CN101923967A - Solid tantalum electrolytic capacitor and manufacturing method thereof - Google Patents
Solid tantalum electrolytic capacitor and manufacturing method thereof Download PDFInfo
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- CN101923967A CN101923967A CN 201010257938 CN201010257938A CN101923967A CN 101923967 A CN101923967 A CN 101923967A CN 201010257938 CN201010257938 CN 201010257938 CN 201010257938 A CN201010257938 A CN 201010257938A CN 101923967 A CN101923967 A CN 101923967A
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Abstract
The invention discloses a solid tantalum electrolytic capacitor. The capacitor comprises a tantalum anode body, a Ta2O5 dielectric envelope, a conducting layer, a graphite layer and a silver-coated layer, wherein the Ta2O5 dielectric envelope is positioned on the surface of the tantalum anode body; the conducting layer is positioned on the Ta2O5 dielectric envelope; and the graphite layer and the silver-coated layer are coated on the conducting layer. The capacitor is characterized in that: the conducting layer is a mixed system consisting of a composite carbon nano-tube and a conducting high molecular material; the composite carbon nano-tube is a carbon nano-tube of which the surface is attached to conductive nano-particles and magnetic nano-particles uniformly; and the length direction of the composite carbon nano-tube is vertical to the surface of the tantalum anode body. Directionally-arrayed composite carbon nano-tubes are adopted in the conducting layer, so that the conductivity of the conducting layer is enhanced, the equivalent series resistance of the capacitor is reduced and the high-frequency characteristic of the capacitor is improved; simultaneously, the carbon nano-tube has high thermal conductivity, so that the capacitor has higher heat resistance, the service life of the capacitor is prolonged and the leakage current is reduced.
Description
Technical field
The present invention relates to the capacitor technology field, be specifically related to a kind of solid tantalum electrolytic capacitor and preparation method thereof.
Background technology
In recent years,, need capacitor small-sized and that jumbo high frequency is used, therefore proposed the solid electrolytic capacitor of solid conduction compound formation solid electrolyte layer along with miniaturization, the lightweight of electronic instrument.
Solid electrolytic capacitor comprises for example Al (aluminium) or Ta (tantalum) metal anode body, the dielectric oxide film that forms through oxidation processes on the surface of anode bodies and by applying the solid conduction compound, for example MnO
2(manganese dioxide), conducting high polymers thing are to oxide-film, and the cathode layer that closely contacts with oxide-film.Because dielectric oxide film thickness is minimum, therefore, compares with film capacitor with paper condenser, the size of electrolytic capacitor more low capacity is bigger.
For solid electrolytic capacitor, if the capacitance that whole block surface metal oxide-film is caused is called constant volume C
1, will be called variation capacitance C with the resulting capacitance of remainder oxide-film of porous body
2, series connection person is additional bath resistance R with it, then obtains total capacitance C to be:
C＝C
1+C
2(1/(1+(ωC
2R)
2)) (1)
By formula (1) as can be seen, after frequency uprises gradually, will cause C
2Partial failure, total capacitance is downward trend, thereby for effectively reducing C
2Loss, inevitable requirement reduces R effectively and remedies frequency and raise to the influence of capacitance.Therefore, adopt the compound of high conductivity better as the high frequency characteristics of the solid electrolytic capacitor of cathode layer.
Though manganese dioxide is regarded as a kind of very potential capacitor electrode material, but the conductivity of manganese dioxide is relatively poor, had by some and had more than manganese dioxide that the organic compound of high conductivity replaces, because the bath resistance R of capacitor has a significant impact the high frequency characteristics of capacitor, therefore, be necessary to adopt the electrolyte of high conductivity more to increase the performance of capacitor.
Summary of the invention
Problem to be solved by this invention is: how a kind of solid tantalum electrolytic capacitor and preparation method thereof is provided, and this device can overcome defective of the prior art, has increased the conductivity of conductive layer, has increased the capacitance of capacitor under high frequency condition.
Technical problem proposed by the invention is to solve like this: a kind of solid tantalum electrolytic capacitor is provided, comprises tantalum anode body, be positioned at the Ta on tantalum anode body surface
2O
5(tantalum pentoxide) dielectric tunicle, be positioned at Ta
2O
5Conductive layer on the dielectric tunicle, the graphite linings that on conductive layer, is covered and silver coating, it is characterized in that, described conductive layer is the mixed system of composite carbon nanometer tube and conducting polymer composite, the carbon nano-tube that described composite carbon nanometer tube evenly adheres to conductive nano-particles and magnetic nanoparticle for the surface, and the length direction of composite carbon nanometer tube is perpendicular to the tantalum anode body surface.
According to solid tantalum electrolytic capacitor provided by the present invention, it is characterized in that, described conducting polymer composite comprises polyaniline and derivative, polypyrrole and derivative thereof, polythiophene, polyphenyl bithiophene, poly-(3-alkylthrophene), poly-(3-methoxythiophene), gathers (3,4-vinyl dioxy thiophene), gathers benzene, coalescence benzene, polyacetylene, polyphenylene ethylene, poly-two alkynes, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-decanedioic acid ethylene glycol or polyethylene glycol imines.
According to solid tantalum electrolytic capacitor provided by the present invention, it is characterized in that the shared mass ratio of composite carbon nanometer tube is 1～30wt% in the mixed system of described conductive layer, wt% is weight percentage.
According to solid tantalum electrolytic capacitor provided by the present invention, it is characterized in that described carbon nano-tube is multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube that length is less than or equal to 100 μ m.
According to solid tantalum electrolytic capacitor provided by the present invention, it is characterized in that the thickness of described conductive layer is more than or equal to the length of carbon nano-tube.
According to solid tantalum electrolytic capacitor provided by the present invention, it is characterized in that described magnetic nanoparticle is the nanometer Fe that diameter is less than or equal to 40nm
3O
4Particle, nanometer γ-Fe
2O
3The ferrite particle of particle, alkaline-earth metal ferrite particle or other nano-grade sizes, the AlNiCo alloying pellet that belongs to the Al-Ni-Co system, the alloying pellet that belongs to the Sm-Co system, the alloying pellet that belongs to the Pt-Co system, the alloying pellet and composition thereof that belongs to the Nd-Fe-B system and other magnetic nanoparticles such as cobalt particle, iron particle, nickel particles etc.
According to solid tantalum electrolytic capacitor provided by the present invention; it is characterized in that; described conductive nano-particles is carbon black, metallic particles or the metal oxide particle that diameter is less than or equal to 40nm; wherein metallic particles is to be made of in gold, silver, copper, platinum, iron, tin, nickel, titanium, indium, palladium, the cobalt one or more, and metal oxide is to be made of in the oxide of cobalt oxide, zinc oxide, tin oxide, manganese dioxide, tin indium oxide and ruthenium, iridium, rhodium one or more.
A kind of preparation method of solid tantalum electrolytic capacitor is characterized in that, may further comprise the steps:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle forms anodal matrix;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and conductive high polymer monomer, will contains tantalum anode body and Ta again
2O
5The anodal matrix of dielectric tunicle immerses in the mixed solution, take out behind the certain hour and on the vertical direction on tantalum anode body surface, apply magnetic field, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use the conductivity type adhesive that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
Preparation method according to solid tantalum electrolytic capacitor provided by the present invention is characterized in that, described conductive layer be coated with by dripping, one or several modes in the spin coating, dip-coating, coating, inkjet printing, roller coat, LB film form.
Beneficial effect of the present invention: the conductive layer in the solid tantalum electrolytic capacitor of the present invention evenly adheres to the carbon nano-tube of conductive nano-particles and magnetic nanoparticle and the mixed system of conducting polymer composite for the surface, because carbon nano-tube has very high conductivity, carbon nano-tube aligns in conductive layer simultaneously, reduced the resistance between the carbon nano-tube, therefore, increased the conductivity of conductive layer greatly, reduced the equivalent series resistance of solid tantalum electrolytic capacitor, made solid tantalum electrolytic capacitor that better high frequency characteristics be arranged; Because carbon nano tube surface evenly is attached with conductive nano-particles, has increased the ratio electric capacity of carbon nano-tube; Because carbon nano-tube has good thermal conductivity, makes at Ta
2O
5The joule heat energy that produces in the dielectric tunicle is effectively transmitted and is exhaled, and has reduced Ta
2O
5The probability that the dielectric tunicle is breakdown makes solid tantalum electrolytic capacitor have higher thermal endurance, has increased the capacitor working life, and has reduced leakage current.
Description of drawings
Fig. 1 is the sectional view of solid tantalum electrolytic capacitor provided by the present invention;
Fig. 2 is the frequency characteristic curve diagram of the solid tantalum electrolytic capacitor in the embodiment of the invention 1 and the comparative example 1.
Wherein, 1, tantalum anode body, 2, Ta
2O
5The dielectric tunicle, 3, conductive layer, 4, graphite linings, 5, silver coating, 6, tantalum wire, 7, conductive adhesive, 8, anode tap, 9, cathode terminal, 10, epoxy resin.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
As shown in Figure 1, this solid tantalum electrolytic capacitor possesses the tantalum anode body 1 of cube shaped in inside, the Ta that forms in anode body surface in the mode of surrounding this anode bodies
2O
5 Dielectric tunicle 2, the conductive layer 3 that on dielectric tunicle 2, forms, the graphite linings 4 that on conductive layer 3, forms, the silver coating 5 that on graphite linings, forms.On anode bodies, be provided with to the outstanding tantalum wire cylindraceous 6 in outside; anode tap 8 utilizes resistance welded to engage with tantalum wire 6; electrically conductive adhesives 7 such as the sticking material of cathode terminal 9 use elargol engage with silver coating 5, utilize epoxy resin 10 protection solid electrolytic capacitor integral body at last.
In the solid tantalum electrolytic capacitor of the present invention in the conductive layer 3 the shared mass ratio of composite carbon nanometer tube be 1～30wt%.
Carbon nano-tube in the solid tantalum electrolytic capacitor of the present invention in the conductive layer 3 is multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube that length is less than or equal to 100 μ m.
The thickness of conductive layer 3 is more than or equal to the length of carbon nano-tube in the solid tantalum electrolytic capacitor of the present invention.
The magnetic nanoparticle that carbon nano tube surface is evenly adhered in the conductive layer 3 in the solid tantalum electrolytic capacitor of the present invention is the nanometer Fe that diameter is less than or equal to 40nm
3O
4Particle, nanometer γ-Fe
2O
3The ferrite particle of particle, alkaline-earth metal ferrite particle or other nano-grade sizes, belong to the Al-Ni-Co system the AlNiCo alloying pellet, belong to the Sm-Co system alloying pellet, belong to the Pt-Co system alloying pellet, belong to alloying pellet of Nd-Fe-B system and composition thereof, and other magnetic nanoparticles such as cobalt particle, iron particle, nickel particles etc.
The conductive nano-particles that carbon nano tube surface is evenly adhered in the conductive layer 3 in the solid tantalum electrolytic capacitor of the present invention is carbon black, metallic particles and the metal oxide particle that diameter is less than or equal to 40nm, wherein metallic particles is to be made of in gold, silver, copper, platinum, iron, tin, nickel, titanium, indium, palladium, the cobalt one or more, and metal oxide is to be made of in the oxide of cobalt oxide, zinc oxide, tin oxide, manganese dioxide, tin indium oxide and ruthenium, iridium, rhodium one or more.
Embodiment 1
Describe based on Fig. 1.Wherein, conductive layer 3 is poly-(3,4-vinyl dioxy thiophene) of doping 1wt% composite carbon nanometer tube, the magnetic Fe that described composite carbon nanometer tube evenly adheres to the 10nm diameter for the surface
3O
4The multi-walled carbon nano-tubes of the conductive silver particle of particle and 10nm diameter, multi-wall carbon nano-tube length of tube are 20 μ m.
The preparation method is as follows:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and poly-(3,4-vinyl dioxy thiophene) monomer, will contains tantalum anode body and Ta
2O
5The anodal matrix of dielectric tunicle immerses in the mixed solution, take out and on the vertical direction on tantalum anode body surface, apply 300mT magnetic field behind the certain hour, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use conductivity type adhesive such as elargol that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
Comparative example 1
Adopting poly-(3,4-vinyl dioxy thiophene) is the conductive layer of solid tantalum electrolytic capacitor, in addition, similarly carries out with enforcement 1.
Table 1 is the various performance parameters of the solid tantalum electrolytic capacitor in embodiment 1 and the comparative example 1.
The preparation method is as follows:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and polyaniline monomer, mixed solution is sprayed to contain tantalum anode body and Ta again
2O
5On the anodal matrix of dielectric tunicle, apply 350mT magnetic field again on the vertical direction on tantalum anode body surface, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use conductivity type adhesive such as elargol that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
The preparation method is as follows:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and polypyrrole monomer, mixed solution is dripped to be coated onto again and contain tantalum anode body and Ta
2O
5On the anodal matrix of dielectric tunicle, apply 400mT magnetic field again on the vertical direction on tantalum anode body surface, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use conductivity type adhesive such as elargol that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
The preparation method is as follows:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle;
3. composite carbon nanometer tube is dispersed in and contains in oxidant and the poly-mixed solution, mixed solution is spun to contains tantalum anode body and Ta again benzene monomer
2O
5On the anodal matrix of dielectric tunicle, apply 450mT magnetic field again on the vertical direction on tantalum anode body surface, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use conductivity type adhesive such as elargol that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
The preparation method is as follows:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and coalescence benzene monomer, with the method for inkjet printing mixed solution is coated to and contains tantalum anode body and Ta
2O
5On the anodal matrix of dielectric tunicle, apply 500mT magnetic field again on the vertical direction on tantalum anode body surface, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use conductivity type adhesive such as elargol that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
The preparation method is similar to embodiment 1.
The preparation method is similar to embodiment 1.
Claims (9)
1. solid tantalum electrolytic capacitor comprises tantalum anode body, is positioned at the Ta on tantalum anode body surface
2O
5The dielectric tunicle, be positioned at Ta
2O
5Conductive layer on the dielectric tunicle, the graphite linings that on conductive layer, is covered and silver coating, it is characterized in that, described conductive layer is the mixed system of composite carbon nanometer tube and conducting polymer composite, the carbon nano-tube that described composite carbon nanometer tube evenly adheres to conductive nano-particles and magnetic nanoparticle for the surface, and the length direction of composite carbon nanometer tube is perpendicular to the tantalum anode body surface.
2. solid tantalum electrolytic capacitor according to claim 1, it is characterized in that, described conducting polymer composite comprises polyaniline and derivative, polypyrrole and derivative thereof, polythiophene, polyphenyl bithiophene, poly-(3-alkylthrophene), poly-(3-methoxythiophene), gathers (3,4-vinyl dioxy thiophene), gathers benzene, coalescence benzene, polyacetylene, polyphenylene ethylene, poly-two alkynes, poly(ethylene oxide), PPOX, polyethylene glycol succinate, poly-decanedioic acid ethylene glycol or polyethylene glycol imines.
3. solid tantalum electrolytic capacitor according to claim 1 is characterized in that, the shared mass ratio of composite carbon nanometer tube is 1～30wt% in the mixed system of described conductive layer, and wt% is weight percentage.
4. solid tantalum electrolytic capacitor according to claim 1 is characterized in that, described carbon nano-tube is multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube that length is less than or equal to 100 μ m.
5. solid tantalum electrolytic capacitor according to claim 1 is characterized in that the thickness of described conductive layer is more than or equal to the length of carbon nano-tube.
6. solid tantalum electrolytic capacitor according to claim 1 is characterized in that, described magnetic nanoparticle is the nanometer Fe that diameter is less than or equal to 40nm
3O
4Particle, nanometer γ-Fe
2O
3Particle, alkaline-earth metal ferrite particle, belong to the Al-Ni-Co system the AlNiCo alloying pellet, belong to the Sm-Co system alloying pellet, belong to the alloying pellet of Pt-Co system or belong to alloying pellet of Nd-Fe-B system and composition thereof.
7. solid tantalum electrolytic capacitor according to claim 1; it is characterized in that; described conductive nano-particles is carbon black, metallic particles or the metal oxide particle that diameter is less than or equal to 40nm; wherein metallic particles is to be made of in gold, silver, copper, platinum, iron, tin, nickel, titanium, indium, palladium, the cobalt one or more, and metal oxide is to be made of in the oxide of cobalt oxide, zinc oxide, tin oxide, manganese dioxide, tin indium oxide and ruthenium, iridium, rhodium one or more.
8. the preparation method of a solid tantalum electrolytic capacitor is characterized in that, may further comprise the steps:
1. the compacting of nanometer tantalum metallic particles is formed piece, in the organizator of tantalum particle, plant upright tantalum wire cylindraceous, under high temperature and vacuum condition, sinter porous shape tantalum anode body into;
2. the tantalum anode body that sinters is carried out anodic oxidation, generate one deck Ta on its surface
2O
5The dielectric tunicle forms anodal matrix;
3. composite carbon nanometer tube is dispersed in the mixed solution that contains oxidant and conductive high polymer monomer, will contains tantalum anode body and Ta again
2O
5The anodal matrix of dielectric tunicle immerses in the mixed solution, take out behind the certain hour and on the vertical direction on tantalum anode body surface, apply magnetic field, the length direction that makes composite carbon nanometer tube heats up gradually in 60～80 ℃ temperature range and removes solvent formation conductive layer perpendicular to the tantalum anode body surface;
4. form the negative pole graphite linings through PROCESS FOR TREATMENT, outside graphite linings, form silver coating again;
5. utilize the resistance welded anode tap that on tantalum wire, continues, use the conductivity type adhesive that cathode terminal is engaged with silver coating;
6. adopt epoxy resin enclosed form that the device of above-mentioned preparation is encapsulated.
9. the preparation method of solid tantalum electrolytic capacitor according to claim 8 is characterized in that, described conductive layer be coated with by dripping, one or several modes in the spin coating, dip-coating, coating, inkjet printing, roller coat, LB film form.
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| CN106497048A (en) * | 2016-10-27 | 2017-03-15 | 中国科学院理化技术研究所 | Preparation method of anisotropic conductive polymer composite film |
| CN114156089A (en) * | 2021-11-24 | 2022-03-08 | 北京七一八友益电子有限责任公司 | Chip conductive polymer tantalum capacitor and preparation method thereof |
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