CN102426927A - Method for improving bonding strength of ruthenium oxide coating and tantalum substrate - Google Patents
Method for improving bonding strength of ruthenium oxide coating and tantalum substrate Download PDFInfo
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- CN102426927A CN102426927A CN2011104101614A CN201110410161A CN102426927A CN 102426927 A CN102426927 A CN 102426927A CN 2011104101614 A CN2011104101614 A CN 2011104101614A CN 201110410161 A CN201110410161 A CN 201110410161A CN 102426927 A CN102426927 A CN 102426927A
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Abstract
The invention discloses a method for improving the bonding strength of a ruthenium oxide coating and a tantalum substrate, and belongs to a preparation method for a capacitor electrode. According to the method, valve metal powder is added into ruthenium-compound-containing slurry which is coated on the surface of the tantalum substrate, and then the dried tantalum substrate is subjected to thermal decomposition in a water-vapor environment to form an amorphous ruthenium dioxide hydrate cathode, so the dehydration and the crystallization of the ruthenium dioxide can be avoided; therefore, the bonding strength of ruthenium oxide and the tantalum substrate is improved. The capacitor electrode prepared by the method has the advantages of high high-temperature resistance, high vibration resistance and the like; and by the method, the reliability of a capacitor is improved.
Description
Technical field: the present invention relates to a kind of preparation method of electrode for capacitors, relate in particular to a kind of method that on electrode for capacitors, prepares ruthenium oxide coatings.
Background technology: well-known, ultracapacitor is a kind of energy storage capacitor that has high-energy-density and merit power density concurrently; And the specific capacity of electrode material is one of key factor that influences the ultracapacitor performance.At present, the material that is used to make electrode of super capacitor mainly contains material with carbon element, metal oxide and conducting polymer three major types; In various electrode materials; Amorphous hydrated ruthenium-oxide (being called ruthenium-oxide usually for short) not only have the high theoretical specific capacity (＞1000F/g) with higher conductivity (＞100S/cm); But also have the electrochemical window of broad and the advantages such as cyclical stability of excellence, be a kind of different electrode material for super capacitor of best performance that is acknowledged as.Usually, the method for preparing ruthenium oxide electrode material mainly is divided into two kinds, and a kind of is to adopt chemical method to prepare the ruthenium-oxide powder earlier, and then it is coated in electrode surface; Another kind is to adopt electrochemical process directly at collector electrode surface preparation ruthenium-oxide.Though the former easily large-scale production need be added binding agent in ruthenium-oxide and conductive agent is processed slurry; There are defectives such as the big and reliability of internal resistance is low.Though the ruthenium-oxide porous coating of latter's preparation has advantages such as internal resistance is low, specific capacity is higher, film forming facility, has defectives such as complex process, ruthenium oxide coatings and tantalum high base strength are low.
The applicant is that " CN102169759A ", name are called in the patent of invention document of " a kind of oxidation the preparation method of electrode material " and disclose a kind of method for preparing the ultracapacitor ruthenium oxide electrode material at publication number; Its practice is the tantalum matrix that contains the ruthenium compound slurry with being coated with; Put into steam ambient and carry out thermal decomposition, thereby directly prepare ruthenium oxide coatings at the tantalum matrix surface.Though this method has overcome the deficiency of traditional handicraft; But because the lattice of ruthenium-oxide and metal tantalum does not match; The adhesion of ruthenium-oxide and tantalum matrix a little less than, when in the higher environment of temperature, or situation about being vibrated under, ruthenium oxide coatings separates with the tantalum matrix easily and comes off.
Summary of the invention: to the above-mentioned defective that exists in the prior art, the present invention aims to provide a kind of method that improves ruthenium oxide coatings and tantalum substrate combinating strength.
To achieve these goals, the technical scheme that the present invention adopts comprises the slurry that contains ruthenium compound is coated on tantalum matrix surface, oven dry, and this tantalum matrix is put into 200～350 ℃ heating furnace, feeds steam, the constant temperature 1～10 hour of 5～90kPa; It is characterized in that said slurry is formulated by following method:
1) will contain ruthenium compound and valve metal powder and mix by 1: 0.5～1.5 weight ratio, mixed powder; The said ruthenium compound that contains is ruthenium halide or hydration ruthenium halide, and said ruthenium halide is ruthenium trichloride or iodate ruthenium; Said valve metal powder is average grain diameter >=Ta powder used or niobium powder of 150 purpose electrolytic capacitors;
2) with above-mentioned mixed powder and solvent by 1: 0.5～5 weight ratio hybrid modulation form slurry; Said solvent is mixture or one of the mixture of water and ethylene glycol or mixture of water and acetone of water or ethanol or ethylene glycol or acetone or water and ethanol.
Optimal technical scheme of the present invention is: furnace temp is that 280 ℃, the pressure of steam are that 30～70kPa, thermal decomposition time are 2～8 hours; The weight ratio that contains ruthenium compound and valve metal powder in the step 1) is 1: 0.8～1.2, step 2) in the weight ratio of mixed powder and solvent be 1: 1～4.
The present invention's optimal technical scheme further is: the pressure of steam is that 40～50kPa, thermal decomposition time are 4～6 hours; The weight ratio that contains ruthenium compound and valve metal powder in the step 1) is 1: 1, step 2) in the weight ratio of mixed powder and solvent be 1: 2～3.
Best-of-breed technology scheme of the present invention is: the pressure of steam is that 45kPa, thermal decomposition time are 5 hours, step 2) in the weight ratio of mixed powder and solvent be 1: 2.5.
Compare with prior art; The present invention is owing to adopted technique scheme; On the basis of original technical scheme, the composition that contains the ruthenium compound slurry has been done improvement; Tantalum powder or the niobium powder identical have been added with tantalum matrix lattice; Therefore can increase substantially the adhesion of ruthenium oxide coatings and tantalum matrix, overcome ruthenium oxide coatings effectively and under hot environment or in vibration environment, separated the defective that comes off with the tantalum matrix easily, not only improve the reliability of capacitor but also widened the operating temperature range of capacitor.Technology of the present invention is simple, is prone to large-scale production.
Embodiment: the embodiment below in conjunction with concrete is described further the present invention:
Embodiment 1
1) ruthenium trichloride 1 gram and Ta powder used 0.5 gram of average grain diameter >=150 purpose electrolytic capacitors are mixed, get mixed powder;
2) 1.5 above-mentioned mixed powders of gram and 0.75 gram water are mixed, be modulated into slurry;
3) with above-mentioned slurry evenly be coated on said tantalum plate surface (slurry not necessarily all has been coated with), the baking oven of putting into 50～100 ℃ dries;
4) the tantalum plate after will drying is put into 200 ℃ heating furnace, feeds steam, the constant temperature 10 hours of 90kPa, makes the capacitor cathode that there is ruthenium oxide coatings on the surface.
Embodiment 2
Each step is with embodiment 1; Wherein, Mixed powder in the step 1) is mixed by 1 gram iodate ruthenium and 1.5 gram average grain diameter >=150 purpose electrolytic capacitor level niobium powder; Step 2) slurry in by the present embodiment step 1) make 2.5 the gram mixed powders with 12.5 the gram ethanol formulated, the heating-up temperature in the step 4) be 350 ℃, the feeding steam pressure be that 5kPa, constant temperature time are 1 hour.
Embodiment 3
Each step is with embodiment 1; Wherein, Rapid 1) mixed powder in restrains average grain diameter >=150 the purpose electrolytic capacitor is Ta powder used by 1 gram hydrate ruthenium trichloride and 0.8 and mixes; Step 2) slurry in by the present embodiment step 1) make 1.8 the gram mixed powders with 1.8 the gram ethylene glycol formulated, the heating-up temperature in the step 4) be 280 ℃, the feeding steam pressure be that 30kPa, constant temperature time are 2 hours.
Embodiment 4
Each step is with embodiment 1; Wherein, Mixed powder in the step 1) is mixed by 1 gram hydration iodate ruthenium and 1.2 gram average grain diameter >=150 purpose electrolytic capacitor level niobium powder; Step 2) slurry in by the present embodiment step 1) make 2.2 the gram mixed powders with 8.8 the gram acetone mixed liquor formulated, in the step 4) heating-up temperature be 300 ℃, the feeding steam pressure be that 70kPa, constant temperature time are 8 hours.
Adopt the prepared electrode for capacitors of above-mentioned each embodiment method, be the dither test of 40g through acceleration after, the ruthenic oxide coating on the electrode does not have and comes off or delamination.
Claims (4)
1. method that improves ruthenium oxide coatings and tantalum substrate combinating strength; Comprise that the slurry that will contain ruthenium compound is coated on tantalum matrix surface, oven dry; This tantalum matrix is put into 200～350 ℃ heating furnace, steam, the constant temperature of feeding 5～90kPa 1～10 hour; It is characterized in that said slurry is formulated by following method:
1) will contain ruthenium compound and valve metal powder and mix by 1: 0.5～1.5 weight ratio, mixed powder; The said ruthenium compound that contains is ruthenium halide or hydration ruthenium halide, and said ruthenium halide is ruthenium trichloride or iodate ruthenium; Said valve metal powder is average grain diameter >=Ta powder used or niobium powder of 150 purpose electrolytic capacitors;
2) with above-mentioned mixed powder and solvent by 1: 0.5～5 weight ratio hybrid modulation form slurry; Said solvent is mixture or one of the mixture of water and ethylene glycol or mixture of water and acetone of water or ethanol or ethylene glycol or acetone or water and ethanol.
2. the method for raising ruthenium oxide coatings according to claim 1 and tantalum substrate combinating strength; It is characterized in that: furnace temp is that 280 ℃, the pressure of steam are that 30～70kPa, thermal decomposition time are 2～8 hours; The weight ratio that contains ruthenium compound and valve metal powder in the step 1) is 1: 0.8～1.2, step 2) in the weight ratio of mixed powder and solvent be 1: 1～4.
3. the method for raising ruthenium oxide coatings according to claim 1 and tantalum substrate combinating strength; It is characterized in that: the pressure of steam is that 40～50kPa, thermal decomposition time are 4～6 hours; The weight ratio that contains ruthenium compound and valve metal powder in the step 1) is 1: 1, step 2) in the weight ratio of mixed powder and solvent be 1: 2～3.
4. the method for raising ruthenium oxide coatings according to claim 1 and tantalum substrate combinating strength is characterized in that: the pressure of steam is that 45kPa, thermal decomposition time are 5 hours, step 2) in the weight ratio of mixed powder and solvent be 1: 2.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104101614A CN102426927A (en) | 2011-12-12 | 2011-12-12 | Method for improving bonding strength of ruthenium oxide coating and tantalum substrate |
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| CN2011104101614A CN102426927A (en) | 2011-12-12 | 2011-12-12 | Method for improving bonding strength of ruthenium oxide coating and tantalum substrate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104021947A (en) * | 2014-06-20 | 2014-09-03 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169759A (en) * | 2010-12-17 | 2011-08-31 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method of ruthenium oxide electrode material |
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- 2011-12-12 CN CN2011104101614A patent/CN102426927A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169759A (en) * | 2010-12-17 | 2011-08-31 | 中国振华（集团）新云电子元器件有限责任公司 | Preparation method of ruthenium oxide electrode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104021947A (en) * | 2014-06-20 | 2014-09-03 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor |
| CN104021947B (en) * | 2014-06-20 | 2017-04-12 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode for hybrid super capacitor |
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Application publication date: 20120425 |