CN103227057B - A kind of method preparing manganese dioxide electrode of super capacitor - Google Patents
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of manganese dioxide electrode of super capacitor.It is characterized in that the preparation process of this electrode comprises following step: first pass through electrochemical co-deposition one deck manganese alloy coating in electrode current collecting surface; Then the electrode of resulting tape manganese alloy coating is carried out anodized and obtain manganese dioxide electrode.The present invention realizes alloying element by electrochemical co-deposition and is uniformly distributed in prepared electrode interior, to improve its electronic conductivity in anodic oxidation and charge and discharge process; The manganese in alloy-layer is made to change into the manganese bioxide material with electro-chemical activity on the one hand by anodic oxidation, simultaneously also can at prepared electrode surface and Internal architecture pore passage structure, thus improve solid phase mass transfer characteristic and the electrochemical reaction activity of material, obtain the electrode of high specific capacitance characteristic.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of method preparing manganese dioxide electrode of super capacitor.
Technical background
Ultracapacitor is a kind of new ideas energy storage device between battery and conventional electrostatic container, compared with the conventional electrostatic capacitors such as aluminium electrolytic capacitor, ultracapacitor has higher ratio capacitance, and storable energy density is more than 10 times of conventional electrostatic capacitor; And compared with battery, ultracapacitor has larger power density, and have that efficiency for charge-discharge is high, the characteristic such as have extended cycle life.Owing to having above many superiority, the exploitation of supercapacitor technologies is subject to the most attention of academia, industrial circle and military service always, and be applied in the some starting ignition power supply of electronic instrument back-up source and rocket, guided missile, artificial satellite, spaceship space station etc. gradually, the super high power capacitor of wherein starting ignition can provide the especially big starting power of MW level.
Along with world climate change and the continuous exhaustion of fossil resource, the exploitation enthusiasm of the mankind to regenerative resource is constantly surging, larger progress has been achieved to the exploitation of solar energy, wind energy, simultaneously in order to save limited petroleum resources, electric automobile and the hybrid electric vehicle technological development that can realize zero discharge and low emission are also extremely paid attention to.Have intermittence owing to relying on sunlight and wind to generate electricity, and we are at any time to the demand of electric energy, energy-storage system plays the part of important role by the productive life of the following mankind.As typical electric energy storage system, can exploitation has the heavy-duty battery of high-power, high energy density characteristic and low cost and ultracapacitor realize one of key link that regenerative resource effectively utilizes by being.
Compared with battery, the subject matter that ultracapacitor faces is that energy density is lower.In order to improve the performance of ultracapacitor, namely while raising specific energy, keep the advantages such as its big specific power rate, the research around the transition metal oxide electrode with electric double layer capacitance and Faraday pseudo-capacitance behavior receives much concern.What be subject to extensively research at present is with RuO
2for electrode material, it can not only realize high-power discharge and recharge, and specific energy is also higher simultaneously, is the class electrode material up to the present all achieving breakthrough in materials processing and application.But it is high that the key issue that this material faces is material cost, be therefore difficult to obtain business promotion in civilian industry.In order to seek cheap electrode material for super capacitor, around NiO, Co
3o
4, V
2o
5, MnO
2in succession launch Deng the preparation of transition metal oxide material and Electrochemical Properties.But, most research is all first above-mentioned transition metal oxide is prepared into powder granule material, be coated with to invest on collector after being mixed with binding agent by these powder body materials again and prepare electrode, this just easily causes loose contact between electrode active material and collector and affects the charge-discharge performance of electrode.In addition, vital effect is played due to electrode material internal structure and with the performance of electrolytical interfacial characteristics to capacitor, be difficult to carry out design effectively to electrode material surface and inner fine structure when adopting chemical precipitation method, hydro thermal method etc. to prepare Powder electrode material, be difficult to the electrode material obtaining high power density and high-energy-density; Prepare electrode material by the production method of the electrolytic manganese dioxide of routine to be then difficult to carry out element doping, the electrode material ratio capacitance prepared can only reach 200F.g usually
-1left and right.The present invention adopts electrochemical method to prepare manganese dioxide electrode of super capacitor, is constructed and realizes active material component and internal structure design, improve the contact between electrode active material and collector simultaneously by electrochemistry, makes it to possess Fabrication of High Specific Capacitance characteristic.
Summary of the invention
The object of the invention is to propose a kind of method preparing manganese dioxide electrode of super capacitor, emphasis is by electrochemical method construction material internal gutter structure and carries out component design, to improve internal mass transfer characteristic and the electronic conductance performance of material, thus obtain the electrode of super capacitor of Fabrication of High Specific Capacitance feature.
The present invention proposes a kind of method preparing manganese dioxide electrode of super capacitor, comprises the steps:
The first step: electrochemical co-deposition manganese alloy coating
Soluble manganese salt, soluble alloy component salt, supporting electrolyte salt, additive are dissolved in water in proportion and are mixed with mixed aqueous solution as electroplate liquid, with being negative electrode through surface finish and cleaned current collector material, inert anode is that anode carries out manganese alloy electrochemical co-deposition, obtains manganese alloy coating electrode;
Second step: the anodic oxidation of manganese alloy coating
Be anode with the manganese alloy coating electrode of first step gained, the inert electrodes such as stainless steel substrates, graphite flake or peptide sheet are cathode, be that electrolyte carries out anodized, obtain porous oxidation manganese electrode with the solution containing solubility haloid;
3rd step: electrode changes into
The porous oxidation manganese electrode obtained with second step is work electrode, the inert electrode such as stainless steel or graphite flake is auxiliary electrode, conventional electrolytic solution for super capacitor is electrolyte, assemble two electrode systems and carry out small area analysis discharge and recharge for several times, make the manganese in porous oxidation manganese electrode be completely oxidized to manganese dioxide.
The preparation method of a kind of manganese dioxide electrode of the present invention, described manganese alloy coating is obtained by electrochemical co-deposition.
A preparation method for manganese dioxide electrode of super capacitor, the soluble manganese salt described in the first step is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate; Alloying element in described soluble alloy component salt comprises one or more in Ni, Co, Mo, Fe, Cu, W, Ag, Ru, Au, Pt; Soluble alloy component salt comprises one or more in the sulfate of Ni, Co, Mo, Fe, Cu, W, Ag, Ru, Au, Pt, nitrate, hydrochloride, cyanate or rhodanate.
A kind of preparation method of manganese dioxide electrode of super capacitor, in the described first step, supporting electrolyte is ammonium sulfate, ammonium chloride, alkali metal sulfates or chloride, additive comprises pH buffer, complexing agent, wherein pH buffer is one or more in boric acid, natrium citricum, ammoniacal liquor, one or more comprising in solubility edetate, citrate, sulphur urine, rhodanate, cyanide of complexing agent can carry out the material of effective complexing to required alloying element, the material as collector comprises conducting metal and conductive non-metals.
A kind of preparation method of manganese dioxide electrode, in the described first step, in electroplate liquid, the concentration of manganese ion is 0.1 ~ 0.8mol/L, the concentration of supporting electrolyte is 0.7 ~ 1.2mol/L, manganese ion is 20 ~ 50 with the ratio of alloying element ion molar concentration, the mol ratio of complexing agent and alloying element is 1 ~ 10, and the pH value range of electroplate liquid is 4 ~ 7.
A preparation method for manganese dioxide electrode, in the described first step, the material as collector comprises conducting metal and conductive non-metals.
A preparation method for manganese dioxide electrode, in the described first step, when carrying out electrochemical co-deposition, can adopt pulse, constant voltage or constant current codeposition.
A preparation method for manganese dioxide electrode, the electrolyte used in described second step is for containing F
-or Cl
-deng the electrolyte of halide ion, the mass concentration scope of halide ion is 0.1 ~ 0.5%.
A preparation method for manganese dioxide electrode, the solvent in the electrolyte used in described second step is water, alcohols or its mixture.
A preparation method for manganese dioxide electrode, can carry out pulse, constant current or constant voltage oxidation when carrying out anodic oxidation in described second step, last obtained be a kind of porous oxidation manganese electrode.
A preparation method for manganese dioxide electrode, can carry out constant current or constant voltage oxidation in described second step when carrying out anodic oxidation, the current density range of constant current oxidation is 0.1 ~ 10mA/cm
2, the tank voltage scope of constant voltage oxidation is 5 ~ 80V.
The preparation method of a kind of manganese dioxide electrode of the present invention, the charging and discharging currents density used when carrying out electrode and changing in described 3rd step is at 0.1 ~ 10mA/cm
2.
The present invention adopts said method, is first 20 ~ 50 weigh soluble manganese salt and soluble alloy component salt and be dissolved in water respectively by manganese and alloying element mol ratio, is mixed with the aqueous solution respectively.Adding by alloying element and complexing agent mol ratio in alloy compositions salting liquid is the complexing agent of 1 ~ 10, fully stirs, and makes it dissolve the solution forming homogeneous transparent.The manganese salt solution prepared and alloy compositions salting liquid are mixed, and supporting electrolyte is added in this mixed solution, make the concentration of wherein supporting electrolyte reach 0.7 ~ 1.2mol/L, finally add pH buffer and other additive, stir after adding the water and within least 30 minutes, obtain required electroplate liquid.In this electroplate liquid, the concentration of manganese ion is 0.1 ~ 0.8mol/L, the concentration of supporting electrolyte is 0.7 ~ 1.2mol/L, manganese ion is 20 ~ 50 with the ratio of alloying element ion molar concentration, the mol ratio of complexing agent and alloying element is 1 ~ 10, the complex ion ligancy formed by complexing agent and alloying element ion determines, the pH value range of electroplate liquid is 4 ~ 7.Alloy compositions salt used herein comprises one or more in the soluble-salt of Ni, Co, Mo, Fe, Cu, W, Ag, Ru, Au, Pt.Electrolyte is one or more in ammonium sulfate, ammonium chloride and alkali metal sulfates or chloride, and pH buffer is one or more in boric acid, natrium citricum, ammoniacal liquor.Complexing agent comprise in solubility edetate, citrate, sulphur urine, rhodanate, cyanide one or more etc. can carry out the material of effective complexing to required alloying element.
By conventional electroplating part surface-treated method, surface treatment is carried out to the collector for ultracapacitor, as the process such as surface finish, cleaning, then with it as negative electrode (work electrode), the inert anode such as titanium, graphite is anode, carries out electro-deposition and prepare manganese alloy coating electrode in the electroplating bath of electroplate liquid that above-mentioned preparation is housed.When carrying out electro-deposition, pulse, constant voltage or constant current codeposition can be adopted, but pulsed cathode current potential or constant voltage cathode potential be not higher than-1.2V(relative hydrogen mark electrode).
Be anode by above-mentioned manganese alloy coating electrode, stainless steel substrates or other sheet metal are cathode, be that electrolyte carries out anodized to manganese alloy coating, obtain porous oxidation manganese electrode with the solution that the mass concentration of halogen-containing ion is 0.1 ~ 0.5%.During in order to improve anodic oxidation, the electrical conductance of electrolyte, can add other supporting electrolyte, as sodium sulphate in this haloid solution.
Because the manganese in the porous oxidation manganese electrode that formed when anodic oxidation can not be completely oxidized the manganese into+4 valencys, affect electrode electro Chemical performance, finally must change into process to this porous oxidation manganese electrode, manganese is wherein converted into have+4 valency manganese of electro-chemical activity.Chemical synthesizing method is identical with the formation process of other energy storage devices such as lead-acid battery, as electrode put into the aqueous sodium persulfate solution 0.5mA/cm of 0.5mol/L
2electric current carry out discharge and recharge for several times, finally obtain manganese dioxide electrode of super capacitor.Advantage of the present invention is: 1) do not need in electrode slice preparation process to carry out the processes such as active material slurry modulation, smear, technical process is simple; 2) prepare manganese alloy by alloy codeposition, the alloy compositions more positive than the corrosion potential of manganese can overcome the more crisp shortcoming of simple manganese coating, improves the processing characteristics of coating, and in anodizing and formation process, manganese is then converted into+4 valency manganese; 3) alloy compositions that corrosion potential is positive due in anode oxidation process difficulty be corroded, it can be electrode and changes into and provide enough electron channels with the electrochemical reaction in charge and discharge process, reduces ohmic polarization; 4) by electrochemical oxidation, manganese metal is while oxidized, and part metals manganese or lower valency manganese oxide are by the H produced because of the decomposition of water in this oxidizing process
+etching, thus form loose structure, for electrochemical reaction and electric double layer capacitance provide large Cathode/Solution Interface, make electrode have Fabrication of High Specific Capacitance feature.
Accompanying drawing explanation
Accompanying drawing 1 is the cyclic voltammetry curve of manganese dioxide electrode of super capacitor prepared by the embodiment of the present invention 1.
From the cyclic voltammetry curve of accompanying drawing 1, the ratio capacitance calculating electrode active material prepared by embodiment 1 is 413F/g.
Specific embodiment
Embodiment one
Configure MnSO respectively
4.H
2o and NiSO
4.7H
2the O aqueous solution is that 1:1 is to NiSO by the mol ratio of nickel and disodium ethylene diamine tetraacetate
4add disodium ethylene diamine tetraacetate in solution and fully stir, making it form the solution of homogeneous transparent.The two kinds of solution containing manganese salt and nickel salt prepared are mixed, mixes in this mixed solution backward and add ammonium sulfate and lauryl sodium sulfate, dissolve after adding water; The concentration of each composition is made to be: the concentration of manganese ion is 0.5mol/L, and ammonium sulfate concentrations is 1.2mol/L, and nickel ion concentration is 0.025mol/L.Regulate the pH value of solution to 5 with ammoniacal liquor, continue stirring for subsequent use after 60 minutes.
304 stainless steel foils being cut into area is 4 × 1cm
2stainless steel band is as collector, and carry out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, final rinse water is also dried.Be titanium net electrode with 4 × 4cm, above-mentioned nickeliferous and solution that is manganese is electroplate liquid, and the collector after surface clean is that (work area is 1 × 1cm to negative electrode
2), carry out the electro-deposition of constant current manganese-nickel, current density 300mA/cm
2, electrodeposition time is 8 minutes, obtains manganese-nickel coating.Find that in alloy, nickel content is 8% with icp analysis.
Be anode by the manganese alloy coating electrode of above-mentioned acquisition, stainless steel substrates (area 4 × 4cm
2) be cathode, with containing NH
4f0.25%, the ethylene glycol solution of water 5% is that electrolyte carries out anodized, and oxidation trough voltage is 20V, and the time is 7 minutes, obtains porous oxidation manganese electrode.Be electrolyte with the aqueous sodium persulfate solution of 0.5mol/L, porous oxidation manganese electrode is anode, and area is 4 × 4cm
2platinum electrode be cathode assembling analog capacitor, use 1mA/cm
2electric current carry out constant current charge-discharge 10 times, finally by water rinse and drying after obtain manganese dioxide electrode of super capacitor.Be electrolyte with the aqueous sodium persulfate solution of 0.5mol/L, the manganese oxide electrode work electrode of above-mentioned preparation, area is 4 × 4cm
2platinum electrode be auxiliary electrode assembling three-electrode system, carry out cyclic voltammetry, test potential scope is 0 ~ 0.8V (relative to silver-silver chloride electrode), and sweep speed is 10mV/s.The ratio capacitance calculating electrode active material according to cyclic voltammetry curve is 413F/g.
Embodiment two
Operating process is with embodiment one, and the manganese sulfate concentration just used is 0.8mol/L, and soluble alloy component salt is CoSO
4.7H
2o, complexing agent is natrium citricum, and the mol ratio of cobalt and natrium citricum is 1:5, and ammonium sulfate concentrations is 0.9mol/L, and concentration of cobalt ions is 0.016mol/L.Regulate the pH value of solution to 7 with ammoniacal liquor.With containing NH
4f0.1%, the ethylene glycol solution of water 5% is that electrolyte carries out anodized, and constant voltage oxidation trough voltage is 80V, and recording cobalt content in alloy layer is 11%, and the ratio capacitance of electrode active material is 381F/g.
Embodiment three
Operating process is with embodiment one, and the manganese sulfate concentration just used is 0.8mol/L, and soluble alloy component salt is AgNO
3, complexing agent is NaCN, and silver is 1:10 with the mol ratio of NaCN, Ag in electroplate liquid
+concentration is 0.02mol/L.Regulate the pH value of solution to 7 with ammoniacal liquor.With containing NH
4cL0.5%, the ethylene glycol solution of water 5% is that electrolyte carries out anodized, and constant voltage oxidation trough voltage is 5V, uses 0.1mA/cm
2electric current carry out constant current charge-discharge 10 times, recording silver content in alloy layer is 4%, and the ratio capacitance of electrode active material is 437F/g.
Embodiment four
Operating process is with embodiment one, and the manganese sulfate concentration just used is 0.1mol/L, and soluble alloy component salt is CoSO
4.7H
2o, complexing agent is natrium citricum, and the mol ratio of cobalt and natrium citricum is 1:5, and ammonium sulfate concentrations is 0.7mol/L, and concentration of cobalt ions is 0.003mol/L.Regulate the pH value of solution to 4 with ammoniacal liquor, use 10mA/cm
2electric current carry out constant current charge-discharge 10 times, recording cobalt content in alloy layer is 5%, and the ratio capacitance of electrode active material is 341F/g.
Claims (7)
1. prepare a method for manganese dioxide electrode of super capacitor, comprise the steps:
The first step: electrochemical co-deposition manganese alloy coating
Soluble manganese salt, soluble alloy component salt, supporting electrolyte salt, additive are dissolved in water in proportion and are mixed with mixed aqueous solution as electroplate liquid, with being negative electrode through surface finish and cleaned current collector material, inert anode is that anode carries out manganese alloy electrochemical co-deposition, obtains manganese alloy coating electrode;
In electroplate liquid, the concentration of manganese ion is 0.1 ~ 0.8mol/L, and electrolytical concentration is 0.7 ~ 1.2mol/L, and manganese ion is 20 ~ 50 with the ratio of alloying element ion molar concentration, and the mol ratio of complexing agent and alloying element is 1 ~ 10, and the pH value range of electroplate liquid is 4 ~ 7;
Second step: the anodic oxidation of manganese alloy coating
Using the manganese alloy coating electrode of first step gained as anode, inert electrode is cathode, is that electrolyte carries out anodized, obtains porous oxidation manganese electrode with the solution containing solubility haloid;
3rd step: electrode changes into
The porous oxidation manganese electrode obtained by second step is anode, and inert electrode is as negative electrode, and conventional electrolytic solution for super capacitor is electrolyte, assembles two electrode systems and carries out small area analysis discharge and recharge for several times, make the manganese in porous oxidation manganese electrode be completely oxidized to manganese dioxide.
2. the preparation method of manganese dioxide electrode of super capacitor according to claim 1, is characterized in that: the soluble manganese salt described in the first step is manganese sulfate, manganese nitrate, manganese chloride or manganese acetate; The alloying element of described soluble alloy component salt comprises one or more in Ni, Co, Mo, Fe, Cu, W, Ag, Ru, Au, Pt; Soluble alloy component salt comprises one or more in the sulfate of Ni, Co, Mo, Fe, Cu, W, Ag, Ru, Au, Pt, nitrate, hydrochloride, cyanate or rhodanate.
3. the preparation method of manganese dioxide electrode of super capacitor according to claim 1 and 2, it is characterized in that: supporting electrolyte salt comprises ammonium sulfate, ammonium chloride or alkali-metal sulfate or chloride, additive comprises pH buffer, complexing agent, wherein pH buffer comprises one or more in boric acid, natrium citricum, ammoniacal liquor, complexing agent comprises one or more in solubility edetate, citrate, sulphur urine, rhodanate, cyanide, and inert anode is titanium or graphite.
4. the preparation method of manganese dioxide electrode of super capacitor according to claim 1, is characterized in that: in the described first step, when carrying out electrochemical co-deposition, adopts pulse, constant voltage or constant current codeposition.
5. the preparation method of manganese dioxide electrode of super capacitor according to claim 1, it is characterized in that: the electrolyte used in second step is the solution of solubility haloid, the mass concentration scope of halide ion is 0.1 ~ 0.5%, and the solvent in this electrolyte is water, alcohols or its mixture.
6. the preparation method of manganese dioxide electrode of super capacitor according to claim 1 or 5, is characterized in that: carry out pulse, constant current or constant voltage oxidation in second step when carrying out anodic oxidation, the current density range of constant current oxidation is 0.1 ~ 10mA/cm
2, the tank voltage scope of constant voltage oxidation is 0 ~ 200V.
7. the preparation method of manganese dioxide electrode of super capacitor according to claim 6, is characterized in that: the charging and discharging currents density used when carrying out electrode and changing in the 3rd step is at 0.1 ~ 10mA/cm
2.
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| JP6202435B2 (en) * | 2013-09-20 | 2017-09-27 | 国立大学法人東北大学 | Porous alloy compound, method for producing the same, and electric double layer capacitor |
| CN103996547B (en) * | 2014-06-12 | 2017-01-25 | 中南大学 | Manganese-contained transition metal composite oxide electrode and preparing method and application thereof |
| CN104843794B (en) * | 2015-04-17 | 2016-06-08 | 辽宁工业大学 | A kind of ��-MnO2Preparation method |
| CN107768146A (en) * | 2016-08-19 | 2018-03-06 | 北京纳米能源与系统研究所 | A kind of transparent flexible super capacitor and preparation method thereof |
| CN106431510A (en) * | 2016-08-25 | 2017-02-22 | 刘长福 | Production process for complex Jing titanium |
| EP3358045A1 (en) * | 2017-02-07 | 2018-08-08 | Dr.Ing. Max Schlötter GmbH & Co. KG | Method for the galvanic deposition of zinc and zinc alloy layers from an alkaline coating bath with reduced degradation of organic bath additives |
| CN108899481A (en) * | 2018-05-24 | 2018-11-27 | 北京长城华冠汽车科技股份有限公司 | A kind of Preparation method and use of manganese dioxide |
| CN114534738A (en) * | 2020-11-27 | 2022-05-27 | 王益成 | Metal manganese or manganese alloy catalyst and preparation method thereof |
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