CN103887085A - High-voltage electrolyte for hybrid super tantalum capacitor and preparation method thereof - Google Patents

High-voltage electrolyte for hybrid super tantalum capacitor and preparation method thereof Download PDF

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CN103887085A
CN103887085A CN201410122493.6A CN201410122493A CN103887085A CN 103887085 A CN103887085 A CN 103887085A CN 201410122493 A CN201410122493 A CN 201410122493A CN 103887085 A CN103887085 A CN 103887085A
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tantalum capacitor
hybrid super
electrolyte
sulfuric acid
liquid
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CN103887085B (en
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陆胜
王杰
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Ju Electricity Science And Technology Ltd Of Guizhou Air China
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Abstract

The invention provides a high-voltage electrolyte for a hybrid super tantalum capacitor and a preparation method of the high-voltage electrolyte. The high-voltage electrolyte comprises, by mass, a polar organic macromolecular substance, a proton inert solvent, imidazolium salt, sulfate of transition metal, concentrated sulfuric acid and deionized water. According to the high-voltage electrolyte, the surface morphology of a ruthenium oxide electrode is effectively improved, the internal resistance of the electrode is reduced, and the adhesion strength of ruthenium oxide is enhanced; finally, the original capacity of the capacitor is increased, and the ESR is lowered.

Description

High-pressure electrolysis matter and preparation method thereof for hybrid super tantalum capacitor
Technical field
The present invention relates to chemical field, relate in particular to a kind of hybrid super tantalum capacitor high-pressure electrolysis matter and preparation method thereof.
Background technology
Along with development and the application of high-tech product, portable chemical power supply, as the important way that electric energy is provided, is the emphasis of various countries' research always.Conventional once battery, secondary cell, fuel cell etc. of chemical power source at present.But recent two decades is next, a kind of novel chemical power source: ultracapacitor has caused people's extensive concern.
Ultracapacitor, also claims electrochemical capacitor, is a kind of energy storage component with advantages such as high-energy-density, high specific power, fast charging and discharging ability, long cycle lives.It has broad application prospects at aspects such as mobile communication information technology, electric automobile, Aero-Space and science and techniques of defence.It possesses battery high energy and the high-power advantage of capacitor simultaneously.And be better than again both in performance.
Ultracapacitor can be divided into 3 classes by energy storage mechanism: adopting the energy storage mechanism of the capacitor of active carbon with high specific surface area is the electric double layer capacitance producing based on separation of charge on carbon electrode/electrolyte interface; Adopt RuO 2the capacitor of making electrode Deng the conducting high polymers such as metal oxide containing precious metals or PPY thing is the redox reaction occurring mutually in oxide electrode surface matrix and the adsorption capacitance producing, and this electric capacity is called as Faraday pseudo-capacitance.Because the mechanism of production of Faraday pseudo-capacitance is similar to cell reaction, in the case of identical electrode area, its capacitance is tens times of left and right of electric double layer capacitance; But the power characteristic of double electric layer capacitor transient large current discharge is better than Faradic electricity container, therefore both respectively have its advantage.In recent years, the third ultracapacitor-mixed capacitor is subject to extensive concern, it adopts two kinds in material with carbon element, metal oxide materials and conducting polymer composite to make respectively two electrodes, also more complicated of energy storage mechanism, still under study for action, it has been generally acknowledged that and have electric double layer and Faraday pseudo-capacitance mechanism concurrently.
In recent years, due to the continuous popularization of Pulse Power Techniques, as energy-storage travelling wave tube, the specific power characteristic of active carbon ultracapacitor can not meet requirement, people start again the faraday's redox reaction by means of active material, carry out the research of another kind of energy storage form, in numerous materials, metal oxide ruthenic oxide is the most outstanding, not only there is higher ratio electric capacity (up to 768F/g), and there is excellent cyclical stability, it is current optimal electrode material, its capacitance is mainly to come from the reversible redox reaction of height occurring between ruthenic oxide and electrolyte solution.
Expensive due to ruthenium-oxide material, various countries only limit to laboratory stage mostly to its research, and ripe commercialization is produced comparatively rare.Although hybrid super tantalum capacitor has excellent electric property, but the emphasis of people's research concentrates in the specific capacity and its manufacture method that improves its cathode oxidation ruthenium electrode, for the medium between negative electrode and anode in the tantalum electrolytic capacitor course of work--dipping electrolyte and work gel electrolyte few people pay close attention to, the dipping electrolyte that present most of hybrid super tantalum electrolytic capacitor uses and catholyte are still continued to use electrolyte and the electrolyte formula that traditional liquid tantalum electrolytic capacitor eighties of last century the eighties is just being used, and domestic liquid tantalum electrolyzer manufacturer, the concentrated sulfuric acid that how single its electrolyte used is, silicon dioxide and Ludox are not, its flash over voltage low (being less than 200V), and viscosity is large when subzero temperature (55 DEG C), when high temperature, (125 DEG C) are volatile again, use like this this system electrolyte assembling hybrid super tantalum electrolytic capacitor, the leakage current of capacitor is large, subzero temperature capacitance loss is large, experience 85 DEG C, after the examination of 2000 hours life tests, properties of product are deteriorated serious, cannot meet military project as the application in aerospace industry, if therefore can develop the catholyte plastidome matching with ruthenium oxide electrode material of function admirable, to there be to certain contribution in country and society.
Summary of the invention
The object of the invention is to solve the defect that above-mentioned prior art exists, the problem existing with electrolyte at present domestic high-performance hybrid super tantalum capacitor, provides a kind of catholyte and preparation method that high voltage, large capacity hybrid super tantalum electrolytic capacitor are used that be suitable for manufacturing.
A kind of hybrid super tantalum capacitor high-pressure electrolysis matter, its raw material by mass percentage, comprising:
Polarity organic macromolecule material 5%-20%;
Aprotic solvent 5-50%;
Imidazole salts 1-10%;
The sulfate 0.5-2% of magnesium-yttrium-transition metal;
Concentrated sulfuric acid 20%-36%;
Surplus: the deionized water of resistivity >=15M Ω .cm;
Described imidazole salts has following general formula:
Figure BDA0000483806850000031
wherein, R 1c 1-C 4alkylhalide group, R 2c 1-C 4alkyl, Y -bF 4-or PF 6-anion.X is F, Cl, Br or I.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, described R 1, R 2preferably n-propyl group or p-butyl are as alkyl, and X is F.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, also comprises that the granular size that replaces part deionized water is at the Ludox of 5-15 nanometer, and the mass ratio of described Ludox and the concentrated sulfuric acid is 1-2.5:1.
Further, hybrid super tantalum capacitor high pressure gel electrolyte as above, its raw material by mass percentage, comprising:
Polarity organic macromolecule material 10%-15%;
Aprotic solvent 10%-30%;
Imidazole salts 3%-6%;
The sulfate 0.5-0.8% of magnesium-yttrium-transition metal;
Concentrated sulfuric acid 26%-32%;
The mass ratio of Ludox and the concentrated sulfuric acid is 1-2.5:1;
Surplus: the deionized water of resistivity >=15M Ω .cm.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, described polarity organic macromolecule material is two or more combination in ethylene glycol, ethylene glycol-methyl ether, ethylene glycol-ether, phenmethylol, glycerol derivatives, polyethylene glycol, vinyl alcohol, polyvinyl alcohol.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, described aprotic solvent is one or more the mixture in acetonitrile, 3-methoxypropionitrile, DMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), ethyl carbonate, 2-methyl ethyl ether, gamma-butyrolacton, ethylene carbonate.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, described aprotic solvent is DMF and 1-METHYLPYRROLIDONE or N, the mixture of dinethylformamide and dimethyl sulfoxide (DMSO), both mixing quality ratios are 1:0.5-3.0.
Further, hybrid super tantalum capacitor high-pressure electrolysis matter as above, the sulfate of described magnesium-yttrium-transition metal can be VOSO 4xH 2o, Ag 2sO 4, CuSO 45H 2o, Fe 2(SO 4) 3, VOSO 4in one.
A method of preparing hybrid super tantalum capacitor high-pressure electrolysis matter as above, comprises the following steps:
(1), accurately measure each component by the mass percent in claim 1;
(2), polarity organic macromolecule material is added in aprotic solvent to mix and blend at normal temperatures in proportion, and be slowly warming up to 80 DEG C;
(3), under the condition of 80 DEG C, add imidazole salts, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, forms and mixes A liquid;
(4), get VOSO 45H 2o, is dissolved in deionized water, then measures the concentrated sulfuric acid, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the O aqueous solution, make PH be controlled at 2.0-5.0, finally form capacitor pellet dipping with mixing B liquid;
(5), added and mix B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain hybrid super tantalum capacitor high-pressure electrolysis matter of the present invention.
Further, the method for preparing hybrid super tantalum capacitor high-pressure electrolysis matter described above, described step 4 comprises: take VOSO 45H 2o, and be dissolved in the Ludox and deionized water measuring by mass percentage, then measure the concentrated sulfuric acid, in it being added dropwise to above-mentioned mixed solution slowly in the process constantly stirring, make PH be controlled at 2.0-5.0, the mass ratio of described Ludox and the concentrated sulfuric acid is 1.0-2.5:1, continue to stir more than 10 minutes, finally make capacitor work mixed gel electrolyte B liquid.
Described polarity organic macromolecule material has lower saturated vapour pressure, and this class organic macromolecule material mainly refers to: two or more mixing in ethylene glycol, ethylene glycol-methyl ether, ethylene glycol-ether, phenmethylol, glycerol derivatives, polyethylene glycol, vinyl alcohol, polyvinyl alcohol etc.Polarity organic macromolecule material can shield extra electric field; the dielectric property of protective medium film, because the viscosity of this two or more adjustable electrolyte solution of organic macromolecule acting in conjunction that can dissolve each other, reduce the saturated vapour pressure of capacitor internal; improve flash over voltage, improve stability.The content of Semi-polarity organic macromolecule material of the present invention is between 5%-20%, and the best is 10%-15%.
The described concentrated sulfuric acid reduces the acidity of working electrolyte within the specific limits.In traditional sulfuric acid aqueous systems working electrolyte, acidity is generally in 38% left and right, and under this acidity condition, electrolyte flash over voltage is lower, conductivity is low, is difficult to meet high pressure, the requirement of low ESR capacitor to electrolyte flash over voltage.Add according to Japanese scholars that to rise just experiment conclusion known, reduce the flash over voltage that electrolytic anion concentration can corresponding raising working electrolyte.Reduce within the specific limits the acidity of working electrolyte, reduced exactly electrolytical anion concentration, so can reach the object that improves flash over voltage.In addition, suitably reduce electrolytical acidity, can also improve to a certain extent electrolytical conductivity, thereby reduce the ESR of capacitor.In the present invention, the content of the concentrated sulfuric acid is between 20%-36%, and the best is 26%-32%.The acidity of system is controlled between PH2.0-5.0, and the best is PH3.0-3.5.
Imidazole salts cation, in conjunction with having chemistry and the alkylhalide group of electrochemical stability, demonstrates very high dissolubility at-55 DEG C in atent solvent, and varies with temperature very littlely, and this can ensure the operating characteristic under capacitor low temperature.Imidazole salts used in the present invention has following general formula:
Figure BDA0000483806850000051
Wherein R 1c 1-C 4for alkylhalide group, R 2c 1-C 4for alkyl, Y -bF 4-or PF 6-anion.X is F, Cl, Br or I; R in the present invention 1, R 2preferably n-propyl group or p-butyl are as alkyl, and X is F.The percentage by weight of imidazole salts in whole electrolyte system is 1-10%, and the best is 3%-6%.
In order to ensure the dipping under electrolyte system low temperature, the protic atent solvent using is one or more the mixture in acetonitrile, 3-methoxypropionitrile, DMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), ethyl carbonate, 2-methyl ethyl ether, gamma-butyrolacton, ethylene carbonate.The present invention selects the N with highly-water-soluble, one or both mixing in dinethylformamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), preferably N, one of dinethylformamide and other two kinds mix, mixed weight ratio is 1:0.5-3.0, and the percentage by weight of atent solvent in whole electrolyte system is 5-50%.The best is 10%-30%.
Described Ludox is selected Nano silica sol, and granular size is in 10-20 nanometer left and right, and solid content is 28-35%, the introducing that there is low electrode current potential, easily produces the anion of electron emission in strict control working electrolyte solution simultaneously, and the harmful cation of restriction is (as Na +, K +) introducing, Na +content≤1000mg/L, K+ content≤30mg/L.In the present invention, the mass ratio of the concentrated sulfuric acid and Ludox is 1:1-2.5.After replacing the whole deionized water preparation of part electrolyte mixed solution to leave standstill a period of time with Ludox, can present immobilising gel, so be again gel electrolyte, but this gel electrolyte has thixotropism, after namely again stirring, can revert to again the mobility liquid that viscosity is very low, raise with temperature, mobility is also better.Therefore, gel electrolyte must be through stirring and suitable intensification fully before using, and temperature is generally 30 DEG C-50 DEG C.Form volatilization and leakage that gel electrolyte can prevent electrolytic capacitor electrolyte inside effectively.
The Sulfates of described magnesium-yttrium-transition metal is for reducing the evolving hydrogen reaction that capacitor course of work electrolyte is on electrode, to reduce saturated vapor pressure inner in the capacitor course of work, extends the useful life of capacitor.Because current electrolyte is sulfate system, select Sulfates can avoid introducing new impurity anion, as Ag 2sO 4, CuSO 45H 2o, Fe 2(SO 4) 3, VOSO 4deng, in the time that capacitor is worked, the metal cation of these salts is attracted near the negative electrode of capacitor together with hydrogen ion, forms electric double layer with negative electrical charge on negative electrode, because the standard electrode EMF of these metal cations is than hydrionic height (E θ [Ag +/ Ag]=0.7994V, E θ [Cu 2+/ Cu]=0.340V, E θ [H +/ H 2]=0V), therefore always they have precedence over hydrogen ion and are reduced into as metallic atom at negative electrode electron gain, are attached on capacitor cathode electrode or become the ion compared with lower valency, make electrode reaction:
Figure BDA0000483806850000071
Cannot carry out to positive direction, suppress hydrogen ion and be reduced into hydrogen atom, also can not generate hydrogen molecule and be adsorbed on electrode surface, so just remained the electric double layer being formed by hydrogen ion, thickness determines by hydrogen ion radius, and this has just stoped the increase of electric double layer thickness.For the cathode oxidation ruthenium electrode that mixes tantalum electrolytic capacitor, the reaction of the going utmost point can also effectively improve the form on ruthenium-oxide electrode surface, reduces electrode internal resistance, improves the adhesive strength of ruthenium-oxide.The present invention uses VOSO 4xH 2o, as depolarizing agent, selects VOSO especially 45H 2o, content is less than total weight 2%, is preferably 0.5-0.8%.
7), except above-mentioned substance, the main solvent of electrolyte system of the present invention is deionized water, requires deionization resistivity of water >=15M Ω .cm.
Electrolyte prepared by the present invention is for flooding the porous sintered tantalum piece of anode, and the work gel electrolyte that is added with Ludox is used to negative electrode and anode that conductive ion transfering channel is provided.Its flash over voltage high (higher than 230V), and viscosity is little when subzero temperature (55 DEG C), boiling point is up to 180 DEG C, when high temperature, (125 DEG C) can not volatilize substantially, and this electrolyte system corrosivity is low, use like this this system electrolyte assembling hybrid super tantalum electrolytic capacitor, the leakage current of capacitor is little, subzero temperature capacitance loss is little, and energy stable for extended periods of time, can meet space flight and aviation system high-frequency, wide temperature, highly reliable instructions for use.
The invention provides and mix the working electrolyte that tantalum electrolytic capacitor is used; for the transport intermediary as conductive ion between anode tantalum core and cathode oxidation ruthenium electrode and tantalum shell; because interpolation has the polarity organic macromolecule material of lower saturated vapour pressure; can shield extra electric field; the dielectric property of protective medium film, the saturated vapour pressure of reduction capacitor internal adopts lower acidity simultaneously; can improve the flash over voltage of electrolyte on anode tantalum oxide-film dielectric, improve stability.In addition, add a little imidazole salts in electrolyte, add the lazy solvent of high boiling proton, this can ensure the operating characteristic under capacitor low temperature, expands the serviceability temperature scope of capacitor.In last electrolyte system of the present invention, also contain a small amount of VOSO 4as depolarizing agent, on negative electrode, depolarising is reacted this and has just been stoped the increase of negative electrode electric double layer thickness to improve the capacity of the electric double layer of negative electrode, going utmost point reaction simultaneously also effectively improves the configuration of surface of ruthenium-oxide electrode, reduce electrode internal resistance, improve the adhesive strength of ruthenium-oxide, finally make capacitor specific capacity improve, ESR reduces.
Brief description of the drawings
Accompanying drawing 1 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 1 and temperature;
Accompanying drawing 2 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 2 and temperature;
Accompanying drawing 3 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 3 and temperature;
Accompanying drawing 4 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 4 and temperature;
Accompanying drawing 5 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 5 and temperature.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The present invention, according to correlation theories such as electrolytical theory of electrolytic conductance, solution interface theories, utilizes the orthogonal test of computer-aided design method and system to study, and optimizes high pressure, the electrolytical formula composition of low ESR tantalum capacitor.In conjunction with the design feature of hybrid super tantalum capacitor, emphasis improves the flash over voltage of working electrolyte, and considers its conductivity of raising and the repairing ability to deielectric-coating, improves its boiling point, reduce its saturated vapor pressure, to improve the electrical property of electrolyte solution and capacitor.Concrete research method and embodiment are as follows:
Embodiment 1:
1, the preparation of dipping electrolyte
A), take ethylene glycol-methyl ether 5g, ethylene glycol-ether 5g and mix, then add mix and blend under DMF 10g, dimethyl sulfoxide (DMSO) 5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-propyl group-3-normal-butyl tetrafluoroborate 4.2g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o0.8g, is dissolved in 44g deionized water, then measures concentrated sulfuric acid 26g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the O aqueous solution, make pH value be controlled at 2.5 left and right, make and mix B liquid;
D), added and mix in B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain dipping electrolyte.
2, the preparation of gel electrolyte
A), take ethylene glycol-methyl ether 5g, ethylene glycol-ether 5g and mix, then add mix and blend under DMF 10g, dimethyl sulfoxide (DMSO) 5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-propyl group-3-normal-butyl tetrafluoroborate 4.2g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o0.8g, is dissolved in 44g Ludox mixed solution, then measures concentrated sulfuric acid 26g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the Ludox mixed solution of O, make and mix B liquid.The mass ratio of this step control Ludox and the concentrated sulfuric acid is 1.69:1;
D), by after mixing A liquid and being added in the process constantly stirring and mix in B liquid, continue to stir more than 30 minutes, can make gel electrolyte.
Accompanying drawing 1 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 1 and temperature, the electrolyte that adopts Shanghai thunder magnetic D101 type electric conductivity instrument to test to prepare and the conductivity of gel electrolyte, it is worth as shown in Figure 1, result shows, the electrolyte of the present invention's design demonstrates quite high conductivity, at room temperature the electrolytical conductivity of gained is 42mS/cm, and at the temperature of-60 DEG C, still has the conductivity of 12mS/cm, shows good temperature characterisitic.The simulation tantalum capacitor course of work is tested its flash over voltage up to 235V, excellent performance.
Embodiment 2:
1, the preparation of dipping electrolyte
A), take polyethylene glycol 2.5g, ethylene glycol-ether 2.5g mixes, then add mix and blend under DMF 12.5g, 1-METHYLPYRROLIDONE 37.5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-methyl imidazolium tetrafluoroborate 1g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take CuSO 45H 2o0.5g, is dissolved in 23.5g deionized water, then measures concentrated sulfuric acid 20g, in the process constantly stirring, it is added dropwise to CuSO slowly 45H 2in the O aqueous solution, make pH value be controlled at 2.0 left and right, make and mix B liquid;
D), added and mix in B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain dipping electrolyte.
2, the preparation of gel electrolyte
A), take polyethylene glycol 2.5g, ethylene glycol-ether 2.5g mixes, then add mix and blend under DMF 12.5g, 1-METHYLPYRROLIDONE 37.5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-methyl imidazolium tetrafluoroborate 1g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take CuSO 45H 2o0.5g, is dissolved in 3.5g deionized water and 20g Ludox mixed solution, then measures concentrated sulfuric acid 20g, in the process constantly stirring, it is added dropwise to CuSO slowly 45H 2in O water and Ludox mixed solution, make and mix B liquid.
D), by after mixing A liquid and being added in the process constantly stirring and mix in B liquid, continue to stir more than 30 minutes, can make gel electrolyte.
Accompanying drawing 2 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 2 and temperature, the electrolyte that adopts Shanghai thunder magnetic D101 type electric conductivity instrument to test to prepare and the conductivity of gel electrolyte, it is worth as shown in Figure 2, result shows, the electrolyte of the present invention's design demonstrates quite high conductivity, at room temperature the electrolytical conductivity of gained is 38mS/cm, and at the temperature of-60 DEG C, still has the conductivity of 17mS/cm, shows good temperature characterisitic.The simulation tantalum capacitor course of work is tested its flash over voltage up to 236V, excellent performance.
Embodiment 3:
1, the preparation of dipping electrolyte
A), take ethylene glycol 10g, ethylene glycol-ether 10g mixes, and then adds dimethyl sulfoxide (DMSO) 10g, mix and blend under normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-propyl group-3-ethyl imidazol(e) tetrafluoroborate 1g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o1.5g, is dissolved in 35.5g deionized water, then measures concentrated sulfuric acid 32g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the O aqueous solution, make pH value be controlled at 2.0 left and right, make and mix B liquid;
D), added and mix in B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain dipping electrolyte.
2, the preparation of gel electrolyte
A) take ethylene glycol 10g, ethylene glycol-ether 10g mixes, and then adds dimethyl sulfoxide (DMSO) 10g, mix and blend under normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-propyl group-3-ethyl imidazol(e) tetrafluoroborate 1g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o1.5g, is dissolved in 0.5g deionized water and 35g Ludox mixed solution, then measures concentrated sulfuric acid 32g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in O water and Ludox mixed solution, make and mix B liquid.
D), by after mixing A liquid and being added in the process constantly stirring and mix in B liquid, continue to stir more than 30 minutes, can make gel electrolyte.
Accompanying drawing 3 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 3 and temperature, the electrolyte that adopts Shanghai thunder magnetic D101 type electric conductivity instrument to test to prepare and the conductivity of gel electrolyte, it is worth as shown in Figure 3, result shows, the electrolyte of the present invention's design demonstrates quite high conductivity, at room temperature the electrolytical conductivity of gained is 41mS/cm, and at the temperature of-60 DEG C, still has the conductivity of 8.6mS/cm, shows good temperature characterisitic.The simulation tantalum capacitor course of work is tested its flash over voltage up to 232V, excellent performance.
Embodiment 4:
1, the preparation of dipping electrolyte
A), take ethylene glycol-methyl ether 5g, vinyl alcohol 5g, ethylene glycol-ether 5g mixes, then add mix and blend under 3-methoxypropionitrile 5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-ethyl imidazol(e) tetrafluoroborate 6g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o2g, is dissolved in 36g deionized water, then measures concentrated sulfuric acid 36g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the O aqueous solution, make pH value be controlled at 2.0 left and right, make and mix B liquid;
D), added and mix in B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain dipping electrolyte.
2, the preparation of gel electrolyte
A), take ethylene glycol-methyl ether 5g, vinyl alcohol 5g, ethylene glycol-ether 5g mixes, mix and blend under then add-methoxypropionitrile 5g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-ethyl imidazol(e) tetrafluoroborate 6g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take VOSO 45H 2o2g, is dissolved in 36g Ludox mixed solution, then measures concentrated sulfuric acid 36g, in the process constantly stirring, it is added dropwise to VOSO slowly 45H 2in the Ludox mixed solution of O, make and mix B liquid.
D), by after mixing A liquid and being added in the process constantly stirring and mix in B liquid, continue to stir more than 30 minutes, can make gel electrolyte.
Accompanying drawing 4 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 4 and temperature, the electrolyte that adopts Shanghai thunder magnetic D101 type electric conductivity instrument to test to prepare and the conductivity of gel electrolyte, it is worth as shown in Figure 2, result shows, the electrolyte of the present invention's design demonstrates quite high conductivity, at room temperature the electrolytical conductivity of gained is 35mS/cm, and at the temperature of-60 DEG C, still has the conductivity of 7mS/cm, shows good temperature characterisitic.The simulation tantalum capacitor course of work is tested its flash over voltage up to 234V, excellent performance.
Embodiment 5:
1, the preparation of dipping electrolyte
A), take ethylene glycol-methyl ether 5g, ethylene glycol-ether 8g and mix, then add mix and blend under 3-methoxypropionitrile 13.4g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-propyl imidazole tetrafluoroborate 3g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take Ag 2sO 40.6g, is dissolved in 50g deionized water, then measures concentrated sulfuric acid 20g, in the process constantly stirring, it is added dropwise to Ag slowly 2sO 4in the aqueous solution, make pH value be controlled at 2.0 left and right, make and mix B liquid;
D), added and mix in B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain dipping electrolyte.
2, the preparation of gel electrolyte
A), take ethylene glycol-methyl ether 5g, ethylene glycol-ether 8g and mix, then add mix and blend under 3-methoxypropionitrile 13.4g normal temperature, and be slowly warming up to 80 DEG C;
B), then take 1-normal-butyl-3-propyl imidazole tetrafluoroborate 3g, under the condition of 80 DEG C, add, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, makes and mixes A liquid;
C), take Ag 2sO 40.6g, is dissolved in 50g Ludox mixed solution, then measures concentrated sulfuric acid 20g, in the process constantly stirring, it is added dropwise to Ag slowly 2sO 4ludox mixed solution in, make and mix B liquid.
D), by after mixing A liquid and being added in the process constantly stirring and mix in B liquid, continue to stir more than 30 minutes, can make gel electrolyte.
Accompanying drawing 5 is the relation line figure of the obtained electrolytical conductivity of the embodiment of the present invention 5 and temperature, the electrolyte that adopts Shanghai thunder magnetic D101 type electric conductivity instrument to test to prepare and the conductivity of gel electrolyte, it is worth as shown in Figure 2, result shows, the electrolyte of the present invention's design demonstrates quite high conductivity, at room temperature the electrolytical conductivity of gained is 30mS/cm, and at the temperature of-60 DEG C, still has the conductivity of 13.2mS/cm, shows good temperature characterisitic.The simulation tantalum capacitor course of work is tested its flash over voltage up to 235V, excellent performance.
In sum.Result of the test of the present invention shows that electrolyte of the present invention has very high conductivity in very wide operating temperature range, and its flash over voltage is up to more than 230V.The raising of flash over voltage, can effectively improve electrolytical oxidation efficiency, reduces the leakage current of capacitor, has ensured the requirement of life of product test high reliability.When low temperature, conductivity is large, and conductive ion mobility is large, shows that electrolyte still can keep lower viscosity in the time of low temperature, thereby can obviously reduce the subzero temperature capacitance loss of product.
In electrolyte system of the present invention, also contain a small amount of VOSO 4as depolarizing agent, on negative electrode, this increase that has just stoped negative electrode electric double layer thickness is reacted in depolarising, improve the capacity of the electric double layer of negative electrode, going utmost point reaction simultaneously can also effectively improve the configuration of surface of ruthenium-oxide electrode, reduce electrode internal resistance, improve the adhesive strength of ruthenium-oxide, finally make the former capacity of capacitor improve, ESR reduces.So high-pressure electrolysis matter of the present invention is suitable for the working electrolyte of hybrid super capacitor tantalum electrolytic capacitor very much.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (10)

1. a hybrid super tantalum capacitor high-pressure electrolysis matter, is characterized in that, its raw material by mass percentage, comprising:
Polarity organic macromolecule material 5%-20%;
Aprotic solvent 5-50%;
Imidazole salts 1-10%;
The sulfate 0.5-2% of magnesium-yttrium-transition metal;
Concentrated sulfuric acid 20%-36%;
Surplus: the deionized water of resistivity >=15M Ω .cm;
Described imidazole salts has following general formula:
Figure FDA0000483806840000011
wherein, R 1c 1-C 4alkylhalide group, R 2c 1-C 4alkyl, Y -bF 4-or PF 6-anion.X is F, Cl, Br or I.
2. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 1, is characterized in that described R 1, R 2preferably n-propyl group or p-butyl are as alkyl, and X is F.
3. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 1 and 2, it is characterized in that, also comprise that the granular size that replaces part deionized water is at the Ludox of 5-15 nanometer, thereby form tantalum capacitor work elevated pressure gel electrolyte, described Ludox and concentrated sulfuric acid mass ratio are 1-2.5:1.
4. hybrid super tantalum capacitor high pressure gel electrolyte according to claim 3, is characterized in that, its raw material by mass percentage, comprising:
Polarity organic macromolecule material 10%-15%;
Aprotic solvent 10%-30%;
Imidazole salts 3%-6%;
The sulfate 0.5-0.8% of magnesium-yttrium-transition metal;
Concentrated sulfuric acid 26%-32%;
The mass ratio of Ludox and the concentrated sulfuric acid is 1-2.5:1;
Surplus: the deionized water of resistivity >=15M Ω .cm.
5. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 3, it is characterized in that, described polarity organic macromolecule material is two or more combination in ethylene glycol, ethylene glycol-methyl ether, ethylene glycol-ether, phenmethylol, glycerol derivatives, polyethylene glycol, vinyl alcohol, polyvinyl alcohol.
6. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 3, it is characterized in that, described aprotic solvent is one or more the mixture in acetonitrile, 3-methoxypropionitrile, DMF, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), ethyl carbonate, 2-methyl ethyl ether, gamma-butyrolacton, ethylene carbonate.
7. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 6, it is characterized in that, described aprotic solvent is N, dinethylformamide and 1-METHYLPYRROLIDONE or N, the mixture of dinethylformamide and dimethyl sulfoxide (DMSO), both mixing quality ratios are 1:0.5-3.0.
8. hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 3, is characterized in that, the sulfate of described magnesium-yttrium-transition metal can be VOSO 4xH 2o, Ag 2sO 4, CuSO 45H 2o, Fe 2(SO 4) 3, VOSO 4in one.
9. the method for preparing hybrid super tantalum capacitor high-pressure electrolysis matter according to claim 1, is characterized in that, comprises the following steps:
(1), accurately measure each component by the mass percent in claim 1;
(2), polarity organic macromolecule material is added in aprotic solvent to mix and blend at normal temperatures in proportion, and be slowly warming up to 80 DEG C;
(3), under the condition of 80 DEG C, add imidazole salts, be warmed up to 110 DEG C, stir and be incubated 1h, then cool to room temperature, forms and mixes A liquid;
(4), get the sulfate of magnesium-yttrium-transition metal, be dissolved in deionized water, then measure the concentrated sulfuric acid, in the process constantly stirring, it is added dropwise to slowly in the sulfate solution of magnesium-yttrium-transition metal and makes PH be controlled at 2.0-5.0, finally form capacitor pellet dipping with mixing B liquid;
(5), added and mix B liquid in the process constantly stirring mixing A liquid, after stirring, can obtain hybrid super tantalum capacitor high-pressure electrolysis matter of the present invention.
10. the method for preparing hybrid super tantalum capacitor high-pressure electrolysis matter of stating according to claim 9, it is characterized in that, described step 4 comprises: the sulfate that takes magnesium-yttrium-transition metal, and be dissolved in the Ludox and deionized water taking in mass ratio, then take the concentrated sulfuric acid, in it being added dropwise to above-mentioned mixed solution slowly in the process constantly stirring, make PH be controlled at 2.0-5.0, the quality of described Ludox and the concentrated sulfuric acid is 1.0-2.5:1, continue to stir more than 10 minutes, finally make capacitor work mixed gel electrolyte B liquid.
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CN104465097A (en) * 2014-11-19 2015-03-25 贵州中航聚电科技有限公司 Method for manufacturing high-temperature-resistant high-reliability electrolytic capacitor
CN105070509A (en) * 2015-07-15 2015-11-18 中国振华（集团）新云电子元器件有限责任公司 Method for preparing middle-and-high-frequency non-solid electrolytic tantalum capacitor
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CN104465097A (en) * 2014-11-19 2015-03-25 贵州中航聚电科技有限公司 Method for manufacturing high-temperature-resistant high-reliability electrolytic capacitor
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