CN101000827B - Solid electrolytic condenser and manufacturing method thereof - Google Patents
Solid electrolytic condenser and manufacturing method thereof Download PDFInfo
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- CN101000827B CN101000827B CN2006100055847A CN200610005584A CN101000827B CN 101000827 B CN101000827 B CN 101000827B CN 2006100055847 A CN2006100055847 A CN 2006100055847A CN 200610005584 A CN200610005584 A CN 200610005584A CN 101000827 B CN101000827 B CN 101000827B
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Abstract
A solid electrolytic capacitor is prepared as forming said capacitor by anode body with anode terminal and cathode terminal, using epoxy to package said capacitor to let said anode and cathode terminals be exposed out, forming media oxidation film on anode body and polymer electrolyte layer on media oxidation layer, coating cathode conductive layer on polymer electrolyte layer and connecting cathode conductive layer to cathode terminal.
Description
Technical field: the invention belongs to technical field of electronic components, particularly a kind of solid electrolytic capacitor that utilizes valve metal (tantalum, niobium, aluminium, titanium etc.) to make.
Background technology: in recent years, particularly for Switching Power Supply, CPU respective drive circuit etc., owing to require low driving voltage, low-power consumption, high frequency, therefore require capacitor to possess big capacity, low ESR value, be the such requirement of correspondence, polypyrrole, polythiophene etc. substitute traditional manganese dioxide as the capacitor cathode solid electrolyte as is known to research and develop the conductive polymer polymer now.
Method in the past is: in one, the mixed liquor with valve metal anode bodies immersion hetero ring type monomer that is formed with dielectric film and oxidant, take out then and carry out polymerization, this process repeats repeatedly; Two, will be formed with the valve metal anode bodies immersion monomer solution of dielectric film, and then immersion oxidizing agent solution, polymerization is carried out in taking-up, and this process repeats repeatedly, and then applies graphite linings, silver resin layer, form capacitor body like this, capacitor body is assembled on the lead frame, and anode tap and framework weld together, and negative electrode bonds together with silver-colored binding agent and lead frame, and use epoxy encapsulation, be formed with and draw the positive and negative electrode capacitor.First kind of above-mentioned method since oxidant and monomer solution mix can polymerization reaction take place, cause the inefficacy of mixing material, so the service time of mixing material is very short, waste very big, the cost height.Second method is flooded monomer and oxidant liquid respectively, though prolong the useful life of material, reaction time is long, and efficient is low.
Summary of the invention: the objective of the invention is to overcome the prior art defective provides a kind of rate of finished products height, steady quality, lower-costly has that suitable capacity is drawn and the electrolytic polymer layer solid electrolytic capacitor of low ESR (ESR).
Purpose of the present invention realizes by following scheme:
A kind of solid electrolytic capacitor, comprise the anode bodies (1) and the cathode terminal (3) that have anode terminal (2), its integral body is encapsulated by epoxy resin (9), anode terminal and cathode terminal expose, it is characterized in that on anode bodies, being formed with dielectric oxide film (4), on the dielectric oxide film layer, be formed with polyelectrolyte floor (5), on polyelectrolyte floor (5), scribble cathode conductive layer (7), (8) and connect cathode terminal;
Above-mentioned anode bodies is a valve metal, is a kind of in tantalum, niobium, aluminium or the titanium;
Above-mentioned polyelectrolyte floor (5) is that the anode bodies that will have dielectric oxide film repeatedly immerses the mixed liquor of heterocyclic monomer and oxidant, and then repeatedly immerses heterocyclic monomer solution and oxidant liquid respectively, then is polymerized in 50-80 ℃ temperature;
Above-mentioned polyelectrolyte floor (5) forms in two steps, the first step, the anode bodies that at first will have a dielectric oxide film immerses in the mixing material of the heterocyclic monomer of ratio 5%-20% and oxidant, take out after 1-5 minute, with it as for carrying out in temperature 50-80 ℃ the environment polymerization reaction 1-2 hour, with methyl alcohol or ethanol cleaning reaction residue, then, mend to form in dilute phosphoric acid solution and repair dielectric layer, repeated impregnations, polymerization, benefit form 3-5 time; Second step, immerse the anode block of finishing preceding step in the oxidant liquid of 40%-60% earlier, immerse in the monomer solution again, take out back polymerization in temperature 50-80 ℃ environment, reaction finishes the back and washes reaction residue with methyl alcohol or ethanol, and mend formation with phosphoric acid,diluted liquid and repair dielectric layer, the preparation of 0.1-0.2mm thickness polyelectrolyte floor is finished in repeated impregnations, polymerization, benefit formation for 3-5 time;
Above-mentioned heterocyclic monomer is pyrroles, thiophene, aniline or 3,4 ethene dioxythiophenes;
Above-mentioned oxidant is ferric salt, persulfate, sulfonic acid molysite or hydrogen peroxide;
Above-mentioned cathode conductive layer has two-layer, is respectively the graphite linings (7) and the silver slurry layer (8) of coating;
Scribble silicones on the above-mentioned anode terminal;
The ESR value scope of above-mentioned solid electrolytic capacitor is at 10-80m Ω.
Invention effect of the present invention can be from hereinafter finding out embodiment and the Comparative Examples.
Description of drawings: Fig. 1 is a structural representation of the present invention.
Embodiment:
Embodiment 1: choose the tantalum powder of CV value for 30000uf/g, the anode block that is processed into 4.6*3.0*1.4 contains the tantalum lead-in wire, subsequently at 1450 ℃ of degree high temperature high vacuum sintering, anode bodies behind the sintering is added the 18-20V direct voltage form dielectric layer in the phosphoric acid,diluted aqueous solution, have capacity 155 μ F and silicon-coating resin on the tantalum line, then this anode bodies is immersed in the mixed liquor of 5% monomer and oxidant, take out after 5 minutes, contain dioxy thiophene, benzene sulfonic acid iron, butanol solution etc. in the mixed liquor.The anode bodies that will contain mixed liquor is placed 30min under 50 ℃ of degree, finish oxidative polymerization.This anode bodies is cleaned, and after in phosphoric acid,diluted liquid, mending formation, dried under 100 ℃ of degree.Repeat aforesaid operations 5 times.Then, the anode bodies that will finish above-mentioned steps immerses 40% oxidizing agent solution earlier and immerses in the monomer liquid again, and at 50 ℃ of placement 30min, clean this anode bodies, in 0.5% dilute phosphoric acid solution, apply voltage then and mend formation, dried under 100 ℃ of degree then, the step 5 that repeated impregnations, polymerization, benefit form time obtains thickness greatly about the conductive polymer coating of 0.1-0.2mm.On conductive polymer coating, apply graphite linings, conductive silver slurry layer then, finish the negative electrode preparation.So just form the conducting polymer capacitor body.
Then with lead frame anode tap is connected on the anode terminal, uses conductive adhesive that cathode terminal is connected with cathode layer and use the epoxy resin plastic packaging, anode and cathode termination portions expose, and so just obtain solid electrolytic capacitor.
Embodiment 2
The tantalum anode through peroxidating forms in the example 1 immerses earlier in 10% monomer and the oxidant mixed liquor and takes out after 8 minutes, places 1hr under 50 ℃ the condition.Subsequently anode bodies is cleaned, in phosphoric acid,diluted liquid, mended and form back drying under 100 ℃.Above-mentioned steps repeats 4 times, then this anode bodies is immersed in 50% oxidant, the monomer solution successively, takes out at 60 ℃ and places 1hr, mends formation after the cleaning, and carry out drying under 100 ℃.Repeated impregnations, benefit forming process just obtain the conductive polymer layer that thickness is 0.15-0.2mm for 3 times.Finish graphite, silver slurry then, finish the welding of the anode and the negative electrode of lead frame, finish the encapsulation of resin bed, form solid electrolytic capacitor.
The anode bodies that forms deielectric-coating through peroxidating in the example 1 immerses 15% monomer earlier and the mixed liquor of oxidant took out after 10 minutes, places 1hr under 50 ℃ the condition.Subsequently anode bodies is cleaned, in phosphoric acid,diluted liquid, mended formation, subsequently 100 ℃ of following dried.Repeat this process 4 times, then this anode bodies is immersed in 60% oxidant and the monomer solution successively, take out at 60 ℃ and place 1hr, after the cleaning, mend formation, and under 100 ℃, carry out drying.Repeat said process and obtain the conductive polymer layer that thickness is approximately 0.15-0.2mm 2 times.Finish graphite, silver slurry then, finish the welding of the anode and the negative electrode of lead frame, finish the encapsulation of resin bed, form solid electrolytic capacitor.
Comparative example 4
Method now commonly used is that the tantalum anode that will form dielectric oxide film immersed earlier in the solution that contains oxidant 5 minutes, takes out in immersion to contain in the solution of monomer 3 minutes, and room temperature is placed 3hr, after the cleaning, mends formation, and carry out drying under 100 ℃.Repeat said process and obtain the conductive polymer layer that thickness is approximately 0.15-0.2mm 12 times
Tantalum anode forms dielectric oxide film through electrochemistry in the embodiment of the invention 1, and wet survey capacitance is 150 μ F, finishes all processes in the example 1, and capacitance is tested under 120Hz, and the capacitance extraction rate reaches 95%.Equivalent series resistance ESR tests at 100KH, and leakage current is tested reading in 30 seconds at voltage 6.3V.Product data see the following form
Table 1
Reflect that by last table comparing the present invention with known mixing method technology or method of fractional steps technology enhances productivity more than one times, and, prolong the service time of mixing material, reduce the waste of monomer and oxidant owing to limited the mixed proportion of oxidant and monomer.The anode bodies internal void is the suitable film of growth easily, and the certain thickness polymeric, conductive layer of the outside easily growth of anode bodies has guaranteed drawing and low ESR value and little leakage current value of capacitance.
Claims (8)
1. solid electrolytic capacitor, comprise the anode bodies (1) and the cathode terminal (3) that have anode terminal (2), its integral body is by epoxy encapsulation, anode terminal and cathode terminal expose, on anode bodies, be formed with dielectric oxide film (4), on dielectric oxide film, be formed with polyelectrolyte floor (5), on polyelectrolyte floor (5), scribble cathode conductive layer (7), (8) and connect cathode terminal, above-mentioned anode bodies is a valve metal, it is tantalum, niobium, a kind of in aluminium or the titanium, it is characterized in that above-mentioned polyelectrolyte floor (5) is the mixed liquor that the anode bodies that will have dielectric oxide film repeatedly immerses heterocyclic monomer and oxidant, and then repeatedly immerse heterocyclic monomer solution and oxidant liquid respectively, then in 50-80 ℃ temperature, be polymerized.
2. solid electrolytic capacitor as claimed in claim 1, it is characterized in that above-mentioned polyelectrolyte floor (5) forms in two steps, the first step, the anode bodies that at first will have a dielectric oxide film immerses in the mixing material of the heterocyclic monomer of ratio 5%-20% and oxidant, take out after 1-5 minute, with it as for carrying out in temperature 50-80 ℃ the environment polymerization reaction 1-2 hour, with methyl alcohol or ethanol cleaning reaction residue, then, mend to form in dilute phosphoric acid solution and repair dielectric layer, repeated impregnations, polymerization, benefit form 3-5 time; Second step, immerse the anode block of finishing preceding step in the oxidant liquid of 40%-60% earlier, immerse in the monomer solution again, take out back polymerization in temperature 50-80 ℃ environment, reaction finishes the back and washes reaction residue with methyl alcohol or ethanol, and mend formation with phosphoric acid,diluted liquid and repair dielectric layer, the preparation of 0.1-0.2mm thickness polyelectrolyte floor is finished in repeated impregnations, polymerization, benefit formation for 3-5 time.
3. solid electrolytic capacitor as claimed in claim 1 is characterized in that above-mentioned heterocyclic monomer is pyrroles, thiophene, aniline or 3,4 ethene dioxythiophenes.
4. solid electrolytic capacitor as claimed in claim 1 is characterized in that above-mentioned oxidant is ferric salt, persulfate, sulfonic acid molysite or hydrogen peroxide.
5. solid electrolytic capacitor as claimed in claim 1, it is two-layer to it is characterized in that above-mentioned cathode conductive layer has, and is respectively the graphite linings (7) and the silver slurry layer (8) of coating.
6. solid electrolytic capacitor as claimed in claim 1 is characterized in that scribbling on the above-mentioned anode terminal silicones (6).
7. solid electrolytic capacitor as claimed in claim 1 is characterized in that its ESR value scope is at 10-80m Ω.
8. the manufacture method of solid electrolytic capacitor as claimed in claim 1, its technical process comprises the anode bodies preparation, the formation of anode bodies dielectric oxide film, on the dielectric oxide film layer, form polyelectrolyte floor, be coated with cathode conductive layer, connect cathode terminal, the epoxy resin embedding, the technical process that it is characterized in that above-mentioned formation polyelectrolyte floor is carried out in two steps, the first step, the anode bodies that at first will have a dielectric oxide film immerses in the mixing material of the heterocyclic monomer of ratio 5%-20% and oxidant, take out after 1-5 minute, with it as for carrying out in temperature 50-80 ℃ the environment polymerization reaction 1-2 hour, with methyl alcohol or ethanol cleaning reaction residue, then, in dilute phosphoric acid solution, mend to form and repair dielectric layer, repeated impregnations, polymerization, mend and form 3-5 time; Second step, immerse the anode block of finishing preceding step in the oxidant liquid of 40%-60% earlier, immerse in the monomer solution again, take out back polymerization in temperature 50-80 ℃ environment, reaction finishes the back and washes reaction residue with methyl alcohol or ethanol, and mend formation with phosphoric acid,diluted liquid and repair dielectric layer, the preparation of 0.1-0.2mm thickness polyelectrolyte floor is finished in repeated impregnations, polymerization, benefit formation for 3-5 time.
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| CN2006100055847A CN101000827B (en) | 2006-01-11 | 2006-01-11 | Solid electrolytic condenser and manufacturing method thereof |
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| CN2006100055847A CN101000827B (en) | 2006-01-11 | 2006-01-11 | Solid electrolytic condenser and manufacturing method thereof |
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| CN101000827B true CN101000827B (en) | 2010-12-08 |
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| CN102464795A (en) * | 2010-11-18 | 2012-05-23 | 财团法人工业技术研究院 | Oxidant for forming solid capacitor, electrolyte composition comprising oxidant, solid capacitor and manufacturing method of solid capacitor |
| CN111909362A (en) * | 2019-05-09 | 2020-11-10 | 深圳新宙邦科技股份有限公司 | Conductive polymer, capacitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237773A (en) * | 1998-05-22 | 1999-12-08 | 松下电器产业株式会社 | Electrolytic condenser and its manufacturing method |
| CN1154132C (en) * | 1997-10-14 | 2004-06-16 | 三洋电机株式会社 | Solid electrolyte capacitor, and process and apparatus for producing same |
| CN1161804C (en) * | 1997-10-09 | 2004-08-11 | 三洋电机株式会社 | Solid electrolyte capacitor and making method and equipment thereof |
| CN1643627A (en) * | 2002-03-14 | 2005-07-20 | 三洋电机株式会社 | Solid electrolytic capacitor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161804C (en) * | 1997-10-09 | 2004-08-11 | 三洋电机株式会社 | Solid electrolyte capacitor and making method and equipment thereof |
| CN1154132C (en) * | 1997-10-14 | 2004-06-16 | 三洋电机株式会社 | Solid electrolyte capacitor, and process and apparatus for producing same |
| CN1237773A (en) * | 1998-05-22 | 1999-12-08 | 松下电器产业株式会社 | Electrolytic condenser and its manufacturing method |
| CN1643627A (en) * | 2002-03-14 | 2005-07-20 | 三洋电机株式会社 | Solid electrolytic capacitor |
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