CN101599367A - 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor and preparation thereof and application - Google Patents
600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor and preparation thereof and application Download PDFInfo
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Abstract
The present invention relates to a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor and preparation and application, comprising: 44.5～80.3% primary solvents, 5～15% secondary solvents, 8～15% solutes, 0.5～2.5% flash over voltage improving agent, 6～10% stabilizers and 0.2～3% hydrogen absorber; Its preparation is that primary solvent is fully mixed with secondary solvent, is heated to 60～90 ℃; Add the flash over voltage improving agent then, be heated to 135～155 ℃; Cool off 65-80 ℃ by recirculated water, add solute, stabilizer again, be heated to 105～135 ℃; Add hydrogen absorber at last, natural cooling, promptly.This electrolyte has adopted suitable flash over voltage improving agent and stabilizer, has improved high pressure resistant, the high-temperature stability of electrolyte, has low aerogenesis performance simultaneously; And make aluminium electrolytic capacitor with this electrolyte, the life-span is long, and is high pressure resistant, can not puncture because the electrolyte flash over voltage is unstable.
Description
Technical field
The invention belongs to working electrolyte for aluminium electrolytic capacitor and preparation thereof and application, particularly relate to a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor and preparation and application.
Background technology
In recent years, the development of frequency converter and AC servo amplifier, electronic car equal energy source e-machine is maked rapid progress.With low fuel consumption, low discharge gas is the hybrid locomotrives and the fuel-cell vehicle of target, and the lightweight of its car body is the trend of development.For this reason, high-power driving is the main target of research with Towards Higher Voltage, the low currentization (Towards Higher Voltage of IGBT) of variable frequency power supply, and present a lot of situations are in power supply capacitors in series to be used.In order to save the space, to reduce cost, e-machine producer more and more requires to reduce the number of series capacitor.In order to adapt to this trend, developed the aluminium electrolytic capacitor of 600V or the above extra-high pressure of 600V.
Electrolyte is the real negative electrode of aluminium electrolytic capacitor, and its performance has a very big influence, particularly electrolyte to the characteristic of aluminium electrolytic capacitor flash over voltage has decisive role to capacitor withstand voltage.General electrolyte prescription mainly is made up of solute, solvent and additive.Chinese patent 96190147.0 (electrolytic capacitor excitation with electrolyte and electrolytic capacitor thereof) invention a kind of will be selected from inorganic acid, more than one acid of organic acid are solute, be dissolved in the solvent that an organic compound is a main body, again to this add, dissolving is with in the copolymer of polyethylene glycol and polypropylene glycol any one or more, perhaps, the two adds simultaneously, dissolves and forms with the copolymer of polyethylene glycol and polypropylene glycol.Thus, can improve the formation performance that flash over voltage and oxide-film are repaired, improve the reliability of electrolytic capacitor.But this electrolyte patent can only be used for the 450V electrolytic capacitor, is used for the puncture that will be short-circuited of more high-tension electrolytic capacitor.
Chinese patent 200410051254.2 (working electrolyte for aluminium electrolytic capacitor and capacitor produced) discloses a kind of working electrolyte for aluminium electrolytic capacitor, comprise solvent, solute, anticorrosive with additive and property-modifying additive, anticorrosive is one or more materials that are selected from oxine, sweet mellow wine, phosphate monoester, the organic acid with additive; The constituent of property-modifying additive comprises: polyvinyl alcohol and/or polyethylene glycol, ortho phosphorous acid and/or ammonium hypophosphite, boric acid and/or ammonium pentaborate, and ethylene glycol; In addition, it can also comprise disappear hydrogen agent and waterproof mixture, has improved the high temperature high voltage resistant and the corrosion resistance of aluminium electrolytic capacitor, has reduced the generation of hydrogen effectively, thereby prevent that capacitor from producing the drum end even blast, and can prevent that capacitor from high temperature hydration taking place and causing its inefficacy.The invention also discloses a kind of aluminium electrolytic capacitor that adopts above-mentioned Working electrolyte, it can be worked under the 315V-500V rated operational voltage.Though this prescription has corrosion resistance, and reduced the generation of hydrogen, the high voltage performance DeGrain can only be made the 500V electrolytic capacitor.Therefore, in order to overcome the unfavorable problem of high voltage performance, the present invention studies the aluminium electrolytic capacitor of 600V or the above extra-high pressure of 600V.
Summary of the invention
Technical problem to be solved by this invention provides a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor and preparation and application, this electrolyte has adopted suitable flash over voltage improving agent and stabilizer, improve high pressure resistant, the high-temperature stability of electrolyte, had low aerogenesis performance simultaneously; And make aluminium electrolytic capacitor with this electrolyte, 90 ℃ of viabilities, 2000 hours, the high pressure resistant 600V 630V even that reaches can not puncture because the electrolyte flash over voltage is unstable.
A kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor of the present invention comprises the component of following weight portion:
Primary solvent: 44.5～80.3%; Flash over voltage improving agent: 0.5～2.5%;
Secondary solvent: 5～15%; Stabilizer: 6～10%;
Solute: 8～15%; Hydrogen absorber: 0.2～3%.
Described primary solvent is ethylene glycol or butyrolactone;
Described secondary solvent is glycerol, diethylene glycol (DEG), phenmethylol, N-methyl pyrrolidone, butyl carbitol, EGME, butyl glycol ether or diethylene glycol methyl ether;
Described solute is selected from boric acid, ammonium borate, ammonium pentaborate, ammonium sebacate, 1,10-dodecandioic acid ammonium, 1, the 7-ammonium sebacate, 1, aliphatic acid, C14, C16, C24, the C30 etc. that 6-dodecandioic acid ammonium, C14, C16, C24, C30 etc. have single-ended side side chain or a both end sides side chain have one or both the mixture in the aliphatic acid ammonium of single-ended side side chain or both end sides side chain;
Described flash over voltage improving agent is selected from polyvinyl alcohol, ammonium polyacrylate, the degree of polymerization 400～30000 polyethylene glycol, polyoxyethylene oxypropylene ether, the SiO of the degree of polymerization 300～2400
2The mixture of one or both in nm level dispersant, polymerized fatty acid, the polymerized fatty acid ammonium;
Described stabilizer is selected from one or both the mixture in acid esterification thing, Phosphation thing, mannitol, D-sorbite, xylitol, sucrose, phosphoric acid, ammonium phosphate, phosphorous acid, ammonium phosphite, ortho phosphorous acid, ammonium hypophosphite, diammonium hydrogen phosphate, polyphosphoric acid, polyphosphoric acid ammonium salt, the alkyl phosphate;
Described hydrogen absorber is p-nitrophenol, metanitrophenol, paranitrobenzoic acid, inclined to one side nitro acetophenone, resorcinol, hydroquinones, adjacent nitro-anisol or p-nitrophenyl methyl alcohol etc.;
Described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 73.5% polyvinyl alcohol 1%
Glycerol 10% sweet mellow wine 7%
Ammonium borate 5% p-nitrophenyl methyl alcohol 0.5%
1,10-dodecandioic acid ammonium 2%
The two carboxylic acid ammoniums 1% of 16 carbocyclic aliphatics;
Described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 60% polyoxyethylene oxypropylene ether 2%
Diethylene glycol (DEG) 15% D-sorbite 8%
Boric acid 8% APP 0.3%
1,6-dodecandioic acid ammonium 4% adjacent nitro-anisol 0.7%
The two carboxylic acid ammoniums 2% of 24 carbocyclic aliphatics;
Described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Butyrolactone 69.5% Macrogol 3000 02%
EGME 15% dibutylphosphoric acid ester 1%
Ammonium pentaborate 5% ammonium hypophosphite 0.5%
1,7-ammonium sebacate 4% inclined to one side nitro acetophenone 1%
The two carboxylic acid ammoniums 2% of 30 carbocyclic aliphatics;
Described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 69.5% SiO
2Nm level dispersant 2%
Butyl carbitol 12% ammonium polyacrylate 0.5%
Boric acid 7% diammonium hydrogen phosphate 0.3%
Ammonium pentaborate 3% p-nitrophenol 0.7%
The last of the ten Heavenly stems two bisgallic acid ammonium 3%
The two carboxylic acid ammoniums 2% of 14 carbocyclic aliphatics.
The preparation method of a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor of the present invention comprises:
(1) being 44.5～80.3% primary solvent with percentage by weight fully mixes with 5～15% secondary solvent, is heated to 60～90 ℃; Adding percentage by weight then is 0.5～2.5% flash over voltage improving agent, stirs, and is heated to 135～155 ℃;
(2) above-mentioned mixed liquor is cooled off 65-80 ℃ by recirculated water, add percentage by weight and be 8～15% solute, mix, add percentage by weight then and be 6～10% stabilizer, be heated to 105～135 ℃ again; Add percentage by weight at last and be 0.2～3% hydrogen absorber, mix the back natural cooling, make 600V ultra-high voltage aluminum electrolytic capacitor Working electrolyte.
600V ultra-high voltage aluminum electrolytic capacitor of the present invention is applied to the preparation of high-voltage electrolysis capacitor with Working electrolyte, and this electrolytic capacitor comprises that capacitor core holds group, fixative, aluminum hull, electrolyte, phenolic resin cover plate etc.
In order to improve the high pressure resistant of electrolyte, the present invention has added the flash over voltage improving agent in electrolyte, obviously reduce the anion concentration at electrolyte and aluminum foil oxidation film interface, thereby improves anionic discharge voltage; These polymer can be prevented the erosion of sealing again after the powerful absorption in aluminum foil oxidation film surface simultaneously, have improved high-temperature stability; Simultaneously, the interpolation of stabilizer not only prevents the withstand voltage instability of capacitor that electrolyte causes because of voltage jump fluctuation in the course of the work, and can avoid capacitor the degenerating of electrical property after high-temperature storage.
In addition, in order to prevent that capacitor from producing hydrogen in aging and the course of work, in electrolyte of the present invention, also add hydrogen absorber, when aging and under the operational environment of HTHP, the capacitor oxide-film can be changed into repairing once more because of there being defective, capacitor cathode will produce hydrogen inevitably in the oxidation mending course, if untimely gas is eliminated in other words digested before hydrogen atom is combined into molecule, that capacitor pressure inside will be increasing, the result can cause the capacitor product drum end, for sort this problem out, utilization has some electronegative group such as nitro compound, phenols absorbs the hydrogen of generation and replaces hydrogen atom in other words, to reduce last Hydrogen Vapor Pressure.
Beneficial effect
The present invention has adopted suitable flash over voltage improving agent and stabilizer, has improved high pressure resistant, the high-temperature stability of electrolyte greatly, has low aerogenesis performance simultaneously; And adopt this electrolyte to make aluminium electrolytic capacitor, 90 ℃ of viabilities, 2000 hours, the high pressure resistant 600V 630V even that reaches, aging and endurance test process does not all puncture because the electrolyte flash over voltage is unstable at capacitor.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The preparation of electrolyte:
(1) presses the prescription of table 1, ethylene glycol is fully mixed with glycerol, be heated to 60～90 ℃; Add polyvinyl alcohol then, stir, be heated to 135～155 ℃;
(2) above-mentioned mixed liquor is cooled off to 65～80 ℃ by recirculated water, add ammonium borate, 1, the two carboxylic acid ammoniums of 10-dodecandioic acid ammonium and 16 carbocyclic aliphatics mix, and add sweet mellow wine then, are heated to 105～135 ℃ again; Add p-nitrophenyl methyl alcohol at last, mix the back natural cooling, make ultra-high voltage aluminum electrolytic capacitor Working electrolyte.
Embodiment 2
Press the component prescription of table 2, adopt the preparation method identical, make ultra-high voltage aluminum electrolytic capacitor Working electrolyte with embodiment 1.
Embodiment 3
Press the component prescription of table 3, adopt the preparation method identical, make ultra-high voltage aluminum electrolytic capacitor Working electrolyte with embodiment 1.
Embodiment 4
Press the component prescription of table 4, adopt the preparation method identical, make ultra-high voltage aluminum electrolytic capacitor Working electrolyte with embodiment 1.
Embodiment 5
The prescription of use table 1～listed electrolyte of table 4 is made electrolytic capacitor: 600V5600uF, and φ 90 * 190, and apply the 600V direct voltage at 90 ℃ of environment, and the time is 2000h, and result of the test sees the following form 5:
Table 5
The result: by the result of the test of table 5 as can be known, the 600V ultra-high voltage aluminum electrolytic capacitor that adopts embodiment 1～4 Working electrolyte is through 90 ℃, and test data and outward appearance are normal behind the 2000h, has reached the target of design.
Claims (9)
1. 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Primary solvent: 44.5～80.3%; Flash over voltage improving agent: 0.5～2.5%;
Secondary solvent: 5～15%; Stabilizer: 6～10%;
Solute: 8～15%; Hydrogen absorber: 0.2～3%.
2. a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 1 is characterized in that:
Described primary solvent is ethylene glycol or butyrolactone;
Described secondary solvent is glycerol, diethylene glycol (DEG), phenmethylol, N-methyl pyrrolidone, butyl carbitol, EGME, butyl glycol ether or diethylene glycol methyl ether;
Described solute is selected from boric acid, ammonium borate, ammonium pentaborate, ammonium sebacate, 1,10-dodecandioic acid ammonium, 1, the 7-ammonium sebacate, 1,6-dodecandioic acid ammonium, the mixture of one or both in the aliphatic acid ammonium of the aliphatic acid of C14, C16, C24, C30, C14, C16, C24, C30 with single-ended side side chain or both end sides side chain with single-ended side side chain or both end sides side chain;
Described flash over voltage improving agent is selected from polyvinyl alcohol, ammonium polyacrylate, the degree of polymerization 400～30000 polyethylene glycol, polyoxyethylene oxypropylene ether, the SiO of the degree of polymerization 300～2400
2The mixture of one or both in nm level dispersant, polymerized fatty acid, the polymerized fatty acid ammonium;
Described stabilizer is selected from one or both the mixture in acid esterification thing, Phosphation thing, mannitol, D-sorbite, xylitol, sucrose, phosphoric acid, ammonium phosphate, phosphorous acid, ammonium phosphite, ortho phosphorous acid, ammonium hypophosphite, diammonium hydrogen phosphate, polyphosphoric acid, polyphosphoric acid ammonium salt, the alkyl phosphate;
Described hydrogen absorber is p-nitrophenol, metanitrophenol, paranitrobenzoic acid, inclined to one side nitro acetophenone, resorcinol, hydroquinones, adjacent nitro-anisol or p-nitrophenyl methyl alcohol.
3. a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 1 is characterized in that: described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 73.5% polyvinyl alcohol 1%
Glycerol 10% sweet mellow wine 7%
Ammonium borate 5% p-nitrophenyl methyl alcohol 0.5%
1,10-dodecandioic acid ammonium 2%
The two carboxylic acid ammoniums 1% of 16 carbocyclic aliphatics.
4. a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 1 is characterized in that: described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 60% polyoxyethylene oxypropylene ether 2%
Diethylene glycol (DEG) 15% D-sorbite 8%
Boric acid 8% APP 0.3%
1,6-dodecandioic acid ammonium 4% adjacent nitro-anisol 0.7%
The two carboxylic acid ammoniums 2% of 24 carbocyclic aliphatics.
5. a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 1 is characterized in that: described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Butyrolactone 69.5% Macrogol 3000 0 2%
EGME 15% dibutylphosphoric acid ester 1%
Ammonium pentaborate 5% ammonium hypophosphite 0.5%
1,7-ammonium sebacate 4% inclined to one side nitro acetophenone 1%
The two carboxylic acid ammoniums 2% of 30 carbocyclic aliphatics.
6. a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 1 is characterized in that: described 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises the component of following weight portion:
Ethylene glycol 69.5% SiO
2Nm level dispersant 2%
Butyl carbitol 12% ammonium polyacrylate 0.5%
Boric acid 7% diammonium hydrogen phosphate 0.3%
Ammonium pentaborate 3% p-nitrophenol 0.7%
The last of the ten Heavenly stems two bisgallic acid ammonium 3%
The two carboxylic acid ammoniums 2% of 14 carbocyclic aliphatics.
7. the preparation method of a 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor comprises:
(1) being 44.5～80.3% primary solvent with percentage by weight fully mixes with 5～15% secondary solvent, is heated to 60～90 ℃; Adding percentage by weight then is 0.5～2.5% flash over voltage improving agent, stirs, and is heated to 135～155 ℃;
(2) above-mentioned mixed liquor is cooled off 65-80 ℃ by recirculated water, add percentage by weight and be 8～15% solute, mix, add percentage by weight then and be 6～10% stabilizer, be heated to 105～135 ℃ again; Add percentage by weight at last and be 0.2～3% hydrogen absorber, mix the back natural cooling, make 600V ultra-high voltage aluminum electrolytic capacitor Working electrolyte.
8. the preparation method of a kind of 600V ultra-high voltage aluminum working electrolyte of electrolytic capacitor according to claim 7 is characterized in that:
Described primary solvent is ethylene glycol or butyrolactone;
Described secondary solvent is glycerol, diethylene glycol (DEG), phenmethylol, N-methyl pyrrolidone, butyl carbitol, EGME, butyl glycol ether or diethylene glycol methyl ether;
Described solute is selected from boric acid, ammonium borate, ammonium pentaborate, ammonium sebacate, 1,10-dodecandioic acid ammonium, 1, the 7-ammonium sebacate, 1,6-dodecandioic acid ammonium, the mixture of one or both in the aliphatic acid ammonium of the aliphatic acid of C14, C16, C24, C30, C14, C16, C24, C30 with single-ended side side chain or both end sides side chain with single-ended side side chain or both end sides side chain;
Described flash over voltage improving agent is selected from polyvinyl alcohol, ammonium polyacrylate, the degree of polymerization 400～30000 polyethylene glycol, polyoxyethylene oxypropylene ether, the SiO of the degree of polymerization 300～2400
2The mixture of one or both in nm level dispersant, polymerized fatty acid, the polymerized fatty acid ammonium;
Described stabilizer is selected from one or both the mixture in acid esterification thing, Phosphation thing, mannitol, D-sorbite, xylitol, sucrose, phosphoric acid, ammonium phosphate, phosphorous acid, ammonium phosphite, ortho phosphorous acid, ammonium hypophosphite, diammonium hydrogen phosphate, polyphosphoric acid, polyphosphoric acid ammonium salt, the alkyl phosphate;
Described hydrogen absorber is p-nitrophenol, metanitrophenol, paranitrobenzoic acid, inclined to one side nitro acetophenone, resorcinol, hydroquinones, adjacent nitro-anisol or p-nitrophenyl methyl alcohol.
9. a 600V ultra-high voltage aluminum electrolytic capacitor is applied to the preparation of high-voltage electrolysis capacitor with Working electrolyte.
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| CN101373666B (en) * | 2007-08-23 | 2012-02-08 | 南通瑞达电子材料有限公司 | High pressure working electrolytic solution of electrolytic capacitor |
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