CN101894675B - Method for preparing titanium-based super capacitor membrane electrode - Google Patents
Method for preparing titanium-based super capacitor membrane electrode Download PDFInfo
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- CN101894675B CN101894675B CN201010230310A CN201010230310A CN101894675B CN 101894675 B CN101894675 B CN 101894675B CN 201010230310 A CN201010230310 A CN 201010230310A CN 201010230310 A CN201010230310 A CN 201010230310A CN 101894675 B CN101894675 B CN 101894675B
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- thermal decomposition
- intermediate layer
- titanium
- coating
- titanium plate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing a titanium-based super capacitor membrane electrode, which is characterized by comprising the following steps: 1) spraying sands; 2) removing oil; 3) carrying out acid-washing and etching; 4) adding an interlayer; and 5) electrochemically depositing an active MnO2 coating. The method has the advantages that: the interlayer of the prepared electrode is firmly combined with the matrix of the electrode, and the MnO2 coating is provided with a plurality of micropores which facilitate exchanging active substances, and is not easy to fall off; the electrode has good cyclical stability, and is high in specific capacity, long in service life and good in adhesion of the coating; and the electrolyte is neutral Na2SO4 solution, which is convenient to promote and apply in industry.
Description
Technical field
The present invention relates to a kind of manufacture method of electrode, relate in particular to a kind of manufacture method of titanium-based super capacitor membrane electrode.
Background technology
Current, the development trend of electronic applications is that the volume of mobile electronic device is significantly reducing, but energy consumption is but increasing.Traditional battery more and more is difficult to deal with growing energy consumption requirement.The charging rate of battery is slow, because it is with the chemical mode stored energy.Comparatively speaking, using general capacitor at electronic applications can be at momentary charge, and the electric weight that still holds but seldom.In recent years; Ultracapacitor since its superelevation charge-discharge performance and energy-storage property (being high-energy-density and power density) being widely used in the stand-by power supply or the servicing unit of electronic equipment and energy composite energy automobile, to satisfy the needs that needs in reality moments provides high-power big electric current.And the materials used nontoxic pollution-free of ultracapacitor, environmentally friendly.Above plurality of advantages has received the concern and the research of the researcher of countries in the world, and its wide application prospect need not be queried.
The electrode material that is used for ultracapacitor at present mainly contains: raw material of wood-charcoal material, transition metal oxide and conducting polymer.Some oxide electrode materials: RuO below wherein metal oxide has successively occurred
2, MnO
2, NiO, CoO
2Deng.As everyone knows, RuO
2Very higher than electric capacity, be desirable super capacitor material, but it cost an arm and a leg, contaminated environment and be not easy to obtain.And MnO
2Production cost low, the source is wide, stable electrochemical property, toxicity are little, environmentally friendly, becomes the research focus of electrode material for super capacitor in recent years.Yet preparation MnO
2Method have a lot, like thermal decomposition method, sol-gal process, electrolysis, electrodeposition process etc.Wherein electrodeposition process is that development in recent years prepares MnO comparatively rapidly
2The method of membrane electrode.The sedimentary deposit of electrodeposition process gained has unique high density and low voidage; Be prone on the technology through changing chemical composition, crystalline structure and the grain size that conditions such as electrical quantity, bath composition are come control material; Existing plating and electroforming simultaneously provided basis widely for it already, turned to the required technology barrier that overcomes of existing plating and electroforming industry little from the laboratory this technology, and cost is low.
Anodic electrodeposition MnO on carbon matrixs such as graphite
2Then might occur owing to the not enough variety of problems that is produced of matrix strength, metal Ti then has higher mechanical strength and extension performance.Because the superiority of Ti as matrix also verified in its extensive use on chlorine industry in recent years.Simultaneously because at electro-deposition active material MnO
2The time anode polarization after, the TiO that generates poorly conductive at the interface easily of matrix and coating
2, make coating come off easily, and influence electrode life.For improving coating and matrix bond is insecure, shortcoming such as anode life is short is the adhesion that promotes coating and Ti matrix, the method toward interpolation intermediate layer between matrix and the coating that the researcher adopts.Simple MnO
2Be that its conductivity of semiconductor is bad, its loose structure also makes shorten electrode life simultaneously.Other material of doping is to change electro-deposition MnO in electrodeposition process
2Effective ways.Mo, being mixed with of Fe is beneficial to raising MnO
2Conductivity, make structure tightr, effectively improve the ratio electric capacity of electrode.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of titanium-based super capacitor membrane electrode, this method uses pure metallic titanium as matrix, on matrix, adopts thermal decomposition method to apply IrO earlier
2, IrO
2+ MnO
2, IrO
2-Ta
2O
5, IrO
2-Ta
2O
5-SnO
2Or IrO
2-Ta
2O
5-SiO
2The intermediate layer obtains doping Mo, the MnO of Fe through being electrochemically-deposited in again on the titanium matrix
2Thereby coating obtains finished product.
The present invention realizes like this, it is characterized in that method step is:
1) sandblast: the pure titanium plate that will process carries out blasting treatment strengthens surface roughness, guarantees that coating and matrix bond are more firm;
2) oil removing: the pure titanium plate that will process is put into beaker, adds degreasing fluid ultrasonic cleaning 20～30min, and heating and temperature control is at 30 ℃～65 ℃; Wash respectively with running water and deionized water again after cleaning completion; Dry up, the prescription of degreasing fluid is again: NaOH 30～80g/L, Na
2CO
320～40g/L;
3) pickling etching: the titanium plate after the alkali cleaning put into 15%～50% sulfuric acid and soak, using concentration then is 98% the further etching of the concentrated sulfuric acid, and etching temperature 70-90 ℃ keeps 1.5h, after solution is darkviolet, takes out sample wash and dries;
4) add the intermediate layer: thermal decomposition method coating sintering IrO on treated titanium plate is adopted in (1)
2Intermediate layer, compound concentration are 0.15～0.30moldm
-3The chloro-iridic acid isobutanol solution is for applying liquid; Be coated on the titanium plate of handling well applying liquid, place 70～100 ℃ of oven dry 10～30min in the baking oven again, then in Muffle furnace 300～600 ℃ carry out thermal decomposition 10min; Take out air cooling; Triplicate, last 300～600 ℃ of thermal decomposition times are 40～90min, obtain uniform titanium base IrO
2The intermediate layer;
5) the active MnO of electrochemical deposition
2Coating: at first anhydrous MnSO
4With H
2SO
4Be after being mixed with the 500ml aqueous solution at 2: 5 solution to be heated to 80～100 ℃ in molar ratio, packaged sample be placed in one soak about 2～5min again that can lead to direct current afterwards, current density is 2～60mA/cm
2, taking out behind electro-deposition 1～20min to clean and dry, electrode is made and is finished.
Described interpolation intermediate layer can also be: adopt thermal decomposition method coating sintering SnO on treated titanium plate
2+ SbOx intermediate layer, the solute of masking liquid are SnCl
4And SbCl
3, solvent is the mixed solution of hydrochloric acid and n-butanol, wherein Sn, Sb atomic ratio are 2～9: 3, total ion concentration 0.2～0.8moldm
-3, hydrochloric acid and n-butanol volume ratio are 1～5: 1, and masking liquid is brushed equably on the titanium plate after the processing; After 70～100 ℃ of oven dry at 450～700 ℃ of following thermal decomposition 10min; Repetitive coatings 3 times at last at 500 ℃ of following thermal decomposition 60min, obtains uniform Ti-base Sn-Sb oxide intermediate layer.
Described interpolation intermediate layer can also be: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5The intermediate layer, the ethanol isopropyl alcohol masking liquid of preparation iridium tantalum, wherein iridium tantalum atom ratio is 7: 3, total ion concentration is 0.2moldm
-3, ethanol and isopropyl alcohol volume ratio are 1: 1, will apply liquid and brush equably on the titanium plate; 100 ℃ of oven dry 10min, 450 ℃ of following thermal decomposition 15min repeat above-mentioned brushing and thermal decomposition process 5 times; Last 450 ℃ of sintering 60min obtain uniform titanium base iridium tantalum pentoxide intermediate layer.
Described interpolation intermediate layer can also be: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2+ MnO
2The intermediate layer applies liquid and is the HIrC of IrMn atomic ratio 1: 9～9: 1
14And Mn (NO
3)
2The aqueous solution, total concentration of metal ions is 0.15～0.4mol/L, and coating liquid is brushed advancing on the pretreated titanium matrix equably; Dry 5～20min down for 70～100 ℃, 350～550 ℃ of following thermal decomposition 8～25min repeat above brushing and thermal decomposition steps; Apply 1～3 layer; At 350～550 ℃ of sintering 0.5～3h, promptly obtain titanium-based manganese-iridium composite oxide coating anode for the last time, the loading of coating composite oxides is 0.5～3g/m
2
Described interpolation intermediate layer can also be: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5-SnO
2The intermediate layer: preparation iridium tantalum tin atom ratio is 3～7: 4～8: 0.5～1 TaCl
5, H
2IrCl
6, SnCl
22H
2O hydrochloric acid aqueous isopropanol is brushed coating liquid on the titanium plate equably, 100 ℃ of oven dry 10min; 450 ℃ of following thermal decomposition 15min; Repeat above-mentioned brushing and thermal decomposition process 1～5 time, last 350～550 ℃ of thermal decomposition 0.5～3h obtain uniform titanium base iridium tantalum stannum oxide intermediate layer.
Advantage of the present invention is: electrode intermediate layer of processing and matrix bond are firm, MnO
2The coating microvoid is many, is convenient to the active material exchange, difficult drop-off; Showing good cyclical stability, the electrode specific capacity is high, the life-span is long, binding force of cladding material good; Electrolyte is neutral Na
2SO
4Solution is convenient in industry, apply.
Description of drawings
Fig. 1 is four kinds of MnO in intermediate layer with Ir-Mn, Ir-Ta, Ir-Ta-Si, Ir-Ta-Sn for the present invention
2The cyclic voltammogram of electrode in the potential window at 0～1.0V under the sweep speed of 20mv/s.
Fig. 2 is four kinds of MnO in intermediate layer with Ir-Mn, Ir-Ta, Ir-Ta-Si, Ir-Ta-Sn for the present invention
2Electrode is with the charging and discharging curve in the potential window of charging and discharging currents at 0～1.0V of 5mA.
Embodiment
The present invention is achieved in that like Fig. 1, shown in Figure 2,
Embodiment 1:
The pure titanium plate that at first will process carries out blasting treatment, again with the titanium plate at NaOH80g/L, NaCO
3Carry out alkali cleaning in the mixed liquor of 40g/L, further oil removing.To use the concentrated sulfuric acid under (80 ℃ of 1.5h), to carry out etching afterwards.Adopt thermal decomposition method coating sintering IrO on treated titanium plate again
2+ MnO
2The intermediate layer.Applying liquid is 3: 7 HIrC of IrMn atomic ratio
14And Mn (NO
3)
2The aqueous solution, total concentration of metal ions is 0.2mol/L.Coating liquid is brushed advancing on the pretreated titanium matrix equably.Dry 15min down for 100 ℃, 450 ℃ of following thermal decomposition 10min repeat above brushing and thermal decomposition steps; Apply 10 layers; At 350～550 ℃ of sintering 1.5h, promptly obtain titanium base iridium manganese composite oxide coated anode for the last time, the loading of coating composite oxides is 10g/m
2Final step is exactly the active MnO of electrochemical deposition
2Coating.Its concrete steps are: at first anhydrous Na
2SO
4With H
2SO
4Be after being mixed with the 500ml aqueous solution at 2: 5 solution to be heated to 98 ℃ in molar ratio, packaged sample be placed in one soak about 3min again.(current density is 20mA/cm can to lead to direct current afterwards
2).Take out behind the electro-deposition 10min to clean and dry, electrode is made and is finished.
Embodiment 2:
Press embodiment 1 illustrated processing titanium plate, adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5The intermediate layer: the ethanol isopropyl alcohol masking liquid of preparation iridium tantalum, wherein iridium tantalum atom ratio is 7: 6, total ion concentration is 0.2moldm
-3, ethanol and isopropyl alcohol volume ratio are 1: 1.To apply liquid and brush equably on the titanium plate, 100 ℃ of oven dry 10min, 450 ℃ of following thermal decomposition 15min repeat above-mentioned brushing and thermal decomposition process 5 times, and last 450 ℃ of sintering 60min obtain uniform titanium base iridium tantalum pentoxide intermediate layer.Final step such as embodiment 1 are said, the active MnO of electrochemical deposition
2Coating.
Embodiment 3:
Press embodiment 1 illustrated processing titanium plate, adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5-SnO
2The intermediate layer: preparation iridium tantalum tin atom ratio is 7: 6: 1 TaCl
5, H
2IrCl
6, SnCl
22H
2O hydrochloric acid aqueous isopropanol is brushed coating liquid on the titanium plate equably, 100 ℃ of oven dry 10min; 450 ℃ of following thermal decomposition 15min; Repeat above-mentioned brushing and thermal decomposition process 5 times, last 450 ℃ of sintering 60min obtain uniform titanium base iridium tantalum stannum oxide intermediate layer.Final step such as embodiment 1 are said, the active MnO of electrochemical deposition
2Coating.
Embodiment 4:
Press embodiment 1 illustrated processing titanium plate, the IrO of preparation
2-Ta
2O
5Solution is identical with instance 1.Add 0.227ml concentration therein and be 25.5% acidic silicasol solution, make SiO
2Percentage by weight therein is 7%, processes IrO
2-Ta
2O
5-SiO
2Coating solution.With fur suede pen masking liquid is brushed on titanium plate two sides, put and under 90 ℃, dry 5min in the baking oven, 350 ℃ of following sintering 5min in Muffle furnace take out back air cooling to room temperature then, repeat above step to applying 3 layers.Then, in baking oven, be still in 90 ℃ of following oven dry 5min, but in Muffle furnace 350 ℃ of following sintering 10min, so repeatedly to applying 3 layers.Final step such as embodiment 1 are said, the active MnO of electrochemical deposition
2Coating.
It is more as shown in the table than electric capacity to record among the embodiment 4 kinds of electrodes through charge-discharge test
| The intermediate layer composition | Ir-Mn | Ir-Ta | Ir-Ta-Si | Ir-Ta-Sn |
Claims (5)
1. the manufacture method of a titanium-based super capacitor membrane electrode is characterized in that method step is:
1) sandblast: the pure titanium plate that will process carries out blasting treatment strengthens surface roughness, guarantees that coating and matrix bond are more firm;
2) oil removing: the pure titanium plate that will process is put into beaker, adds degreasing fluid ultrasonic cleaning 20～30min, and heating and temperature control is at 30 ℃～65 ℃; Wash respectively with running water and deionized water again after cleaning completion; Dry up, the prescription of degreasing fluid is again: NaOH 30～80g/L, Na
2CO
320～40g/L;
3) pickling etching: the titanium plate after the alkali cleaning put into 15%～50% sulfuric acid and soak, using concentration then is 98% the further etching of the concentrated sulfuric acid, and etching temperature 70-90 ℃ keeps 1.5h, after solution is darkviolet, takes out sample wash and dries;
4) add the intermediate layer: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2Intermediate layer, compound concentration are 0.15～0.30moldm
-3The chloro-iridic acid isobutanol solution is for applying liquid; Be coated on the titanium plate of handling well applying liquid, place 70～100 ℃ of oven dry 10～30min in the baking oven again, then in Muffle furnace 300～600 ℃ carry out thermal decomposition 10min; Take out air cooling; Triplicate, last 300～600 ℃ of thermal decomposition times are 40～90min, obtain uniform titanium base IrO
2The intermediate layer;
5) the active MnO of electrochemical deposition
2Coating: at first anhydrous MnSO
4With H
2SO
4Be after being mixed with the 500ml aqueous solution at 2: 5 solution to be heated to 80～100 ℃ in molar ratio, packaged sample be placed in one soak 2～5min again, the logical afterwards direct current of going up, current density is 2～60mA/cm
2, taking out behind electro-deposition 1～20min to clean and dry, electrode is made and is finished.
2. the manufacture method of a kind of titanium-based super capacitor membrane electrode according to claim 1 is characterized in that the making in described interpolation intermediate layer can replace with following steps: adopt thermal decomposition method coating sintering SnO on treated titanium plate
2+ SbOx intermediate layer, the solute of masking liquid are SnCl
4And SbCl
3, solvent is the mixed solution of hydrochloric acid and n-butanol, wherein Sn, Sb atomic ratio are 2～9: 3, total ion concentration 0.2～0.8moldm
-3, hydrochloric acid and n-butanol volume ratio are 1～5: 1, and masking liquid is brushed equably on the titanium plate after the processing; After 70～100 ℃ of oven dry at 450～700 ℃ of following thermal decomposition 10min; Repetitive coatings 3 times at last at 500 ℃ of following thermal decomposition 60min, obtains uniform Ti-base Sn-Sb oxide intermediate layer.
3. the manufacture method of a kind of titanium-based super capacitor membrane electrode according to claim 1 is characterized in that the making in described interpolation intermediate layer can replace with following steps: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5The intermediate layer, the ethanol isopropyl alcohol masking liquid of preparation iridium tantalum, wherein iridium tantalum atom ratio is 7: 3, total ion concentration is 0.2moldm
-3, ethanol and isopropyl alcohol volume ratio are 1: 1, will apply liquid and brush equably on the titanium plate; 100 ℃ of oven dry 10min, 450 ℃ of following thermal decomposition 15min repeat above-mentioned brushing and thermal decomposition process 5 times; Last 450 ℃ of sintering 60min obtain uniform titanium base iridium tantalum pentoxide intermediate layer.
4. the manufacture method of a kind of titanium-based super capacitor membrane electrode according to claim 1 is characterized in that the making in described interpolation intermediate layer can replace with following steps: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2+ MnO
2The intermediate layer applies liquid and is the HIrC of IrMn atomic ratio 1: 9～9: 1
14And Mn (NO
3)
2The aqueous solution, total concentration of metal ions is 0.15～0.4mol/L, and coating liquid is brushed advancing on the pretreated titanium matrix equably; Dry 5～20min down for 70～100 ℃, 350～550 ℃ of following thermal decomposition 8～25min repeat above brushing and thermal decomposition steps; Apply 1～3 layer; At 350～550 ℃ of sintering 0.5～3h, promptly obtain titanium-based manganese-iridium composite oxide coating anode for the last time, the loading of coating composite oxides is 0.5～3g/m
2
5. the manufacture method of a kind of titanium-based super capacitor membrane electrode according to claim 1 is characterized in that the making in described interpolation intermediate layer can replace with following steps: adopt thermal decomposition method coating sintering IrO on treated titanium plate
2-Ta
2O
5-SnO
2The intermediate layer: preparation iridium tantalum tin atom ratio is 3～7: 4～8: 0.5～1 TaCl
5, H
2IrCl
6, SnCl
22H
2O hydrochloric acid aqueous isopropanol is brushed coating liquid on the titanium plate equably, 100 ℃ of oven dry 10min; 450 ℃ of following thermal decomposition 15min; Repeat above-mentioned brushing and thermal decomposition process 1～5 time, last 350～550 ℃ of thermal decomposition 0.5～3h obtain uniform titanium base iridium tantalum stannum oxide intermediate layer.
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|---|---|---|---|
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| CN101894675B true CN101894675B (en) | 2012-10-03 |
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| KR20140037022A (en) * | 2010-12-21 | 2014-03-26 | 고쿠리츠다이가쿠호진 도호쿠다이가쿠 | Nanoporous ceramic composite metal |
| CN102275995B (en) * | 2011-06-09 | 2013-07-03 | 南昌航空大学 | Method for preparing high-stability nano manganese dioxide powder for water system super capacitor |
| CN102350228A (en) * | 2011-07-12 | 2012-02-15 | 上海中科高等研究院 | Nano loaded titanium-based electric catalytic film and preparation method thereof |
| CN105836854A (en) * | 2016-05-23 | 2016-08-10 | 张家富 | Water treatment device with wide application, water treatment electrode and manufacturing method for water treatment electrode |
| CN107699912A (en) * | 2017-09-01 | 2018-02-16 | 广东省稀有金属研究所 | A kind of coating solution of coated electrode and its preparation method of coated electrode |
| CN109518168B (en) * | 2018-12-14 | 2020-11-03 | 广西大学 | Preparation method of active titanium-based electrode plate with high-stability coating |
| CN111088493A (en) * | 2019-12-26 | 2020-05-01 | 西安泰金工业电化学技术有限公司 | Preparation method of titanium anode with titanium-based coating |
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| CN1179068C (en) * | 2000-08-22 | 2004-12-08 | 黄永昌 | Titanium base iridium dioxide electrode with tin-antiomony intermediate layer |
| CN1995464A (en) * | 2006-11-28 | 2007-07-11 | 北京科技大学 | Nanocrystalline iridium series oxide coating electrode preparation method |
| CN101225526A (en) * | 2007-10-29 | 2008-07-23 | 北京科技大学 | Nanocrystalline manganese bioxide coated anode and method for making same |
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