CN1805088A - Preparation method of dielectric film of aluminum electrolytic capacitor - Google Patents
Preparation method of dielectric film of aluminum electrolytic capacitor Download PDFInfo
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- CN1805088A CN1805088A CN 200510110670 CN200510110670A CN1805088A CN 1805088 A CN1805088 A CN 1805088A CN 200510110670 CN200510110670 CN 200510110670 CN 200510110670 A CN200510110670 A CN 200510110670A CN 1805088 A CN1805088 A CN 1805088A
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- anode foils
- electrolytic capacitor
- anode
- dielectric film
- deionized water
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Abstract
The invention relates to a method for preparing the dielectric film of aluminum electrolytic capacitor. First, processing pretreatment on the anode foil; processing anode polarization inside the ion liquid to attain the dielectric film. The invention has better corrosive resistance, and its voltage resistance can reach 90V. The invention is easy and clear, and the aluminum electrolytic capacitor made from said invention has high safety and the voltage resistance more than 40V.
Description
Technical field
The present invention relates to a kind of preparation method of electrolytic capacitor, particularly a kind of preparation method who utilizes ionic liquid to prepare dielectric film of aluminum electrolytic capacitor as electrolyte.
Background technology
Electrolytic capacitor is one of indispensable element in the electric equipment products.Aluminium electrolytic capacitor obtains very big development with its function admirable, characteristics such as cheap, of many uses at recent two decades.It is estimated that the output value of aluminium electrolytic capacitor accounts for 50% of all types capacitor output value.Development along with aluminium electrolytic capacitor production, China also increases rapidly the demand of aluminum foil for electrolytic condenser, in estimating in recent years its demand is approximately risen with 15% average amplification, year demand aluminium foil is more than 30,000 tons, and China has become one of main production and consumption ground of world aluminum aluminium foil for electrolytic capacitor.
Compact is the trend of development of electronic devices in recent years, and the miniaturization of aluminium electrolytic capacitor requires also more and more higher.Therefore, people's expectation is done further to improve to the anode oxidation process of aluminum electric pole foil.The problem that mainly solves is at present, can be under identical formation voltage, obtain the better finer and close dielectric film of anode foils that forms than aqueous electrolyte in the past, thereby it is the same and static capacity is higher or static capacity is the same and aluminium electrolytic capacitor that size is littler to make size.
General aluminium electrolytic capacitor mainly is made up of anode foils, Cathode Foil and electrolyte.Anode foils is generally aluminium foil, carries out etch earlier and handles, to increase the specific area of anode foils.By anodic oxidation, form oxide-film or layer on the surface again, adopting the aqueous solution such as boric acid, citric acid, phosphoric acid or adipic acid when anode polarization is handled is electrolyte, and negative electrode is similarly aluminium foil and obtains by the etch processing.Between above-mentioned anode foils and Cathode Foil, add electrolytic paper as membrane coil around, method of impregnation adds electrolyte, inserts and promptly makes electrolytic capacitor in the metal-back.
For aluminum electrolysis capacitor anode foil, mainly be to utilize the principle of alumilite process to make.This principle long ago just is familiar with by people and in industrial extensive use.Anodic oxidation is carried out in aqueous electrolyte usually.According to using different electrolyte, can form porous type and barrier formula two big class oxide-films.Wherein barrier formula oxide-film electric insulating quality height is applied in the aluminium electrolytic capacitor.The temperature range of electrolyte was 0～125 ℃ when anode polarization was handled, and current density is 5～50mA/cm
2Traditional electrolyte can make sparking voltage reach 300V by reducing electrolytical concentration, but the internal resistance of electrolyte increases, and generate heat in a large number when changing into, thereby energy loss is bigger.
For the electrolyte in the aluminium electrolytic capacitor, adopt water solution system as electrolyte usually, because of fusing point and the boiling point that is subjected to water limits, the serviceability temperature scope is little to be its defective always.Because the oxide-film of aluminium will lean on the moisture reparation, so the moisture content in the electrolyte can't be removed fully.In order to overcome above-mentioned shortcoming, existing technology generally adopts ethylene glycol as primary solvent, adds straight chain organic dicarboxylic acid or their salt composition electrolyte [the male youth of Chinese toon etc., Chinese patents such as adipic acid, azelaic acid, decanedioic acid, application number: CN99121506.0, publication number: CN1250942; Former straight U.S. of grain etc., Japan Patent, application number: 94103155.1, publication number: CN1092823A].But, along with the increase of carboxylic acid molecules amount, in the dissolving of the ethylene glycol equal solvent difficulty that can become, in addition, if the carboxylic acid of HMW is used as main solute, though can improve the proof voltage of electrolyte, but its conductivity obviously descends, and is difficult to improve simultaneously proof voltage and conductivity.Also there are in changing into electrolyte the borate of interpolation or phosphatic solution make active material, and add citric acid or tartaric acid and salting liquid thereof and make complexing agent, but the withstand voltage high-temperature behavior and the not high [Wu Wei of withstand voltage properties of the aluminium electrolytic capacitor that forms, Chinese patent, application number: 03139816.2, publication number: CN1484259A].At present, in lithium ion battery, LiBF
4, LiPF
6When being used for electrolyte of lithium-ion secondary battery, can make the aluminium surface form passivating film, but its proof voltage lower (Liao Hongying, Cheng Baoying, lithium-ion battery electrolytes, new material industry, 09,2003; Yu Bitao, Li Fu Son, the progress of lithium ion battery novel electrolytes lithium salts, battery, 06,2004), be difficult to use as the electrolyte of electrolytic capacitor.In addition, it is flammable that this class electrolyte is met fire, and poor heat stability, has potential safety hazard during actual the use.
Summary of the invention
The purpose of this invention is to provide a kind of employing ionic liquid as electrolyte, anode foils passivation therein forms the dielectric film preparation method of the aluminium electrolytic capacitor of high withstand voltage.
The preparation method of electrolytic capacitor dielectric film of the present invention is as follows:
(1) preliminary treatment of anode foils: the anode foils of electrolytic capacitor is made by the polycrystalline aluminium foil, and the thickness of aluminium foil is 0.1～10mm, and purity 〉=99.9% is pressed 0.6～1molL with anode foils
-1Sodium hydroxide solution, deionized water, 0.5～0.7molL
-1Salpeter solution, the order of deionized water soaked 60～120 seconds successively, and wherein the deionized water conductivity is 0.06 * 10
-4Sm
-1Below, removed moisture content in 10～30 seconds with washed with methanol again, obtain the preliminary treatment anode foils;
(2) anode polarization of anode foils: the preliminary treatment anode foils is put into glove box, assemble airtight electrolytic cell, electrolyte is ionic liquid, reference electrode is the Ag/AgCl electrode, to electrode is the platinum electrode of diameter 2～4mm, the preliminary treatment anode foils soaked .3～6 minute in electrolyte after, with 1～1.5mA/cm
2The anode polarization of current density constant current, take out the anode foils after the polarization, use deionized water rinsing, again with obtaining the electrolytic capacitor dielectric film after the washed with methanol.
Ion liquid chemical structural formula of the present invention is
Wherein R is selected from CH respectively
2CH
3, CH
2CH
2CH
3Or CH
2CH
2CH
2CH
3
1-ethyl-3-methyl-tetrafluoroborate EMI (1-ethyl-3-methyl-imida-zolium)-BF is wherein arranged
4, 1-propyl group-3-methyl-tetrafluoroborate PMI (1-propyn-3-methyl-imidazolium)-BF
4Or 1-butyl-3-methyl-tetrafluoroborate BMI (1-Butyl-3-methyl-imidazolium)-BF
4
Dielectric film of aluminum electrolytic capacitor of the present invention has adopted ionic liquid, because ionic liquid has higher ionic conductivity, thermal stability, characteristic such as chemical stability, electrochemical window broad and fluid temperature scope are wide, thereby the electrolytic capacitor that makes has the good temperature scope of application.Simultaneously, anode aluminium foil carries out the dielectric film that anode polarization obtains in ionic liquid, and corrosion resistance is good, and proof voltage is up to more than the 90V.This preparation method is simple, cleanliness without any pollution, and can obtain proof voltage is the aluminium electrolytic capacitor of the above high security of 40V.
Description of drawings
Fig. 1 anode foils shape schematic diagram
Fig. 2 anode foils is at ionic liquid BMI-BF
4In the electric current-time curve of anode polarization
Fig. 3 anode foils is at ionic liquid BMI-BF
4Surface topography after the middle anode polarization
Fig. 4 anode foils is at ionic liquid EMI-BF
4, BMI-BF
4And PMI-BF
4In cyclic voltammetry curve
Embodiment
The following examples are to further specify of the present invention, but do not limit the scope of the invention.
Ion liquid structural formula and water content thereof that following table adopts for the present invention
The anode foils shape that the embodiment of the invention adopted as shown in Figure 1.Wherein dash area is anode foils effective area (comprising positive and negative two surface areas).
Anode foils (is called for short EMI-BF at ionic liquid 1-ethyl-3-methyl-tetrafluoroborate
4) the middle preparation method who forms dielectric film
(1) preliminary treatment of anode foils: the anode foils of electrolytic capacitor is made by the polycrystalline aluminium foil, the thickness 0.1mm of aluminium foil, and purity is 99.9%, and anode foils is pressed 1molL
-1NaOH, deionized water, 0.5molL
-1Nitric acid, the order of deionized water soaked 60 seconds successively, and wherein the deionized water conductivity is 0.06 * 10
-4Sm
-1Below, in order to remove moisture content, use washed with methanol 10 seconds, obtain the preliminary treatment anode foils;
(2) anode polarization of anode foils: the preliminary treatment anode foils is put into glove box, assemble airtight electrolytic cell, electrolyte is ionic liquid 1-ethyl-3-methyl-tetrafluoroborate (EMI-BF
4), its structural formula is as above shown, and water content is 28ppm, and reference electrode is the Ag/AgCl electrode, is the Pt electrode to electrode.The preliminary treatment anode foils is used 1mAcm soak 5min in electrolyte after
-2The anode polarization of current density constant current, take out the anode foils after the polarization, use deionized water rinsing earlier, again with obtaining the electrolytic capacitor dielectric film after the washed with methanol.
Fig. 2 is the voltage graph of relation over time of the electrolytic capacitor dielectric film that obtains of embodiment 1, as seen from the figure current potential in time straight line rise, rate of voltage rise dV/dt is 1.078VS
-1, arriving puncture voltage 94.58V after 88 seconds, reference electrode is the Ag/AgCl electrode, resulting dielectric film has very high withstand voltage properties.Fig. 3 is the surface topography sem photograph of the electrolytic capacitor dielectric film that obtains of embodiment 1.Can see that from figure the surface of aluminium foil is very smooth, not have the obvious corrosion phenomenon to take place, the electrolytic capacitor dielectric film of gained also has good corrosion resistance simultaneously.
Anode foils is at ionic liquid 1-propyl group-3-methyl-tetrafluoroborate (PMI-BF
4) the middle preparation method who forms dielectric film
(1) preliminary treatment of anode foils: the anode foils of electrolytic capacitor is made by the polycrystalline aluminium foil, the thickness 0.1mm of aluminium foil, and purity is 99.9%, and anode foils is pressed 1molL
-1NaOH, deionized water, 0.5molL
-1Nitric acid, the order of deionized water soaked 60 seconds successively, and wherein the deionized water conductivity is 0.06 * 10
-4Sm
-1Below, removed moisture content in 10 seconds with washed with methanol again, obtain the preliminary treatment anode foils;
(2) anode polarization of anode foils: the preliminary treatment anode foils is put into glove box, assemble airtight electrolytic cell, electrolyte is ionic liquid 1-propyl group-3-methyl-tetrafluoroborate (PMI-BF
4), its structural formula and water content are as above shown, and reference electrode is the Ag/AgCl electrode, is the Pt electrode to electrode.The preliminary treatment anode foils is used 1mAcm soak 5min in electrolyte after
-2The anode polarization of current density constant current, take out the anode foils after the polarization, use deionized water rinsing earlier, again with obtaining the electrolytic capacitor dielectric film after the washed with methanol.
Embodiment 3
Anode foils is at ionic liquid 1-butyl-3-methyl-tetrafluoroborate (BMI-BF
4) the middle preparation method who forms dielectric film
(1) preliminary treatment of anode foils: the anode foils of electrolytic capacitor is made by the polycrystalline aluminium foil, the thickness 0.1mm of aluminium foil, and purity is 99.9%, and anode foils is pressed 1molL
-1NaOH, deionized water, 0.5molL
-1Nitric acid, the order of deionized water soaked 60 seconds successively, and wherein the deionized water conductivity is 0.06 * 10
-4Sm
-1Below, removed moisture content in 10 seconds with washed with methanol again, obtain the preliminary treatment anode foils;
(2) anode polarization of anode foils: the preliminary treatment anode foils is put into glove box, assemble airtight electrolytic cell, electrolyte is ionic liquid 1-butyl-3-methyl-tetrafluoroborate (EMI-BF
4), its structural formula and water content are as above shown, and reference electrode is the Ag/AgCl electrode, is the Pt electrode to electrode.The preliminary treatment anode foils is used 1mAcm soak 5min in electrolyte after
-2The anode polarization of current density constant current, take out the anode foils after the polarization, use deionized water rinsing earlier, again with obtaining the electrolytic capacitor dielectric film after the washed with methanol.
Fig. 4 is the cyclic voltammetry curve of preliminary treatment anode foils anode polarization among embodiment 2 and the embodiment 3, and as can be seen from the figure, the preliminary treatment anode foils is at ionic liquid EMI-BF
4, BMI-BF
4And PMI-BF
4In the anode polarization electric current reduce gradually along with the increase of cycle-index, passivation takes place in anode foils surface, thereby resulting dielectric film has decay resistance preferably in above-mentioned three kinds of ionic liquids.Ionic liquid EMI-BF
4, BMI-BF
4And PMI-BF
4Its structural formula and water content are as above shown, wherein the ionic liquid EMI-BF of Cai Yonging
4Water content be 870ppm.
Claims (2)
1. the preparation method of a dielectric film of aluminum electrolytic capacitor is characterized in that the preparation method is as follows:
(1) preliminary treatment of anode foils: the anode foils of electrolytic capacitor is made by the polycrystalline aluminium foil, and the thickness of aluminium foil is 0.1～10mm, and purity 〉=99.9% is pressed 0.6～1molL with anode foils
-1Sodium hydroxide solution, deionized water, 0.5～0.7molL
-1Salpeter solution, the order of deionized water soaked 60～120 seconds successively, and wherein the deionized water conductivity is 0.06 * 10
-4Sm
-1Below, removed moisture content in 10～30 seconds with washed with methanol again, obtain the preliminary treatment anode foils;
(2) anode polarization of anode foils: the preliminary treatment anode foils is put into glove box, assemble airtight electrolytic cell, electrolyte is ionic liquid, reference electrode is the Ag/AgCl electrode, to electrode is the platinum electrode of diameter 2～4mm, the preliminary treatment anode foils is soaked 3～6 minutes in electrolyte after, with 1～1.5mA/cm
2The anode polarization of current density constant current, take out the anode foils after the polarization, use deionized water rinsing, again with obtaining the electrolytic capacitor dielectric film after the washed with methanol.
2. the preparation method of a kind of dielectric film of aluminum electrolytic capacitor according to claim 1 is characterized in that ionic liquid is selected from 1-ethyl-3-methyl-tetrafluoroborate, 1-propyl group-3-methyl-tetrafluoroborate or 1-butyl-3-methyl-tetrafluoroborate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532322A (en) * | 2014-12-19 | 2015-04-22 | 浙江工业大学 | Anodic oxidation method for titanium-aluminum alloy in ionic liquid |
| CN104532323A (en) * | 2014-12-19 | 2015-04-22 | 浙江工业大学 | Method for oxidizing anode of titanium-aluminum alloy in ion liquid-added ethylene glycol solution |
| CN106637336B (en) * | 2016-10-21 | 2018-11-30 | 重庆南涪铝业有限公司 | A kind of method for oxidation of aluminum profile |
| CN110592637A (en) * | 2019-09-26 | 2019-12-20 | 东莞东阳光科研发有限公司 | Preparation method and application of formed foil |
| CN110760913A (en) * | 2019-09-30 | 2020-02-07 | 东莞东阳光科研发有限公司 | Formation liquid, low-pressure formation foil and preparation method thereof |
-
2005
- 2005-11-24 CN CN 200510110670 patent/CN1805088A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532322A (en) * | 2014-12-19 | 2015-04-22 | 浙江工业大学 | Anodic oxidation method for titanium-aluminum alloy in ionic liquid |
| CN104532323A (en) * | 2014-12-19 | 2015-04-22 | 浙江工业大学 | Method for oxidizing anode of titanium-aluminum alloy in ion liquid-added ethylene glycol solution |
| CN106637336B (en) * | 2016-10-21 | 2018-11-30 | 重庆南涪铝业有限公司 | A kind of method for oxidation of aluminum profile |
| CN110592637A (en) * | 2019-09-26 | 2019-12-20 | 东莞东阳光科研发有限公司 | Preparation method and application of formed foil |
| CN110592637B (en) * | 2019-09-26 | 2020-08-07 | 东莞东阳光科研发有限公司 | Preparation method and application of formed foil |
| CN110760913A (en) * | 2019-09-30 | 2020-02-07 | 东莞东阳光科研发有限公司 | Formation liquid, low-pressure formation foil and preparation method thereof |
| CN110760913B (en) * | 2019-09-30 | 2021-04-20 | 东莞东阳光科研发有限公司 | Formation liquid, low-pressure formation foil and preparation method thereof |
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