CN104021947A - Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor - Google Patents
Method for preparing ruthenium oxide electrode with high specific capacitance rate for hybrid super capacitor Download PDFInfo
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Abstract
The invention provides a method for preparing a ruthenium oxide electrode with the high specific capacitance rate for a hybrid super capacitor. The method includes the following steps that firstly, electroplating liquid containing ruthenium is prepared, and tantalum foil is electroplated with a layer of ruthenium oxide with the thickness being about 80 nm to 200 nm in a deposition mode through a cyclic voltammetry method; secondly, the tantalum foil is coated with a sizing agent, and thermal decomposition is conducted; thirdly, a ruthenium oxide cathode post-processing process is conducted, and finally the cathode electrode containing ruthenium and containing ruthenium oxide is prepared, wherein the thickness of the cathode electrode ranges from 0.1 mm to 0.5 mm. By the adoption of the electrode prepared through the method, the specific capacitance is large, the surface energy storage density is high, and equivalent series internal resistance is low.
Description
Technical field
The present invention relates to a kind of preparation method of mixed type electrolytic capacitor cathode, relate in particular to a kind of preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode.
Background technology
Pulse Power Techniques are one of New Electricals, and its application is power supply and energy-storage travelling wave tube thereof with promoting key, and traditional energy-storage travelling wave tube mainly contains two classes: i.e. electrostatic condenser and storage battery.Conventionally the energy of accumulators store is higher, but the speed of transferring energy is limited; On the contrary, electrostatic condenser is transferring energy fast, but the energy that it is stored is very low, shortcoming in view of above-mentioned two kinds of energy-storage travelling wave tubes existence, a kind of novel energy storage device----ultracapacitor has grown up recent years, its energy storage density and power density, between electrostatic condenser and storage battery, can be used for making up the deficiency of storage battery power characteristic and electrostatic condenser energy storage characteristic.Current, due to the continuous increase to great power pulse power source demand, the energy-storage travelling wave tube that research and development have high energy storage density and high power density seems particularly important, and therefore, people have invested ultracapacitor sight, and have given great expectations to it.
Electric energy weapon is one of new concept weapon that is main energy sources with electric energy or the electric energy of take, it mainly comprises magnetic artillery, coilgun, electric heating and electrothermal chemical gun, microwave weapon, laser weapon etc., in the advantage of the aspects such as interception guided missile, air defense and armour-piercing far above the weapon driving with chemical energy at present.Various countries competitively develop in recent years, have obtained very large breakthrough, and in succession enter target range, estimate that at Future Ten in year, some projects will reach fighting capability.But, it is to need miniaturization, high efficiency pulse power system that electric energy weapon moves towards one of difficult point under battle conditions, because alleviate weaponry, it is present modern an urgent demand under battle conditions, the associated energy storage device with high energy storage density and high power density is crucial, obviously, ultracapacitor is one of desirable selection.
The research of electrode material for super capacitor at present mainly concentrates on active carbon series, transition metal oxide and conductive polymer polymer, because these materials all have higher ratio electric capacity in electrolyte.Electrolyte tends to the liquid electrolyte that adopts conductance higher, and object is in order to reduce interior resistance.Due in the internal structure of ultracapacitor, there is no dielectric, make its operating voltage be subject to the restriction of electrolyte puncture voltage, cause the cell operation voltage of ultracapacitor very low.The puncture voltage of general aqueous electrolyte is less than 1.2V, even organic bath, it is also no more than 3.5V, and this has just limited the operating voltage range of ultracapacitor.The major defect of existing ultracapacitor is that operating voltage is low, and interior resistance is large, affects the quick release of energy, thereby has limited its application.
In recent years, continuous popularization due to Pulse Power Techniques, as energy-storage travelling wave tube, the specific power characteristic of active carbon ultracapacitor can not meet requirement, people start again the faraday's redox reaction by means of active material, carried out the research of another kind of energy storage form, in numerous materials, metal oxide ruthenic oxide (RuO
2) the most outstanding, not only there is higher ratio electric capacity (up to 768F/g), and there is excellent cyclical stability, and be current optimal electrode material, its capacitance is mainly to come from the reversible redox reaction of height occurring between ruthenic oxide and electrolyte solution.Conventionally the method for preparing ruthenium oxide electrode material is mainly divided into two kinds, a kind of is first to adopt chemical method oxygenerating ruthenium end, then be coated in conducting base surface, the common negative electrode that forms ultracapacitor, although easily large-scale production of the method, but its operating voltage is low, a little less than adhesive force, the weak explanation of adhesive force contact resistance is large, cause internal resistance large, internal resistance greatly causes capacitor large in work power consumption, heating is many, properties of product are deteriorated fast, reliability is low, therefore need in ruthenium-oxide powder, add the adhesive force that binding agent increases product, but the meeting of binding agent increases the internal resistance of final products, reduce its reliability, another kind is to adopt electrochemical process directly on collector electrode surface, to prepare ruthenium-oxide, and ruthenium-oxide internal resistance prepared by the method is low, and film forming characteristics is good, but has complex process, and efficiency is low, is not suitable for the defects such as large-scale production.
Summary of the invention
The object of the invention is to solve the defect that above-mentioned prior art exists, provide that a kind of technique is simple, equivalent series internal resistance is low, the preparation method of the hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode of ruthenium strong adhesion.
A preparation method for hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode, comprises the following steps:
(1), preparation is containing ruthenium plating soluton, adopt cyclic voltammetry on tantalum paper tinsel electroplating deposition a layer thickness at the ruthenium-oxide electrodeposited coating of 80-200nm;
(2), by containing ruthenium compound, containing iridic compound, solubility organic binder bond, to press the mixed in molar ratio of 2-6:1:1-2 even;
(3), after being mixed, step 2 by the mixed in molar ratio of 1:0.05-1, evenly forms mixed powder containing ruthenium mixture and active conducting metal or active conducting metal oxide powder;
(4), above-mentioned mixed powder is become to mixed slurry by the quality of 1:0.5-10 than hybrid modulation with solvent, described solvent is one or more in water, ethanol, ethylene glycol, acetone, isopropyl alcohol, 1-METHYLPYRROLIDONE, oxolane;
(5), above-mentioned mixed slurry being brushed or is sprayed on step 1 has on the tantalum paper tinsel matrix of ruthenium-oxide electrodeposited coating through cyclic voltammetric electroplating deposition, then obtained electrode is dried 10 minutes at the drying box of 50-120 ℃, tantalum paper tinsel after oven dry is put into the thermal decomposition furnace of 150-350 ℃, pass into the saturated vapor of 5-50KPa, thermal decomposition 1-8 hour;
(6), aftertreatment technology is to remove impurity and the part active function group on electrode.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, described aftertreatment technology is for being placed on electrode in the high temperature saturated vapor of 250 ℃ and processing 30 minutes.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, described aftertreatment technology, for electrode is immersed in the aqueous sulfuric acid of 0.1-1mol/L, applies constant anode current to electrode, and current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 3-5 time so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide electrode.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, in step 2 containing ruthenium compound, containing the mol ratio of iridic compound, solubility organic binder bond, be 5:1:1.5.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, the mol ratio containing ruthenium mixture and active conducting metal or active conducting metal oxide powder in step 3 is 1:0.2.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, in step 4, the mass ratio of mixed powder and solvent is 1:2-3.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, in step 5, the bake out temperature of drying box is 80 ℃, the temperature of thermal decomposition furnace is 230 ℃, steam pressure 20-40KPa, thermal decomposition time is 2-4 hour.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, on tantalum paper tinsel, the method for electroplating deposition ruthenium-oxide electrodeposited coating comprises the following steps:
1. containing ruthenium plating soluton preparation: ruthenium trichloride 3-7mmol/L, iridous chloride 0.5-2mmol/L, potassium chloride 0.08-0.15mol/L, hydrochloric acid 0.005-0.02mol/L, initial pH value is 1.5-3.0, solution is deionized water, temperature of electroplating solution: 20-70 ℃;
2. utilize three-electrode system to carry out cyclic voltammetry deposition, with tantalum paper tinsel as work electrode, platinized platinum is as auxiliary electrode, silver/silver chloride electrode is as reference electrode, voltage range is-300-1500mV, sweep speed is 30-80mV/s, and the scan period is 50-200 circulation, deposits one deck ruthenium oxide hydration on tantalum paper tinsel;
3. the tantalum paper tinsel that deposits ruthenium oxide hydration is placed in to 100 ℃ of above air 1-3h that anneals.
Further, the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode as above, it is characterized in that, described active conducting metal or active conducting metal oxide powder are that high specific volume capacitor is Ta powder used, one or more in tantalum oxide, zirconia, vanadium oxide, molybdenum oxide and niobium oxide.
Further, the as above preparation method of arbitrary described hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode, is a kind of in ruthenium trichloride, iodate ruthenium, hydrate ruthenium trichloride, hydration iodate ruthenium containing ruthenium compound described in step 2; Described is a kind of in iridous chloride, iodate iridium, hydration iridous chloride, hydration iodate iridium containing iridic compound; Described binding agent is a kind of in camphor, stearic acid, metatitanic acid four fourth fat, methymethacrylate.
The present invention does substrate with cyclic voltammetry depositing nano level ruthenium-oxide, take again and as basis, adopt mixed pyrolysis legal system to make the ruthenium-oxide of adequate thickness a bit, two kinds of technology combine, in order to sulfuric acid solution, be finally electrolyte, obtained electrode has been carried out to surperficial electrolytic treatments, improved the surface energy density of electrode.Solubility organic binder bond of the present invention is to be added in the solution of ruthenium compound (being ruthenium-oxide presoma), ruthenium compound forms in the process of ruthenium-oxide in thermal decomposition like this, adhesive is to be other chemistry of intermolecular level to contact with ruthenium-oxide, can not affect product internal resistance and reliability.If ruthenium-oxide powder is directly mixed with adhesive, this is a kind of Mechanical Contact of simple physical layer, and adhesive can obviously increase product internal resistance.
Accompanying drawing explanation
Accompanying drawing 1 is ruthenium-oxide cathode base tantalum paper tinsel contour structures of the present invention.
Accompanying drawing 2 is the obtained ruthenium-oxide electrode surface scan of the embodiment of the present invention 1 Electronic Speculum micro-structure diagrams;
Accompanying drawing 3 is the obtained ruthenium-oxide electrode surface scan of the embodiment of the present invention 2 Electronic Speculum micro-structure diagrams;
Accompanying drawing 4 is the obtained ruthenium-oxide electrode surface scan of the embodiment of the present invention 3 Electronic Speculum micro-structure diagrams.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The present invention is directed to existing ultracapacitor operating voltage low, the problem that interior resistance is large, adopts the anode of tantalum electrolytic capacitor and the negative electrode of electrochemical capacitor, adds suitable electrolyte solution, forms a kind of novel hybrid super capacitor structure.From theory, this hybrid super capacitor should have advantages of electrolytic capacitor and electrochemical capacitor simultaneously, and operating voltage is high, energy storage density is large, interior resistance is little, can fast charging and discharging etc.Thus, the present invention aims to provide a kind of preparation method of the Fabrication of High Specific Capacitance rate ruthenium-oxide electrode for hybrid super capacitor negative electrode.Strong adhesion, the specific capacity of ruthenium-oxide electrode ruthenium oxide coatings prepared by this method are large, static good cycling stability, be used in conjunction with the anode of tantalum electrolytic capacitor, can fully realize, the requirement of high pressure, large capacity, small size, the large explanation ruthenium-oxide of specific capacity epigranular, particle diameter is very thin, and with the strong adhesion of electrode, contact resistance is little, reduce product internal resistance, improve reliability.The present invention is specifically for required 50V24000 μ F high energy storage density tantalum electrolytic capacitor in modern Aviation, space flight miniaturization, high efficiency pulse power system, its volume package dimension is φ 35mm * 16mm, provide a kind of and take tantalum paper tinsel as matrix, surface-coated ruthenium-oxide than the preparation method of capacity rate negative electrode.
To achieve these goals, the technical solution used in the present invention mainly comprises three phases: the first stage, preparation, containing the electrolyte of ruthenium compound, adopts cyclic voltammetry electroplating deposition a layer thickness ruthenium-oxide about 80-200nm on the tantalum paper tinsel of 0.06-0.12mm thickness; Second stage, preparation is containing the mixed slurry of ruthenium compound and conductive agent and binding agent, slurry is evenly spun on above-mentioned tantalum paper tinsel, and the thermal decomposition furnace of then putting into 150-350 degree under certain overheated saturated steam environment decomposes, and makes the ruthenium oxide hydration that thickness is about 0.1-0.5mm; Phase III, ruthenium-oxide negative electrode aftertreatment technology, is about to electrode and is immersed in and in sulfuric acid solution, carries out electrochemical redox processing, thereby electrode structure and performance reaches stable.Concrete grammar is described below:
First stage: cyclic voltammetric electro-deposition
1, the preparation of electroplate liquid: ruthenium trichloride 3-7mmol/L; Iridous chloride 0.5-2mmol/L; Potassium chloride 0.08-0.15mol/L; Hydrochloric acid 0.005-0.02mol/L; Initial pH value: 1.5-3.0; Solution is deionized water, temperature of electroplating solution: 20-70 ℃.
2, adopt TD73000PCI type constant current/potentiostat, utilize three-electrode system to carry out cyclic voltammetry deposition, with parent metal sheet (selecting tantalum piece herein), as work electrode, platinized platinum is as auxiliary electrode, and silver/silver chloride electrode (in saturated potassium chloride solution) is as reference electrode.
In three-electrode system, electrode should carry out pre-treatment according to the difference of function.
The pre-treatment of work electrode: surperficial machinery and electrochemical treatments.
The pre-treatment of auxiliary electrode: clean and polished surface.
The pre-treatment of reference electrode: the saturated KCl solution through 12 hours soaks.
Voltage range is-300-1500mV; Sweep speed is 30-80mV/s; Scan period is that (" a cyclic voltammetric cycle is " spike potential 1 " → " spike potential 3 " → " termination current potential " → " spike potential 1 " in 50-200 circulation.By instrument, set, sweep speed is 50mV/S conventionally, and in the present invention, voltage is-300-1500mV, and one-period change in voltage is 2* (1500+300)=3600mV, and the time is 72S, 50-200 circulation, total time is 3600S-14400S).
3, annealing, will deposit the tantalum paper tinsel of ruthenium oxide hydration, is placed in 100 ℃ of above air 1-3h that anneals, to increase stability and the compactness of oxide on electrode.
The preferred technical scheme of the present invention is: electrolyte forms: ruthenium trichloride 5mmol/L; Iridous chloride 1mmol/L; Potassium chloride 0.1mol/L; Hydrochloric acid 0.01mol/L; Initial pH value: 2.3; Solution is deionized water, temperature of electroplating solution: 50 ℃.Voltage range is-200-1000mV; Sweep speed is 50mV/s; Scan period is 100 circulations.Annealing in process is 200 ℃ of air 2h.
Second stage: slurry applies thermal decomposition
1,, by the mixed in molar ratio that contains ruthenium compound, presses 2-6:1:1-2 containing iridic compound, solubility organic binder bond, wherein, described is ruthenium trichloride or iodate ruthenium or hydrate ruthenium trichloride or hydration iodate ruthenium containing ruthenium compound; Described is iridous chloride or iodate iridium or hydration iridous chloride or hydration iodate iridium containing iridic compound; Described solubility organic binder bond is a kind of in the solubility organic binder bonds such as camphor or stearic acid or metatitanic acid four fourth fat or methymethacrylate.
2, described mixed in molar ratio of pressing 1:0.2-2 containing ruthenium mixture and active conducting metal or active conducting metal oxide powder is even, described active conductive powder body is that high specific volume capacitor is Ta powder used, one or more in tantalum oxide, zirconia, vanadium oxide, molybdenum oxide and niobium oxide.
The quality of 3, above-mentioned mixed powder and solvent being pressed to 1:0.5-10 is than hybrid modulation form slurry, and wherein, described solvent is one or more mixing in water, ethanol, ethylene glycol, acetone, isopropyl alcohol, 1-METHYLPYRROLIDONE and oxolane.
4, above-mentioned mixed-powder slurry is brushed or is sprayed on through cyclic voltammetric deposited on the tantalum paper tinsel matrix of ruthenium-oxide electrodeposited coating, then obtained electrode is dried 10 minutes at the drying box of 50-120 ℃, tantalum paper tinsel after oven dry is put into the thermal decomposition furnace of 150-350 ℃, pass into the saturated vapor of 5-50KPa, thermal decomposition 1-8 hour.
The preferred technical conditions of the present invention are: by the mol ratio that contains ruthenium compound, is 5:1:1.5 containing iridic compound, solubility organic binder bond ratio; Contain the mol ratio that ruthenium mixture and active conductive powder body are pressed 1:0.2; The mass ratio of compound and solvent is 1:2-3; The 4th step bake out temperature is 80 ℃, and the temperature of heating furnace is 230 ℃, steam pressure 20-40KPa, and thermal decomposition time is 2-4 hour.
Phase III: ruthenium-oxide negative electrode aftertreatment technology
Tantalum foil electrode after above-mentioned thermal decomposition also needs to carry out special processing could be for mixing the assembling of tantalum electrolytic capacitor with impurity and the part active function group of removing wherein.Processing mode has two kinds, and a kind of is that electrode is placed in the high temperature saturated vapor of 250 ℃ and is processed 30 minutes; Another kind is that electrode is immersed in sulfuric acid solution and carries out electrochemical redox processing, and the working electrolyte of tantalum electrolytic capacitor is exactly aqueous sulfuric acid conventionally, so the present invention also adopts sulfuric acid to carry out reprocessing to electrode.Concrete method is that electrode is immersed in the aqueous sulfuric acid of 0.1-1mol/L (being preferably 0.5mol/L), and electrode is applied to constant anode current, and current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 3-5 time so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide negative electrode.
Compared with the prior art, this is bright owing to having adopted technique scheme, and cyclic voltammetry is combined with heat of mixing solution, has improved the adhesive force of ruthenium-oxide; In saturated vapor, carry out thermal decomposition, and form codeposition with iridic compound, suppress and delayed the crystallization of amorphous state ruthenium oxide hydration, guaranteed the Fabrication of High Specific Capacitance rate of electrode.In thermal decomposition process, add a small amount of active conducting metal oxide powder, by carrying out in sulfuric acid solution after electrochemical redox processing, increased stability and the reliability of ruthenium-oxide electrode.
Embodiment 1:
1, hybrid battery electrolysis condenser ruthenium-oxide negative electrode tantalum metallic matrix preliminary treatment
The tantalum paper tinsel that is 0.08mm by thickness is cut into the tantalum piece of φ 33mm by shape shown in Fig. 1, with thick abrasive paper for metallograph, polish, then it is soaked to 10-20 minute in the hot nitric acid acid of the 30wt% of 40-60 ℃ and the hydrofluoric acid mix acid liquor of 1wt%, after taking-up with deionized water repeatedly rinsing after drying, be immersed in ethanolic solution standby;
2, cyclic voltammetry depositing nano ruthenium-oxide substrate
By ruthenium trichloride, iridous chloride, potassium chloride in the ratio mixed dissolution of 5mmol/L:1mmol/L:0.1mol/L in deionized water, and splash into the hydrochloric acid of 0.01mol/L, the initial pH value of adjusting mixed solution is 2.3; At 50 ℃, voltage range is-200-1000mV; Sweep speed is 50mV/s; Scan period is, under the condition of 100 circulations, the tantalum paper tinsel through surface preparation is carried out to cyclic voltammetric electroplating deposition ruthenium-oxide electrodeposited coating, carries out 2h annealing in process afterwards in 200 ℃ of air.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 100nm of a layer thickness.
3, slurry applies thermal decomposition
By ruthenium trichloride, iridous chloride, stearic acid, be that the mixed in molar ratio of 5:1:1.5 is even in proportion, obtain containing ruthenium mixture; Take containing ruthenium mixture 2g and mix with Ta powder used in capacitor 0.2g, and obtain containing ruthenium mixture paste after adding 5g isopropyl alcohol to grind evenly in agate mortar, then this slurry is brushed and circulated and depositing on the tantalum piece matrix of ruthenium-oxide substrate through volt-ampere, in temperature, be at 80 ℃, to dry after 10 minutes, it in temperature, is the heating furnace of 230 ℃, pass into the saturated vapor pressure of 35KPa, thermal decomposition time is 2-4 hour.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 0.2mm of a layer thickness, and surface is fine and close porous form, as shown in Figure 2, as can be seen from Figure 2, the ruthenium-oxide electrode epigranular that adopts the inventive method to prepare, granularity is very thin, contact is tight, strong adhesion.
4, ruthenium-oxide negative electrode reprocessing
The electrode that deposits ruthenium-oxide after above-mentioned thermal decomposition is immersed in the aqueous sulfuric acid of 0.5mol/L, electrode is applied to constant anode current, current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 5 times so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide negative electrode.
Embodiment 2:
1. hybrid battery electrolysis condenser ruthenium-oxide negative electrode tantalum metallic matrix preliminary treatment
The tantalum paper tinsel that is 0.06mm by thickness is cut into the tantalum piece of φ 33mm by shape shown in Fig. 1, with thick abrasive paper for metallograph, polish, then it is soaked to 10-20 minute in the hot nitric acid acid of the 30wt% of 40-60 ℃ and the hydrofluoric acid mix acid liquor of 1wt%, after taking-up with deionized water repeatedly rinsing after drying, be immersed in ethanolic solution standby;
2, cyclic voltammetry depositing nano ruthenium-oxide substrate
By ruthenium trichloride, iridous chloride, potassium chloride in the ratio mixed dissolution of 3mmol/L:2mmol/L:0.15mol/L in deionized water, and splash into the hydrochloric acid of 0.02mol/L, the initial pH value of adjusting mixed solution is 1.5; At 70 ℃, voltage range is-300-1000mV; Sweep speed is 30mV/s; Scan period is, under the condition of 50 circulations, the tantalum paper tinsel through surface preparation is carried out to cyclic voltammetric electroplating deposition ruthenium-oxide electrodeposited coating, carries out 1h annealing in process afterwards in 150 ℃ of air.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 100nm of a layer thickness.
3, slurry applies thermal decomposition
By ruthenium trichloride, iridous chloride, stearic acid, be that the mixed in molar ratio of 2:1:1 is even in proportion, obtain containing ruthenium mixture; Take containing ruthenium mixture 2g and mix with Ta powder used in capacitor 0.1g, and obtain containing ruthenium mixture paste after adding 1.05g acetone to grind evenly in agate mortar, then this slurry is brushed and circulated and depositing on the tantalum piece matrix of ruthenium-oxide substrate through volt-ampere, in temperature, be at 50 ℃, to dry after 10 minutes, it in temperature, is the heating furnace of 150 ℃, pass into the saturated vapor pressure of 50KPa, thermal decomposition time is 8 hours.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 0.2mm of a layer thickness, and surface is fine and close porous form, as shown in Figure 3, as can be seen from Figure 3, the ruthenium-oxide electrode epigranular that adopts the inventive method to prepare, granularity is very thin, contact is tight, strong adhesion.
4, ruthenium-oxide negative electrode reprocessing
The electrode that deposits ruthenium-oxide after above-mentioned thermal decomposition is immersed in the aqueous sulfuric acid of 0.1mol/L, electrode is applied to constant anode current, current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 4 times so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide negative electrode.
Embodiment 3:
1. hybrid battery electrolysis condenser ruthenium-oxide negative electrode tantalum metallic matrix preliminary treatment
The tantalum paper tinsel that is 0.12mm by thickness is cut into the tantalum piece of φ 33mm by shape shown in Fig. 1, with thick abrasive paper for metallograph, polish, then it is soaked to 10-20 minute in the hot nitric acid acid of the 30wt% of 40-60 ℃ and the hydrofluoric acid mix acid liquor of 1wt%, after taking-up with deionized water repeatedly rinsing after drying, be immersed in ethanolic solution standby;
2, cyclic voltammetry depositing nano ruthenium-oxide substrate
By ruthenium trichloride, iridous chloride, potassium chloride in the ratio mixed dissolution of 7mmol/L:0.5mmol/L:0.08mol/L in deionized water, and splash into the hydrochloric acid of 0.005mol/L, the initial pH value of adjusting mixed solution is 3.0; At 20 ℃, voltage range is-100-1500mV; Sweep speed is 80mV/s; Scan period is, under the condition of 200 circulations, the tantalum paper tinsel through surface preparation is carried out to cyclic voltammetric electroplating deposition ruthenium-oxide electrodeposited coating, carries out 3h annealing in process afterwards in 100 ℃ of air.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 100nm of a layer thickness.
3, slurry applies thermal decomposition
By ruthenium trichloride, iridous chloride, stearic acid, be that the mixed in molar ratio of 6:1:2 is even in proportion, obtain containing ruthenium mixture; Take containing ruthenium mixture 2g and mix with Ta powder used in capacitor 2g, and the mixture that adds 40g isopropyl alcohol and ethylene glycol grinds evenly rear acquisition containing ruthenium mixture paste in agate mortar, then this slurry is brushed and circulated and depositing on the tantalum piece matrix of ruthenium-oxide substrate through volt-ampere, in temperature, be at 120 ℃, to dry after 10 minutes, it in temperature, is the heating furnace of 350 ℃, pass into the saturated vapor pressure of 50KPa, thermal decomposition time is 1 hour.
Adopt said method can deposit at electrode surface the ruthenium-oxide of the about 0.2mm of a layer thickness, and surface is fine and close porous form, as shown in Figure 4, as can be seen from Figure 4, the ruthenium-oxide electrode epigranular that adopts the inventive method to prepare, granularity is very thin, contact is tight, strong adhesion.
4, ruthenium-oxide negative electrode reprocessing
The electrode that deposits ruthenium-oxide after above-mentioned thermal decomposition is immersed in the aqueous sulfuric acid of 1mol/L, electrode is applied to constant anode current, current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 3 times so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide negative electrode.
Comparative example 1:
According to the mode of embodiment 1, carry out the preparation of negative electrode tantalum paper tinsel matrix, but without the cyclic voltammetry depositing nano level ruthenium-oxide electrodeposited coating tantalum paper tinsel of first stage, do the making of substrate, and according to the step that enters second stage and phase III, make the preparation of ruthenium-oxide negative electrode.
Comparative example 2:
According to the mode of embodiment 1, carry out the preparation of negative electrode tantalum paper tinsel matrix, but only pass through the processing of first stage and second stage, there is no phase III ruthenium-oxide negative electrode aftertreatment technology.
The CHI660A electrochemical analyser that adopts Shanghai Chen Hua instrument company to produce carries out cyclic voltammetry experiment to be tested the electrochemical properties of above-described embodiment and the obtained electrode of comparative example.Test result is as following table one.
Table one
Test result shows, the prepared ruthenium-oxide mixed electrode specific capacity of embodiment 1,2,3 is relatively large, and equivalent series internal resistance is low, therefore, the electrode performance that adopts the inventive method to prepare is very excellent, is suitable for hybrid super capacitor tantalum electrolytic capacitor negative electrode.Mixed electrode specific capacity is large, and equivalent series internal resistance is low, and ruthenium-oxide epigranular prepared by the present invention has directly been described, granularity is very thin, and contact is tight, strong adhesion.Because only have epigranular, fine size, guarantee electrode has very large effective ratio area, and long-pending larger than table, the specific capacity of mixed electrode is large, and (capacity is directly proportional to specific area) also illustrates that surperficial energy storage density is high, and equivalent internal resistance is low, and reliability is high.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a preparation method for hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode, is characterized in that, comprises the following steps:
(1), preparation is containing ruthenium plating soluton, adopt cyclic voltammetry on tantalum paper tinsel electroplating deposition a layer thickness at the ruthenium-oxide electrodeposited coating of 80-200nm;
(2), by containing ruthenium compound, containing iridic compound, solubility organic binder bond, to press the mixed in molar ratio of 2-6:1:1-2 even;
(3), after being mixed, step 2 by the mixed in molar ratio of 1:0.05-1, evenly forms mixed powder containing ruthenium mixture and active conducting metal or active conducting metal oxide powder;
(4), above-mentioned mixed powder is become to mixed slurry by the quality of 1:0.5-10 than hybrid modulation with solvent, described solvent is one or more in water, ethanol, ethylene glycol, acetone, isopropyl alcohol, 1-METHYLPYRROLIDONE, oxolane;
(5), above-mentioned mixed slurry being brushed or is sprayed on step 1 has on the tantalum paper tinsel matrix of ruthenium-oxide electrodeposited coating through cyclic voltammetric electroplating deposition, then obtained electrode is dried 10 minutes at the drying box of 50-120 ℃, tantalum paper tinsel after oven dry is put into the thermal decomposition furnace of 150-350 ℃, pass into the saturated vapor of 5-50KPa, thermal decomposition 1-8 hour;
(6), aftertreatment technology is to remove impurity and the part active function group on electrode.
2. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, is characterized in that, described aftertreatment technology is for being placed on electrode in the high temperature saturated vapor of 250 ℃ and processing 30 minutes.
3. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, it is characterized in that, described aftertreatment technology, for electrode is immersed in the aqueous sulfuric acid of 0.1-1mol/L, applies constant anode current to electrode, and current strength is controlled as 5-10mA/cm
2, after 10 minutes, electric current is adjusted into 20-30mA/cm
2, controlling conduction time is 5 minutes, and then electric current is adjusted into 5-10mA/cm
2, 3-5 time so repeatedly, electrode is taken out, use rinsed with deionized water 30 minutes, and be placed in the preparation that 50 ℃ of following baking ovens oven dry complete ruthenium-oxide electrode.
4. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, is characterized in that, in step 2 containing ruthenium compound, containing the mol ratio of iridic compound, solubility organic binder bond, be 5:1:1.5.
5. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, is characterized in that, the mol ratio containing ruthenium mixture and active conducting metal or active conducting metal oxide powder in step 3 is 1:0.2.
6. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, is characterized in that, in step 4, the mass ratio of mixed powder and solvent is 1:2-3.
7. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, it is characterized in that, in step 5, the bake out temperature of drying box is 80 ℃, and the temperature of thermal decomposition furnace is 230 ℃, steam pressure 20-40KPa, thermal decomposition time is 2-4 hour.
8. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, is characterized in that, on tantalum paper tinsel, the method for electroplating deposition ruthenium-oxide electrodeposited coating comprises the following steps:
1. containing ruthenium plating soluton preparation: ruthenium trichloride 3-7mmol/L, iridous chloride 0.5-2mmol/L, potassium chloride 0.08-0.15mol/L, hydrochloric acid 0.005-0.02mol/L, initial pH value is 1.5-3.0, solution is deionized water, temperature of electroplating solution: 20-70 ℃;
2. utilize three-electrode system to carry out cyclic voltammetry deposition, with tantalum paper tinsel as work electrode, platinized platinum is as auxiliary electrode, silver/silver chloride electrode is as reference electrode, voltage range is-300-1500mV, sweep speed is 30-80mV/s, and the scan period is 50-200 circulation, deposits one deck ruthenium oxide hydration on tantalum paper tinsel;
3. the tantalum paper tinsel that deposits ruthenium oxide hydration is placed in to 100 ℃ of above air 1-3h that anneals.
9. the preparation method of hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode according to claim 1, it is characterized in that, described active conducting metal or active conducting metal oxide powder are that high specific volume capacitor is Ta powder used, one or more in tantalum oxide, zirconia, vanadium oxide, molybdenum oxide and niobium oxide.
10. according to the preparation method of the arbitrary described hybrid super capacitor Fabrication of High Specific Capacitance rate ruthenium-oxide electrode of claim 1-9, it is characterized in that, is a kind of in ruthenium trichloride, iodate ruthenium, hydrate ruthenium trichloride, hydration iodate ruthenium containing ruthenium compound described in step 2; Described is a kind of in iridous chloride, iodate iridium, hydration iridous chloride, hydration iodate iridium containing iridic compound; Described binding agent is a kind of in camphor, stearic acid, metatitanic acid four fourth fat, methymethacrylate.
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