CN117275948A - Preparation method of high-energy sheet type laminated solid aluminum electrolytic capacitor - Google Patents
Preparation method of high-energy sheet type laminated solid aluminum electrolytic capacitor Download PDFInfo
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- CN117275948A CN117275948A CN202311344399.0A CN202311344399A CN117275948A CN 117275948 A CN117275948 A CN 117275948A CN 202311344399 A CN202311344399 A CN 202311344399A CN 117275948 A CN117275948 A CN 117275948A
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- anode foil
- foil strip
- aluminum electrolytic
- electrolytic capacitor
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- 239000003990 capacitor Substances 0.000 title claims abstract description 68
- 239000007787 solid Substances 0.000 title claims abstract description 51
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011888 foil Substances 0.000 claims abstract description 80
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000011810 insulating material Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 230000008439 repair process Effects 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- 230000003712 anti-aging effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 230000002950 deficient Effects 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 238000002955 isolation Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- H01G9/07—Dielectric layers
-
- 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
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- 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
- H01G9/14—Structural combinations or circuits for modifying, or compensating for, electric characteristics of electrolytic capacitors
-
- 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)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a preparation method of a high-energy sheet type laminated solid aluminum electrolytic capacitor, which has the following beneficial effects that firstly, a separation belt is arranged, and then a high-temperature resistant insulating material is arranged, so that a surface dielectric medium is repaired in an oxidation mode, and the isolation purpose can be well realized; the separation belt occupies a small space, so that the occupied space of the capacitor can be increased, the capacitance is increased, and the yield and reliability of the product are improved. Secondly, in the microscopic state, the surface of the anode foil strip is in a porous state, and the nano conductive polymer in the nano dispersion liquid is embedded into the holes on the surface of the porous anode foil strip, so that the growth and coverage of the polymer solid conductive layer in the later stage are facilitated, and the polymer solid conductive layer is prepared, thereby improving the problems of equivalent series resistance, yield and stability of the product, and the antioxidant is added into the nano dispersion liquid, so that the prepared polymer solid conductive layer is more stable.
Description
Technical Field
The invention relates to the technical field of aluminum electrolytic capacitor preparation, in particular to a preparation method of a high-energy chip type laminated solid aluminum electrolytic capacitor.
Background
The digitization of electronic devices requires that the high energy capacitor have a small volume, large capacitance, and low impedance characteristics for high frequency applications. Early capacitors applied at high operating frequencies were substantially occupied by thin film capacitors, multilayer ceramic capacitors, and the like. With the rapid development of modern electronic technology, both thin film capacitors and multilayer ceramic capacitors are generally large in size, and the technical difficulty is high and the manufacturing cost is extremely high in order to achieve large capacitance. Although the liquid aluminum electrolytic capacitor can meet the application requirement in the high-capacitance performance, the electric capacity attenuation is very remarkable in the high-working frequency state due to the fact that the electric resistivity of the electrolyte ion conduction is relatively large, the frequency characteristic is extremely poor, and the high-capacitance characteristic can not be realized in the high-frequency state. As solid conductive polymers have been found and rapidly grown, solid aluminum electrolytic capacitors have been developed that employ solid conductive polymers instead of liquid electrolytes. The solid aluminum electrolytic capacitors can be classified into a roll-type solid aluminum electrolytic capacitor and a chip type solid aluminum electrolytic capacitor according to structural characteristics. Compared with the traditional aluminum electrolytic capacitor adopting liquid electrolyte, the chip laminated solid aluminum electrolytic capacitor has the advantages of small volume, large capacitance, good frequency performance, long service life, high reliability, more environmental protection and the like, and can better meet the requirements of the electronic information industry on miniaturization, high frequency, high reliability and high environmental protection.
However, conventional chip stacked solid aluminum electrolytic capacitor fabrication: on the one hand, when distinguishing the anode and the cathode, the anode area and the cathode area are distinguished by directly coating the surface with the barrier adhesive after cutting the aluminum foil, and in order to ensure that the isolation purpose can be achieved, the barrier adhesive occupies a large space, so that the effective capacitance is reduced, and the barrier adhesive is difficult to permeate into the porous medium layer, so that the yield and the reliability are insufficient; on the other hand, the process for manufacturing the solid electrolyte required by the chip type laminated solid aluminum electrolytic capacitor adopts a two-step method preparation of a monomer solution system of the conductive polymer, namely chemical synthesis and electrochemical synthesis. All of them adopt monomer solution system of conductive polymer, firstly, a layer of conductive polymer is synthesized on the dielectric surface of aluminium capacitor by means of chemical method. Next, a layer of the complete conductive polymer is electrochemically synthesized as an electrolyte of the solid aluminum electrolytic capacitor on the basis of the chemically synthesized conductive polymer layer. The conductive polymer monomer solution system synthesis mode is difficult to control uniformly in the application capacitor, so that the electrolyte synthesized by the chemical method has low conductivity and poor stability, the performance of the electrolyte synthesized by the electrochemical method is further affected, and the finally prepared chip type laminated solid aluminum electrolytic capacitor has large equivalent series resistance, low yield and low reliability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a high-energy chip type laminated solid aluminum electrolytic capacitor, which solves the problems mentioned in the background art.
The invention is realized by the following technical scheme:
the preparation method of the high-energy sheet type laminated solid aluminum electrolytic capacitor comprises the following steps:
s1, arranging an electrode leading-out end on a foil strip base band; stamping foil strip base bands at intervals along the length direction to form separating bands, and arranging high-temperature resistant insulating materials in the separating bands to form anode foil strips;
s2, immersing the anode foil strip in repair liquid, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s3, immersing the anode foil strip in a silane solution to form a pre-transition layer on the surface of the anode foil strip;
s4, immersing the anode foil strip in the nano dispersion liquid, drying under a set condition, immersing the anode foil strip in an initiating solution, drying under the set condition, immersing the anode foil strip in the nano dispersion liquid, and circulating the anode foil strip for a plurality of times to prepare a first conductive layer;
s5, the first conductive layer is communicated with the external electrode, and an anodic oxidation reaction is carried out in the conductive polymer stock solution to form a second conductive layer with a repairing function;
s6, immersing the anode foil strip in electrolyte, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s7, preparing a polymer solid conductive layer on the surface of the anode foil strip;
s8, conducting, bonding and stacking a plurality of anode foil strips and arranging the anode foil strips on a conducting frame to obtain a laminated capacitor core strip;
s9, wrapping and protecting the laminated capacitor core strip to prepare a capacitor core group; and cutting the capacitor core group to form the solid aluminum electrolytic capacitor.
Further, step S10 is further included after step S9;
s10, the solid aluminum electrolytic capacitor is subjected to a temperature environment of 80-90 ℃ and a humidity environment of 90%
After the placing treatment is carried out under the condition of R.H to 100 percent of R.H, the defective products are removed by electrifying detection.
Further, in step S1, the separating band is smaller than or equal to 90% of the total thickness of the anode foil strip, and the width of the separating band is not smaller than 5-10 times of the thickness of the anode foil strip.
Further, in the step S2, the temperature of the repair liquid is 55-125 ℃; the pH value of the repair liquid is 5.0-7.0, and the conductivity of the repair liquid is as follows: 30-50 ms/cm.
Further, in step S3, the silane solution is composed of an amino-functional silane, ethanol, and water.
Further, in step S4, the nano dispersion liquid is composed of nano conductive polymer particles, conductive polymer monomers, an adhesive, an antioxidant, a stabilizer and a solvent, and the components in percentage by weight are as follows: 0.01 to 0.10 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.01 to 0.05 percent of adhesive, 0.005 to 0.010 percent of anti-aging agent, 1.00 to 10.00 percent of stabilizer and the balance of solvent.
Further, the conductive polymer is conductive polypyrrole, conductive polyaniline or conductive polythiophene;
the conductive polymer monomer is pyrrole, aniline or thiophene;
the adhesive is aqueous polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber or a combination of the three;
the antioxidant is bisphenol, triphenol, polyphenol or hydroquinone;
the stabilizer is one or more of sodium p-toluenesulfonate, sodium dodecyl sulfonate, sodium alkyl naphthalene sulfonate and sodium lignin sulfonate.
Further, in step S4, the initiating solution is composed of phosphoric acid, sodium sulfonate, potassium permanganate and a solvent, wherein the components are as follows in percentage by weight: phosphoric acid 0.01%, sodium sulfonate 0.3%, potassium permanganate 3%, and the rest weight of the components is solvent.
Further, in step S5, the conductive polymer stock solution is composed of nano conductive polymer particles, conductive polymer monomers, antioxidants, stabilizers and solvents, wherein the components in percentage by weight are as follows: 0.01 to 0.05 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.005 to 0.010 percent of anti-aging agents, 1.00 to 10.00 percent of stabilizers and the balance of solvents.
Further, in step S6, the electrolyte is composed of an organic acid salt, a phosphate and an organic acid, the pH value of the electrolyte is 4.5-7.0, and the conductivity of the electrolyte is: 30-50 ms/cm.
The beneficial effects of the invention are as follows: firstly, a separation belt is arranged, and then a high-temperature resistant insulating material is arranged, so that the surface dielectric medium is repaired in an oxidation mode, and the isolation purpose can be well realized; the separation belt occupies a small space, so that the occupied space of the capacitor can be increased, the capacitance is increased, and the yield and reliability of the product are improved. Secondly, under the microscopic state, the surface of the anode foil strip is in a porous state, and the nano conductive polymer in the nano dispersion liquid is embedded into the holes on the surface of the porous anode foil strip, so that the growth and coverage of the polymer solid conductive layer at the later stage are facilitated, and the polymer solid conductive layer is prepared, thereby improving the problems of equivalent series resistance, yield and stability of the product.
Drawings
FIG. 1 is a schematic diagram of the preparation method of the present invention.
Fig. 2 is a schematic view of an anode foil strip of the present invention.
Fig. 3 is a schematic view of the microstructure of the portion a in fig. 2.
Wherein the above figures include the following reference numerals:
foil strip base band 1, separator 2, high temperature resistant insulating material 3.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
Referring to fig. 1 to 3, a method for manufacturing a high-energy chip type laminated solid aluminum electrolytic capacitor, the method comprising the steps of:
s1, arranging an electrode leading-out end on a foil strip base band 1; stamping foil strip base bands 1 at intervals along the length direction to form separating bands 2, and arranging high-temperature resistant insulating materials 3 in the separating bands 2 to form anode foil strips;
s2, immersing the anode foil strip in repair liquid, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s3, immersing the anode foil strip in a silane solution to form a pre-transition layer on the surface of the anode foil strip;
s4, immersing the anode foil strip in the nano dispersion liquid, drying under a set condition, immersing the anode foil strip in an initiating solution, drying under the set condition, immersing the anode foil strip in the nano dispersion liquid, and circulating the anode foil strip for a plurality of times to prepare a first conductive layer;
s5, the first conductive layer is communicated with the external electrode, and an anodic oxidation reaction is carried out in the conductive polymer stock solution to form a second conductive layer with a repairing function;
s6, immersing the anode foil strip in electrolyte, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s7, preparing a polymer solid conductive layer on the surface of the anode foil strip;
s8, conducting, bonding and stacking a plurality of anode foil strips and arranging the anode foil strips on a conducting frame to obtain a laminated capacitor core strip;
s9, wrapping and protecting the laminated capacitor core strip to prepare a capacitor core group; and cutting the capacitor core group to form the solid aluminum electrolytic capacitor.
S10, the solid aluminum electrolytic capacitor is subjected to a temperature environment of 80-90 ℃ and a humidity environment of 90%
After the placing treatment is carried out under the condition of R.H to 100 percent of R.H, the defective products are removed by electrifying detection.
Referring to fig. 3, after the steps S1 to S7, a microscopic schematic diagram of the anode foil strip is obtained, which is a dielectric layer, a first conductive layer, a second conductive layer, a dielectric layer and a polymer solid conductive layer from top to bottom.
Further detailed parameters in step S1 are as follows:
the electrode lead-out terminal is made of metal materials including, but not limited to, stainless steel, titanium metal and alloys thereof, nickel metal and alloys thereof, and the materials are selected so that the electrode lead-out terminal has a longer service life.
The separator 2 is less than or equal to 90% of the total thickness of the anode foil strip, and the separator 2 has a width not less than 5 to 10 times, and most preferably 3 times, the thickness of the anode foil strip. The parameter setting purpose of the separation belt 2 is as follows: the insulation blocking function is achieved, the leakage current of the finished capacitor is small when the capacitor is manufactured in the later period, and the yield of the capacitor is high. Wherein, the thickness of the anode foil strip is 120 micrometers, the working voltage is 2V, and the main material of the anode foil strip is metallic aluminum.
Since the high temperature resistant insulating material 3 needs to meet the following parameters during use: the high-temperature working temperature is more than or equal to 350 ℃, the surface drying time (min) is more than or equal to 3, and the tensile strength (Mpa) is more than or equal to 1.0; more preferably, the high temperature resistant insulating material 3 needs to satisfy during use: the high-temperature working temperature is more than or equal to 400 ℃, the surface drying time (min) is more than or equal to 6, and the tensile strength (MPa) is more than or equal to 1.5. The surface drying time refers to the time required for the coating to be coated on the surface of an object to reach a dry state. Therefore, the high temperature resistant insulating material 3 can be selected from silicon rubber, polyimide and the like.
Further detailed parameters in step S2 are as follows:
the repairing liquid consists of organic acid salt, phosphate and organic acid; the use temperature of the repair liquid is 55-125 ℃; the pH value of the repair liquid is 5.0-7.0, and the conductivity of the repair liquid is as follows: 30-50 ms/cm. The optimal use conditions are as follows: the high temperature condition is 80 ℃; the pH value of the repair liquid is 5.5, and the conductivity is as follows: 40ms/cm. The repair liquid mainly utilizes the conductivity and the pH value of the repair liquid so that the anode foil strip has oxidation-reduction reaction in the repair liquid.
The positive output of the power supply can be selected as follows: the optimal power supply positive electrode output mode is a constant voltage mode, so that the capacitor yield is high.
Further detailed parameters in step S3 are as follows:
the silane solution is composed of amino-functional silane, ethanol and water, and the amino-functional silane can link inorganic matters and organic polymers to form a pre-transition layer.
Further detailed parameters in step S4 are as follows:
the use temperature of the nano dispersion liquid is 25-45 ℃, the time for immersing the anode foil strips in the nano dispersion liquid is 30-45 sec, and the drying temperature is 45-65 ℃. Most preferably, the nanodispersion is used at a temperature of 40℃and the anode foil strip is immersed in the nanodispersion for 45sec at a drying temperature of 60 ℃. The number of cycles in step S4 is 5 to 16, most preferably 8, and the first conductive layer prepared by the multiple cycles has excellent conductivity.
The nano dispersion liquid consists of nano conductive polymer particles, conductive polymer monomers, an adhesive, an antioxidant, a stabilizer and a solvent. Wherein, each component comprises the following components in percentage by weight: 0.01 to 0.10 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.01 to 0.05 percent of adhesive, 0.005 to 0.010 percent of anti-aging agent, 1.00 to 10.00 percent of stabilizer and the balance of solvent. Most preferably, the conductive polymer particles are 0.02%, the conductive polymer monomer is 4.00%, the adhesive is 0.01%, the anti-aging agent is 0.005%, the stabilizer is 8.00%, and the balance of the components is solvent.
The conductive polymer is conductive polypyrrole, conductive polyaniline, conductive polythiophene or derivatives of the above materials, the purity of the conductive polymer is not lower than 99.5%, the median particle is 15-50 nm, and the preferred median particle is 20-40 nm. Most preferably, the median particle is 30nm. Therefore, the conductive polymer can be conveniently embedded into the holes on the surface of the hole anode foil strip, and the growth and coverage of the polymer solid conductive layer in the later stage are facilitated, so that the polymer solid conductive layer is prepared, and the problems of equivalent series resistance, yield and stability of the product can be improved.
The conductive polymer monomer is pyrrole, aniline, thiophene or derivatives of the above materials.
The adhesive is aqueous polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber or a combination of the three;
the antioxidant is preferably phenol, and the phenol can make the prepared polymer solid conductive layer more stable, and can improve the equivalent series resistance performance and product stability of the product more easily, and the antioxidant is selected from phenols including but not limited to bisphenol, triphenol, polyphenol or hydroquinone.
The stabilizer is one or more of sodium p-benzene sulfonate, sodium p-toluene sulfonate, sodium dodecyl sulfonate, sodium alkyl naphthalene sulfonate and sodium lignin sulfonate.
The solvent may be water, an organic solvent or a combination of two, preferably two, more preferably water and an organic system in a weight ratio of 9:1. the organic solvent may be ethylene glycol or the like, and is a prior art, and is not described here.
The initiating solution consists of phosphoric acid, sodium sulfonate, potassium permanganate and a solvent, wherein the initiating solution comprises the following components in percentage by weight: phosphoric acid 0.01%, sodium sulfonate 0.3%, potassium permanganate 3%, and the rest weight of the components is solvent.
Further detailed parameters in step S5 are as follows:
the use temperature of the conductive polymer stock solution is-5 ℃ to 15 ℃, and the constant temperature of 5 ℃ is preferably kept.
The conductive polymer stock solution consists of nano conductive polymer particles, conductive polymer monomers, an antioxidant, a stabilizer and a solvent. Wherein, each component comprises the following components in percentage by weight: 0.01 to 0.05 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.005 to 0.010 percent of anti-aging agents, 1.00 to 10.00 percent of stabilizers and the balance of solvents.
The composition of the nano conductive polymer particles, the conductive polymer monomer, the antioxidant, the stabilizer and the solvent in the conductive polymer stock solution is the same as that selected in the step S4.
The positive output of the power supply can be selected as follows: the single-stage constant current output mode, the multi-stage constant current output mode or the curve constant current output mode is preferably selected from the following positive electrode output modes: a multi-stage constant current output mode.
Further detailed parameters in step S6 are as follows:
the electrolyte consists of organic acid salt, phosphate and organic acid, the pH value of the electrolyte is 4.5-7.0, and the conductivity of the electrolyte is as follows: the most preferable pH value of the electrolyte is 5.5, and the conductivity of the electrolyte is 30-50 ms/cm: 40ms/cm, thereby ensuring the rate and effect of dielectric layer formation.
Further detailed parameters in step S7 are as follows:
the polymer solid conductive layer is a carbon layer and a silver layer, and the carbon layer and the silver layer are covered on the anode foil strip in a chemical polymerization mode or an electrochemical polymerization mode.
Further detailed parameters in step S8 are as follows:
the plurality of anode foil strips are stacked in a conductive bonding mode and are arranged on the conductive frame, the bonding material is a conductive connecting material, the conductive connecting material contains silver components, adjacent anode foil strips are stacked by utilizing the bonding capability of conductive silver, and then the adjacent anode foil strips are bonded on the conductive frame.
Further detailed parameters in step S9 are as follows:
and cutting the capacitor core group to form the solid aluminum electrolytic capacitor, wherein the cutting mode can adopt modes such as wire cutting, laser cutting and the like.
Further detailed parameters in step S10 are as follows:
and (3) placing the solid aluminum electrolytic capacitor under the conditions of 85 ℃ temperature and 95% R.H humidity, and then electrifying to detect and screen out unqualified products.
The beneficial effects of the invention are as follows: firstly, the isolation purpose can be well realized by arranging the separation belt 2 and then arranging the high-temperature resistant insulating material 3 so as to repair the surface dielectric medium in an oxidation mode; and the separating belt 2 occupies a smaller space, so that the occupied space of the capacitor can be increased, the capacitance can be increased, and the yield and reliability of the product can be improved. Secondly, under the microscopic state, the surface of the anode foil strip is in a porous state, and the nano conductive polymer in the nano dispersion liquid is embedded into the holes on the surface of the porous anode foil strip, so that the growth and coverage of the polymer solid conductive layer at the later stage are facilitated, and the polymer solid conductive layer is prepared, thereby improving the problems of equivalent series resistance, yield and stability of the product.
The electrical property data of the formed capacitor product of 2V/470uF supported by the invention and the capacitor parameters manufactured by the prior method are shown in the following table:
| examples of the invention | Capacitance/. Mu.F | Loss/% | ESR/mΩ | Yield is% |
| Modes of the invention | 491 | 1.0 | 4.2 | 88％ |
| Existing mode | 445 | 1.5 | 5.3 | 79％ |
As can be seen from the table above, the capacitor manufactured by the invention has more excellent capacitance and lower loss rate. The lower the ESR (i.e., equivalent series resistance), the smaller the loss of the capacitor, the greater the output current, the higher the quality of the capacitor, and the more excellent the yield of the present invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-energy sheet type laminated solid aluminum electrolytic capacitor is characterized by comprising the following steps of:
s1, arranging an electrode leading-out end on a foil strip base band; stamping foil strip base bands at intervals along the length direction to form separating bands, and arranging high-temperature resistant insulating materials in the separating bands to form anode foil strips;
s2, immersing the anode foil strip in repair liquid, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s3, immersing the anode foil strip in a silane solution to form a pre-transition layer on the surface of the anode foil strip;
s4, immersing the anode foil strip in the nano dispersion liquid, drying under a set condition, immersing the anode foil strip in an initiating solution, drying under the set condition, immersing the anode foil strip in the nano dispersion liquid, and circulating the anode foil strip for a plurality of times to prepare a first conductive layer;
s5, the first conductive layer is communicated with the external electrode, and an anodic oxidation reaction is carried out in the conductive polymer stock solution to form a second conductive layer with a repairing function;
s6, immersing the anode foil strip in electrolyte, and connecting an electrode leading-out end of the anode foil strip with a positive electrode of a power supply to form a dielectric layer on the outer surface of the anode foil strip;
s7, preparing a polymer solid conductive layer on the surface of the anode foil strip;
s8, conducting, bonding and stacking a plurality of anode foil strips and arranging the anode foil strips on a conducting frame to obtain a laminated capacitor core strip;
s9, wrapping and protecting the laminated capacitor core strip to prepare a capacitor core group; and cutting the capacitor core group to form the solid aluminum electrolytic capacitor.
2. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: step S10 is further included after step S9;
s10, the solid aluminum electrolytic capacitor is subjected to a temperature environment of 80-90 ℃ and a humidity environment of 90%
After the placing treatment is carried out under the condition of R.H to 100 percent of R.H, the defective products are removed by electrifying detection.
3. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the separation belt is smaller than or equal to 90% of the total thickness of the anode foil strip, and the width of the separation belt is not smaller than 5-10 times of the thickness of the anode foil strip.
4. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in the step S2, the temperature of the repair liquid is 55-125 ℃; the pH value of the repair liquid is 5.0-7.0, and the conductivity of the repair liquid is as follows: 30-50 ms/cm.
5. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in step S3, the silane solution is composed of an amino-functional silane, ethanol, and water.
6. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in step S4, the nano dispersion liquid is composed of nano conductive polymer particles, conductive polymer monomers, an adhesive, an antioxidant, a stabilizer and a solvent, and the components in percentage by weight are as follows: 0.01 to 0.10 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.01 to 0.05 percent of adhesive, 0.005 to 0.010 percent of anti-aging agent, 1.00 to 10.00 percent of stabilizer and the balance of solvent.
7. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 6, wherein:
the conductive polymer is conductive polypyrrole, conductive polyaniline or conductive polythiophene;
the conductive polymer monomer is pyrrole, aniline or thiophene;
the adhesive is aqueous polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber or a combination of the three;
the antioxidant is bisphenol, triphenol, polyphenol or hydroquinone;
the stabilizer is one or more of sodium p-toluenesulfonate, sodium dodecyl sulfonate, sodium alkyl naphthalene sulfonate and sodium lignin sulfonate.
8. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 6, wherein: in the step S4, the initiating solution consists of phosphoric acid, sodium sulfonate, potassium permanganate and a solvent, wherein the initiating solution consists of the following components in percentage by weight: phosphoric acid 0.01%, sodium sulfonate 0.3%, potassium permanganate 3%, and the rest weight of the components is solvent.
9. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in step S5, the conductive polymer stock solution is composed of nano conductive polymer particles, conductive polymer monomers, an antioxidant, a stabilizer and a solvent, wherein the components are as follows in percentage by weight: 0.01 to 0.05 percent of conductive polymer particles, 1.00 to 4.00 percent of conductive polymer monomers, 0.005 to 0.010 percent of anti-aging agents, 1.00 to 10.00 percent of stabilizers and the balance of solvents.
10. The method for manufacturing the high-energy chip type laminated solid aluminum electrolytic capacitor as claimed in claim 1, wherein the method comprises the following steps: in step S6, the electrolyte consists of organic acid salt, phosphate and organic acid, wherein the pH value of the electrolyte is 4.5-7.0, and the conductivity of the electrolyte is as follows: 30-50 ms/cm.
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