CN110983409B - Formation solution, solid aluminum electrolytic capacitor and preparation method thereof - Google Patents
Formation solution, solid aluminum electrolytic capacitor and preparation method thereof Download PDFInfo
- Publication number
- CN110983409B CN110983409B CN201911363169.2A CN201911363169A CN110983409B CN 110983409 B CN110983409 B CN 110983409B CN 201911363169 A CN201911363169 A CN 201911363169A CN 110983409 B CN110983409 B CN 110983409B
- Authority
- CN
- China
- Prior art keywords
- solid
- electrolytic capacitor
- aluminum electrolytic
- formation
- trifluoromethanesulfonyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 103
- 239000003990 capacitor Substances 0.000 title claims abstract description 87
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007787 solid Substances 0.000 title claims description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 46
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001413 amino acids Chemical class 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000011888 foil Substances 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 47
- -1 imide salt Chemical class 0.000 claims description 32
- 230000008439 repair process Effects 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 28
- 229920000767 polyaniline Polymers 0.000 claims description 21
- 238000004804 winding Methods 0.000 claims description 19
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 18
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 16
- 238000005253 cladding Methods 0.000 claims description 15
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004471 Glycine Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 6
- 229960004063 propylene glycol Drugs 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000012797 qualification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 6
- 239000001741 Ammonium adipate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 235000019293 ammonium adipate Nutrition 0.000 description 6
- ZATMQQFXKCSCSO-UHFFFAOYSA-N 2-(3-methylimidazol-3-ium-1-yl)acetate Chemical compound C[N+]=1C=CN(CC([O-])=O)C=1 ZATMQQFXKCSCSO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- 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)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a solid-state aluminum electrolytic capacitor forming solution, a solid-state aluminum electrolytic capacitor and a preparation method thereof. The formation liquid comprises: organic phosphine functionalized amino acid, ionic liquid and alcohol solvent. The invention also provides a method for preparing the solid-state aluminum electrolytic capacitor by using the chemical forming liquid. The preparation method provided by the invention has the advantages of high formation efficiency and high qualification rate, and the obtained solid-state aluminum electrolytic capacitor has low loss, ESR and leakage current.
Description
Technical Field
The invention belongs to the technical field of solid-state capacitors, and particularly relates to a formation solution for formation and repair of a solid-state aluminum electrolytic capacitor, the solid-state aluminum electrolytic capacitor and a preparation method thereof.
Background
The solid capacitor is a new type capacitor developed from liquid electrolytic capacitor, and compared with the liquid electrolytic capacitor, it has the advantages of high frequency, low impedance, excellent temperature characteristic, strong ripple resistance, etc. Therefore, the solid-state capacitor has higher use value. The current preparation process of the solid capacitor mainly comprises the following steps: cutting, nailing and rolling, forming, impregnating, curing and assembling.
The cathode in the solid capacitor is made of conductive polymer material, and the anode foil oxide film of the liquid capacitor cannot have self-repairing capability through ion conduction, so that the oxide film is generally subjected to chemical conversion repair before impregnation. The currently widely used chemical solutions are aqueous solutions of ammonium adipate, ammonium dihydrogen phosphate, phosphoric acid, and ammonium carbonate.
CN109786137A discloses a method for preparing a solid-state capacitor, comprising the following steps: obtaining a capacitor element: winding the anode foil, the cathode foil, the electrolytic paper and the guide pin into a capacitor element, and welding the capacitor element on an iron bar; formation repair: placing the capacitor element in a formation liquid, wherein the formation liquid is an ammonium carbonate solution, applying direct current voltage to the capacitor element for formation, repairing an oxide film, taking out the capacitor element after formation, and performing heat treatment at 100-300 ℃; forming a cathode electrolyte; and assembling to obtain the capacitor.
CN108074748A discloses a method for manufacturing a solid-state capacitor dedicated for vehicle-mounted electronics, comprising the following steps: 1) winding electrolytic paper into elements at intervals between the anode foil and the cathode foil; 2) immersing the element into a formation solution for formation repair treatment for 10-60 minutes, wherein the formation solution is a phosphoric acid aqueous solution; 3) carrying out dry distillation treatment on the element subjected to the formation and repair treatment; 4) soaking the element in the soaking solution for soaking treatment; 5) after the impregnation treatment is finished, heating and drying the element; 6) impregnating the element with electrolyte after the heating and drying treatment is finished; 7) and (4) assembling the elements, filling the elements into an aluminum shell after a rubber cover is assembled, and performing girdling and sealing, and then performing aging treatment to obtain a finished product.
However, after the capacitor core package is subjected to chemical conversion treatment and impregnated and polymerized to form the cathode electrolyte, the performance of the capacitor is still poor, and the problems of large loss and ESR (equivalent series resistance), high leakage current, low yield and the like exist.
Disclosure of Invention
The present application is based on the discovery and recognition by the inventors of the following facts and problems:
the inventor finds, through a large amount of experimental data, that the reasons for poor performance or failure of the solid-state capacitor mainly include the following two aspects: firstly, burrs and foil ash generated when the cathode foil, the anode foil and the electrolytic paper are cut are attached to the surfaces of the cathode foil, the anode foil and the electrolytic paper; secondly, when the conventional method is used for forming the capacitor core package, substances such as ammonium adipate, ammonium dihydrogen phosphate, phosphate and the like in the forming liquid are easy to be separated out from the aqueous solution and remain on the surface of the anode foil. These two factors seriously affect the capacity, loss and ESR of the solid-state capacitor, and even cause the solid-state capacitor to fail.
In the case of chemical conversion of a solid capacitor, an oxide film is mainly formed on a bare edge portion formed by slitting, and when an aqueous chemical conversion solution is used, a large amount of hydrated alumina and aluminum hydroxide are often formed, and the dielectric strength is not good.
Chinese patent CN102169758B provides a method for preparing a solid capacitor by impregnating an ionic liquid, but the technical solution has the disadvantages that when only the ionic liquid is used as a repair liquid, the ionic liquid has high viscosity and poor fluidity; the repair liquid is easy to decompose under a strong electric field, so that the stability of the repair liquid is poor, and the repair effects of different parts are inconsistent; on the other hand, pure ionic liquid has strong corrosivity and solubility, and long-time contact with a dielectric can cause corrosion and dissolution of an oxide film, so that the capacity of the solid capacitor is attenuated, the ESR value is increased, and the leakage current is increased.
On the basis, the ionic liquid has the characteristics of strong oxidation and high oxidation efficiency; on the other hand, the stability of the formed liquid is improved by adding other components, the synergistic effect is realized, the uniformity of the formed quality is ensured, and the limitation of the formed liquid in production application is overcome. The invention adopts organic phosphine functionalized amino acid as a formation primary solute, adopts ionic liquid as a formation secondary solute and adopts alcohols as a solvent, the formation liquid has good stability and high oxidation efficiency, and the generated oxide film component is crystal-form alumina, does not contain a hydration film and is compact. The formation solute is a liquid solute, and the problems of solute precipitation and residue in the formation process in the existing solid capacitor manufacturing process are avoided.
Specifically, the technical scheme provided by the invention is as follows:
firstly, the invention provides a solid-state aluminum electrolytic capacitor chemical solution, which comprises: organic phosphine functionalized amino acid, ionic liquid and alcohol solvent.
Further, the organic phosphine functionalized amino acid is at least one of N- (phosphonomethyl) glycine, N-bis (phosphonomethyl) glycine, N-phosphonomethyl-glycine and dimethylidene glycine.
Further, the ionic liquid is an imide salt ionic liquid with a trifluoromethanesulfonyl group.
Further preferably, the ionic liquid is at least one of 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphinobis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methyldiethylammonium bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -hexylpyridinebis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt.
Further, the alcohol solvent is a mono-alcohol solvent or a diol solvent.
Further preferably, the mono-alcohol solvent is at least one of cyclohexanol, isopropanol, isobutanol, diacetone alcohol; the glycol solvent is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, ethoxy diglycol and polyethylene glycol.
Further, the mass ratio of the organic phosphine functionalized amino acid to the ionic liquid to the alcohol solvent is 1-10:1-5: 85-98.
In a second aspect, the invention provides a method for preparing a solid-state aluminum electrolytic capacitor, which comprises the step of performing chemical repair by using the chemical solution.
Specifically, the preparation method comprises the following steps:
1) riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare a core package;
2) carrying out formation repair on the core bag in the formation solution of any one of claims 1 to 6, and then drying;
3) impregnating the core cladding processed in the step 2) with electrolyte, and drying;
4) assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Further, when the formation repair is carried out, ultrasonic treatment is applied, the ultrasonic frequency is 20-40KHz, and the ultrasonic time is 10-30 min.
Furthermore, the temperature of the formation repair is 40-70 ℃, and the time of the formation repair is 10-30 min.
Further, in the step 2), the drying temperature is 100-200 ℃ and the drying time is 1-5 h.
Further, in the step 3), the drying temperature is 150-220 ℃, and the time is 1-5 h.
Further, in the step 3), the electrolyte is ethanol dispersion of polyaniline, and the mass fraction of the polyaniline is 15-18%.
On the other hand, the invention also provides the solid-state aluminum electrolytic capacitor obtained by the preparation method.
Compared with the prior art, the invention has the following technical effects:
(1) the core formation repair in the preparation process of the solid-state aluminum electrolytic capacitor adopts an organic formation system of organic phosphine functional amino acid, ionic liquid and alcohol solvent, and compared with the existing formation system of aqueous solutions of boric acid, phosphoric acid, ammonium adipate and the like, the method avoids the introduction of water and the generation of hydrated alumina. Compared with a single ionic liquid forming solution, the organic phosphine functionalized amino acid has the characteristics of phosphorus and acid, on one hand, the original hydrated alumina on the surface of an oxide film is dissolved and removed under an acidic condition, and simultaneously, the compact crystal form alumina with good acid resistance is generated; on the other hand, the organic phosphine functionalized amino acid has strong complexation, promotes the oxidation of aluminum when complexed with aluminum, and simultaneously forms a phosphating film layer on the surface of the aluminum oxide to protect the aluminum oxide, so that the finally obtained formed solid aluminum electrolytic capacitor has good water resistance and acid resistance.
(2) Compared with a single ionic liquid formed liquid, the imide salt ionic liquid with the trifluoromethanesulfonyl group has higher conductivity, and is beneficial to improving the formation oxidation efficiency and saving energy; meanwhile, the trifluoromethanesulfonyl group has strong electronegativity, can be complexed with the organic phosphine functionalized amino acid, ensures the stability of the organic phosphine functionalized amino acid and the ionic liquid, further improves the stability of the formed liquid, and meets the production requirement.
(3) The ultrasonic oscillation process is introduced in the formation repair process, so that on one hand, when the core bag enters the formation liquid, the gas in the core bag and the holes of the formation foil can be exhausted as much as possible, the formation liquid is convenient to permeate the core bag and enter the holes of the formation foil, and the formation effect of the core bag is improved; on the other hand, the core bag is internally provided with a large amount of gas during formation, the gas can be accelerated to be discharged by using ultrasonic oscillation, the volume expansion of the core bag caused by untimely discharge of the produced gas is avoided, and the yield of the core bag is improved.
(4) The preparation method provided by the invention has the advantages of high formation efficiency and high qualification rate, and the obtained solid-state aluminum electrolytic capacitor has low loss, ESR and leakage current.
Detailed Description
The method for manufacturing the solid-state aluminum electrolytic capacitor will now be described in detail.
The invention provides a preparation method of a solid-state aluminum electrolytic capacitor, which comprises the following steps:
1) riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare a core package;
2) carrying out formation repair on the core bag in a formation solution containing organic phosphine functionalized amino acid, ionic liquid and alcohol solvent, and then drying;
3) impregnating the core cladding processed in the step 2) with electrolyte, and drying;
4) assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Said step 1) may be carried out using any method known in the art.
According to an embodiment of the present invention, in step 2), the chemical solution has the following specific composition.
The organic phosphine functionalized amino acid has the characteristics of phosphorus and acid, on one hand, the original hydrated alumina on the surface of an oxidation film is dissolved and removed under the acidic condition, and simultaneously, the compact crystal form alumina with good acid resistance is generated; on the other hand, the organic phosphine functionalized amino acid has strong complexation, promotes the oxidation of aluminum when complexed with aluminum, and simultaneously forms a phosphating film layer on the surface of the aluminum oxide to protect the aluminum oxide, so that the finally obtained formed solid aluminum electrolytic capacitor has good water resistance and acid resistance.
Preferably, the organophosphine functionalized amino acid is at least one of N- (phosphonomethyl) glycine, N-bis (phosphonomethyl) glycine, N-phosphonomethyl-glycine, dimethylidene glycine.
In some embodiments, the organophosphine functionalized amino acid is any one of N- (phosphonomethyl) glycine, N-bis (phosphonomethyl) glycine, N-phosphonomethyl-glycine, dimethylidene glycine.
In addition to the organophosphine functionalized amino acids listed above, other organophosphine functionalized amino acids capable of achieving the same or equivalent technical effect may also be used in the present invention.
Preferably, the ionic liquid is an imide salt ionic liquid with a trifluoromethanesulfonyl group. The conductivity of the imide ionic liquid with the trifluoromethanesulfonyl group is high, and the improvement of the formation oxidation efficiency and the energy conservation are facilitated; meanwhile, the trifluoromethanesulfonyl group has strong electronegativity, and can be complexed with the organic phosphine functionalized amino acid, so that the thermal stability of the organic phosphine functionalized amino acid is ensured.
Non-limiting examples of the ionic liquid include 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, tributylhexylphosphinobis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphinobis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methyldiethylammonium bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -hexylpyridinebis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide salt, and the above-listed ionic liquids may be used alone or in combination. In addition to the ionic liquids listed above, other ionic liquids that achieve the same or equivalent technical effects may also be used in the present invention.
In some embodiments, the ionic liquid is one of 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, tributylhexylphosphine bis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphine bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methyldiethylammonium bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -hexylpyridine bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
The alcohol solvent has good intersolubility with the ionic liquid and the organic phosphine functionalized amino acid, and the alcoholic hydroxyl group can form a complexing effect with the ionic liquid and the organic phosphine functionalized amino acid, so that the stability of a formed solution is ensured; meanwhile, the decomposition voltage of the ionic liquid is improved, and the voltage application range of the formed liquid is widened.
Preferably, the alcohol solvent is a mono-alcohol solvent or a diol solvent.
The monoalcohol solvent may be exemplified by: cyclohexanol, isopropanol, isobutanol, diacetone alcohol, etc.; the glycol solvents are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, ethoxydiglycol, polyethylene glycol and the like.
The alcohol solvents listed above may be used alone or in combination. Since polyethylene glycol is used as a solvent, the polyethylene glycol of the present invention is a liquid polyethylene glycol having a molecular weight of less than 700, such as PEG200, PEG400, PEG600, and the like.
In some embodiments, the alcohol solvent is one or a combination of two of cyclohexanol, isopropanol, isobutanol, diacetone alcohol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, ethoxydiglycol, polyethylene glycol.
In some embodiments, the alcohol solvent is one of cyclohexanol, isopropanol, isobutanol, diacetone alcohol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, ethoxydiglycol, polyethylene glycol.
In the formation liquid, when the content of the organic phosphorus functionalized amino acid is low, the formation effect is poor, and the water resistance of an oxidation film is poor; when the content is too high, the oxide film is corroded. When the content of the ionic liquid is low, the conductivity of the formed liquid is not enough, so that the formation efficiency is low; when the content of the ionic liquid is higher, the viscosity of the formed liquid is too high, and the formed liquid is difficult to enter the holes of the formed foil. Therefore, the content of each component needs to be controlled.
Preferably, the mass ratio of the organic phosphine functionalized amino acid to the ionic liquid to the alcohol solvent is 1-10:1-5: 85-98.
Preferred ranges of the mass ratio of the organophosphine functionalized amino acid, ionic liquid, alcohol solvent include, but are not limited to: 1:1-5:85-98, 2:1-5:85-98, 3:1-5:85-98, 4:1-5:85-98, 5:1-5:85-98, 6:1-5:85-98, 7:1-5:85-98, 8:1-5:85-98, 9:1-5:85-98, 10:1-5:85-98, 1-10:1:85-98, 1-10:2:85-98, 1-10:3:85-98, 1-10:4:85-98, 1-10:5:85-98, 1-10:1-5:85, 1-10:1-5:86, 1-10:1-5:87, 1-10:1-5:88, 1-10:1-5:89, 1-10:1-5:90, 1-10:1-5:91, 1-10:1-5:92, 1-10:1-5:93, 1-10:1-5:94, 1-10:1-5:95, 1-10:1-5:96, 1-10:1-5:97, 1-10:1-5: 98.
In some embodiments, the mass ratio of the organophosphine functionalized amino acid, ionic liquid, alcohol solvent is 5-10:1-5:85-94, for example: 5:1-5:85-94, 6:1-5:85-94, 7:1-5:85-94, 8:1-5:85-94, 9:1-5:85-94, 10:1-5:85-94, 5-10:1:85-94, 5-10:2:85-94, 5-10:3:85-94, 5-10:4:85-94, 5-10:5:85-94, 5-10:1-5:85, 5-10:1-5:86, 5-10:1-5:87, 5-10:1-5:88, 5-10:1-5:89, 5-10:1-5:90, 5-10:1-5:91, 5-10:1-5:92, 5-10:1-5:93 and 5-10:1-5: 94.
Examples of mass ratios of the organophosphine functionalized amino acid, ionic liquid, alcohol solvent include, but are not limited to: 5:1:94, 6:3:91, 7:4:89, 8:2:90, 9:3:88, 10:5: 85.
Preferably, the temperature of the formation repair is 40-70 ℃, for example: 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C.
The time for formation repair is 10-30min, for example: 10min, 15min, 20min, 25min and 30 min.
The formation voltage may be selected according to the specification of the product, and in the embodiment of the present invention, the formation voltage is 21V.
Preferably, in the formation repair, ultrasonic treatment is applied, which has two functions: (1) the gas discharge is promoted, when the core bag enters the formation liquid, the ultrasonic treatment can discharge the gas in the core bag and the formation foil holes as much as possible, so that the formation liquid can permeate the core bag and enter the formation foil holes conveniently, and the formation effect of the core bag is improved; the core bag is also internally provided with a large amount of gas during formation, the gas can be accelerated to be discharged by using ultrasonic oscillation, the volume expansion of the core bag caused by untimely discharge of the generated gas is avoided, and the yield of the core bag is improved. (2) Cleaning, namely applying ultrasonic treatment while forming, so that burrs, foil ash, pollutants and the like in the core bag can be stripped, and the risk of short circuit of the capacitor due to the burrs in the later period is reduced; meanwhile, the compactness of the core cladding can be improved through oscillation, and the ESR value of the capacitor is reduced.
When the ultrasonic treatment frequency is lower than 20KHz, the impact force is too large, so that the displacement and deformation of each component of the core package are easily caused, and the yield is reduced. When the frequency is higher than 40KHz, the impact force is too small, and the particles such as gas, dust, burrs and the like in the discharged core bag cannot be effectively cleaned.
Preferably, the frequency of the ultrasound is 20-40KHz, for example: 20KHz, 25KHz, 30KHz, 35KHz, 40 KHz.
The time of the ultrasound is the same as the formation repair time, preferably 10-30min, for example: 10min, 15min, 20min, 25min and 30 min.
After the core package formation repair, the core package formation repair needs to be dried to remove the solvent, the drying temperature and time are not particularly limited, and the solvent is removed completely, wherein the drying temperature is preferably 100 ℃ or 150 ℃, for example: 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃; the drying time is 30-60min, for example: 30min, 40min, 50min and 60 min.
In some embodiments, after the core formation repair, the solvent is removed by drying at a drying temperature of 150 ℃ for 30 min.
And impregnating the dried core package with electrolyte, and drying to obtain the core package saturated with the electrolyte.
The core bag is dried after being impregnated with the electrolyte at the temperature of 150-.
In some embodiments, the core package is dried at 220 ℃ for 1-5h after impregnation with electrolyte.
The electrolyte is preferably ethanol dispersion of polyaniline, and the mass fraction of the polyaniline is 15-18%, for example: 15%, 16%, 17% and 18%.
In some embodiments, the polyaniline is 15% by mass.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications based on the inventive concept herein will occur to those skilled in the art and are intended to be included within the scope of the present invention.
Example 1
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 8:2:90) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 20min, the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Example 2
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 10:5:85) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 30min, the formation temperature is 40 ℃, the ultrasonic oscillation frequency is 40KHz, and the time is 30 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 5 hours.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Example 3
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in a 1, 2-propylene glycol solution (mass ratio is 5:1:94) of N, N-bis (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 10min, the formation temperature is 40 ℃, the ultrasonic oscillation frequency is 40KHz, and the time is 10 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying the core cladding at 220 ℃ for 1 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Example 4
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 6:3:91) of N- (phosphonomethyl) -glycine and tributylhexylphosphine bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 15min, the formation temperature is 60 ℃, the ultrasonic oscillation frequency is 40KHz, and the formation time is 15 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core package treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 4 hours.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Example 5
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 6:3:91) of dimethylidene phosphonic acid glycine and tetrabutyl phosphine bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 25min, the formation temperature is 60 ℃, the ultrasonic oscillation frequency is 40KHz, and the time is 25 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core package treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 4 hours.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Example 6
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in a cyclohexanol solution (mass ratio is 8:2:90) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid, electrifying to 21V for 20min, wherein the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 1
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in 15% ammonium adipate water solution by mass fraction, electrifying to form 21V, forming time is 20min, and forming temperature is 70 ℃; and (5) after formation, drying the core bag at 150 ℃ for 30min to remove water.
3) Impregnating the core package treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare a finished product of the solid aluminum electrolytic capacitor, and preparing the finished product of the solid aluminum electrolytic capacitor into a finished product of the solid capacitor.
Comparative example 2
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in 7% ammonium dihydrogen phosphate water solution, and electrifying to form 21V at 70 deg.C for 20 min; and (5) after formation, drying the core bag at 150 ℃ for 30min to remove water.
3) Impregnating the core package treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and drying at 220 ℃ for 3 hours.
4) Assembling the core packages treated in the step 3) to prepare a finished product of the solid aluminum electrolytic capacitor, and preparing the finished product of the solid aluminum electrolytic capacitor into a finished product of the solid capacitor.
Comparative example 3
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 15:5:80) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 20min, the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 4
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 2:0.5:97.5) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid, electrifying to 21V for 20min, wherein the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 5
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 5:95) of 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 20min, the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 6
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 8:2:90) of ammonium adipate and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to form 21V, wherein the formation time is 20min, the formation temperature is 70 ℃, the ultrasonic oscillation frequency is 30KHz, and the time is 20 min; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 7
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core wrap in 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid, electrifying to form 21V, wherein the formation time is 20min, the formation temperature is 70 ℃, and the ultrasonic oscillation frequency is 30KHz and the time is 20 min; after the formation is finished, the core is wrapped at 150 ℃ to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Comparative example 8
1) And riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare the core package.
2) Placing the core bag in an ethylene glycol solution (mass ratio is 8:2:90) of N- (phosphonomethyl) glycine and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt ionic liquid, electrifying to 21V, wherein the formation time is 20min, and the formation temperature is 70 ℃; and (5) after the formation is finished, drying the core package at 150 ℃ for 30min to remove the solvent.
3) Impregnating the core cladding treated in the step 2) with polyaniline electrolyte with the mass fraction of 15%, and then drying at 220 ℃ for 3 h.
4) Assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
Performance testing
The solid aluminum electrolytic capacitors prepared in the above examples and comparative examples were subjected to performance tests according to GB/T2693-2001 standard, and the results are shown in Table 1 below.
TABLE 1
From the test results in the table, compared with the conventional capacitor core formation repair process (comparative examples 1 and 2), the preparation process provided by the invention can effectively improve and improve various electrical properties of the solid aluminum electrolytic capacitor, and the loss, ESR and leakage current are obviously reduced.
From the results of comparative examples 3, 4 and 5, it can be seen that the composition ratio of organic phosphine functionalized amino acid, ionic liquid and alcohol N- (phosphonomethyl) glycine, 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ionic liquid and ethylene glycol has a direct effect on the performance of solid state capacitors, and when the solute component is too high, too strong acidity causes capacity fading due to too much dissolution of the formed foil in the core package; or too low or even not, the hydration film is not dissolved sufficiently and the phosphating film is not compact enough to cause the formed foil to have poor acid resistance, so that the performance of the solid-state aluminum electrolytic capacitor which can reduce the performance of the solid-state capacitor is poor.
As can be seen from comparative example 6, when ammonium adipate was used in place of the organophosphine functionalized amino acid, the solid aluminum electrolytic capacitor was deteriorated in performance due to insufficient core repair, similar to comparative example 5.
As can be seen from comparative example 7, when only the ionic liquid was used as the formation liquid, the ionic liquid was not easy to enter the core package due to its viscosity, and the formation was insufficient, so that the capacity was low and the leakage current was large.
It can be seen from comparative example 8 that the solid-state aluminum electrolytic capacitor was degraded in all aspects as compared with example 1 without applying ultrasonic vibration.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes in the method can be made without departing from the spirit of the invention.
Claims (11)
1. The solid-state aluminum electrolytic capacitor chemical solution is characterized by comprising the following components: organic phosphine functionalized amino acid, ionic liquid and alcohol solvent; the ionic liquid is an imide salt ionic liquid with a trifluoromethanesulfonyl group; the alcohol solvent is a mono-alcohol solvent or a diol solvent; the single-alcohol solvent is at least one of cyclohexanol, isopropanol, isobutanol and diacetone alcohol; the glycol solvent is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, ethoxy diglycol and polyethylene glycol; the mass ratio of the organic phosphine functionalized amino acid to the ionic liquid to the alcohol solvent is 1-10:1-5: 85-98.
2. The solid-state aluminum electrolytic capacitor electrolyte composition of claim 1, wherein the organic phosphine-functionalized amino acid is at least one of N- (phosphonomethyl) glycine, N-bis (phosphonomethyl) glycine, N-phosphonomethyl-glycine, dimethylidene glycine.
3. The solid-state aluminum electrolytic capacitor forming liquid according to claim 1, the ionic liquid is at least one of 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, tributylhexylphosphine bis (trifluoromethanesulfonyl) imide salt, tetrabutylphosphine bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -butyl-N-methyldiethylammonium bis (trifluoromethanesulfonyl) imide salt, N- (3-hydroxy) -hexylpyridine bis (trifluoromethanesulfonyl) imide salt and N- (3-hydroxy) -butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
4. A preparation method of a solid-state aluminum electrolytic capacitor is characterized by comprising the step of carrying out chemical conversion repair by using the chemical conversion solution according to any one of claims 1 to 3, wherein the process of the chemical conversion repair is introduced with an ultrasonic oscillation process.
5. The method for manufacturing a solid-state aluminum electrolytic capacitor according to claim 4, comprising:
1) riveting and winding the anode foil, the cathode foil, the electrolytic paper and the guide pin to prepare a core package;
2) carrying out formation repair on the core bag in the formation solution of any one of claims 1-3, and then drying;
3) impregnating the core cladding processed in the step 2) with electrolyte, and drying;
4) assembling the core packages treated in the step 3) to prepare the finished product of the solid aluminum electrolytic capacitor.
6. The method for preparing the solid-state aluminum electrolytic capacitor according to claim 5, wherein ultrasonic treatment is applied during the formation repair, the ultrasonic frequency is 20-40KHz, and the ultrasonic time is 10-30 min.
7. The preparation method of the solid-state aluminum electrolytic capacitor according to claim 5, wherein the temperature of the formation repair is 40-70 ℃, and the time of the formation repair is 10-30 min.
8. The method for preparing a solid-state aluminum electrolytic capacitor as claimed in claim 5, wherein the drying temperature in step 2) is 100-200 ℃ and the drying time is 30-60 min.
9. The method for preparing a solid-state aluminum electrolytic capacitor as claimed in claim 5, wherein the drying temperature in step 3) is 150-220 ℃ for 1-5 h.
10. The method for preparing the solid-state aluminum electrolytic capacitor according to claim 5, wherein in the step 3), the electrolyte is ethanol dispersion of polyaniline, and the mass fraction of the polyaniline is 15-18%.
11. Solid-state aluminum electrolytic capacitor obtained by the production method according to any one of claims 4 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911363169.2A CN110983409B (en) | 2019-12-26 | 2019-12-26 | Formation solution, solid aluminum electrolytic capacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911363169.2A CN110983409B (en) | 2019-12-26 | 2019-12-26 | Formation solution, solid aluminum electrolytic capacitor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110983409A CN110983409A (en) | 2020-04-10 |
| CN110983409B true CN110983409B (en) | 2021-05-11 |
Family
ID=70077087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911363169.2A Active CN110983409B (en) | 2019-12-26 | 2019-12-26 | Formation solution, solid aluminum electrolytic capacitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110983409B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111681877B (en) * | 2020-06-28 | 2021-09-07 | 上海交通大学 | Ionic liquid electrolyte for ultra-high stability aluminum electrolytic capacitor and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304386B (en) * | 2013-06-07 | 2015-06-17 | 青岛科技大学 | Method for preparing acetal through alkene hydroformylation-acetalation one-pot method |
| CN103814468B (en) * | 2013-09-27 | 2018-07-06 | 惠州亿纬锂能股份有限公司 | A kind of electrolyte for lithium cells and the lithium battery using the electrolyte |
-
2019
- 2019-12-26 CN CN201911363169.2A patent/CN110983409B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110983409A (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110692115B (en) | Hybrid aluminum electrolytic capacitor and manufacturing method thereof | |
| JP3623113B2 (en) | Electrolytic capacitor | |
| EP3671781B1 (en) | Hybrid aluminum electrolytic capacitor and manufacturing method therefor | |
| CN110600268A (en) | Manufacturing method of solid-liquid mixed capacitor with electrolyte injected quantitatively | |
| WO2016088300A1 (en) | Electrolytic capacitor and method for manufacturing same | |
| CN110983409B (en) | Formation solution, solid aluminum electrolytic capacitor and preparation method thereof | |
| CN102867651A (en) | High-reliability solid electrolytic capacitor manufacturing method | |
| WO2009113285A1 (en) | Solid electrolytic capacitor and method for manufacturing the same | |
| JP2008172277A (en) | Solid-state electrolytic capacitor | |
| CN112582180B (en) | Electrolyte for high-hydration-resistance medium-high voltage aluminum electrolytic capacitor and preparation method | |
| US20140085774A1 (en) | Electrolyte and electric double-layer capacitor using same | |
| CN106663541A (en) | Method for producing electrolytic capacitor | |
| CN110592637B (en) | Preparation method and application of formed foil | |
| CN110970221B (en) | Method for manufacturing electrolytic capacitor and electrolytic capacitor | |
| JP2000195758A (en) | Solid electrolytic capacitor and its manufacture | |
| CN109920646A (en) | A kind of preparation process improving high-voltage solid-state aluminium electrolutic capacitor low-temperature characteristics | |
| CN112582181B (en) | Electrolyte for low-voltage aluminum electrolytic capacitor with high hydration resistance and preparation method | |
| CN113178331B (en) | Low-leakage-current solid-liquid mixed electrolytic capacitor | |
| US11081287B2 (en) | Electrolytic capacitor and method for manufacturing electrolytic capacitor | |
| CN113593909B (en) | Solid-liquid mixed capacitor and preparation method thereof | |
| CN108074748A (en) | A kind of special solid-state capacitor manufacturing method of vehicle electronics | |
| WO2013054691A1 (en) | Electrolytic solution for aluminum electrolyte capacitor and aluminum electrolyte capacitor using same | |
| CN114267543B (en) | Wide-temperature aluminum electrolytic capacitor and preparation method thereof | |
| JP2013138145A (en) | Manufacturing method of solid state electrolytic capacitor | |
| JP4998089B2 (en) | Electric double layer capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |