherein, the negative current collector 5 of super capacitor anode sheet 7 is aluminium foil, and surface coverage comprises the negative electrode active layer 6 of activated carbon, is made into super capacitor anode sheet 7; The negative current collector 5 of super capacitor anode sheet 7 is connected with negative pole 11.Between the electrolytic capacitor positive plate 4 of surface coverage solid-state conductive layer 3 and super capacitor anode sheet 7, barrier film 8 is set, adds electrolyte 9, reel and be packaged into cylindric mixed type electrolytic capacitor.
comparative example 1:the aluminium electrolytic capacitor of same volume prepared by conventional method.
embodiment 2:as shown in Figure 2, wherein, the valve metal 1 of electrolytic capacitor positive plate is sintering tantalum block, surface coverage valve metal oxides 2 is tantalum pentoxide, be made into electrolytic capacitor positive plate 4, wherein, the negative current collector 5 of super capacitor anode sheet is tantalum paper tinsel, surface coverage comprises the negative electrode active layer 6 of activated carbon, is made into super capacitor anode sheet 7; The negative current collector 5 of super capacitor anode sheet 7 is connected with negative pole 11.Arrange barrier film 8 between electrolytic capacitor positive plate 4 and super capacitor anode sheet 7, add electrolyte 9, lamination is also packaged into sheet mixed type electrolytic capacitor.
comparative example 2:same volume tantalum electrolytic capacitor prepared by conventional method.
Embodiment 1, the energy density of 2 mixed type electrolytic capacitors and comparative example 1,2 electrolytic capacitor, as shown in table 1.
The mixed type electrolytic capacitor comparatively electrolytic capacitor prepared of comparative example 1 ~ 2 conventional method prepared by the embodiment of the present invention 1 ~ 2, energy density improves more than 2 times.
embodiment 3:as different from Example 1, the solid-state conductive layer 3 of electrolytic capacitor comprises electric polypyrrole.
embodiment 4:as different from Example 1, the solid-state conductive layer 3 of electrolytic capacitor comprises manganese dioxide and electrically conductive polyaniline.
embodiment 5:as different from Example 1, mixed type electrolytic capacitor comprises 2 electrolytic capacitor positive plates and 1 super capacitor anode sheet, overlapping arrangement between electrolytic capacitor positive plate; Insert barrier film 8 between electrolytic capacitor positive plate 4 and super capacitor anode sheet 7, add electrolyte 9, reel and be packaged into cylindric mixed type electrolytic capacitor.
embodiment 6:as different from Example 1, mixed type electrolytic capacitor comprises 2 electrolytic capacitor positive plates and 2 super capacitor anode sheets, be spaced between electrolytic capacitor positive plate 4 and super capacitor anode sheet 7, and insert barrier film 8 respectively, add electrolyte 9, many group pole piece laminatings are also packaged into sheet mixed type electrolytic capacitor.
embodiment 7:as different from Example 1, mixed type electrolytic capacitor comprises 1 electrolytic capacitor positive plate and 2 super capacitor anode sheets, overlapping arrangement between super capacitor anode sheet; Insert barrier film 8 between electrolytic capacitor positive plate 4 and super capacitor anode sheet 7, add electrolyte 9, many group pole piece coilings are also packaged into cylindric mixed type electrolytic capacitor.
embodiment 8:as different from Example 2, the surface of electrolytic capacitor positive plate 4 also covers solid-state conductive layer 3, and solid-state conductive layer 3 comprises manganese dioxide.
embodiment 9:as different from Example 2, ultracapacitor active layer 6 comprises Graphene and electric polypyrrole.
embodiment 10:as different from Example 2, ultracapacitor active layer 6 comprises cobalt acid lithium.
embodiment 11:as different from Example 2, ultracapacitor active layer 6 comprises the activated carbon of elements doped lithium.
The data of the mixed type electrolytic capacitor of embodiment 3 ~ 10 are as shown in table 2.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. a mixed type electrolytic capacitor, by positive pole, negative pole, barrier film and electrolyte composition, it is characterized in that: described positive pole connects electrolytic capacitor positive plate, described electrolytic capacitor positive plate is by valve metal or columbium monoxide and be covered in the corresponding oxide of valve metal of valve metal or columbium monoxide surface or the oxide of columbium monoxide is formed, described negative pole connects super capacitor anode sheet, described super capacitor anode sheet is by negative current collector and be covered in the negative electrode active layer that negative pole currect collecting surface comprises negative active core-shell material and form, described super capacitor anode active material is conducting polymer, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite or the conducting polymer of elements doped lithium, lithium compound, Graphene, active carbon, nano-sized carbon, carbon gel, carbon fiber, soft carbon, hard carbon, at least one in graphite.
2. mixed type electrolytic capacitor according to claim 1, is characterized in that: described valve metal is any one in aluminium, tantalum, niobium, titanium, zirconium.
3. mixed type electrolytic capacitor according to claim 1 and 2, it is characterized in that: described electrolytic capacitor positive plate surface is also coated with solid-state conductive layer, the material of described solid-state conductive layer comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.
4. mixed type electrolytic capacitor according to claim 1, is characterized in that: the conducting polymer in described super capacitor anode active material is polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, polypyridine and derivative thereof, gathers at least one in benzene and its derivative, poly quinoline and derivative thereof.
5. mixed type electrolytic capacitor according to claim 1, is characterized in that: the lithium compound in described super capacitor anode active material is at least one in cobalt acid lithium, LiMn2O4, LiFePO4, lithium nickel cobalt manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium titanate, lithium nickelate, lithium vanadate, ferric metasilicate lithium.
6. mixed type electrolytic capacitor according to claim 1, it is characterized in that: described electrolyte is liquid electrolyte or solid electrolyte, described liquid electrolyte is at least one in aqueous electrolyte, organic system electrolyte, il electrolyte, and described solid electrolyte is at least one in inorganic solid electrolyte, gel solid state electrolyte, organic solid-state electrolyte.
7. mixed type electrolytic capacitor according to claim 1, it is characterized in that: described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
8. the manufacture method of mixed type electrolytic capacitor according to claim 1, is characterized in that, carries out according to the following steps:
(1) preparation of electrolytic capacitor positive plate: at valve metal or the oxide of the corresponding valve metal of columbium monoxide surface coverage one deck or the oxide of columbium monoxide, make electrolytic capacitor positive plate;
(2) connection of positive pole: the valve metal of electrolytic capacitor positive plate or columbium monoxide are connected with positive pole;
(3) preparation of super capacitor anode sheet: cover at super capacitor anode collection liquid surface the negative electrode active layer that at least one deck comprises negative active core-shell material, make super capacitor anode sheet;
(4) connection of negative pole: the negative current collector of super capacitor anode sheet is connected with negative pole;
(5) encapsulate: between electrolytic capacitor positive plate and super capacitor anode sheet, arrange barrier film, add electrolyte, many group pole pieces are assembled at least one mode in series, parallel and are packaged into mixed type electrolytic capacitor.
9. the manufacture method of mixed type electrolytic capacitor according to claim 8, it is characterized in that: in step (1), also cover at least one deck solid-state conductive layer on electrolytic capacitor positive plate surface, the material of described solid-state conductive layer comprises polypyrrole and derivative, polythiophene and derivative thereof, Polyaniline and its derivative, polystyrene and derivative, at least one of gathering in Furan and its derivatives, manganese dioxide.
10. the manufacture method of mixed type electrolytic capacitor according to claim 8, it is characterized in that: described mixed type electrolytic capacitor also comprises multiple electrolytic capacitor positive plate and multiple super capacitor anode sheet, and multiple electrolytic capacitor positive plate is connected at least one mode in series, parallel with multiple super capacitor anode sheet.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106876146A (en) * | 2017-03-31 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of high-voltage solid-state lithium-ion capacitor |
| CN108417408A (en) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | A kind of ultracapacitor and preparation method thereof |
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| US20120063059A1 (en) * | 2010-09-09 | 2012-03-15 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor and method of manufacturing the same |
| CN103021670A (en) * | 2012-12-25 | 2013-04-03 | 上海奥威科技开发有限公司 | Tantalum anode and activated carbon cathode based hybrid super capacitor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101256902A (en) * | 2007-02-28 | 2008-09-03 | 三洋电机株式会社 | Solid electrolytic capacitor and method for manufacturing same |
| US20120063059A1 (en) * | 2010-09-09 | 2012-03-15 | Samsung Electro-Mechanics Co., Ltd. | Hybrid supercapacitor and method of manufacturing the same |
| CN103021670A (en) * | 2012-12-25 | 2013-04-03 | 上海奥威科技开发有限公司 | Tantalum anode and activated carbon cathode based hybrid super capacitor |
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| CN106876146A (en) * | 2017-03-31 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of high-voltage solid-state lithium-ion capacitor |
| CN108417408A (en) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | A kind of ultracapacitor and preparation method thereof |
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