CN103310994A - Double-electrode-layer capacitor electrode material and manufacturing method thereof - Google Patents
Double-electrode-layer capacitor electrode material and manufacturing method thereof Download PDFInfo
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Abstract
Disclosed are a double-electrode-layer capacitor electrode material and a manufacturing method thereof. The double-electrode-layer capacitor electrode material is a high-energy tantalum hybrid capacitor cathode piece which is a composite cathode piece with a matrix of tantalum-based ruthenium dioxide (RuO2); the composite cathode piece comprises a basic tantalum piece, and a multi-metal oxide layer formed by blending ruthenium oxide, tantalum oxide and other metal oxides is covered on a surface of the tantalum piece; the multi-metal oxide layer is formed by blending the ruthenium oxide, the tantalum oxide and more than one of activated carbons, copper oxide, potassium oxide and manganese oxide, and subjected to chemical dipping processing to be formed.
Description
Technical field
The present invention relates to a kind of ultracapacitor is electrode material for electric double layer capacitor and preparation method thereof, is specifically related to a kind of RuO that is comprised of the composite materials such as ruthenium-oxide, active carbon, tantalum oxide and tantalum base
2-Ta
2O
5/ Ta electrode material and preparation method belong to electronic technology field.
Background technology
High-energy tantalum mixed capacitor is the vast capacity mixed capacitor that forms with tantalum electrolytic capacitor and double electric layer capacitor, specifically by sintered type tantalum anode fuse, tantalum pentoxide (Ta
2O
5)Medium, sulfuric acid solution electrolyte and tantalum base ruthenic oxide (RuO
2) the cathode sheets composition, sulfuric acid solution electrolyte and tantalum base ruthenic oxide (RuO
2) cathode sheets composition capacitor cathode, tantalum base ruthenic oxide (RuO
2) cathode sheets improved the electrolytical contact area of sulfuric acid solution, generates double electric layer capacitor, can draw to greatest extent anode capacity.The high-energy tantalum mixed capacitor volume is little, electrical property is excellent, product reliability is good, stable performance, life-span is long, energy density and the power density of unit volume and Unit Weight are large, are applicable to direct current, pulsation and low ripple circuit that Aeronautics and Astronautics, weapons, boats and ships, electronics etc. have the Military Electronic Equipment of reliability requirement.
Ruthenic oxide (RuO
2) material is transition metal oxide, can form unusual specific capacitance, has good conductivity, and stable in sulfuric acid solution, be a kind of different cathode material of best performance of generally acknowledging at present.Tantalum base RuO
2Cathode sheets is with ruthenic oxide (RuO
2) the main cathode material of material conduct, adopt the method for high temperature thermal decomposition oxidation (300 ℃ ~ 800 ℃) ruthenium compound to prepare ruthenic oxide (RuO more
2) crystal.Because ruthenic oxide (RuO
2) material belongs to noble metal, resource-constrained, expensive, many cathode material researchers and manufacturer are seeking or are partly substituting ruthenic oxide (RuO with cheap transition metal oxide or other material
2) material.
Find that by the Searches of Patent Literature a relevant patent documentation is arranged, this number of patent application is CN201210302311.4, and denomination of invention is " RuO
2-SnO
2-TiO
2-Ta
2O
5/ Ta cathode sheets and preparation method thereof ", this patent discloses novel high-capacity tantalum capacitor cathode sheets of a kind of remarkable saving noble metal Ru and preparation method thereof.Cathode sheets consists of: RuO
2-SnO
2-TiO
2-Ta
2O
5/ Ta; RuO
2-SnO
2-TiO
2-Ta
2O
5For cathode sheets composite coating, each constituent mass mark are: 20-70%RuO
2, 5-70%SnO
2, 0-70%TiO
2, 1-30%Ta
2O
5The Ta sheet is the cathode sheets substrate, and its thickness is the 0.05-0.1 millimeter.Described cathode sheets preparation method is: the alcohol solution of hydrate ruthenium trichloride, stannous chloride, tantalic chloride, butyl titanate is mixed and is brushed on the Ta of cleaning and roughening treatment substrate in 100-150 ℃ of oven dry, then at 250-400 ℃ of thermal decomposition 30-60 minute acquisition RuO
2-SnO
2-TiO
2-Ta
2O
5/ Ta cathode sheets.The mode that but this patent is employing brushes mixes the alcohol solution of hydrate ruthenium trichloride, stannous chloride, tantalic chloride, butyl titanate and be brushed on the Ta of cleaning and roughening treatment substrate, so surface ratio is more coarse, adhesive force is not high, and the consistency of product is not fine, has especially adopted 5-70%SnO
2And 0-70%TiO
2, after deliberation, experiment or actual checking proof, the doped Ti O of using
2, SnO
2Ruthenic oxide (RuO Deng cheap transition metal oxide preparation
2) cathode material can save ruthenic oxide (RuO
2) consumption, but the overall performance of product obviously descends after improving like this, this is not all right for the high high-energy tantalum mixed capacitor of reliability requirement, therefore how to accomplish to lower ruthenic oxide (RuO
2) consumption, can guarantee again simultaneously the performance of product, can satisfy the cathode material of the high-energy tantalum mixed capacitor of high reliability request, still remain further research.
Summary of the invention
The object of the invention is to the deficiency for existing electrode material, a kind of high-energy tantalum mixed capacitor of being applicable to is provided, electrode material for electric double layer capacitor with vast capacity, excellent electrical, long-life, high reliability request, and this electrode material can be saved part ruthenic oxide (RuO
2).
Another object of the present invention provides a kind of electrode material for electric double layer capacitor preparation method, to realize guaranteeing ruthenic oxide (RuO
2) on the basis of cathode material comprehensive electrochemical properties, improve the cathode sheets capacity, improve cathode material adhesive force, strengthen cathode material stability.
For realizing that implementer's case that the object of the invention proposes is: a kind of electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor are the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
Further, described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix with more than one poly-metal deoxides in cupric oxide, potassium oxide, the manganese oxide, and processes formed poly-metal deoxide layer by chemical impregnation.
Further, the content of described cupric oxide, potassium oxide, manganese oxide is than being arbitrary proportion, and optimal proportion is that the ratio of cupric oxide, potassium oxide, manganese oxide is 2:1:0.5.
Further, the quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 48% ~ 88%, tantalum oxide 10% ~ 50%, active carbon 1% ~ 4%; One or more metal oxides 1% ~ 5% in cupric oxide, potassium oxide, the manganese oxide, be understood that, high-energy tantalum mixed capacitor cathode sheets of the present invention contains one or more metal oxides in cupric oxide, potassium oxide, the manganese oxide, proportioning between one or more metal oxides is not done requirement, each component total amount is 100%, be 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
Electrode material for electric double layer capacitor preparation method of the present invention the steps include:
A, tantalum piece preparation
1, be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2, to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3, with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvents such as propyl ether or methyl ethers, RuCl
3XH
2O concentration is 0.1mol/L ~ 5mol/L;
4, with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 1% ~ 30% of the solution total amount that step 3 prepares;
The mass percent 1% ~ 4% of the solution total amount that 5, active carbon powder is prepared by step 3 joins in the solution for preparing by step 4;
6, with one or more metal compound powders in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, the potassium permanganate, the mass percent 1% ~ 5% for preparing solution by step 3 joins in the solution for preparing by step 5; Be understood that herein, electrode material for electric double layer capacitor preparation method of the present invention adds one or more metal compound powders in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, the potassium permanganate, and the proportioning between one or more metal compound powders is not done requirement;
The mass percent 1% ~ 3% of the solution that 7, cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and preferred cellulose ether has hydroxyethylcellulose, hydroxypropyl methylcellulose or carboxymethyl cellulose;
8, will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9, will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 3 times ~ 12 times as stated above;
E, high-temperature heat treatment
10, will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
Further, immersing rapidly by referring in the deployed solution of step 8 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 1-15 immediately of described step 9, and in afterwards rapidly proposition dipping 1-20 second, tantalum piece is stopped 5-15 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
Further, the oven dry of described step 9 is tantalum piece vertically to be suspended in the drying oven dry.
The invention has the advantages that: according to the high-energy tantalum mixed capacitor RuO of made of the present invention
2-Ta
2O
5/ Ta cathode sheets, in preparation process, main cathode material adopts RuCl
3XH
2O is for guaranteeing RuO
2The comprehensive electrochemical properties of cathode material excellence is added simultaneously cheap transistion metal compound and is partly substituted ruthenium compound; Add Ta by above-mentioned steps 4 ratio requirement
2O
5, accelerated RuO
2The formation of crystal has improved cathode material adhesive force, has increased the specific area of cathode sheets, has improved the cathode sheets capacity; And add in right amount one or more metal compound powders in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, the potassium permanganate as depolarizing agent, strengthened the stability of cathode material; An amount of cellulose ether that adds has improved cathode material adhesive force as organic binder bond; Be applicable to vast capacity, excellent electrical, long-life, the high reliability request of high-energy tantalum mixed capacitor.
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention to have more than be the cited scope of embodiment, any related art scheme that proposes according to the present invention's design all belongs to protection scope of the present invention.
Embodiment one
A kind of electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor are the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
Described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix with three kinds of metal oxides in cupric oxide, potassium oxide, the manganese oxide, and processes formed poly-metal deoxide layer by chemical impregnation.
The content of described cupric oxide, potassium oxide, manganese oxide is than being arbitrary proportion, and optimum content is 2:1:0.5 than the weight ratio that is cupric oxide, potassium oxide, manganese oxide.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 68%, tantalum oxide 24%, active carbon 4%; Cupric oxide, potassium oxide, three kinds of metal oxides 4% of manganese oxide, the component total amount is 100%, is 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
Described electrode material for electric double layer capacitor preparation method the steps include:
A, tantalum piece preparation
1, be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2, to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3, with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvents such as propyl ether or methyl ethers, so that RuCl
3XH
2O concentration reaches 0.1mol/L ~ 5mol/L;
4, with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 24% of the solution total amount that step 3 prepares;
5, the mass percent 4% of active carbon powder by the solution total amount solution for preparing by step 3 joined in the solution for preparing by step 4;
6, cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate are joined in the solution for preparing by step 5 by the mass percent 4% of the solution total amount that step 3 prepares; It should be understood that herein the described electrode material for electric double layer capacitor preparation method of the present embodiment adds cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate, the proportioning between three kinds of metal compound powders is 1:1:1;
The mass percent 1% of the solution that 7, cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and the cellulose ether of specifically selecting is hydroxyethylcellulose;
8, will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9, will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 8 times ~ 10 times as stated above;
E, high-temperature heat treatment
10, will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
Immersing rapidly by referring in the deployed solution of step 8 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 1-5 immediately of described step 9, and in afterwards rapidly proposition dipping 1-5 second, tantalum piece is stopped 10-15 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
The oven dry of described step 9 is tantalum piece vertically to be suspended in the drying oven dry.
Embodiment two
The basic principle of embodiment two is the same with embodiment one, be that described cathode of composite material sheet comprises basic tantalum piece, in being mixed with cupric oxide, potassium oxide, three kinds of metal oxides of manganese oxide by ruthenium-oxide, tantalum oxide and active carbon of the surface coverage of tantalum piece, and it is different to process the component content of formed poly-metal deoxide layer by chemical impregnation.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 88%, tantalum oxide 10%, active carbon 1%; Cupric oxide, potassium oxide, three kinds of metal oxides 1% of manganese oxide, the component total amount is 100%, is 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets is processed formed Multimetal oxide layer by chemical impregnation.
The content of described cupric oxide, potassium oxide, manganese oxide is than being 2:1:0.5.
Described electrode material for electric double layer capacitor preparation method the steps include:
A, tantalum piece preparation
1, be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2, to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3, with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvents such as propyl ether or methyl ethers, so that RuCl
3XH
2O concentration reaches 0.1mol/L ~ 5mol/L;
4, with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 10% of the solution total amount that step 3 prepares;
5, the mass percent 1% of active carbon powder by the solution total amount solution for preparing by step 3 joined in the solution for preparing by step 4;
6, cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate are joined in the solution for preparing by step 5 by the mass percent 1% of the solution total amount that step 3 prepares; It should be understood that herein the described electrode material for electric double layer capacitor preparation method of the present embodiment adds cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate, the proportioning between three kinds of metal compound powders is 1:1:1;
The mass percent 1% of the solution that 7, cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and the cellulose ether of specifically selecting is hydroxypropyl methylcellulose;
8, will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9, will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 3 times ~ 5 times as stated above;
E, high-temperature heat treatment
10, will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
Immersing rapidly by referring in the deployed solution of step 8 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 5-8 immediately of described step 9, and in afterwards rapidly proposition dipping 5-10 second, tantalum piece is stopped 5-10 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
The oven dry of described step 9 is that the tantalum piece lateral suspension is dried in drying oven.
Embodiment three
Embodiment three is consistent with embodiment one basic ideas, be that described cathode of composite material sheet comprises basic tantalum piece, in being mixed with cupric oxide, potassium oxide, three kinds of metal oxides of manganese oxide by ruthenium-oxide, tantalum oxide and active carbon of the surface coverage of tantalum piece, and it is different to process the component content of formed poly-metal deoxide layer by chemical impregnation.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 48%, tantalum oxide 50%, active carbon 1%; Cupric oxide, potassium oxide, three kinds of metal oxides 1% of manganese oxide, the component total amount is 100%, is 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets is processed formed Multimetal oxide layer by chemical impregnation.
The proportioning of described cupric oxide, potassium oxide, manganese oxide is 1:1:0.5.
Described electrode material for electric double layer capacitor preparation method the steps include:
A, tantalum piece preparation
1, be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2, to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3, with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvents such as propyl ether or methyl ethers, so that RuCl
3XH
2O concentration reaches 0.1mol/L ~ 5mol/L;
4, with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 50% of the solution total amount that step 3 prepares;
5, the mass percent 1% of active carbon powder by the solution total amount solution for preparing by step 3 joined in the solution for preparing by step 4;
6, cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate are joined in the solution for preparing by step 5 by the mass percent 1% of the solution total amount that step 3 prepares; It should be understood that herein the described electrode material for electric double layer capacitor preparation method of the present embodiment adds cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate, the proportioning between three kinds of metal compound powders is 1:1:2;
The mass percent 1% of the solution that 7, cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and the cellulose ether of specifically selecting is carboxymethyl cellulose;
8, will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9, will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 10 times ~ 12 times as stated above;
E, high-temperature heat treatment
10, will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
Embodiment four
A kind of electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor are the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
Described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix, and process formed poly-metal deoxide layer by chemical impregnation with cupric oxide, potassium oxide, three kinds of metal oxides of manganese oxide.
The content of described cupric oxide, potassium oxide, manganese oxide is than being arbitrary proportion, and optimum content is 1:1:0.5 than the weight ratio that is cupric oxide, potassium oxide, manganese oxide.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 67%, tantalum oxide 24%, active carbon 4%; Cupric oxide, manganese oxide, three kinds of metal oxides 5% of potassium oxide, the component total amount is 100%, is 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
Described electrode material for electric double layer capacitor preparation method the steps include:
A, tantalum piece preparation
1, be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2, to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3, with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvents such as propyl ether or methyl ethers, so that RuCl
3XH
2O concentration reaches 0.1mol/L ~ 5mol/L;
4, with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 24% of the solution total amount that step 3 prepares;
5, the mass percent 4% of active carbon powder by the solution total amount solution for preparing by step 3 joined in the solution for preparing by step 4;
6, cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate are joined in the solution for preparing by step 5 by the mass percent 5% of the solution total amount that step 3 prepares; It should be understood that herein the described electrode material for electric double layer capacitor preparation method of the present embodiment adds cupric oxide, anhydrous cupric sulfate, three kinds of metal compound powders of potassium permanganate, the proportioning between three kinds of metal compound powders is 1:1:2;
The mass percent 2% of the solution that 7, cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and the cellulose ether of specifically selecting is hydroxyethylcellulose;
8, will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9, will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 3 times ~ 12 times as stated above;
E, high-temperature heat treatment
10, will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
Immersing rapidly by referring in the deployed solution of step 8 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 3-15 immediately of described step 9, and in afterwards rapidly proposition dipping 5-20 second, tantalum piece is stopped 5-15 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
Immersing rapidly by referring in the deployed solution of step 8 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 3-15 immediately of described step 9, and in afterwards rapidly proposition dipping 5-20 second, tantalum piece is stopped 5-15 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
The oven dry of described step 9 is tantalum piece vertically to be suspended in the drying oven dry.
Embodiment five
A kind of electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor are the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
Described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix with cupric oxide, two kinds of metal oxides of potassium oxide, and processes formed poly-metal deoxide layer by chemical impregnation.
The content of described cupric oxide, potassium oxide is than being arbitrary proportion, and optimum content is 1:1 than the weight ratio that is cupric oxide, potassium oxide.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 67%, tantalum oxide 24%, active carbon 4%; Two kinds of metal oxides 5% in cupric oxide and the potassium oxide, be understood that, electrode material for electric double layer capacitor of the present invention contains cupric oxide, two kinds of metal oxides of potassium oxide, the component total amount is 100%, be 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
Described electrode material for electric double layer capacitor preparation method is the same with embodiment four, no longer is repeated in this description at this.
Embodiment six
A kind of electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor are the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
Described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix with cupric oxide, two kinds of metal oxides of manganese oxide, and processes formed poly-metal deoxide layer by chemical impregnation.
The content of described cupric oxide, manganese oxide is than being arbitrary proportion, and optimum content is 1:1 than the weight ratio that is cupric oxide, manganese oxide.
The quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 67%, tantalum oxide 24%, active carbon 4%; Two kinds of metal oxides 5% of cupric oxide and manganese oxide, it should be understood that electrode material for electric double layer capacitor of the present invention contains cupric oxide, two kinds of metal oxides of manganese oxide, the component total amount is 100%, be 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
Described electrode material for electric double layer capacitor preparation method is the same with embodiment four, no longer is repeated in this description at this.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. electrode material for electric double layer capacitor, described electrode material for electric double layer capacitor is the high-energy tantalum mixed capacitor cathode sheets, for tantalum base ruthenic oxide (RuO
2) be the cathode of composite material sheet of matrix; Described cathode of composite material sheet comprises basic tantalum piece, has one deck to mix the Multimetal oxide layer that forms with other metal oxide by ruthenium-oxide and tantalum oxide in the surface coverage of tantalum piece.
2. electrode material for electric double layer capacitor as claimed in claim 1, it is characterized in that, described Multimetal oxide layer is that ruthenium-oxide, tantalum oxide and active carbon mix with more than one poly-metal deoxides in cupric oxide, potassium oxide, the manganese oxide, and processes formed poly-metal deoxide layer by chemical impregnation.
3. electrode material for electric double layer capacitor as claimed in claim 2 is characterized in that, the content of described cupric oxide, potassium oxide, manganese oxide is than being arbitrary proportion, and optimal proportion is that the ratio of cupric oxide, potassium oxide, manganese oxide is 2:1:0.5.
4. electrode material for electric double layer capacitor as claimed in claim 3 is characterized in that, the quality of materials percentage composition of described Multimetal oxide layer is: ruthenium-oxide 48% ~ 88%, tantalum oxide 10% ~ 50%, active carbon 1% ~ 4%; One or more metal oxides 1% ~ 5% in cupric oxide, manganese oxide, the potassium oxide, be understood that, high-energy tantalum mixed capacitor cathode sheets of the present invention contains one or more metal oxides in cupric oxide, potassium oxide, the manganese oxide, proportioning between one or more metal oxides is not done requirement, each component total amount is 100%, be 0.05mm ~ 0.12mm with thickness, the RuO that purity consists of as substrate greater than 99.9% tantalum piece
2-Ta
2O
5/ Ta cathode sheets.
5. a preparation method who makes electrode material for electric double layer capacitor claimed in claim 1 is characterized in that, described electrode material for electric double layer capacitor preparation method's step is:
A, tantalum piece preparation
1) be 0.05mm ~ 0.12mm with thickness, purity is cut or the punch process moulding greater than 99.9% tantalum paper tinsel warp, obtains the tantalum piece of required given configuration and size;
B, tantalum piece are processed
2) to the prepared tantalum piece of step 1 polish alligatoring, polishing, alkali liquor oil removing, chemical polishing, cleaning and oven dry;
C, solution preparation
3) with ruthenium trichloride hydrate (RuCl
3XH
2O) powder dissolution is in ether solvent, RuCl
3XH
2O concentration is 0.1mol/L ~ 5mol/L;
4) with tantalum pentoxide (Ta
2O
5) powder joins in the solution for preparing by step 3 by the mass percent 1% ~ 30% of the solution total amount that step 3 prepares;
The mass percent 1% ~ 4% of the solution total amount that 5) active carbon powder is prepared by step 3 joins in the solution for preparing by step 4;
6) with one or more metal compound powders in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, the potassium permanganate, the mass percent 1% ~ 5% for preparing solution by step 3 joins in the solution for preparing by step 5; Be understood that herein, electrode material for electric double layer capacitor preparation method of the present invention adds one or more metal compound powders in cupric oxide, potassium oxide, manganese oxide, anhydrous cupric sulfate, the potassium permanganate, and the proportioning between one or more metal compound powders is not done requirement;
The mass percent 1% ~ 3% of the solution that 7) cellulose ether is prepared by step 3 joins in the solution for preparing by step 6, and preferred cellulose ether has hydroxyethylcellulose, hydroxypropyl methylcellulose or carboxymethyl cellulose;
8) will stir by the solution that step 7 prepares with the magnetic agitation instrument;
D, dipping, oven dry
9) will immerse rapidly by the tantalum piece that step 2 is handled well by in the deployed solution of step 8, should propose rapidly after the immersion, to answer short stay after the tantalum piece proposition, treat that redundant solution flows away, the tantalum piece that then will adhere to solution is sent in the drying oven and is dried, and bake out temperature is 100 ℃ ~ 200 ℃, and the time is 5min ~ 30min, drying time is to namely finishing a dipping, drying cycle, and circular treatment is 3 times ~ 12 times as stated above;
E, high-temperature heat treatment
10) will send into the high-temperature heat treatment baking oven by the tantalum piece that step 9 is finished dealing with and carry out the soak processing, temperature is 260 ℃ ~ 380 ℃, time is 30min ~ 120min, and naturally cooling obtained the RuO for high-energy tantalum mixed capacitor of the present invention after high-temperature heat treatment was finished
2-Ta
2O
5/ Ta cathode sheets.
6. electrode material for electric double layer capacitor preparation method as claimed in claim 5, it is characterized in that, immersing rapidly by referring in the deployed solution of step 7 that the tantalum piece with completing steps 2 is processed drops in second in the deployed solution of step 8 at 1-15 immediately of described step 9, and in afterwards rapidly proposition dipping 1-20 second, tantalum piece is stopped 5-15 second aloft, after redundant solution flowed away, the tantalum piece that will adhere to again solution carried out drying and processing.
7. electrode material for electric double layer capacitor preparation method as claimed in claim 6 is characterized in that, the oven dry of described step 9 is tantalum piece vertically to be suspended in the drying oven dry.
8. electrode material for electric double layer capacitor preparation method as claimed in claim 5 is characterized in that, described ether solvent is propyl ether or methyl ether.
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