CN100380548C - Method of mfg. solid electrolytic condenser - Google Patents
Method of mfg. solid electrolytic condenser Download PDFInfo
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- CN100380548C CN100380548C CNB2003101143752A CN200310114375A CN100380548C CN 100380548 C CN100380548 C CN 100380548C CN B2003101143752 A CNB2003101143752 A CN B2003101143752A CN 200310114375 A CN200310114375 A CN 200310114375A CN 100380548 C CN100380548 C CN 100380548C
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- aliphat
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007787 solid Substances 0.000 title claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- 239000003990 capacitor Substances 0.000 claims abstract description 40
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000003863 ammonium salts Chemical class 0.000 claims description 19
- 230000003068 static effect Effects 0.000 claims description 19
- 150000001261 hydroxy acids Chemical class 0.000 claims description 16
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229940085991 phosphate ion Drugs 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- -1 hydroxy acid ammonium salt Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
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Abstract
The anodic oxidation is made in the electrolyte using an aliphatic saturated carboxylic acid or the salt as a solute, thus quick removing of a solute constituent in the electrolyte remaining on the surface of a dielectric oxide layer with a high-temperature demineralized-water cleaning is made possible, uniform forming of the solid electrolytic layer up to the inside of the element of an anode body in the next process is made possible, and the dielectric oxide layer is made uniform and stable and the excellent solid electrolytic capacitor having a small amount of the leakage current can be stably produced since solute anion does not mix with the dielectric oxide layer.
Description
Technical field
The present invention relates to be used for the manufacture method of the solid electrolytic capacitor of various electronic equipments.
Background technology
Fig. 1 is the sectional view of solid electrolytic capacitor.Porous sintered article 1 is that sintering formed after valve-use metal powder pressings such as tantalum or niobium were desirable shape.Tantalum line system positive wire 2 is embedded in the sintered body 1.Dielectric oxidized surface rete 3 is sintered body 1 to be carried out anodized and the outer surface that is formed at sintered body 1.Solid electrolyte layer 4 is made of manganese oxide and functional high-polymer.Carbon-coating 5 and silver paste layer 6 constitute cathode layer.
Fig. 2 shows the manufacture method of above-mentioned solid electrolytic capacitor.Tantalum or niobium metal powders and positive wire 2 together are filled in the hollow sectors of the required form that the form metal mould had, press molding obtains formed body.With the sintered body (anode bodies) 1 of this formed body sintering to obtain porous matter., sintered body 1 carried out anodic oxidation, form dielectric oxidized surface rete 3 at its outer surface thereafter.After its cleaning, on superficial film 3, form solid electrolyte layer 4.On superficial film 3, form carbon-coating 5 and silver paste layer 6, form cathode layer.
Fig. 3 is for showing the schematic diagram of anodic oxidation operation principle.In the open flat 5-182869 of the communique number disclosed anodic oxidation operation of Japan's special permission, sintered body 1 is put into phosphate aqueous solution as electrolyte 32, apply between sintered body 1 and minus plate 33 and be approximately working voltage 2-3 voltage doubly, sintered body 1 is by anodic oxidation.Like this, on the surface of the tantalum particle that forms porous sintered article 1, formed dielectric oxidized surface rete 3 with dielectric that can the thickness of anti-the working voltage.
In the manufacture method of above-mentioned solid electrolytic capacitor in the past, on the outer surface of sintered body 1, form in the anodic oxidation operation of dielectric oxidized surface rete 3, use phosphate aqueous solution as used electrolyte.Because of also non-volatile decomposition in phosphate ion adsorptivity height, the high temperature gas medium, so remain on the surface of dielectric oxidized surface rete 3.This residual phosphate ion can not be removed even clean in the high temperature pure water fully until the inside of anode bodies 1.
As the solid electrolyte mother liquor of electrolyte 32, when using manganese dioxide as solid electrolyte, available manganese nitrate aqueous solution; And with electroconductive polymer during as solid electrolyte, available monomer whose and oxidizing agent solution.
The phosphate ion that remains in dielectric oxidized surface rete 3 surfaces hinders the solid electrolyte mother liquor to immerse the inside of anode bodies 1.Therefore, solid electrolyte layer 4 is difficult to the inside that homogeneous are formed into anode bodies 1, and actual static capacity is formed into the ratio of static capacity of the lip-deep anode bodies 1 of internal particle for solid electrolyte layer, and promptly capacity reaches rate and reduces significantly.Particularly in recent years, with the tantalum powder of static capacity height, high CV value the time, because of its by the cause of micronized powder, the emptying aperture number of channels of the sintered body 1 of porous matter reduces gradually, dwindles, it is insufficient that solid electrolyte layer 4 is formed into sintered body 1 inside.
Be oxidized to its oxide through the formed dielectric oxidized surface of anodic oxidation rete 3 reason metals, make its volumetric expansion, when applying high voltage and form oxide, make the emptying aperture passage in the sintered body 1 reduce, dwindle along with anodic oxidation.Therefore, as the powder micronizing, solid electrolyte layer 4 is difficult to be formed into the inside of sintered body 1.Predict the reduction part of such static capacity, the voltage that applied is reduced and in advance the static capacity of the element of anode bodies 1 is increased to replenish and reduce part.But, adopt this method, because of not having to form the dielectric oxidized surface rete 3 that working voltage is had the thickness of enough proof voltages, cause the increase and the short circuit of condenser leakage current sometimes.
Before forming capacitor case, at solid electrolyte layer 4 in appearance,, the static capacity composition of sintered body 1 element internal drawn so that this capacity reaches the reduction degree of rate shades because of the caused adsorbed water of outside moisture can play electrolytical effect.But after capacitor case formed, during user mode under the high temperature gas medium, above-mentioned adsorbed water can slowly be distributed, and solid electrolyte layer 4 becomes obviously poor reliability because of self caused static capacity reduces.
Known is, adopt inorganic acids such as phosphate ion and sulfate ion as the formed dielectric oxidized surface of the anodic oxidation of the electrolyte of solute rete 3 in, sneak into the solute anion.People are attempting coming dielectric oxidized surface rete 3 is improved by this solute anion always.But in reality, be difficult to control the anionic amount of the solute of sneaking into fully because of this anodic oxidation and be immersed in solute contained in the electrolyte such as the degree of depth in the dielectric oxidized surface rete 3 anionic through the time change.The anionic non-quantitation of solute is sneaked into the quality fluctuation and the leakage current that can increase dielectric oxidized surface rete 3.
Summary of the invention
The above-mentioned anode bodies of valve-use metal system in electrolyte by anodic oxidation, form dielectric oxidized surface rete on the surface of this anode bodies making solid electrolytic capacitor, this electrolyte adopts and is selected from a kind of as solute in aliphat saturated carboxylic acid and salt, the saturated hydroxy acid of aliphat and the salt thereof.
If with this manufacture method, in solid electrolytic capacitor, can stablize the dielectric oxidized surface rete that forms homogeneous, thus can fluctuation of inhibition capacity and reduction leakage current.
Description of drawings
Fig. 1 is the sectional view of the capacitor of solid electrolytic capacitor.
Fig. 2 shows the manufacture method of capacitor.
Fig. 3 is the schematic diagram of the anodic oxidation operation of capacitor.
Fig. 4 shows the residual quantity of solute in the anode bodies after the anodic oxidation of capacitor.
Fig. 5 shows the volume change rate after capacitor is finished.
Fig. 6 shows the relation of the conductance of the static capacity of having carried out anodised solid electrolytic capacitor in electrolyte of embodiment 15 and electrolyte.
Fig. 7 shows the relation of electrolyte temperature and the condenser leakage current of embodiment 15.
The relation that voltage when Fig. 8 shows the anodic oxidation in electrolyte of embodiment 15 and capacitor element capacity reach rate.
Fig. 9 show embodiment 15 with electrolyte the time tantalum or the static capacity of the anode bodies of niobium metal powders and the relation that capacity reaches rate.
Figure 10 shows the characteristic of the capacitor in the execution mode.
Embodiment
Fig. 1 is the sectional view of the solid electrolytic capacitor of embodiments of the present invention.The porous sintered article 1 of present embodiment is and the parts of being drawn by anode, promptly positive wire 2 together, the tantalum metal powder press forming of valve-use metal is desirable shape after, sintering forms.The positive wire 2 that is embedded in the sintered body 1 is made of the tantalum line.The formed dielectric oxidized surface of sintered body 1 outer surface rete 3 is to form through anodized.Solid electrolyte layer 4 is made of functional high-polymer (also can be the oxide of manganese).Carbon-coating 5 and silver paste layer 6 constitute cathode layer.
Fig. 2 shows the manufacture method of such solid electrolytic capacitor.Fill tantalum metal powder in the hollow sectors of the desirable shape that the form metal mould is had, press molding is to make formed body.This formed body of sintering makes the sintered body 1 (anode bodies) of porous matter, thereafter, anode bodies 1 by anodic oxidation, is formed dielectric oxidized surface rete 3 on its outer surface.It is cleaned 1 hour in 85 ℃ pure water flowing water after, form the solid electrolyte layer 4 that constitutes by functional high-polymer.Form the cathode layer that constitutes by carbon-coating 5 and silver paste layer 6 more in its surface.
Fig. 3 is for showing the schematic diagram of above-mentioned anodic oxidation operation principle.Anode bodies 1 be impregnated in the electrolyte 32, apply between anode bodies 1 and minus plate 33 and approximately be to use voltage 2-3 voltage doubly, anode bodies 1 is by anodic oxidation.Like this, on the surface of the tantalum particle that forms porous sintered article 1, form the dielectric oxidized surface rete 3 that the dielectric by the thickness of ability working voltage constitutes.
Below, the embodiment of the solid electrolytic capacitor that adopts execution mode is described.
(embodiment 1)
Adopt the solute of the formic acid of aliphat saturated carboxylic acid as electrolyte 32.
(embodiment 2)
Adopt the solute of the oxalic acid of aliphat saturated carboxylic acid as electrolyte 32.
(embodiment 3)
Adopt the solute of the malonic acid of aliphat saturated carboxylic acid as electrolyte 32.
(embodiment 4)
Adopt the solute of the butanedioic acid of aliphat saturated carboxylic acid as electrolyte 32.
(embodiment 5)
Adopt the solute of the adipic acid of aliphat saturated carboxylic acid as electrolyte 32.
(embodiment 6)
Adopt the solute of the citric acid of the saturated hydroxy acid of aliphat as electrolyte 32.
(embodiment 7)
Adopt the solute of the malic acid of the saturated hydroxy acid of aliphat as electrolyte 32.
(embodiment 8)
Adopt the solute of the tartaric acid of the saturated hydroxy acid of aliphat as electrolyte 32.
(embodiment 9)
Adopt the solute of the ammonium salt of aliphat saturated carboxylic acid, adopt ammonium formate as ammonium salt as electrolyte 32.
(embodiment 10)
Adopt the solute of the ammonium salt of aliphat saturated carboxylic acid, adopt ammonium oxalate as ammonium salt as electrolyte 32.
(embodiment 11)
Adopt the solute of the ammonium salt of aliphat saturated carboxylic acid, adopt ammonium succinate as ammonium salt as electrolyte 32.
(embodiment 12)
Adopt the solute of the ammonium salt of aliphat saturated carboxylic acid, adopt ammonium adipate as ammonium salt as electrolyte 32.
(embodiment 13)
Adopt the solute of the ammonium salt of the saturated hydroxy acid of aliphat, adopt ammonium citrate as ammonium salt as electrolyte 32.
(embodiment 14)
Adopt the solute of the ammonium salt of the saturated hydroxy acid of aliphat, adopt the malic acid ammonium as ammonium salt as electrolyte 32.
(embodiment 15)
Adopt the solute of the ammonium salt of the saturated hydroxy acid of aliphat, adopt ammonium tartrate as ammonium salt as electrolyte 32.
(comparative example)
Adopt the solute of the phosphoric acid of the inorganic acid of solid electrolytic capacitor in the past as electrolyte 32.
The result that the capacity of measuring the solid electrolytic capacitor of embodiment 1-15 and comparative example reaches rate and leakage current as shown in figure 10.In addition, capacity reaches the ratio of the static capacity of static capacity that rate is meant the anode bodies 1 after solid electrolyte layer the forms anode bodies 1 after for anodic oxidation.Leakage current represents that rated voltage is put on value that solid electrolytic capacitor measured after 30 seconds is decided to be 100 relative value with respect to the leakage current of the comparative example of capacitor in the past.The static capacity of anode bodies 1 is measured under the following conditions: apply frequency 120Hz, DC bias voltage 1.5V, carry out in the 30.5vol% aqueous sulfuric acid with the negative electrode of platinum-carbon black system.
As shown in figure 10, using the aliphat saturated carboxylic acid in the execution mode or its salt electrolyte as solute, carried out in the solid electrolytic capacitor of anodised embodiment, the surface of the dielectric oxidized surface rete after the anodic oxidation the solute of residual electrolyte, different with the adsorptivity solute of phosphate ion in the comparative example and so on, in matting, clean and can be removed rapidly with the high temperature pure water.Thus, in follow-up operation, when forming solid electrolyte layer, solution can fully impregnated in the inside of anode bodies 1, and homogeneous forms solid electrolyte layer, does not reduce dielectric oxidized surface thicknesses of layers and obtains big static capacity, makes capacity reach rate and improves.
Adopt the capacitor of the saturated hydroxy acid of aliphat as the solute of the electrolyte that is used for the anodic oxidation operation, than the capacitor that adopts the aliphat saturated carboxylic acid as solute, reach more remarkable on the effect of rate at the raising capacity, and with the capacitor of the saturated hydroxy acid ammonium salt of aliphat than more obvious with this effect of capacitor of the saturated hydroxy acid of aliphat.This effect maximum be the electrolyte of embodiment 15, promptly used the electrolyte of ammonium tartrate as the saturated hydroxy acid ammonium salt of aliphat of ammonium salt, brought into play the most excellent effect.
The saturated hydroxy acid of the aliphat of embodiment 6-8 is because of having a plurality of hydroxyls, so hydrability is good, dissolubility is also high, can easily the solute composition be removed in high temperature pure water matting thus, and the effect that the raising capacity reaches rate is bigger.
Fig. 4 has shown the high temperature pure water scavenging period of anode bodies 1 after the anodic oxidation of embodiment 13 and comparative example and the relation of the solute residual quantity in the anode bodies, and Fig. 5 has shown the volume change rate under the high temperature service life of anode bodies 1.In addition, with the solute residual quantity in high-frequency induction plasma luminescence spectroscopy apparatus (ICP) the mensuration anode bodies 1.
Aliphat saturated carboxylic acid ammonium salt is used for electrolyte to carry out anodised embodiment 9-12 and the saturated hydroxy acid ammonium salt of aliphat is used for the solid electrolytic capacitor that electrolyte carries out anodised embodiment 13-15, when the high temperature drying of matting, ammonium salt forms ammonium and has volatility.Like this, the residual solute of failing to remove fully when the high temperature pure water cleans further reduces, so can form solid electrolyte layer more efficiently.
It is that the electrolyte of the embodiment 15 of 30mS/cm carries out the static capacity of anodised solid electrolytic capacitor and the relation of electrolyte conductance that Fig. 6 shows with conductance.Be further to reduce the thickness deviation that makes dielectric oxidized surface rete because of anodic oxidation, i.e. the deviation of static capacity is so be decided to be the conductance of 80 ℃ electrolyte more than the 1mS/cm.With the ammonium salt of the saturated hydroxy acid of aliphat solute as electrolyte, than the consumption of the saturated hydroxy acid monomer of aliphat as the solute of electrolyte lacked, just can obtain excellent electric conductivity, thus, can reduce material cost.In addition, the aliphat saturated carboxylic acid is also identical, also is applicable to above-mentioned.In addition, electrolyte is warmed up to more than 80 ℃, can further reduces the deviation of static capacity.
Fig. 7 shows that having used conductance is the electrolyte temperature of capacitor and the leakage current relation of electrolyte of the embodiment 15 of 30mS/cm.As shown in Figure 7, the temperature of electrolyte is more fortunately more than 50 ℃, in special 60-85 ℃ the scope fortunately.When if temperature is lower than this scope, be difficult to homogeneous and tight through the formed dielectric oxidized surface of anodic oxidation rete, so leakage current increases.When surpassing this scope as if temperature, the solute of electrolyte significantly decomposes and volatilization, and the electrolyte composition changes, and can not stablize and form dielectric oxidized surface rete, causes the electrical characteristic deviation of capacitor.
Fig. 8 shows that having used conductance is that the capacitor of electrolyte of the embodiment 15 of 30mS/cm applies the relation that voltage and capacity reach rate when anodic oxidation.As shown in Figure 8, the voltage that anodic oxidation applied is more fortunately below the 120V.If voltage is more remarkable through the volumetric expansion of the formed dielectric oxidized surface of anodic oxidation rete when 120V is above, the emptying aperture passage of the sintered body inside that tantalum and niobium constitute reduces or dwindles.Thus, in matting, be difficult to residual solute is removed from the surface of dielectric oxidized surface rete.It is effective when low to apply voltage.
Fig. 9 shows the static capacity of metal dust of anode bodies 1 material of capacitor and the relation that capacity reaches rate, and it is the electrolyte of the embodiment 15 of 30mS/cm that this capacitor has been used conductance.As this metal dust, more handy static capacity is 30, the powder of the high CV that 000CV/g (μ FV/g) is above.Usually, the emptying aperture passage of the sintered body inside that the high CV powder of reason is constituted is reduced, so in matting, be difficult to residual solute is removed from the surface of dielectric oxidized surface rete.But, used in the capacitor of electrolyte of embodiment of the present invention, adopt 30, the above high CV powder of 000CV/g (μ FV/g) also can easily be removed residual solute during as anode bodies 1.
And the anode bodies 1 of above-mentioned execution mode with the desirable shape of tantalum metal powder press forming after sintering form.But the present invention is not limited by this, and anode bodies 1 also can carry out the asperities processing with the surface of valve-use metal paper tinsel and form, and the sinter layer that tantalum metal powder is formed can be formed on the valve-use metal paper tinsel to form yet, and can obtain identical action effect yet.
Claims (12)
1. the manufacture method of solid electrolytic capacitor, it is characterized in that, it comprises the operation of the anode bodies of the valve-use metal system of preparing: by in electrolyte above-mentioned anode bodies anodic oxidation being formed the operation of dielectric oxidized surface rete in above-mentioned anode body surface, this electrolyte adopts a kind of as solute in the salt that is selected from aliphat saturated carboxylic acid, the salt of aliphat saturated carboxylic acid, the saturated hydroxy acid of aliphat and the saturated hydroxy acid of aliphat.
2. method according to claim 1, it is characterized in that, the operation of preparing above-mentioned anode bodies comprises that the metal dust with tantalum or niobium is filled in the cavity of the required form that the form metal mould had, press molding and make the operation of formed body and with the operation of above-mentioned formed body sintering.
3. method according to claim 2 is characterized in that, the static capacity of above-mentioned metal dust is more than 30,000 μ FV/g.
4. method according to claim 1 is characterized in that, the operation of preparing above-mentioned anode bodies comprises the operation of the surface of valve-use metal paper tinsel being carried out asperitiesization.
5. method according to claim 1 is characterized in that, the operation of preparing above-mentioned anode bodies is included in the operation of coating tantalum or niobium metal powders on the valve-use metal paper tinsel and with the operation of above-mentioned metal powder sintered formation sinter layer.
6. method according to claim 1 is characterized in that, also comprises the operation of cleaning above-mentioned dielectric oxidized surface rete.
7. method according to claim 1 is characterized in that the salt of above-mentioned aliphat saturated carboxylic acid comprises the ammonium salt of aliphat saturated carboxylic acid.
8. method according to claim 1 is characterized in that, the salt of the saturated hydroxy acid of above-mentioned aliphat comprises the ammonium salt of the saturated hydroxy acid of aliphat.
9. method according to claim 1 is characterized in that the conductance of above-mentioned electrolyte is more than 1mS/cm.
10. method according to claim 9 is characterized in that, the conductance of above-mentioned electrolyte in the time of 80 ℃ is more than 1mS/cm.
11. method according to claim 1 is characterized in that, the temperature of above-mentioned electrolyte is more than 50 ℃.
12. method according to claim 1 is characterized in that, the operation that forms dielectric oxidized surface rete is included in the operation that in the above-mentioned electrolyte above-mentioned anode bodies is applied the voltage below the 120V.
Applications Claiming Priority (2)
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| JP2002328058 | 2002-11-12 | ||
| JP2002328058A JP2004165340A (en) | 2002-11-12 | 2002-11-12 | Manufacturing method of solid electrolytic capacitor |
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| CN100380548C true CN100380548C (en) | 2008-04-09 |
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| JP4653687B2 (en) * | 2006-03-31 | 2011-03-16 | ニチコン株式会社 | Method for producing electrode foil for electrolytic capacitor |
| US7626802B2 (en) * | 2007-10-19 | 2009-12-01 | Oh Young Joo | Metal capacitor and manufacturing method thereof |
| US8159811B2 (en) * | 2007-10-19 | 2012-04-17 | Oh Young Joo | Metal capacitor and manufacturing method thereof |
| US7965492B2 (en) * | 2007-10-19 | 2011-06-21 | Oh Young Joo | Metal capacitor and manufacturing method thereof |
| US8116062B2 (en) * | 2007-10-19 | 2012-02-14 | Oh Young Joo | Metal capacitor to improve electric conductivity |
| CN101354965B (en) * | 2008-09-16 | 2011-03-16 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing high-temperature electrolytic capacitor anodized film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000173870A (en) * | 1998-12-01 | 2000-06-23 | Rubycon Corp | Electrolytic capacitor drive electrolyte and electrolytic capacitor provided therewith |
| JP2000311516A (en) * | 1999-02-24 | 2000-11-07 | Mitsui Chemicals Inc | Polymeric solid electrolyte |
| JP2002110469A (en) * | 2000-09-29 | 2002-04-12 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000173870A (en) * | 1998-12-01 | 2000-06-23 | Rubycon Corp | Electrolytic capacitor drive electrolyte and electrolytic capacitor provided therewith |
| JP2000311516A (en) * | 1999-02-24 | 2000-11-07 | Mitsui Chemicals Inc | Polymeric solid electrolyte |
| JP2002110469A (en) * | 2000-09-29 | 2002-04-12 | Nippon Chemicon Corp | Electrolyte for electrolytic capacitor |
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| CN1499549A (en) | 2004-05-26 |
| JP2004165340A (en) | 2004-06-10 |
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