CN104143441A - Solid electrolytic capacitor - Google Patents
Solid electrolytic capacitor Download PDFInfo
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- CN104143441A CN104143441A CN201310374966.7A CN201310374966A CN104143441A CN 104143441 A CN104143441 A CN 104143441A CN 201310374966 A CN201310374966 A CN 201310374966A CN 104143441 A CN104143441 A CN 104143441A
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- electrolytic capacitor
- solid electrolytic
- chip
- anode
- type solid
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Abstract
The invention provides a piece-typed solid electrolytic capacitor which contains compound crystal shown in the formula I of the piece-typed solid electrolytic capacitor, the compound crystal is crystal which belongs to the orthorthombic system, and the space group of the compound crystal is that P21, , , , and .
Description
Technical field
The present invention relates to a kind of chip-type solid electrolytic capacitor, there is the low and little excellent specific property of the initial disqualification rate of leakage current of equivalent series resistance.
Background technology
Along with the high frequency of electronic equipment, in the capacitor as one of electronic unit, require the large value capacitor in the impedance operator excellence of high frequency region.Recently, in order to reduce the impedance of this high frequency region, start using the electrolytic capacitor of the electroconductive polymer that conductivity is high to study and carrying out goods.Electrolytic capacitor possesses: anode foils, the dielectric overlay film forming on the surface of anode foils and the electroconductive polymer layer forming on dielectric overlay film.The surface process of anode foils is roughened, and is formed with a plurality of holes.Method as forming electroconductive polymer layer, except chemical polymerization and electrolysis polymerization, also comprises and makes preformed electroconductive polymer particle be impregnated in the dispersion method of capacitor element.With regard to chemical polymerization, the existence because of oxidant damages dielectric overlay film sometimes.In addition, for chemical polymerization and electrolysis polymerization, be difficult to be formed uniformly electroconductive polymer layer.So, can form electroconductive polymer layer compared with heavy back, use a large amount of electroconductive polymers.Little molecular organic compound, particularly little molecular organic compound crystal is compared with polymer has preparation simply, and coating is even, rate of finished products is high, and feature easily and effectively, therefore still needs application organic micromolecule compound, particularly organic micromolecule compound crystal current electrolysis condenser.
Summary of the invention
The general manufacture method of electrolytic capacitor comprises following steps: the step of a plurality of holes that prepare to have surperficial anode foils, form on the surface of anode foils and the dielectric overlay film forming on the surface of anode foils; The first dispersion solution that anode foils is impregnated in contain the first electroconductive polymer particle and the first solvent, forms the step of the first electroconductive polymer layer on the surface of dielectric overlay film; And, the second dispersion solution that anode foils is impregnated in contain the second electroconductive polymer particle and the second solvent, form the step of the second electroconductive polymer layer that covers the first electroconductive polymer layer, wherein, compare with described the first dispersion solution, the pH of described the second dispersion solution and 7 differs farther.
But electric capacity of the present invention comprises a plurality of solid electrolytic capacitor element, each element is by making to form cathode portion on the anode substrate surface the anode part except its one end with this sequence stack with insulation oxide rete, semiconductor layer and conductive layer, the metal that anode substrate comprises valve acting or the sintered body of conductive oxide or comprise the sintered body being connected with plain conductor.
Wherein semiconductor layer is organic semiconductor layer, and it contains the organic compound crystal shown in following formula I:
I，
It is crystal, and described crystal belongs to orthorhombic system, and its space group is P2
1, a=6.30, b=7.90, c=9.10, β=89.5 °, V=452.9
3.
Wherein anode part comprises the end of anode substrate; Wherein anode part comprises the plain conductor being connected with sintered body; Wherein plain conductor is selected from these metals and the alloy of tantalum, niobium, aluminium, titanium, the alloy that mainly comprises this metalloid and partial oxidation and/or nitrogenize; Wherein with insulating resin, make the interface insulation between anode part and the part except anode part; Wherein insulation oxide rete mainly comprises and is selected from Ta
2o
5, Al
2o
3, Zr
2o
3and Nb
2o
5at least one.
Accompanying drawing explanation
Fig. 1 means the perspective view of an example of chip-type solid electrolytic capacitor of the present invention, wherein each is had to three solid electrolytic capacitor element of positive wire (anode part) are parallel to be lain on a terminal part of lead frame every ground continuously.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that described in the embodiment of the present invention and make
Preparation Method is only used for illustrating the present invention, rather than limitation of the present invention, under design prerequisite of the present invention, preparation method's of the present invention simple modifications is all belonged to the scope of protection of present invention.All raw materials of using in embodiment and solvent are all purchased from Sigma Biochemical and Organic Compounds for Research and Diagnostic Clinical Reagents company.
Embodiment 1:
Fig. 1 is the perspective view of an example of chip-type solid electrolytic capacitor of the present invention.In this example, adopt three solid electrolytic capacitor element (2), each element passes through insulation oxide rete, semiconductor layer and conductive layer are manufactured to form cathode portion (3) on the surface in anode substrate (4) with this sequence stack, the metal that anode substrate comprises valve acting or conductive oxide are also connected with anode part wire, this chip-type solid electrolytic capacitor has this structure: part cathode portion is parallel to be lain on the terminal part (1a) in the terminal part of pair of opposing of lead frame (1) every ground continuously, anode part wire (4a) is lain on another terminal part (1b), each part is electrically connected to or mechanical connection, outside partly staying by resin molded integral body but by the external cabling of lead frame (1), at predetermined part (not shown) cutting and the lead frame outside bending resin mold.
In the manufacture of chip-type solid electrolytic capacitor of the present invention, prepare the solid electrolytic capacitor element of a plurality of manufactures like this; Continuously every ground, lie on the terminal part of lead frame of the terminal part with pair of opposing of separately manufacturing the part cathode portion of each solid electrolytic capacitor element is parallel; The anode part of anode substrate is lain on another terminal part; Each part is electrically connected to or mechanical connection, and for example the former adopts conduction lotion to solidify and the latter adopts spot welding; Outside staying by resin molded integral body but by the part that forms lead frame external terminal; Then at predetermined part (not shown) cutting and the lead frame outside bending resin mold.Particularly, for example as shown in fig. 1, continuously every ground, lie on the terminal part of pair of opposing of lead frame and molded three solid electrolytic capacitor element are parallel, to manufacture a kind of polygonal and the chip-type solid electrolytic capacitor of parallelepiped normally.While manufacturing this solid electrolytic capacitor, can the position that be configured for holding the lead frame after cutting on part side and/or bottom surface will be placed in jagged part, can will be with jagged part to be for example placed on end face to distinguish anode and negative electrode, or can end face and/or bottom surface be reduced to be convenient to take out the chip-type solid electrolytic capacitor of manufacturing when resin molded from metal die with certain angle.The semiconductor layer forming on insulating barrier of the present invention is organic semiconductor layer, wherein contains the organic compound crystal shown in formula I.
In an embodiment, the chip-type solid electrolytic capacitor of manufacturing is welded under the following conditions: make capacitor pass reflow ovens three times, setting this reflow ovens takes at 260 ℃ of temperature curves with peak value (keeping 40 seconds at 150 ℃, after intensification, 230 ℃ or higher maintenance 30 seconds).After being welded, under 4V, measure LC 30 seconds.Units in each measurement is n=320, and those capacitors with 0.1CV or lower LC value are judged as and can be accepted.
(quality of tantalum and size (Wmm) are shown in Table 1 with the tantalum powder that CV (product of capacitance and electrochemical voltage) is 50,000/g, to prepare the sintered body that is of a size of 4.0 * W * 1.8mm as shown in table 1; Sintering temperature: 20 ℃ of Isosorbide-5-Nitraes, sintering time: 20 minutes, sintered density: 6.4g/cm
3, Ta lead-in wire: 0.24mm φ; Part Ta lead-in wire is imbedded in sintered body and stretched into 4mm with parallel longitudinal, the lead portion of being stretched out by sintering is used as to anode part).The sintered body that serves as anode is immersed in 0.1% phosphate aqueous solution except lead portion, and by apply the voltage of 18V between anode and the Ta plate electrode as negative electrode, come electrochemistry to form 3 hours at 80 ℃, to form by Ta
2o
5the insulation oxide rete forming.Then, this sintered body is immersed except lead-in wire in 20% lead acetate water solution and the solution of 35% ammonium persulfate aqueous solution with mixing in 1: 1, make its at 40 ℃ standing 1 hour, then extract, wash and be dried this sintered body, repeat this and operate 25 times to form the mixture (brown lead oxide: the semiconductor layer 96%) forming by brown lead oxide and lead sulfate on insulation oxide rete.On semiconductor layer, sequence stack carbon paste and silver paste, to be made into cathode portion, are manufactured solid electrolytic capacitor element thus.
On a pair of terminal part of the thick copper alloy lead frame with zinc-plated surface of the independent 100 μ m that manufacture, (there are 32 pairs of paired terminal parts, each wide 3.4mm; The terminal part that keeps flat cathode portion on it has the ladder corresponding to the 0.9mm of the ladder in Fig. 1, and the part that cathode portion is put has the length of 4.3mm; During coplanar projection, between two terminal parts, there is the gap of 1mm), by three solid electrolytic capacitor element as above manufacturing parallel without compartment of terrain level connection joint (by the cathode side of solid electrolytic capacitor, 4.0 * W the face that is sintered body lies on the stepped terminal part of tool, and the anode-side of solid electrolytic capacitor is lain on another terminal part; Each is all electrically connected to or is mechanically connected to front one and is connected to rear one by spot welding by silver paste is solidified; In a lead frame, on every pair of terminal part, connect three solid electrolytic capacitor element, altogether connect 96 solid electrolytic capacitor element).After this, a part and the solid electrolytic capacitor element of two terminal parts of lead frame are all come molded with epoxy resin by transfer moudling, the chip-type solid electrolytic capacitor that the manufacturing dimension of take is 7.3 * 4.3 * 2.8mm is (after molding, by each in outer two terminal parts of pattern in the position cutting apart from pattern end face 3.4mm, the lead frame of excision is removed, will be connected with chip-type solid electrolytic capacitor and each terminal part of staying the lead frame of outside be bent and be used as external terminal along the periphery of capacitor; From a lead frame, 32 chip-type solid electrolytic capacitors have been manufactured).
Embodiment 2: the preparation of formula I compound crystal
In the reaction bulb of being furnished with mechanical agitation and reflux condensing tube, add Cymag 0.041mo1 and 10mL water, keep stirring, after Cymag is dissolved completely, the aqueous solution (10mL) that adds again ammonium chloride 0.043mo1, methyl alcohol (10mL) solution of 20% ammoniacal liquor (4mL) and cyclohexanone 0.032mo1, stirring at room 1.5h, is warming up to 60 ℃ and stirs 45min again, stop heating, continue to stir 45min; Be chilled to 25 ℃, with carrene (15mL * 6) extraction, organic phase anhydrous magnesium sulfate drying, filters, filtrate is concentrated, remaining grease (4.1g) is dissolved in 25mL acetone, adds acetone (20mL) solution of oxalic acid 0.033mo1 under stirring, separates out solid, filter, filter cake is washed with acetone, is dried to obtain white solid a 4.8g, yield 72%.
In the reaction bulb of being furnished with mechanical agitation and reflux condensing tube, add concentrated sulfuric acid 15mL, compound a 0.025mo1 is slowly added, stir, have Bubble formation, temperature rises to 90 ℃; After compound a adds completely, keep equality of temperature to stir lh, be cooled to again 35 ℃, pour in the frozen water containing concentrated ammonia liquor (50mL), with containing the chloroform recovery of 10% methyl alcohol 6 times, organic phase merges, after anhydrous magnesium sulfate drying, filter, filtrate is concentrated, obtains white solid crude product b 3.7g, after recrystallization, obtain white solid 3.1g, yield 63%.
In the reaction bulb of being furnished with mechanical agitation and reflux condensing tube, add compound b 0.023 mo1, 10mL triethylamine and 40mLTHF are in THF (20mL) solution that stirs the lower 3-of dropping yl pyridines-1-acyl chlorides 0.025mo1, continue to stir 0.5h, add 20mL water, 40mL methyl alcohol and 10g potassium hydroxide, back flow reaction 5h, after being cooled to room temperature, add again ammonium chloride 0.05 mo1, after at room temperature stirring 0.5h, concentrate, in residue after concentrated, add water (20mL), ethyl acetate (25mL * 3) extracts, organic phase merges, after anhydrous magnesium sulfate drying, filter, filtrate is concentrated, obtain white solid crude product c 3.1g, after recrystallization, obtain white solid 2.8g, yield 46%.
In the reaction bulb of being furnished with mechanical agitation and reflux condensing tube, add compound c 0.020 mo1, benzyl bromide a-bromotoluene 0.023mo1, potassium carbonate powder 0.030mo1 and 2g bromination tetrabutylammonium back flow reaction 10h in THF (50mL), let cool rear filtration, filtrate is concentrated, ethyl acetate for residue (40mL) dissolves, water (40mL), salt solution (40mL) washing successively again, anhydrous magnesium sulfate drying, filter, filtrate decompression is concentrated, residue is crossed silica gel column chromatography and is purified, obtain yellow solid d5.1g, yield 69%.
Nuclear-magnetism: δ (ppm), 7.08-7.54 (m, 4H, ArH), 7.56 (d, 1H, J=8.4Hz), 7.98 (dd, 1H, J
1=8.4Hz, J
2=2.4Hz), 8.51 (d, 1H, J=8.4Hz), 4.64 (s, 2H ,-CH
2n), 1.43-1.92 (m, 10H ,-5 CH
2).
The organic compound of above-mentioned preparation is placed in quartz ampoule (quartz ampoule).At 100 ℃ of temperature, the compound vacuum dehydration that this is prepared.This pipe is thrown off, and be placed in crystal growing furnace.In thering is the dual stove of barrier film (double furnace), pass through Bridgman (Bridgman) method grown crystal.Finally, obtain colourless acicular crystal.This crystal is carried out to Advances in crystal X-ray diffraction crystallographic analysis, and its crystallographic parameter is as follows: be orthorhombic system, its space group is P2
1, a=6.30, b=7.90, c=9.10, β=89.5 °, V=452.9
3.
The indices of the electrolytic capacitor of the present invention of use formula I compound crystal is shown in Table 1.
Table 1
Claims (7)
1. a chip-type solid electrolytic capacitor, comprise a plurality of solid electrolytic capacitor element, each element is by making with this sequence stack insulation oxide rete, semiconductor layer and conductive layer to form cathode portion on the anode substrate surface the anode part except its one end, the metal that anode substrate comprises valve acting or the sintered body of conductive oxide or comprise the sintered body being connected with plain conductor, wherein semiconductor layer is organic semiconductor layer, and it contains the organic compound crystal shown in following formula I:
I，
It is crystal, and described crystal belongs to orthorhombic system, and its space group is P2
1, a=6.30, b=7.90, c=9.10, β=89.5 °, V=452.9
3.
2. chip-type solid electrolytic capacitor as described in claim 1, wherein anode part comprises the end of anode substrate.
3. chip-type solid electrolytic capacitor as described in claim 1, wherein anode part comprises the plain conductor being connected with sintered body.
4. chip-type solid electrolytic capacitor as described in claim 3, wherein plain conductor is selected from these metals and the alloy of tantalum, niobium, aluminium, titanium, the alloy that mainly comprises this metalloid and partial oxidation and/or nitrogenize.
5. chip-type solid electrolytic capacitor as described in claim 1, wherein makes the interface insulation between anode part and the part except anode part with insulating resin.
6. chip-type solid electrolytic capacitor as described in claim 1, wherein insulation oxide rete mainly comprises and is selected from Ta
2o
5, Al
2o
3, Zr
2o
3and Nb
2o
5at least one.
7.
.an organic compound crystal, it has the structure shown in formula I:
i, it is crystal, and described crystal belongs to orthorhombic system, and its space group is P2
1, a=6.30, b=7.90, c=9.10, β=89.5 °, V=452.9
3.
Priority Applications (1)
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|---|---|---|---|
| CN201310374966.7A CN104143441A (en) | 2013-08-26 | 2013-08-26 | Solid electrolytic capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310374966.7A CN104143441A (en) | 2013-08-26 | 2013-08-26 | Solid electrolytic capacitor |
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|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0350812A (en) * | 1989-07-19 | 1991-03-05 | Nippon Chemicon Corp | Manufacture of solid electrolytic capacitor |
| JP2000208369A (en) * | 1999-01-13 | 2000-07-28 | Hitachi Chem Co Ltd | Solid electrolytic capacitor and manufacture thereof |
| JP2001139805A (en) * | 1999-11-16 | 2001-05-22 | Mitsui Chemicals Inc | Electroconductive polymeric material and solid electrolytic condenser |
| JP2002158144A (en) * | 2000-01-17 | 2002-05-31 | Matsushita Electric Ind Co Ltd | Manufacturing method of solid electrolytic capacitor and the electrolytic capacitor |
| JP2003036727A (en) * | 2001-07-23 | 2003-02-07 | Mitsui Chemicals Inc | Conductive polymeric material and solid electrolytic capacitor |
| CN101081896A (en) * | 2006-06-02 | 2007-12-05 | 气体产品与化学公司 | Electrically conductive polymers and method of making electrically conductive polymers |
-
2013
- 2013-08-26 CN CN201310374966.7A patent/CN104143441A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0350812A (en) * | 1989-07-19 | 1991-03-05 | Nippon Chemicon Corp | Manufacture of solid electrolytic capacitor |
| JP2000208369A (en) * | 1999-01-13 | 2000-07-28 | Hitachi Chem Co Ltd | Solid electrolytic capacitor and manufacture thereof |
| JP2001139805A (en) * | 1999-11-16 | 2001-05-22 | Mitsui Chemicals Inc | Electroconductive polymeric material and solid electrolytic condenser |
| JP2002158144A (en) * | 2000-01-17 | 2002-05-31 | Matsushita Electric Ind Co Ltd | Manufacturing method of solid electrolytic capacitor and the electrolytic capacitor |
| JP2003036727A (en) * | 2001-07-23 | 2003-02-07 | Mitsui Chemicals Inc | Conductive polymeric material and solid electrolytic capacitor |
| CN101081896A (en) * | 2006-06-02 | 2007-12-05 | 气体产品与化学公司 | Electrically conductive polymers and method of making electrically conductive polymers |
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Application publication date: 20141112 |
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