CN101356610A - Polymer based solid state capacitors and a method of manufacturing them - Google Patents
Polymer based solid state capacitors and a method of manufacturing them Download PDFInfo
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- CN101356610A CN101356610A CNA2006800351849A CN200680035184A CN101356610A CN 101356610 A CN101356610 A CN 101356610A CN A2006800351849 A CNA2006800351849 A CN A2006800351849A CN 200680035184 A CN200680035184 A CN 200680035184A CN 101356610 A CN101356610 A CN 101356610A
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Abstract
The present invention relates to a solid state capacitor having a conductive polymer cathode layer counter electrode comprising acrylate binder and a method for its manufacture. In particular the present invention relates to a solid state capacitor comprising: providing a porous anode body of valve action material; forming a dielectric layer on said porous body; forming a cathode layer in contact with said dielectric layer, which cathode layer comprises a conductive polymer and an acrylic binder; and providing an anode terminal in electrical connection with the porous body anode and a cathode terminal in electrical connection with the cathode layer and a method for its manufacture.
Description
Invention field
The present invention relates to a kind of solid-state capacitor, this solid-state capacitor has the counterelectrode of conductive polymer coating, and described counterelectrode comprises acrylic polymer; The invention still further relates to the manufacture method of this capacitor.This capacitor is compared based on the capacitor of conducting polymer with routine, demonstrates the electrical property and the mechanical performance of raising.
Background of invention
The chief value of solid-state capacitor is, because this capacitor has bigger serface and thin dielectric, therefore can provide high electric capacity in more limited volumetric spaces.The art methods of making solid-state capacitor may further comprise the steps: the powdered rubber that the material that forms solid-state capacitor is provided, the powdered rubber compacting is formed reservation shape, material through compacting is carried out sintering, make it be combined into porous integral, carry out chemical reaction, as porous integral is carried out anodization, thereby form dielectric coat in its surface, on described dielectric coat, form conductive coating then.In this solid-state capacitor, the anodized parts of process become the anode of described capacitor, and the conductive coating on the dielectric forms negative electrode or counterelectrode.
The multiple solid-state material of available technology adopting forms anode and dielectric.The main material that forms solid-state capacitor is so-called valve action (valve action) material that forms dielectric layer easily on conductive base.The important example of this material is tantalum (niobium (columbium)) metal, niobium (niobium) metal and conduction niobium protoxide (as monoxide).It also can be the conduction niobium nitride.Niobium based capacitor is known 30 years, but the performance of this capacitor partly is subjected to the restriction of obtainable niobium powder quality.
According in (Salisbury EP patent 0688030, AVX Corp.) tantalum capacitor of the method manufacturing of Jie Shiing successfully provides very high volume efficiency and minimum part dimension, and this capacitor can be used for mobile communication equipment especially and other require the application of miniaturization.
Recently the capacitor of exploitation has anode that columbium monoxide makes and based on the dielectric of niobium pentoxide.Described the formation of capacitor level niobium oxide anode among US6322912 (Fife etc.), US 6391275 (Fife etc.), US 6416730 (Fife etc.), US 6576099 (Kimmel etc.), US 6592740 (Fife etc.) and the US 6639787 (Kimmel etc.), it is derived from the niobium oxide powder that obtains by reduced oxide.
The negative electrode of conventional solid-state capacitor forms by the method that is referred to as " oozing manganese (manganizing) " mainly by the manganese dioxide manufacturing.In the method, on the dielectric that forms by anodization, form the conductive counter electrode coating.Carry out in the following manner as the step 1 of " oozing manganese ": will immerse in manganese nitrate (II) solution through anodized device, heating changes into solid-state conduction manganese dioxide through the device of dipping with nitrate in humid atmosphere.Use manganese dioxide to have some shortcomings as negative electrode.At first, manganese dioxide is applied in the loose structure of conventional capacitor after, its volume conductance is generally 0.1 Siemens/cm.So high volume conductance can have a negative impact to the overall ESR (equivalent series resistance) of capacitor under low frequency and intermediate frequency condition.And manganese dioxide is a kind of strong oxidizer.When the part of capacitor was overheated, manganese dioxide can provide many oxygen, thus the heat dissipation (thermal runaway) of aggravation capacitor.
Developed the capacitor that comprises conducting polymer, in tantalum capacitor, used the problem that manganese dioxide produced thereby overcome.The conductivity of these polymer-matrix capacitors is enough to electric current is passed to external contact and not significantly loss from dielectric up to the 10-100 Siemens/cm.This capacitor can be used for frequency applications because the loss that is caused by low ESR is lower.Polymer based counter electrodes also shows repairing performance and enough thermal stabilitys.
Yet there are many defectives in the polymer based counter electrodes of this area.These defectives comprise that the fragility because of polymeric layer may cause losing efficacy, and can not remain intact under the thermal-mechanical stress in manufacturing, test and the use.
US 5,729, and 428 (Sakata etc.) have described in the organic layer as adhesive and used electron donor, to improve the adhesiveness of conducting polymer and valve metal oxides film.US 5,729, and 428 suggestions are immersed solution by steam or with dielectric, and adhesive directly is applied to dielectric.According to the description of this patent, aliphatic acid, aromatic carboxylic acid, anion surfactant, as carboxylate radical or sulfonate radical, phenol and derivative thereof, silane or aluminium or titanium coupling agent are possible adhesives, because they can form covalent bond with the valve metal atom in the dielectric.As a result, electronics is supplied with oxide, rebuild potential barrier, allow electron donor organic compound stable existence simultaneously on oxidation film.The capacitor of making demonstrates the leakage current that has improved and has a high-temperature stability.
US 6,072, and 694 (Hahn etc.) have described the silylation coupling agent is directly joined in the polymer solution.Viewed effect may with US 5,729, therefore 428 result compares, and has improved the adhesive effect of conducting polymer and metal oxide, has reduced dissipation factor, ESR and DCL.Form the silane network structure by physical bond, under the situation that changes solvent composition or pH, this combination is reversible.Therefore, this network structure in use may lose efficacy.
Though foregoing method can be used for making capacitor, but still presses for the substitute that finds silane coupler,, and therefore improve leakage current so that can make the polymer-matrix capacitor that electrical property and mechanical stability are improved.The method that the present invention seeks to address these problems.
Summary of the invention
According to an aspect of the present invention, provide a kind of method of making solid-state capacitor, this method may further comprise the steps:
The porous anode body of valve action materials is provided;
On described porous body, form dielectric layer;
Form the cathode layer that contacts with described dielectric layer, this cathode layer comprises conducting polymer and acrylic polymer adhesive; With
Anode terminal (terminal) that is electrically connected with porous anode body and the cathode terminal that is electrically connected with cathode layer are provided.
According to another aspect of the present invention, provide a kind of solid-state capacitor, this solid-state capacitor comprises:
The porous anode body of valve action materials;
Be formed on the dielectric layer on the described porous body;
With the cathode layer that described dielectric layer contacts, described cathode layer comprises conducting polymer and acrylic adhesives; With
Anode terminal that is electrically connected with porous anode body and the cathode terminal that is electrically connected with cathode layer.
Use esters of acrylic acid such as methacrylate, the advantage of the adhesive of or derivatives thereof is the internal intensity (internal strength) that has improved conductive polymer coating, therefore, compare with those polymer-matrix solid-state capacitors in prior art field, leaking at direct current with the capacitor of said method manufacturing has surprising improvement aspect (DCL), the polymeric layer high-temperature stability, can bear the variation of solvent composition and/or pH.
Described conducting polymer preferably includes the polymer of intrinsic conduction and to the dopant of this polymer.The polymer of intrinsic conduction (ICP) is not need to add conductive filler (as carbon black) to obtain the polymer of conductivity.The conductivity of ICP depends on the availability of excessive charge.These free charges are by dopant, and normally oxidant or reducing agent provide.At Plastics Materials (plastic material), in the 7th edition (1999) 886-889 pages or leaves of JA Brydson ICP is discussed.At present case, conducting polymer preferably is selected from following polymer of monomers: acetylene, thiophene, pyrroles or aniline, or their mixture and copolymer.
Acrylic adhesives is methyl acrylic ester preferably.Methyl acrylic ester can be the methacrylate or derivatives thereof with following general formula:
In preferred embodiment, described methyl acrylic ester is a methacrylic acid hydroxyl ethyl ester (HEMA).
Concentration such as the such adhesive of HEMA in the polymer is 0.1-20 weight %, preferred 0.5-15 weight %, or 1-5 weight %.
The dopant of conducting polymer can comprise metal cation and organic acid complex compound.In preferred embodiment, organic acid is a sulfonic acid.In a particularly preferred execution mode, dopant is toluenesulfonic acid Fe (III).
The conductive polymer cathode layer can be with liquid application.The conductive polymer cathode layer can comprise the polymer coating that many layers apply successively.In all cases, described conductive polymer coating can comprise the sandwich of multiple layer polymer.
In preferred embodiment, conductive polymer coating applies with the precursor solution of liquid monomer, and the precursor solution of described monomer can in-situ polymerization.This precursor solution preferably also comprises adhesive, so that during polymerization reaction adhesive is combined in the conducting polymer.Monomer solution can carry out electrochemical polymerization easily.
In capacitor of the present invention, can be less than the DCL of 50nA/CV, (specificcharge capacity) is about 1 than lotus capacity, 000-400,000CV/g.
When carrying out anodization formation dielectric layer by the antianode body, being used for anodized formation voltage (formation voltage) is 6-150V.
In the capacitor of the present invention, porous anode body generally forms in the following manner: powder or particle " fresh " mixture in suitable bonding/lubricant to capacitor level carry out molded, to suppress then or molded anode raw material particle sintering curing, lubricant is burnouted or remove, for example remove by chemical method with additive method.That the example of operable precursor powder kind comprises is laminar, combination or version that corner angle are arranged, warty and these shapes.Powder comprises that granularity is the powder of 0.1-500 μ m.Porous anode body can be 1,100-1, and 900 ℃, preferably 1,300-1 forms under 500 ℃ the sintering temperature.
Owing to adopted powder metallurgy route, can form and have the very porous anode body of high surface area.
The powder of valve action materials can mix with nitrogen, and its content is at least 2000ppm.
Dielectric layer is formed on the surface of porous anode body by anodic oxidation (anodization, this area are also referred to as " formation ").Dielectric layer should have high-k, high electric strength (electrical strength) and low current leakage.These character can be used dielectric as thin as a wafer, and have made full use of the sponge structure of anode.Dielectric layer is the steady oxide of the valve action anode material of lower floor's conduction normally.For example, dielectric layer can be included in niobium pentoxide on the niobium metal, at niobium pentoxide on the niobium protoxide or the tantalum pentoxide on the tantalum metal.Dielectric layer can form on the surface of porous sintered body anode by anodic oxidation or additive method known in the art.
Conductive polymer coating can be formed directly on the dielectric layer by the polymerization of proper monomer.Can adopt chemical polymerization or electricity to cause polymerization and form polymeric layer.Can use and to produce the right monomer formation conductive polymer coating of conjugated electrons.Monomer is preferably from aniline, thiophene, pyrroles or their arbitrary derivative.Preferred monomer is 3,4-ethylidene dioxy thiophene.
Should use suitable oxidant, carry out polymerization on the surface of dielectric layer to help required monomer.Monomer and oxidant can be simultaneously or are deposited on the surface of dielectric layer in succession.Dielectric surface can apply oxidant, uses monomer then on dielectric surface, perhaps, uses oxidant earlier, uses monomer then, and vice versa.
When adopting electricity to cause polymerization formation counterelectrode, do not need oxidant.Dielectric layer is precoating one electrically conductive layer at first, and for example, the conducting polymer of chemical monolayer deposition is to provide and the electrically contacting of anode.Then, by apply voltage on anode, in the presence of dopant, monomer carries out electrochemical polymerization on anode.
Can be adopted as any technology that applies porous body or porous chips and develop, for example be immersed in the liquid or cover with paint, lacquer, colour wash, etc., monomer or oxidant are applied in the surface of dielectric layer.Monomer or oxidant can be used with solution, spraying or steam form.The oxidant that is used for high conducting polymer polymerization can be any conventional cation with oxidative function and enough electron affinity.Suitable oxidant is a ferric ion.Can use toluenesulfonic acid Fe (III).
Need dopant to make the polymeric layer of intrinsic conduction have conductivity.Can or apply dopant, monomer and oxidant in succession in the dielectric layer surface while.Can apply monomer on anode before applying oxidant and/or dopant solution, vice versa.Oxidant and dopant can be same compounds.In this case, toluenesulfonic acid iron (III) is preferred oxidant/dopant.Organic lewis acid and inorganic lewis acid are the dopants of sulfonic acid.For example, can use the ion of organic sulfonic acid.
Any time that can be used for polymerization process, acrylic adhesives is joined in oxidant, dopant and/or the monomer solution any in these components of oxidant, dopant and/or monomer solution.Acrylic adhesives can mix with monomer or oxidant and/or dopant, is coated in then on the described dielectric layer.Monomer, oxidant, dopant and acrylic adhesives can be blended in the solution, be coated on the anode.Dopant, monomer, oxidant and acrylic adhesives can be coated in dielectric surface simultaneously.Monomer, dopant and oxidant can be coated in dielectric surface in any order one by one.Can before applying oxidant and dopant on the dielectric surface monomer be coated in dielectric surface, vice versa.Any technology that can be adopted as coating porous body or porous chips and develop is applied in acrylic adhesives, oxidant, dopant and monomer on the anode.Preferred employing dip-coating.
Can repeat above series of steps, thereby form the polymeric layer of requested number.A plurality of conductive polymer coatings can be provided.Can directly on the surface of described dielectric layer, provide and be positioned at first polymeric layer lip-deep 1,2,3 or more a plurality of conductive polymer coating.
The DCL of solid-state capacitor (DC leakage) less than 50nA/CV, preferably less than 20nA/CV, is more preferably less than 10nA/CV.
The ratio lotus of capacitor of the present invention is about 1,000-400,000CV/g.Be preferably 30,000-150,000CV/g, more preferably 50,000-100,000CV/g.
Capacitor of the present invention can have at about 6-150V, the anode that preferred 10-50V voltage forms down.Can use other higher formation voltage.
Anode and cathode termination means are provided.Anode and cathode termination means can comprise lead-in wire, lead or plate or face coat.Typical terminal can weld with circuit or circuit board.
Anode wire can also be arranged, and its effect is that the porous anode body with sintering links to each other with the positive pole terminal device.Positive wire can be pressed in the porous anode body of sintering, perhaps make on the porous anode body of positive wire attached to sintering by welding, sintering or additive method.Described positive wire can be imbedded or adhere in any moment before anodization.
Can the cathode terminal device be connected on lip-deep graphite of cathode layer and the silver layer by welding, gluing or soft soldering, cathode termination means is linked to each other with cathode layer.
The porous anode body of sintering, dielectric layer, cathode layer and negative electrode and positive pole terminal device can be sealed (making bared end sub-surface or connector) at the inertia insulating material, in the thermosets as epoxides or filling silicon dioxide.
Only be described by way of example below implementing modes more of the present invention.Also provide comparative example to confirm benefit of the present invention.
The accompanying drawing summary
In the accompanying drawing:
Fig. 1 is unleaded (lead-free) backflow distribution map that is illustrated in the condition that is adopted in the result of the test of mensuration table 1.
Fig. 2 is illustrated in the structure that does not have the counterelectrode under the HEMA existence.
Fig. 3 illustrates the structure of the counterelectrode of the present invention in the presence of HEMA.
Comparison diagram 2 and Fig. 3 as can be known, (Fig. 3) compares with the counterelectrode that contains acrylic adhesives, the counterelectrode that does not contain acrylic adhesives has loose structure (Fig. 2). Therefore, the existence of acrylic adhesives makes the structure that counterelectrode can adopt can provide to counterelectrode more favourable electrical property.
Embodiment
Following examples have shown the ability of acrylic polymer adhesive, the particularly polymer adhesive that is formed by methyl acrylic ester, can form the tantalum capacitor with excellent electrical properties.
Make 900 anode bodies that electric capacity is 100 μ F/10V levels.Each free CV of described anode bodies is the spherolite that the tantalum powder of 50,000 μ FV/g forms compacting, and spherolite is of a size of long 4.05mm, wide 3.6mm, high 1.05mm.Then,, adopt the formation voltage of 31.4V, these parts are carried out dielectric form processing, on each pellet/anode body, make dielectric layer by anodization.
Sample A-comparative example
Do not having to make first 180 anode bodies (numbering 1-180), example in contrast in the presence of the methacrylate.On anode component, apply eight layers of conductive polymer coating, form electroconductive polymer coating.Particularly, at first in visit logical CB40 (Baytron CB40) as the butanol solution that contains 40% tosilate (p-toluenesulphonate) of oxidant/dopant, each sample was soaked 5 minutes.Make sample drying at least 30 minutes at room temperature, immerse then as in the ethylidene dioxy thiophene (EDT) of monomer 30 seconds.Make sample drying at least 30 minutes at room temperature, to carry out polymerization.Then, washing sample in two ethanol bath, each is 5 minutes.This process can repeat eight times.
As mentioned above, apply after the conductive polymer coating, with this parts anodization at every turn; These parts were immersed in 10% sulfuric acid and 2% phosphoric acid solution 5 minutes, and apply 20V voltage.
Then, by the technology of flooding successively, be this sample end of envelope with graphite and silver coating.
Sample B is (3-glycidoxypropyltrime,hoxysilane in as 4% tosilate of oxidant/dopant) relatively.
On second batch of 180 anode bodies (numbering 181-360), be coated in the 3-glycidoxy-propyltrimethoxy silane in the oxidant/dopant in succession.The 3-glycidoxypropyltrime,hoxysilane is joined in the butanol solution of 40% tosilate, concentration is 5 weight %, dissolves after 1 hour by continuous mixing.
On anode component, apply eight layers of conducting polymer, form electroconductive polymer coating.Particularly, each sample is at first immersed as in the butanol solution that contains 40% tosilate of oxidant/dopant 5 minutes.Make sample drying at least 30 minutes at room temperature, immersed then in the EDT monomer 30 seconds.Make sample drying at least 30 minutes at room temperature, to carry out polymerization.Then, washing sample in two ethanol bath, each is 5 minutes.This process repeats eight times.
As mentioned above, apply after the conductive polymer coating, with this anode bodies anodization at every turn; This anode bodies was immersed in 10% sulfuric acid and 2% phosphoric acid solution 5 minutes, and apply 20V voltage.
Then, by dipping technique, be this sample end-blocking with graphite and silver coating.
Sample C (5% 2-hydroxyethyl methacrylate is in the butanol solution as 40% tosilate of oxidant/dopant)
On the 3rd batch of 180 anode bodies (numbering 361-540), be coated in the 2-hydroxyethyl methacrylate in the oxidant/dopant successively.2-hydroxyethyl methacrylate is joined in the butanol solution of 40% tosilate, concentration is 5 weight %, dissolves after 1 hour by continuous mixing.
On anode bodies, apply eight layers of conducting polymer, form electroconductive polymer coating.Particularly, each sample is at first immersed as in the butanol solution that contains 40% tosilate of oxidant/dopant 5 minutes.Make sample drying at least 30 minutes at room temperature, immersed then in the EDT monomer 30 seconds.Make sample drying at least 30 minutes at room temperature, to carry out polymerization.Then, washing sample in two ethanol bath, each is 5 minutes.This process repeats eight times.
As mentioned above, apply after the conductive polymer coating, with this anode bodies anodization at every turn; This anode bodies was immersed in 10% sulfuric acid and 2% phosphoric acid solution 5 minutes, and apply 20V voltage.
Then, by dipping technique, be this sample end-blocking with graphite and silver coating.
Sample D (as 1% 2-hydroxyethyl methacrylate among the EDT of monomer)
Be coated in the 2-hydroxyethyl methacrylate in the monomer on the 4th batch of 180 anode bodies (numbering 541-720) successively.2-hydroxyethyl methacrylate is joined in the PEDT monomer, and concentration is 5 weight %, dissolves after 1 hour by continuous mixing.
On anode bodies, apply eight layers of conducting polymer, form electroconductive polymer coating.Particularly, each sample is at first immersed as in the butanol solution that contains 40% tosilate of oxidant/dopant 5 minutes.Make sample drying at least 30 minutes at room temperature, immersed then in the EDT monomer 30 seconds.Make sample drying at least 30 minutes at room temperature, to carry out polymerization.Then, washing sample in two ethanol bath, each is 5 minutes.This process repeats eight times.
As mentioned above, apply after the conductive polymer coating, with this anode bodies anodization at every turn; This anode bodies was immersed in 10% sulfuric acid and 2% phosphoric acid solution 5 minutes, and apply 20V voltage.
Then, by dipping technique, be this sample end-blocking with graphite and silver coating.
Sample E (as 5% 2-hydroxyethyl methacrylate among the EDT of monomer)
On the 5th batch of 180 anode bodies (numbering 721-900), be coated in the 2-hydroxyethyl methacrylate in the monomer successively.2-hydroxyethyl methacrylate is joined in the EDT monomer, and concentration is 5 weight %, dissolves after 1 hour by continuous mixing.
On anode component, apply eight layers of conducting polymer, form electroconductive polymer coating.Particularly, each sample is at first immersed in the oxidant/dopant of butanol solution of 40% tosilate 5 minutes.Make sample drying at least 30 minutes at room temperature, immersed then in the EDT monomer 30 seconds.Make sample drying at least 30 minutes at room temperature, to carry out polymerization.Then, washing sample in two ethanol bath, each is 5 minutes.This process repeats eight times.
As mentioned above, apply after the conductive polymer coating, with this anode bodies anodization at every turn; This anode bodies was immersed in 10% sulfuric acid and 2% phosphoric acid solution 5 minutes, and apply 20V voltage.
Then, by dipping technique, be this sample end-blocking with graphite and silver coating.
After all samples is finished above-mentioned processing, has the finished product capacitor of anode and cathode terminal by the packaging technology formation of routine.Measure the performance of finished part.After the mensuration, described parts are carried out unleaded reflow treatment under condition shown in Figure 1.Measure electrical quantity 24 hours annealing backs.
The humidity measurement that quickens is with the moisture effect before the outstanding unleaded backflow.Described parts carry out unleaded backflow according to Fig. 1.After the backflow, allow described parts lax (relax) 1 hour, and in 121 ℃ pressure digester, handled 4 hours.Lax after 1 hour, described parts are refluxed once more with same treatment conditions.
The result
In the following Table 1, listed the electrical property of the control sample that does not have adhesive (2-hydroxyethyl methacrylate) or silane.Also be illustrated in the test result of the sample that has adhesive in the conducting polymer, particularly in the oxidant/dopant of the butanol solution of 40% tosilate, perhaps in the EDT of two kinds of concentration monomer, add the test result of acrylate derivative:
| Sample number into spectrum | A | B | C | D | E |
| Sample description | Contrast | Silane | HEMA in the oxidant | HEMA in the monomer | HEMA in the monomer |
| Additive concentration (weight %) | 0 | 5 | 5 | 1 | 5 |
| The DCL amount is improved (%) | N.A | 3％ | 6％ | 4％ | 10％ |
| DCL(μA) | 3.7 | 3.0 | 3.5 | 3.6 | 3.4 |
| CAP(μF) | 104 | 92 | 101 | 102 | 100 |
| DF(％) | 1.5 | 2.2 | 2.0 | 2.1 | 2.0 |
| ESR(mΩ) | 38 | 36 | 36 | 37 | 35 |
| Backflow DCL lost efficacy (%) | 1.1％ | 0％ | 0％ | 0％ | 0％ |
| Pressure digester+backflow DCL lost efficacy (%) | 7.2％ | 3.8％ | 0.6％ | 1.2％ | 0.6％ |
Table 1 shows, exists acrylic polymer can improve various character in the conductive polymer cathode layer.Compare when having 5% silane, this improvement has wonderful effect, also is like this even only contain under the situation of 1% acrylate at sample.
Can see that also DCL amount improved 4%-10%.Compare with the silane reference examples, capacitance improves.Initial back DCL does not take place lost efficacy, particularly after pressure boiling (being thermal shock), the incidence that DCL lost efficacy is extremely low.
Claims (24)
1. method of making solid-state capacitor, this method comprises:
A kind of porous anode body of valve action materials is provided;
On described porous body, form dielectric layer;
Form the cathode layer that contacts with described dielectric layer, this cathode layer comprises conducting polymer and acrylic adhesives; With
Anode terminal that is electrically connected with porous anode body and the cathode terminal that is electrically connected with cathode layer are provided.
2. one or more solid-state capacitors comprise:
The porous anode body of valve action materials;
The dielectric layer that on described porous body, forms;
With the cathode layer that described dielectric layer contacts, this cathode layer comprises conducting polymer and acrylic adhesives; With
Anode terminal that is electrically connected with porous anode body and the cathode terminal that is electrically connected with cathode layer.
3. the method for claim 1 or capacitor as claimed in claim 2 is characterized in that, described conducting polymer comprises the polymer of intrinsic conduction and to the dopant of this polymer.
4. method as claimed in claim 3 or capacitor is characterized in that described conducting polymer is to be selected from following polymer of monomers: acetylene, thiophene, pyrroles or aniline, perhaps their mixture or copolymer.
5. as claim 3 or 4 described method or capacitors, it is characterized in that described dopant is to realize conducting electricity oxidant or the reducing agent that polymer is carried out modification by producing excessive charge.
6. each described method or capacitor in the claim as described above is characterized in that described acrylic adhesives is a methyl acrylic ester.
7. method as claimed in claim 6 or capacitor is characterized in that, described methyl acrylic ester is the methacrylate or derivatives thereof with following general formula:
8. method as claimed in claim 9 or capacitor is characterized in that, described methyl acrylic ester is a methacrylic acid hydroxyl ethyl ester.
9. each described method or capacitor in the claim as described above is characterized in that the concentration of adhesive is 0.1-20 weight % in the polymer.
10. method as claimed in claim 9 or capacitor is characterized in that, the concentration of adhesive is 0.5-15 weight %.
11. as each described method or capacitor among the claim 3-10, it is characterized in that, comprise metal cation and organic acid complex compound at the dopant described in the claim 3.
12. method as claimed in claim 11 or capacitor is characterized in that, described organic acid is a sulfonic acid.
13. method as claimed in claim 12 or capacitor is characterized in that, described dopant is toluenesulfonic acid Fe (III).
14. each described method or capacitor in the claim is characterized in that the conductive polymer cathode layer is with liquid application as described above.
15. each described method or capacitor in the claim is characterized in that the conductive polymer cathode layer comprises the polymer coating that multilayer applies successively as described above.
16. each described method or capacitor in the claim is characterized in that described conductive polymer coating is used with the liquid monomer precursor solution as described above, this monomer precursor solution original position is carried out polymerization.
17. method as claimed in claim 16 or capacitor is characterized in that, described precursor solution also comprises adhesive.
18. method as claimed in claim 18 or capacitor is characterized in that, described monomer solution is electrochemical polymerization.
19. each described method or capacitor in the claim is characterized in that described conductive polymer coating comprises the sandwich of multiple layer polymer as described above.
20. each described method or capacitor in the claim is characterized in that described valve action materials comprises the niobium oxide of metal tantalum or metal niobium or conduction as described above.
21. a solid-state capacitor is according to each described method manufacturing among claim 1 or the claim 3-20.
22., it is characterized in that the DCL of described capacitor is less than 50nA/CV as each described capacitor among claim 2 or the claim 3-21.
23. as each described capacitor among claim 2 or the claim 3-22, it is characterized in that, described capacitor be about 1 than lotus capacity, 000-400,000CV/g.
24. each described method or capacitor in the claim is characterized in that described dielectric layer forms in the following manner as described above, the antianode body carries out anodization, and the formation voltage that uses in anodizing process is 6-150V.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0517084.0 | 2005-08-19 | ||
| GB0517084A GB0517084D0 (en) | 2005-08-19 | 2005-08-19 | Polymer based solid state capacitors and a method of manufacturing them |
| GB0517475.0 | 2005-08-26 |
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| CN101356610A true CN101356610A (en) | 2009-01-28 |
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| CNA2006800351849A Pending CN101356610A (en) | 2005-08-19 | 2006-08-18 | Polymer based solid state capacitors and a method of manufacturing them |
| CNA2006800351745A Pending CN101273425A (en) | 2005-08-19 | 2006-08-18 | Solid state capacitors and method of manufacturing them |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103310989A (en) * | 2012-03-16 | 2013-09-18 | Avx公司 | Abrasive blasted cathode of a wet electrolytic capacitor |
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2005
- 2005-08-19 GB GB0517084A patent/GB0517084D0/en not_active Ceased
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2006
- 2006-08-18 CN CNA2006800351849A patent/CN101356610A/en active Pending
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103310989A (en) * | 2012-03-16 | 2013-09-18 | Avx公司 | Abrasive blasted cathode of a wet electrolytic capacitor |
| CN103310989B (en) * | 2012-03-16 | 2018-04-24 | Avx公司 | The sandblasting cathode of wet electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0517084D0 (en) | 2005-09-28 |
| CN101273425A (en) | 2008-09-24 |
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Application publication date: 20090128 |