CN101533716B - Preparation technique of composite film electrode used for a super capacitor - Google Patents

Preparation technique of composite film electrode used for a super capacitor Download PDF

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CN101533716B
CN101533716B CN2009100431124A CN200910043112A CN101533716B CN 101533716 B CN101533716 B CN 101533716B CN 2009100431124 A CN2009100431124 A CN 2009100431124A CN 200910043112 A CN200910043112 A CN 200910043112A CN 101533716 B CN101533716 B CN 101533716B
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composite film
concentration
film electrode
electrode
polishing
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CN101533716A (en
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甘卫平
师响
刘泓
刘继宇
李祥
马贺然
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Central South University
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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
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    • 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 preparation technique of a composite film electrode used for a super capacitor; the preparation technique is characterized by comprising the following steps: pre-processing on high-purity metal tantalum foil with the purity of more than 99.95 percent: grinding and roughening, grinding and polishing, removing oil and cleaning to the metal tantalum foil; 2) electrodeposition technique; and 3) heat processing to the composite film electrode. The composite film electrode prepared by adopting the technique can reduce the using amount of noble metal ruthenium on the basis of guaranteeing capacitance characteristic, thus reducing the cost.

Description

A kind of ultracapacitor preparation technology of composite film electrode
Technical field
The invention belongs to the electrochemical capacitor field, relate to the preparation technology of a kind of ultracapacitor, be specifically related to a kind of ultracapacitor tantalum base (RuO with composite film electrode 2/ SnO 2) nH 2The preparation technology of O composite film electrode.
Background technology
Ultracapacitor (super capacitor) is a kind of novel green energy-storage travelling wave tube, it has good characteristics such as pulse charge-discharge performance, vast capacity and high energy storage density, capacity is 20～200 times of traditional capacitor, power density is high nearly ten times than battery, and efficiency for charge-discharge height, do not need care and maintenance, life-span is long, is with a wide range of applications and development potentiality in mobile communication, electronic information technology, environmental protection energy industry, electric automobile, Aeronautics and Astronautics, weapons and science and techniques of defence.Ultracapacitor can be divided into double electric layer capacitor and pseudo capacitance device according to the storage mechanism of electric charge.Double electric layer capacitor uses carbon materials as electrode, and generally about 200F/g, the pseudo capacitance device uses metal oxide ruthenic oxide (RuO to specific capacitance 2) as electrode, specific capacitance is up to 788F/g.RuO 2Electrode is than carbon electrode, and its specific capacitance is bigger more than 3 times than carbon electrode, big 1 order of magnitude of specific power, big 2 orders of magnitude of conductivity, and RuO 2Electrode is stable in sulfuric acid electrolyte, and cycle life and charge-discharge performance are also fairly good, so metal oxide RuO 2It is the optimal electrode material of present high specific energy ultracapacitor.But because the costing an arm and a leg of ruthenium-oxide, its application is restricted, so people are seeking the ruthenic oxide base composite electric utmost point material of low cost, high specific capacitance always, in the hope of reducing electrode material cost significantly.
Summary of the invention
The object of the present invention is to provide the preparation technology of a kind of ultracapacitor,, can reduce metal oxide containing precious metals RuO to be implemented on the basis that guarantees capacitance characteristic with composite film electrode 2Consumption, and then reduce its cost.
For achieving the above object, technical scheme of the present invention is:
A kind of ultracapacitor is characterized in that with the preparation technology of composite film electrode, may further comprise the steps:
1) purity is carried out preliminary treatment greater than 99.95% high purity metal tantalum paper tinsel: to described metal tantalum foil polishing alligatoring, sanding and polishing, oil removing and cleaning;
2) electrodeposition technology: with acid chlorization ruthenium/stannous chloride composite colloid aqueous solution is that electrodeposit liquid carries out electro-deposition, in the described electrodeposit liquid, and RuCl 32H 2O concentration is 0.5～5mmol/L, SnCl 22H 2O concentration is 2～20mmol/L, and HCl concentration is 8～40mmol/L, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25,25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, negative electrode is described high purity metal tantalum paper tinsel in the preparation process, anode be graphite to electrode, make composite film electrode thus;
3) to composite film electrode heat treatment: with step 2) composite film electrode for preparing puts into thermostatic drying chamber, under air atmosphere successively with 80～120 ℃ with 180～220 ℃ of temperature under respectively carry out the heat treatment of 1h, under 280～320 ℃, carry out the heat treatment of 1～3h again, with the stove cooling, make described ultracapacitor composite film electrode then.
Described step 1) may further comprise the steps:
With the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, at last with stand-by after the washed with de-ionized water, in the cleaning process, all cleans with ultrasonic wave is auxiliary.
As improvement, in described step 2) electrodeposition process in, electrodeposit liquid is aided with continuous stirring, the solution stir speed (S.S.) is 10～60 rev/mins.
Thinking of the present invention is:
At RuO 2In add base metal oxide, as transition group metallic oxides such as Sn, Mn, Ni etc., be prepared into combination electrode material, on the basis that guarantees capacitance characteristic, can reduce the consumption of noble ruthenium, and then reduce its cost.For example, because there is the multivalence attitude in the tin of chemical combination attitude, add the conductive characteristic of tin oxide, the capacitance of the SnO 2 thin film electrode by the electrokinetic potential prepared by electrodeposition can reach 285Fg -1, so tin ash can be used as the material of preparation super capacitor composite electrode.Technical scheme is as follows:
1. high-purity tantalum paper tinsel: purity 〉=99.95%, area 15mm * 15mm, thickness are 0.08mm.
2. tantalum paper tinsel preliminary treatment: with the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, and the back, is all cleaned with ultrasonic wave is auxiliary in the cleaning process with stand-by after the washed with de-ionized water.
3. electrodeposit liquid prescription: with acid chlorization ruthenium/stannous chloride composite colloid aqueous solution is that electrodeposit liquid carries out electro-deposition, in the electrodeposit liquid, and RuCl 32H 2O concentration is 0.5～5mmol/L, SnCl 22H 2O concentration is 2～20mmol/L, and HCl concentration is 8～40mmol/L, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25;
4. electrodeposition technology: 25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, electrodeposition time 1～5h, negative electrode is a metal tantalum foil in the preparation process, anode be graphite to electrode, and solution is aided with continuous stirring, it is 10～60 rev/mins that solution stirs speed.
5. the heat treatment of composite film electrode: the heat treatment of composite film electrode be under air atmosphere with 80～120 ℃ with 180～220 ℃ of temperature under respectively carry out the heat treatment of 1h, under 280～320 ℃, carry out the heat treatment of 1～3h again, cool off with stove then.
Beneficial effect of the present invention is as follows:
At electrolyte is the H of 0.5mol/L 2SO 4In the solution, by CHI660B type electrochemical workstation, use cyclic voltammetry that the prepared composite film electrode of the present invention is carried out electrochemical property test, as auxiliary electrode, the Ag/AgCl electrode is as reference electrode with the platinized platinum electrode, (RuO 2/ SnO 2) nH 2The O membrane electrode is as work electrode.Draw (the RuO under the different scanning rates 2/ SnO 2) nH 2The cyclic voltammetry curve figure of O composite film electrode sees Fig. 1.[embodiment 2 in the corresponding this patent of Fig. 1 and Fig. 2] as shown in Figure 1 should (RuO 2/ SnO 2) nH 2Even the O composite film electrode also has highly reversible oxidation and reduction volt-ampere curve under higher sweep speed, have capacitance characteristic clearly, and the volt-ampere curve of this mirror image symmetry there is repeatedly recordable repeatability.Reversible this kind of the curve shows material of this pseudo-capacitance has following character: (1) oxidation and reduction reaction are reversible on chemical constitution; (2) oxide-film has good electrical conductivity; (3) in the hydrous oxide lattice structure, more easily carry out the transition of electronics and proton, thereby cause the embedding and the extraction of proton.This process is similar to Li +Embed transition metal oxide and sulfide electrode material.
Fig. 2 is at 5mAcm -2Current density under (RuO 2/ SnO 2) nH 2The charging and discharging curve of O membrane electrode.(RuO as seen from the figure 2/ SnO 2) nH 2The charging and discharging curve of O membrane electrode is linear change in time substantially, show capacitance characteristic preferably, charging curve and discharge curve be symmetry substantially, demonstrate cyclic reversibility preferably, voltage drop simultaneously is also smaller, this illustrative material has lower internal resistance, provides guarantee for material still can keep higher capacity under bigger discharging current.
The adhesive force evaluation criterion: generally adopt physical criterion, this is a kind of by some performance factors of curing material being carried out the method for simulation test, and operation sequence is simple, quick, cost is few.The film bonding strength of facing a charge is peeled off method with 180 degree and is measured with the adhesive force index expression among standard GB/T120-2000, and standard code is greater than 10N/10mm 2Promptly qualified, adhesive force index of the present invention reaches 12.62N/10mm at tantalum surface 2More than, be higher than national standard.Sample sectional dimension a * b=12.30 * 4.70Fm=0.650KN δ b=12.620MPa.
The ultracapacitor that adopts the present invention to make, or cooperates with other batteries and to form the composite battery group, solved the difficult problem that existing battery can not satisfy high power, big capacity, fast charging and discharging, long-life requirement, compare pure RuO 2Electrode material has improved the adhesive force between film and matrix and has reduced electrode material cost significantly.Technology of the present invention is simple, easy and simple to handle, the tantalum base (RuO for preparing 2/ SnO 2) nH 2The O composite film electrode has the specific capacitance of 440F/g.The hybrid super capacitor that this kind electrode material is made has height ratio capacity and good cycle performance, and premium properties such as charging quickly, long-life and multiplying power discharging characteristic.
Description of drawings:
Fig. 1 is (RuO 2/ SnO 2) nH 2The cyclic voltammetry curve figure of O composite film electrode;
Fig. 2 is (RuO 2/ SnO 2) nH 2O composite film electrode charge-discharge test result.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment 1:
1. preprocessing process: at first with the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, and the back, is all cleaned with ultrasonic wave is auxiliary in the cleaning process with stand-by after the washed with de-ionized water.
2. dispose electrodeposit liquid, RuCl 32H 2The concentration of O is that 5mmol/L immobilizes SnCl 22H 2The concentration of O is pressed Sn in the solution 2+With Ru 3+Molar concentration rate is 1: 1, HCl that adds in the embryo deposit liquid and SnCl 22H 2The molar concentration rate of O is 4: 1, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25;
3. electrodeposition technology: 25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, electrodeposition time 1～5h, negative electrode is a metal tantalum foil in the preparation process, anode be graphite to electrode, and solution is aided with continuous stirring, it is 10～60 rev/mins that solution stirs speed.
4. composite film electrode heat treatment: composite film electrode heat treatment is in thermostatic drying chamber, under air atmosphere successively with 80～120 ℃, 180～220 ℃ with 280～320 ℃ of temperature under respectively carry out the heat treatment of 1h, cool off with stove then.
By CHI660B type electrochemical workstation, use cyclic voltammetry that the chemical property of composite film electrode is tested, as auxiliary electrode, the Ag/AgCl electrode is as reference electrode with the platinized platinum electrode, (RuO 2/ SnO 2) nH 2The O membrane electrode is as work electrode, and electrolyte is the H of 0.5mol/L 2SO 4Solution, sweep speed are 50mV/s.By the cyclic voltammetric test, it reaches 380F/g than electric capacity.
Embodiment 2
1. preprocessing process: at first with the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, and the back, is all cleaned with ultrasonic wave is auxiliary in the cleaning process with stand-by after the washed with de-ionized water.
2. dispose electrodeposit liquid, RuCl 32H 2The concentration of O is that 5mmol/L immobilizes SnCl 22H 2The concentration of O is pressed Sn in the solution 2+With Ru 3+Molar concentration rate is 2: 1, HCl that adds in the embryo deposit liquid and SnCl 22H 2The molar concentration rate of O is 4: 1, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25;
3. electrodeposition technology: 25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, electrodeposition time 1～5h, negative electrode is a metal tantalum foil in the preparation process, anode be graphite to electrode, and solution is aided with continuous stirring, it is 10～60 rev/mins that solution stirs speed.
4. composite film electrode heat treatment: it is in thermostatic drying chamber that the composite film electrode thermode is handled, under air atmosphere successively with 80～120 ℃ with 180～220 ℃ of temperature under respectively carry out the heat treatment of 1h, under 280～320 ℃, carry out the heat treatment of 2h again, cool off with stove then.
By CHI660B type electrochemical workstation, use cyclic voltammetry that the chemical property of composite film electrode is tested, as auxiliary electrode, the Ag/AgCl electrode is as reference electrode with the platinized platinum electrode, (RuO 2/ SnO 2) nH 2The O membrane electrode is as work electrode, and electrolyte is the H of 0.5mol/L 2SO 4Solution, sweep speed are 50mV/s.By the cyclic voltammetric test, it reaches 440F/g than electric capacity.
Embodiment 3
1. preprocessing process: at first with the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, and the back, is all cleaned with ultrasonic wave is auxiliary in the cleaning process with stand-by after the washed with de-ionized water.
2. dispose electrodeposit liquid, RuCl 32H 2The concentration of O is that 5mmol/L immobilizes SnCl 22H 2The concentration of O is pressed Sn in the solution 2+With Ru 3+Molar concentration rate, configuration proportion are 3: 1, HCl that adds in the embryo deposit liquid and SnCl 22H 2The molar concentration rate of O is 4: 1, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25;
3. electrodeposition technology: 25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, electrodeposition time 1～5h, negative electrode is a metal tantalum foil in the preparation process, anode be graphite to electrode, and solution is aided with continuous stirring, it is 10～60 rev/mins that solution stirs speed.
4. composite film electrode heat treatment: it is in thermostatic drying chamber that the composite film electrode thermode is handled, under air atmosphere successively with 80～120 ℃ with 180～220 ℃ of temperature under respectively carry out the heat treatment of 1h, under 280～320 ℃, carry out the heat treatment of 3h again, cool off with stove then.
By CHI660B type electrochemical workstation, use cyclic voltammetry that the chemical property of composite film electrode is tested, as auxiliary electrode, the Ag/AgCl electrode is as reference electrode with the platinized platinum electrode, (RuO 2/ SnO 2) nH 2The O membrane electrode is as work electrode, and electrolyte is the H of 0.5mol/L 2SO 4Solution, sweep speed are 50mV/s.By the cyclic voltammetric test, it reaches 410F/g than electric capacity.

Claims (3)

1. the preparation technology of a ultracapacitor usefulness composite film electrode is characterized in that, may further comprise the steps:
1) purity is carried out preliminary treatment greater than 99.95% high purity metal tantalum paper tinsel: to described high purity metal tantalum paper tinsel polishing alligatoring, sanding and polishing, oil removing and cleaning;
2) electrodeposition technology: with acid chlorization ruthenium/stannous chloride composite colloid aqueous solution is that electrodeposit liquid carries out electro-deposition, in the described electrodeposit liquid, and RuCl 32H 2O concentration is 0.5～5mmol/L, SnCl 22H 2O concentration is 2～20mmol/L, and HCl concentration is 8～40mmol/L, and KCl concentration is 40～75mmol/L, surfactant (CH 3) 4N (OH) 5H 2The concentration of O is 5～35mmol/L, pH value 1.85～4.25,25～45 ℃ of electrodeposit liquid temperature, electro-deposition current density 3～30mA/cm 2, negative electrode is described high purity metal tantalum paper tinsel in the preparation process, anode be graphite to electrode, make composite film electrode thus;
3) to composite film electrode heat treatment: with step 2) composite film electrode for preparing puts into thermostatic drying chamber, under air atmosphere, under 80～120 ℃, 180～220 ℃, respectively carry out 1h heat treatment successively, under 280～320 ℃, carry out 1～3h heat treatment again, with the stove cooling, make described ultracapacitor composite film electrode then.
2. the ultracapacitor according to claim 1 preparation technology of composite film electrode is characterized in that described step 1) may further comprise the steps:
With the roughening treatment of polishing of 400# abrasive paper for metallograph, behind the 800# abrasive paper for metallograph sanding and polishing, acetone cleans 5～10min; The alkali lye of forming with phosphatase 24 0g/L, NaOH 5g/L, sodium metasilicate 20g/L and sodium carbonate 10g/L adds heat soaking 10～15min, at 100mA/cm 2, 70～80 ℃ of catholyte oil removings; Heat is washed in the mixed acid that 20mL concentration is 40% hydrofluoric acid, 10mL concentration is 1.4g/mL nitric acid and 15mL concentration are formed for 1.84g/mL sulfuric acid, at last with stand-by after the washed with de-ionized water, in the cleaning process, all cleans with ultrasonic wave is auxiliary.
3. ultracapacitor according to claim 1 and 2 is characterized in that, in described step 2 with the preparation technology of composite film electrode) electrodeposition process in, electrodeposit liquid is aided with continuous stirring, the solution stir speed (S.S.) is 10～60 rev/mins.
CN2009100431124A 2009-04-15 2009-04-15 Preparation technique of composite film electrode used for a super capacitor Expired - Fee Related CN101533716B (en)

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CN101728084B (en) * 2010-01-19 2012-02-29 西安华泰有色金属实业有限责任公司 Method for preparing cathode of fully-sealed liquid mixed tantalum capacitor
CN103042451A (en) * 2012-12-05 2013-04-17 上海师范大学 Method for changing constant temperature magnetic stirrer into electrode grinding machine for laboratories
RU2623969C1 (en) * 2016-08-22 2017-06-29 Открытое акционерное общество "Элеконд" Production technique of a cathodic conductive plates of sintered-slug tantalum electrolytic capacitor
CN109087819B (en) * 2018-08-13 2020-07-31 贵州理工学院 Preparation method of polyaniline/ruthenium oxide/tin dioxide composite electrode material

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KR20040047108A (en) * 2002-11-29 2004-06-05 주식회사 기노리텍 Manufacturing method of metaloxide for super capacitor and manufacturing methode of metaloxidic super capacitor
CN101083171A (en) * 2006-05-30 2007-12-05 中南大学 Method for preparing RuO2 coating cathode film material of super capacitor
CN101122040A (en) * 2007-05-21 2008-02-13 哈尔滨工程大学 Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material
CN101290835A (en) * 2007-04-16 2008-10-22 韩国科学技术研究院 Electrode for supercapacitor and the fabrication method thereof
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KR20040047108A (en) * 2002-11-29 2004-06-05 주식회사 기노리텍 Manufacturing method of metaloxide for super capacitor and manufacturing methode of metaloxidic super capacitor
CN101083171A (en) * 2006-05-30 2007-12-05 中南大学 Method for preparing RuO2 coating cathode film material of super capacitor
CN101290835A (en) * 2007-04-16 2008-10-22 韩国科学技术研究院 Electrode for supercapacitor and the fabrication method thereof
CN101122040A (en) * 2007-05-21 2008-02-13 哈尔滨工程大学 Method for preparing carbon nano-tube loading ruthenium oxide hydration composite material
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