CN110437454A - The rush infiltration purposes and electrolyte for aluminum electrolytic capacitor of Siloxane-Oxyalkylene Copolymers - Google Patents
The rush infiltration purposes and electrolyte for aluminum electrolytic capacitor of Siloxane-Oxyalkylene Copolymers Download PDFInfo
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- CN110437454A CN110437454A CN201910754805.8A CN201910754805A CN110437454A CN 110437454 A CN110437454 A CN 110437454A CN 201910754805 A CN201910754805 A CN 201910754805A CN 110437454 A CN110437454 A CN 110437454A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
Abstract
The present invention relates to the rush of Siloxane-Oxyalkylene Copolymers infiltration purposes and electrolyte for aluminum electrolytic capacitor.Specifically, the present invention provides a kind of Siloxane-Oxyalkylene Copolymers, as shown in formula (I)；The electrolyte is the electrolyte of polar solvent system, and contains the Siloxane-Oxyalkylene Copolymers as shown in formula (I):Wherein, R1, R2, R3, R4Independently selected from C1~4Alkyl, n, m, y are independently selected from 2~10000；The electrolyte also contains solvent, solute and selectable auxiliary agent, and the solvent is preferably at least one of alcohols, esters, ethers.Present invention improves the amphipathic properties of electrolyte for aluminum electrolytic capacitor, especially to the compatibility of Waste Acid From Hua Cheng Foil, so as to improve many-sided performance of electrolyte.
Description
Technical field
The present invention relates to capacitor material fields, in particular to the rush infiltration purposes and aluminium electroloysis of Siloxane-Oxyalkylene Copolymers
Electrolyte for capacitor.
Background technique
Aluminium electrolutic capacitor recruitment at present is mainly water system (low pressure) or organic system (mesohigh) etc. as electrolyte, is all pole
Property dicyandiamide solution, and capacitor anode is hydrophilic foil with Waste Acid From Hua Cheng Foil, there are preferable compatibilities for the two.However, with all kinds of electricity
Device equipment updates, and requirement of the market to characteristics such as capacitor high voltage, high heat resistance, long-lives is gradually increased, common to work
Electrolyte is unable to satisfy the requirement of capacitor use environment.To improve capacitor product characteristic, it will usually more alkane be added wherein
The solute of base branch improves pressure-resistant performance, heat resistance of Working electrolyte etc., to extend capacitor service life.But
This kind of more alkyl solutes contain more nonpolar alkyl, not only reduce its own dissolubility, can also reduce the pole of Working electrolyte
Property, greatly influence electrolyte is to the compatibility of Waste Acid From Hua Cheng Foil, and such solute is more difficult penetrates into Waste Acid From Hua Cheng Foil oxide-film micropore,
The capacity for not only influencing capacitor is drawn, its loss can also increased, fever increases, the lost of life, the wasting of resources.
Summary of the invention
The first object of the present invention is to provide rush of the Siloxane-Oxyalkylene Copolymers in electrolyte for aluminum electrolytic capacitor
Purposes is permeated, adding Siloxane-Oxyalkylene Copolymers in the electrolytic solution can reach rush osmotic effect, improve electrolyte to Waste Acid From Hua Cheng Foil
Compatibility improves electric conductivity.
The second object of the present invention is to provide a kind of electrolyte for aluminum electrolytic capacitor, containing good close in the electrolyte
The lipophilic Siloxane-Oxyalkylene Copolymers of water solve the problems, such as that electrolyte is poor to Waste Acid From Hua Cheng Foil compatibility.
In order to achieve the goal above, the present invention provides following technical schemes:
A kind of Siloxane-Oxyalkylene Copolymers, with following molecular formula:
Wherein, R1, R2, R3, R4It is each independently selected from C1~4Alkyl, n, m, y are independently selected from whole between 2~10000
Number.
In the present invention, R1, R2, R3, R4It is each independently selected from C1~4Alkyl, C1~4The alkyl of alkyl groups mean linear or its isomery
Body, including-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH(CH3)2、-CH2CH(CH3)2、-CH(CH3)
CH2CH3、-CHCH2(CH3)CH3Deng.
N, m, y can select the arbitrary integer between 2~10000, for example, 2,10,20,25,50,100,200,300,500,
1000,2000,3000,5000,7000,10000 etc..The preferred range of n has the preferred range of 10~1000, m to have 50~200, y
Preferred range has 6~24 etc..
The a large amount of alkyl contained due to above-mentioned Siloxane-Oxyalkylene Copolymers are to organic branched macromolecule solute in electrolyte
With preferable compatibility, and the polarity polyether segment of modifying and decorating can be with dicyandiamide solution, chemical conversion foil oxide film etc. poles in molecule
Property part have preferable compatibility, each other formed hydrogen bond the effects of power, to reinforce solute, (especially organic branch divides greatly
Son) it is dissolved in dicyandiamide solution, and increase infiltration of the solute to Waste Acid From Hua Cheng Foil oxide-film micropore or defect, to improve capacitor and resistance to
Hot resistance to pressure, prolongs the service life.Therefore, above-mentioned Siloxane-Oxyalkylene Copolymers can be played for electrolyte for aluminum electrolytic capacitor
The effect for promoting infiltration, in particular for the electrolyte significant effect of polar solvent system.For this purpose, claimed above-mentioned poly-
Rush of the ether modified polyorganosiloxane in electrolyte for aluminum electrolytic capacitor permeates purposes.
The present invention also provides a kind of electrolyte for aluminum electrolytic capacitor, the electrolyte is the electrolysis of polar solvent system
Liquid, and contain the Siloxane-Oxyalkylene Copolymers of following molecular formula:
Wherein, R1, R2, R3, R4Independently selected from C1~4Alkyl, n, m, y are independently selected from 2~10000；N is preferably 1000,
M is preferably 200, y preferably 24.
The electrolyte also contains solvent, solute and selectable auxiliary agent, and the solvent is preferably alcohols, esters, ethers
At least one of.
As described above, R1, R2, R3, R4, n, m, y are suitable for the type of above-mentioned restriction.
In the present invention, alcohols solvent refers to solvent liquid under any room temperature, including but not limited to C2~11Straight chain or branch
Chain saturated fatty alcohol can be monohydric alcohol or polyalcohol, such as ethyl alcohol, ethylene glycol, glycerol, propyl alcohol, propylene glycol, butanol, fourth two
Alcohol, amylalcohol, isoamyl alcohol, pentanediol, hexanol, hexylene glycol, enanthol, heptandiol, octanol, ethohexadiol, nonyl alcohol, nonanediol, decyl alcohol, the last of the ten Heavenly stems
Glycol, undecyl alcohol etc. stablize not volatile alcohols preferably under room temperature.
Ether solvent refers to ether liquid under any room temperature, the preferably multi-functional biggish ether of polarity, such as butyl ether, two
Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether etc..
Esters solvent refers to ester liquid under any room temperature, the including but not limited to positive fourth of methyl acetate, ethyl acetate, acetic acid
Ester, ethyl hexanoate, ethyl propionate etc..
In electrolyte of the invention, the content of Siloxane-Oxyalkylene Copolymers is unsuitable excessively high, to prevent reducing the conduction of electrolyte
Property, preferred range is 0.2~5.0wt%, more preferable 0.5~5.0wt%, more preferable 1.0~5.0wt%, 1.5~
5.0wt%, more preferable 1.0~4.5wt%, 1.0~2.5wt%.
In the present invention, the solute in the electrolyte is at least one of inorganic acid, substituted or unsubstituted and its salt.
Inorganic acid includes but is not limited to boric acid, acid salt etc..Dicarboxylic Acids can be saturation or unsaturation organic acid, such as fat
Acid, aromatic acid etc., salt include inorganic ammonium salt or organic amine salt, the preferred dimethylamine salt of the organic amine salt, diethylamine salt, three second
At least one of amine salt, diisopropyl ethyl amine salt.
Preferably, solute contains the compound of following molecular formula II and its chemical combination of salt, molecular formula III in the electrolyte
At least one of object and its salt:
Wherein, K, Z are separately selected from 1~8, such as are separately selected from 1,2,3,4,5,6,7,8 etc..
R5And R6Separately it is selected from alkyl, alkoxy, phenyl, ester group, ether or amide groups；
Preferably, the salt of the salt of the compound II and the compound III are independently selected from inorganic ammonium salt or organic amine
Salt, at least one of the preferred dimethylamine salt of the organic amine salt, diethylamine salt, triethylamine salt, diisopropyl ethyl amine salt.
Siloxane-Oxyalkylene Copolymers are more significant to the rush infiltration of above two class (the II, III) solute, rush solute effect.
Wherein, the preferred C of alkyl1-7Alkyl, including but not limited to methyl, ethyl, propyl, butyl, isobutyl group, amyl and its
Isomers, hexyl and its isomers, heptyl and its isomers etc..
The preferred C of alkoxy1-7Alkoxy, including but not limited to methoxyl group, ethyoxyl, propoxyl group, butoxy, isobutoxy,
Amoxy and its isomers, hexyloxy and its isomers, oxygroup in heptan and its isomers etc..
Ester group includes but is not limited to methyl acetate base, ethyl acetate base, n-butyl acetate base, ethyl hexanoate base, propionic acid second
Ester group etc..
Ether includes but is not limited to ether base, propyl ether base, butyl ether base, diethylene glycol monobutyl ether base, propylene glycol monomethyl ether base, dipropyl
Glycol methyl ether base, tripropylene glycol methyl ether base.
Amide groups includes but is not limited to formamido, acetamido, propionamido-.
Preferably, solute is 2- butyl ammonium octanedioic acid, 2- butyl octanoic acid dimethylamine, 2,7- dibutyl in the electrolyte
At least one of ammonium octanedioic acid, 2,7- dibutyl suberic acid diethylamine or 2- butyl -5- ethyoxyl ammonium adipate.
Preferably, the solute of the electrolyte also contains boric acid.The inorganic acids solute such as boric acid molecule itself is smaller, and can
Occur certain chemical reaction or interaction with chemical conversion foil oxide film, improve electron-transport effect, thus by boric acid with it is above-mentioned
Organic carboxyl acid combination after electrolyte performance more preferably.
Preferably, in the electrolyte solutes content be 3.25~11wt%, such as 3.25wt%, 5.0wt%,
5.5wt%, 6.0wt%, 6.5wt%, 7.0wt%, 7.5wt%, 8.0wt%, 8.5wt%, 8.6wt%, 9.0wt%,
9.1wt%, 9.5wt%, 10.0wt%, 10.5wt%, 11.0wt% etc..
Preferably, the auxiliary agent is scintillation elevator, anticorrosive, waterproof mixture, disappear at least one of hydrogen agent, such as
Optional scintillation elevator, anticorrosive, waterproof mixture or disappear hydrogen agent or the combination of scintillation elevator and anticorrosive or scintillation
The combination of elevator, the combination of anticorrosive and waterproof mixture or scintillation elevator, anticorrosive, waterproof mixture and the hydrogen agent that disappears.
The scintillation elevator can be any type commonly used in the art, including but not limited to polyvinyl alcohol, citric acid,
At least one of modified silicon oil etc..
The anticorrosive includes but is not limited to mannitol, ortho-nitrophenyl formamide, in methyl ortho-nitraniline etc.
It is at least one.
The waterproof mixture includes but is not limited in ammonium hypophosphite, phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, aluminium salt etc.
It is at least one.
The hydrogen agent that disappears include but is not limited to resorcinol, p-nitrophenol, p nitrobenzyl alcohol, 1,4-benzoquinone, to nitro
At least one of benzoic acid etc..
Preferably, the scintillation elevator is polyvinyl alcohol, and the anticorrosive is preferably mannitol, the waterproof mixture
Preferably ammonium hypophosphite, the hydrogen agent that disappears is preferably paranitrobenzoic acid.
Preferably, the electrolyte mainly consists of the following compositions:
By weight percentage, Siloxane-Oxyalkylene Copolymers 0.5~5.0%, solute 3.25~11%, scintillation elevator
0.5~3.0%, anticorrosive 1.0~6.0%, waterproof mixture 0.01~0.3%, disappear hydrogen agent 0.5~2.8%, balance of solvent.
It is highly preferred that the electrolyte mainly consists of the following compositions:
By weight percentage, Siloxane-Oxyalkylene Copolymers 0.5~5.0%, solute 5.0~10.0%, scintillation elevator
0.5~1.0%, anticorrosive 3.5~5.0%, waterproof mixture 0.15~0.2%, disappear hydrogen agent 1.0~2.4%, balance of solvent.
To sum up, compared with prior art, invention achieves following technical effects:
(1) using Siloxane-Oxyalkylene Copolymers as additive, the amphipathic property of electrolyte for aluminum electrolytic capacitor is improved,
Especially to the compatibility of Waste Acid From Hua Cheng Foil, so as to improve many-sided performance of electrolyte, including heat resistance, resistance to pressure, surface
Power also improves capacitor life-span；
(2) compatibility for optimizing electrolyte improves the electrolyte such as Siloxane-Oxyalkylene Copolymers and solute, solvent and auxiliary agent
The synergy of main component significantly improves the function of electrolyte.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The Siloxane-Oxyalkylene Copolymers of following embodiment have:
The above Siloxane-Oxyalkylene Copolymers preparation process is as follows:
Step 1: preparing polysiloxanes
Step 2: prepared by Siloxane-Oxyalkylene Copolymers
Each Siloxane-Oxyalkylene Copolymers in I1~I5 embodiment can control silane coupling agent dosage and reaction as needed
Time, simultaneous selection containing hydrogen silicone oil molecular chain length and hexamethyl siloxane, then control reaction prepare polysiloxane molecule；So
After select suitable polyethers to be modified polysiloxanes.To be prepared into Siloxane-Oxyalkylene Copolymers bleeding agent.
Wherein Siloxane-Oxyalkylene Copolymers preparation method teaches team's Master's thesis " polyether-modified poly- silicon see also Guo Rui
The preparation and application of oxygen alkane surfactant " partially modified method and Feng Zongcai " synthesis of Siloxane-Oxyalkylene Copolymers and its
Surface-active research " documents such as the method for modifying that refers to；Polysiloxanes preparation method can use for reference Huang Yanhua's Master's thesis " organosilicon
The research and application of resin and polyether modified siloxane " etc. documents and materials.
Siloxane-Oxyalkylene Copolymers structure I 1, the specific preparation process of I2, I3, I4, I5 and the characterizing method that embodiment is used
It is as follows:
I1 preparation method:
Prepolymerization: the dimethoxydimethylsilane of certain mass is first taken to be added in round-bottomed flask, then the quality such as addition
20% dilute acetic acid solution, is sufficiently stirred, and then vacuum distillation obtains prepolymer M to no fraction.Prepolymer M is all 2~4
The molecular weight polymers of a dimethoxydimethylsilane.
Step 1: taking the prepolymer M of above-mentioned certain mass, the concentrated sulfuric acid that gross mass 6.0% is added makees catalyst, quickly stirs
10min is mixed, the containing hydrogen silicone oil and end-capping reagent hexamethyldisiloxane (different molecular weight of molecular weight about 2027g/mol is then added
Containing hydrogen silicone oil and hexamethyldisiloxane can be obtained by commercially available method), react 2 hours at 55~65 DEG C of water-bath, be added
Alkali neutralization, extraction remove impurity, and vacuum distillation removes low-boiling-point substance, can be obtained polysiloxanes, detect polysiloxanes number by GPC
Average molecular weight about 2780.32g/mol.
Step 2: taking the above-mentioned polysiloxanes of certain mass, Br is first used2The abundant halogenation of illumination, is then added enough second
Pure and mild sodium hydroxide solution, is sufficiently stirred 3 hours, then filters and with ethanol rinse, and obtained dope is carried out decompression pumping
Filter, removal of impurities and low-boiling-point substance；Then the ethyl polyethers ethyl alcohol that molecular weight is about 517g/mol is added, and (such alkyl polyol ether can pass through
Commercially available method obtains), the concentrated sulfuric acid of gross mass 1.0% is added after being sufficiently stirred, while being evaporated under reduced pressure to no aqueous distillate, then extracts
It removes miscellaneous suction filtration and obtains colorless transparent viscous liquid, as Siloxane-Oxyalkylene Copolymers (I1).The polymer is detected by GPC
Number-average molecular weight is about 3284.11g/mol, identifies then referring to nuclear-magnetism and judges polymer for Siloxane-Oxyalkylene Copolymers I1 knot
Structure.
I1 nuclear magnetic data: 300MHz, 1H-NMR (DMSO)
σ=0.14 (s, 3H), σ=0.19 (s, 3H), σ=0.21 (s, 3H), σ=0.89 (t, J=8Hz, 3H), σ=
1.18 (t, J=8Hz, 3H), σ=1.44 (m, J=7Hz, 2H), σ=3.36 (d, J=7Hz, 2H), σ=3.40 (m, J=7Hz,
1H), σ=3.61 (s, J=7Hz, 2H), σ=3.88 (q, J=8Hz, 2H), σ=3.96 (s, J=7Hz, 2H).
I2, I3, I4 preparation method:
Prepolymerization method is identical as I1, and it is identical as I1 that the first step prepares polysiloxanes technical process, main difference is that I2
The quality that the concentrated sulfuric acid is added is the 4.5% of gross mass, and 55~65 DEG C of water-bath are reacted 12 hours, detects polysiloxanes number by GPC
Average molecular weight about 86202.63g/mol；The quality that the concentrated sulfuric acid is added in I3 is the 3.5% of gross mass, 55~65 DEG C of water-bath reactions 36
Hour, polysiloxanes number-average molecular weight about 382234.55g/mol is detected by GPC；The quality that the concentrated sulfuric acid is added in I4 is gross mass
2.0%, 55~65 DEG C of water-bath react 96 hours, by GPC detect polysiloxanes number-average molecular weight about 732378.41g/mol,
The containing hydrogen silicone oil molecular weight being added in reaction process is 12162g/mol, other processes and reagent are all identical.Second step polyethers changes
Property method it is identical as the polyether-modified method of I1, wherein modified polyether be molecular weight 1818g/mol ethyl polyethers ethyl alcohol, other mistakes
Journey and reagent are all identical.
It is about 87795.43g/mol by the I2 number-average molecular weight that GPC is detected, I3 number-average molecular weight is about
383751.22g/mol, I4 number-average molecular weight are about 733897.17g/mol.Each polyether-modified poly- silicon is identified then referring to nuclear-magnetism
Oxygen alkyl structure coincide with I2, I3 and I4 respectively.Detailed nuclear magnetic data is as follows:
I2, I3 and I4 nuclear magnetic data: 300MHz, 1H-NMR (DMSO)
σ=0.14 (s, 3H), σ=0.19 (s, 3H), σ=0.21 (s, 3H), σ=0.89 (t, J=8Hz, 3H), σ=
1.18 (t, J=8Hz, 3H), σ=1.44 (m, J=7Hz, 2H), σ=3.36 (d, J=7Hz, 2H), σ=3.40 (m, J=7Hz,
1H), σ=3.61 (s, J=7Hz, 2H), σ=3.88 (q, J=8Hz, 2H), σ=3.96 (s, J=7Hz, 2H).
On the Siloxane-Oxyalkylene Copolymers nuclear magnetic spectrum of three of the above structure, as silicon oxygen segmental repeat unit quantity increases
Add, chemical shift is gradually increased in the response intensity of σ=0.14, and on I2, I3 and I4 nuclear magnetic spectrum chemical shift in σ=0.19, σ
=1.44, the positions such as σ=3.36 and σ=3.40 response intensity ratio I1 is stronger.
I5 preparation method:
Prepolymerization method is identical as I1, and it is identical as I2 preparation method that the first step prepares polysiloxanes method, second step polyethers
Modified polyorganosiloxane preparation process is identical as I2, only difference is that the polyethers reagent selected is the second of molecular weight 2490g/mol
Base polyethers ethyl alcohol, other processes and reagent are all identical.The I5 number-average molecular weight of GPC detection is about 88467.52g/mol, with reference to core
Magnetic identifies that each Siloxane-Oxyalkylene Copolymers structure is I5, and detailed nuclear magnetic data is as follows:
I5 nuclear magnetic data: 300MHz, 1H-NMR (DMSO)
σ=0.14 (s, 3H), σ=0.19 (s, 3H), σ=0.21 (s, 3H), σ=0.88 (t, J=8Hz, 3H), σ=
1.18 (t, J=8Hz, 3H), σ=1.25 (m, J=7Hz, 2H), σ=1.31 (m, J=7Hz, 2H), σ=1.38 (m, J=7Hz,
2H), σ=3.36 (d, J=7Hz, 2H), σ=3.40 (m, J=7Hz, 1H), σ=3.61 (s, J=7Hz, 2H), σ=3.88 (q,
J=8Hz, 2H), σ=3.96 (s, J=7Hz, 2H).
I5 with I2 nuclear magnetic spectrum is similar, and only in chemical shift σ=1.38 or so, there are more multiplets, and are not easy area
Point.
Embodiment 1
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.65g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I1
0.2g。
Embodiment 2
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g, bleeding agent select Siloxane-Oxyalkylene Copolymers I1
1.5g。
Embodiment 3
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 71.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I1
4.5g。
Embodiment 4
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I1
0.5g。
Embodiment 5
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 70.85g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I1
5.0g。
Comparative example 1
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.85g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, azelaic acid
Ammonium 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g.
Comparative example 2
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.85g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g.
The electrolyte property of above embodiments and comparative example is as shown in table 1.
Table 1
Test method used in the present invention is as follows.
1, surface tension test method: the surface of different electrolytes is tested respectively using Germany's sigma700 surface tension instrument
Tension.
2, heat resistance test method: storing 1000Hr in 115 DEG C of constant temperature ovens for different electrolytes, and test is different respectively
Moisture change rate, conductivity variations rate, pH change rate before and after electrolyte high temperature storage.
Moisture content before moisture change rate (%)=100* (moisture content before moisture content-storage after storage)/storage,
Conductivity before conductivity variations rate (%)=100* (conductivity before conductivity-storage after storage)/storage,
PH change rate (%)=100* (pH before pH- is stored after storage)/store preceding pH.
3, the resistance to overvoltage test method of capacitor: different electrolytes are fabricated to capacitor respectively, capacitor arrangement is main
Including core packet, aluminum hull, cover board etc., herein different electrolytes be fabricated to capacitor structure and material it is identical.Each sampling 10
Only, every charging current of condenser is 1.0A, adds 1.5 times of voltage ratings, constant pressure to positive normally open valve is ended, no breakdown spark phenomenon
It is determined as qualification；
Qualification rate (%)=100* qualification quantity/test total quantity.
4, capacitor life-span test and method for testing temperature rise: different electrolytes are fabricated to capacitor respectively, respectively sample 4
Only, life test, while test capacitors internal temperature rise are carried out in 105 DEG C of constant temperature convection oven.
As shown in Table 1, comparative example 1 is compared with comparative example 2, using the main solute of branched chain type than straight chain type master in Working electrolyte
Solute heat resistance and pressure-resistant performance are more excellent, and capacitor internal temperature rise is substantially reduced, and life test extends.Therefore branched chain type solute
The preferred of the following exploitation high heat resistance long-service-life capacitor electrolyte will be become.
Examples 1 to 5 relatively example 2 is deposited it is found that since branched chain type solute molecule space structure is larger, polarity reduces
It, can be obvious when Siloxane-Oxyalkylene Copolymers are added in the system electrolyte the shortcomings that dissolving and penetrating into oxide-film micropore
Improve disadvantage mentioned above, it will be substantially reduced electrolyte surface tension, capacitor internal temperature rise reduces, and the service life extends.But for
The electrolyte of different systems needs to match appropriate and different types of Siloxane-Oxyalkylene Copolymers, such as excessive polyether-modified poly- silicon
Oxygen alkane may result in branched chain type solute and be emulsified into micelle, is unfavorable for solute and immerses anode foils oxide-film micropore；In addition, for viscous
Biggish Working electrolyte is spent, then needs to match the bleeding agent of short molecular chain, otherwise will affect electrolyte whole performance.
Embodiment 6
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2,7- bis-
Butyl ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g, bleeding agent select Siloxane-Oxyalkylene Copolymers
I1 1.5g。
Embodiment 7
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Suberic acid dimethylamine 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g, bleeding agent select Siloxane-Oxyalkylene Copolymers
I1 1.5g。
(2- butyl octanoic acid dimethylamine).
Embodiment 8
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2,7- bis-
Butyl octanoic acid diethylamine 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g, bleeding agent select polyether-modified poly- silicon
Oxygen alkane I1 1.5g.
(2,7- dibutyl suberic acid diethylamine).
The performance of the electrolyte such as table 2.
Table 2
It can be found from above embodiments comparison, the Working electrolyte of organic amine solute is heat-resisting compared to Inorganic Ammonium class solute
Property is more preferable, and capacitor life-span is longer.High-temperature storage test after organic amine solute electrolyte moisture variation, conductivity variations more
It is small, it is less to illustrate that acylation reaction occurs for organic amine solute.And after electrolyte is added in Siloxane-Oxyalkylene Copolymers, be conducive to organic
The dissolution and permeability of amine solute.
Embodiment 9
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I2
1.5g。
Embodiment 10
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.35g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I3
1.5g。
Embodiment 11
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.35g；Diethylene glycol monobutyl ether 8.5g；；Boric acid 3.0g, mannitol 3.5g, 2- butyl ammonium octanedioic acid
5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I4 1.5g.
Embodiment 12
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 74.85g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 0.5g；Boric acid 3.0g, mannitol 3.5g, 2- butyl
Ammonium octanedioic acid 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent selects Siloxane-Oxyalkylene Copolymers I5
1.5g。
The performance of the above electrolyte such as table 3.
Table 3
It compares from table 3 it can be found that when Siloxane-Oxyalkylene Copolymers are a certain amount of, capacitor life-span and temperature rise will all obtain
Greatly improve.But the structure or siloxane chain segment length difference of Siloxane-Oxyalkylene Copolymers need to match suitable work electrolysis
Liquid can also match short segment silicon if the electrolyte of low viscosity can match the Siloxane-Oxyalkylene Copolymers of long-chain-segment silicone-type
The Siloxane-Oxyalkylene Copolymers of oxygen alkane type；Siloxane-Oxyalkylene Copolymers of the highly viscous electrolyte as far as possible with short segment silicone-type
Match；In addition, needing to match the polyether-modified poly- silicon oxygen of lower alkyloxy for the electrolyte of low polarity or non-polar system
Alkane；It can match with the Siloxane-Oxyalkylene Copolymers of long-chain alkoxy base for the electrolyte of polar system.It is above only simply to explain
The applicability of Siloxane-Oxyalkylene Copolymers and electrolyte is stated, practical application is not limited only to this.
Embodiment 13
A kind of high-pressure aluminum electrolytic capacitor electrolyte, each component are as follows:
Ethylene glycol 75.65g；Diethylene glycol monobutyl ether 8.5g；Polyvinyl alcohol 1.0g；Boric acid 3.0g, mannitol 3.5g, 2- fourth
Base -5- ethyoxyl ammonium adipate 5.6g；Ammonium hypophosphite 0.15g；Paranitrobenzoic acid 2.4g；Bleeding agent is selected polyether-modified poly-
Siloxanes I2 0.2g.
The performance of the electrolyte such as table 4.
Table 4
It can be found from table 4, the electrolyte heat resistance of highly branched chain solute compares the electrolyte heat resistance of single branch solute without bright
It is aobvious to improve, but 14.3% is increased using the liquid electrolytic capacitor service life of highly branched chain solute, internal temperature rise reduces 22.2%, table
Face tension reduces 7.7%, illustrates that Siloxane-Oxyalkylene Copolymers have more obvious modified effect to highly branched chain type solute.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of the claim
Subject to enclosing.
Claims (11)
1. a kind of Siloxane-Oxyalkylene Copolymers, with following molecular formula:
Wherein, R1, R2, R3, R4It is each independently selected from C1~4Alkyl, n, m, y are independently selected from the integer between 2~10000；
Preferably, R1, R2, R3It is methyl, R4For ethyl.
2. rush of the Siloxane-Oxyalkylene Copolymers described in claim 1 in electrolyte for aluminum electrolytic capacitor permeates purposes.
3. a kind of electrolyte for aluminum electrolytic capacitor, which is characterized in that the electrolyte is the electrolyte of polar solvent system, and
And containing Siloxane-Oxyalkylene Copolymers described in claim 1, the electrolyte also contains solvent, solute and selectable helps
Agent, the solvent are preferably at least one of alcohols, esters, ethers.
4. electrolyte according to claim 3, which is characterized in that the content of Siloxane-Oxyalkylene Copolymers in the electrolyte
For 0.2~5.0wt%, preferably 0.5~5.0wt%, more preferable 1.5~5.0wt%.
5. electrolyte according to claim 3, which is characterized in that in the electrolyte solute include inorganic acid, replace or
At least one of unsubstituted Dicarboxylic Acids and its salt.
6. electrolyte according to claim 5, which is characterized in that solute contains following molecular formula II's in the electrolyte
At least one of compound and its salt, the compound of molecular formula III and its salt:
Wherein, K, Z are separately selected from 1~8；
R5And R6Separately it is selected from alkyl, alkoxy, phenyl, ester group, ether or amide groups；
Preferably, the salt of the salt of the compound II and the compound III are independently selected from inorganic ammonium salt or organic amine salt, institute
State at least one of the preferred dimethylamine salt of organic amine salt, diethylamine salt, triethylamine salt, diisopropyl ethyl amine salt.
7. electrolyte according to claim 6, which is characterized in that the solute also contains boric acid.
8. according to the described in any item electrolyte of claim 3-7, which is characterized in that solutes content is 3.25 in the electrolyte
~11wt%.
9. electrolyte according to claim 3, which is characterized in that the auxiliary agent is scintillation elevator, anticorrosive, waterproof
Mixture, disappear at least one of hydrogen agent.
10. electrolyte according to claim 9, which is characterized in that the scintillation elevator is polyvinyl alcohol, the anti-corrosion
Losing agent is preferably mannitol, and the waterproof mixture is preferably ammonium hypophosphite, and the hydrogen agent that disappears is preferably paranitrobenzoic acid.
11. electrolyte according to claim 3, which is characterized in that the electrolyte mainly consists of the following compositions:
By weight percentage, Siloxane-Oxyalkylene Copolymers 0.5~5.0%, solute 3.25~11%, scintillation elevator 0.5~
3.0%, anticorrosive 1.0~6.0%, waterproof mixture 0.01~0.3%, disappear hydrogen agent 0.5~2.8%, balance of solvent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040262566A1 (en) * | 2003-06-26 | 2004-12-30 | Ryoko Takaoka | Driving electrolyte and electrolytic capacitor using the same |
| CN102294132A (en) * | 2011-06-29 | 2011-12-28 | 南京四新科技应用研究所有限公司 | Defoamer for cleaning printed circuit board |
| CN106252079A (en) * | 2016-08-31 | 2016-12-21 | 湖南艾华集团股份有限公司 | A kind of electrolyte of 700V high-pressure aluminum electrolytic capacitor |
| CN107481859A (en) * | 2017-08-11 | 2017-12-15 | 惠州市宙邦化工有限公司 | Electrolyte for aluminum electrolytic capacitor and aluminium electrolutic capacitor |
-
2019
- 2019-08-15 CN CN201910754805.8A patent/CN110437454B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040262566A1 (en) * | 2003-06-26 | 2004-12-30 | Ryoko Takaoka | Driving electrolyte and electrolytic capacitor using the same |
| CN102294132A (en) * | 2011-06-29 | 2011-12-28 | 南京四新科技应用研究所有限公司 | Defoamer for cleaning printed circuit board |
| CN106252079A (en) * | 2016-08-31 | 2016-12-21 | 湖南艾华集团股份有限公司 | A kind of electrolyte of 700V high-pressure aluminum electrolytic capacitor |
| CN107481859A (en) * | 2017-08-11 | 2017-12-15 | 惠州市宙邦化工有限公司 | Electrolyte for aluminum electrolytic capacitor and aluminium electrolutic capacitor |
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