CN103996547A - Manganese-contained transition metal composite oxide electrode and preparing method and application thereof - Google Patents
Manganese-contained transition metal composite oxide electrode and preparing method and application thereof Download PDFInfo
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Abstract
The invention discloses a manganese-contained transition metal composite oxide electrode. The manganese-contained transition metal composite oxide electrode comprises a current collector material and an active material adhering to the current collector material. The active material is mainly oxide and/or hydroxide of the manganese-contained transition metal and does not contain binding agent ingredients. The preparing method for the oxide electrode comprises the steps that soluble salt solution of the manganese-contained transition metal is used as electroplate liquid, the current collector material is used as a cathode, an inertia anode is used for preparing a manganese-contained transition metal and hydroxide composite coating on a current collector through an electrochemical deposition method, the prepared composite coating electrode is used as the anode, the inert electrode is used as the cathode, and the electrolytic solution of the super capacitor is used as the electrolytic solution for carrying out anodic oxidation treatment to obtain the manganese-contained transition metal composite oxide electrode. The manganese-contained transition metal composite oxide electrode can be used for preparing the electrochemical super-capacitor, and has the advantages of being large in overall energy density and saving energy sources, influence on the environment is little, and the process is easy to control.
Description
Technical field
The invention belongs to technical field of electrochemistry, relate in particular to a kind of composite oxides electrode and its preparation method and application.
Background technology
Electric chemical super capacitor (electrochemical supercapacitors, ES), also be called electrochemical capacitor (electrochemical capacittors, EC), or be called for short ultracapacitor (supercapacitorsor, ultracapacitors), be the novel energy device of widely paying close attention in recent years.Electric chemical super capacitor is to depend on the element that the electrochemical process on electrode and solution interface carries out energy storage, its capacity is traditional capacitor 20～200 times, can reach farad level, thousand farads of levels even; The high decades of times of its power density ratio battery, can meet the needs of the high-power outputs such as electric automobile Acceleration of starting.Electric chemical super capacitor has conventional capacitor power density concurrently greatly and the high advantage of rechargeable battery energy density, is considered to a kind of efficient, practical novel energy-storing element.
Because ultracapacitor has good chemical property, from its birth, be subject to countries in the world dealer's extensive concern.Compare with battery, the subject matter that ultracapacitor faces is that energy density is lower.In order to improve the performance of ultracapacitor, when improving specific energy, keep the advantages such as its big specific power rate, around the research with the transition metal oxide electrode of electric double layer capacitance and Faraday pseudo-capacitance behavior, receive much concern.What be subject at present broad research is with RuO
2for the electrode material of active material, it not only can realize high-power discharging and recharging, and specific energy is also higher simultaneously, and this is the class electrode material up to the present all having made a breakthrough in materials processing and application.Yet the key issue that this electrode material faces is that material cost is high, 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
2deng the preparation technology of transition metal oxide material and the research of chemical property, also in succession launch.
Yet, existing most research is all first transition metal oxide to be prepared into powder granule material, after these powder granule materials being mixed with binding agent, be coated with to invest on collector again and prepare electrode, this affects the charge-discharge performance of electrode with regard to easily causing loose contact between electrode active material and collector.In addition,, because added binding agent is non-electroactive material, it must reduce the energy density of whole electrode.In a lot of documents, mention directly and prepare by anodic oxidation manganese sulfate solution the manganese dioxide electrode that electrolytic manganese dioxide can prepare binder free, but the ratio electric capacity of gained manganese dioxide electrode is common, can only reach 100 F/g left and right.
Generally speaking, there is many deficiencies such as complex process, cost is high, large to environmental impact, energy consumption is high in the preparation of existing electrode material, and the energy density of the electrode material product preparing also has much room for improvement.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide that a kind of integral energy density is large, environmental impact is little, technique is easily controlled, save the energy containing manganese compound transition metal oxide electrode, the also corresponding preparation method and application that provide this to contain manganese compound transition metal oxide electrode.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of containing manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, described active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in described active material.
Above-mentioned contains in manganese compound transition metal oxide electrode, preferred, and the described oxide containing manganese transition metal at least comprises MnO
2and comprise NiO, CoO, Co
3o
4in at least one; The described hydroxide containing manganese transition metal comprises Ni (OH)
2, Co (OH)
2, at least one in NiOOH, CoOOH.
Above-mentioned contains in manganese compound transition metal oxide electrode, preferred, and the described manganese transition metal that contains comprises manganese metal and transition metal, and described transition metal is Ni and/or Co, and in described active material, the quality percentage composition of transition metal is less than 5%.
As a total technical conceive, the present invention also provides a kind of above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) the soluble-salt solution of usining containing manganese transition metal is as electroplate liquid, with one through surface finish and cleaned current collector material as negative electrode, with an inert anode as anode, adopt electrochemical deposition method in described current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, obtain composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal ions reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and transition metal ions in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode;
(2) composite coating anode above-mentioned steps (1) being made is as anode, and inert electrode, as cathode, is usingd electrolytic solution for super capacitor as electrolyte, carries out anodized, obtains containing manganese compound transition metal oxide electrode.
Above-mentioned preparation method, preferred, the described manganese transition metal that contains comprises manganese metal and transition metal, and described transition metal is Ni and/or Co; Described soluble-salt refers to the sulfate of respective metal element.
Above-mentioned preparation method, preferred, in described electroplate liquid, the concentration of manganese ion is 0.5～1 mol/L, in described electroplate liquid, manganese ion is 100～700 with the ratio of the ion molal quantity of other transition metals.
Above-mentioned preparation method, preferred, in described electroplate liquid, except being also added with and being only added with ammonium sulfate containing the soluble-salt of manganese transition metal, in electroplate liquid, the concentration of ammonium sulfate is 1～2 mol/L, the pH value scope of electroplate liquid is 2～5.
Above-mentioned preparation method, preferred, in described step (1), the electrochemical deposition method of employing comprises pulsed deposition, constant voltage deposition or constant current deposition;
It is 3～9V that tank voltage when described pulsed deposition or constant voltage deposition is controlled, and it is 80～300 mA/cm that cathode-current density during described constant current deposition is controlled
2.
Above-mentioned preparation method, preferred, in described step (2), the anodic current density scope control when carrying out anodized is 0.1～5 mA/cm
2.
As a total technical conceive, the present invention also provide a kind of above-mentioned containing manganese compound transition metal oxide electrode in the application for the preparation of in electric chemical super capacitor.
Compare with existing preparation technology, technical thought of the present invention and technological principle have outstanding feature and technical advantage: existing preparation technology often wishes first to plate out containing manganese alloy, so just to overcome the hydrolysis of manganese salt, need to add a large amount of chemical reaction additives such as boric acid, edetate, citrate, sulphur urine, rhodanate, cyanide, this has not only produced very adverse influence to environment, and the more difficult control of technical process, product quality is difficult to guarantee.And electroplating bath components in the present invention is very simple, can not add any additive or additive sulfuric acid ammonium only, when electro-deposition, do not need deliberately to avoid the hydrolysis of manganese salt etc., technological operation is simple, electroplating bath components used during electro-deposition composite coating is simple, do not need in electroplate liquid, to add a large amount of additives such as boric acid as plating alloy coating, little to environmental impact, electrodeposition technology is also controlled than being easier to; Based on aforementioned thinking, in the composite coating of electrochemical deposition gained of the present invention, part manganese, nickel or cobalt have been the hydroxide of divalence just, because existing a part of metal is hydroxide, such as Mn (OH)
2, only the manganese of divalence need be oxidized to tetravalence (MnO during anodic oxidation like this
2), and the alloying component often that in existing technique, electro-deposition obtains, its valence state is 0, as metal M n, during anodic oxidation, it need to be oxidized to tetravalence from 0 valency, the time needing is longer, energy consumption is higher, so the present invention can shorten follow-up anodizing time, the saving energy.
Compared with prior art, the invention has the advantages that:
(1) containing in manganese compound transition metal oxide electrode that prepared by the present invention do not contain the non-electric active matters such as binding agent, therefore can improve the integral energy density of electrode;
(2) in preparation method of the present invention, electroplating bath components used during electro-deposition composite coating is simple, does not need in electroplate liquid, to add a large amount of additives such as boric acid as plating alloy coating, little to environmental impact, and electrodeposition technology is also controlled than being easier to;
(3), in the composite coating due to electrochemical deposition gained, part manganese, nickel or cobalt have been the hydroxide of high price, therefore can shorten the follow-up anodised time, save the energy.
Embodiment
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit the scope of the invention.
Apart from special instruction, various reagent, the raw material of using in the present invention is the commodity that can buy from the market or the product that can make by known method.
The specific embodiment of the present invention is as follows:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal, transition metal is Ni and/or Co, and in active material, the quality percentage composition of Ni and/or Co is less than 5%.Oxide containing manganese transition metal at least comprises MnO
2, also comprise NiO, CoO, Co
3o
4in at least one.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) sulfate solution of usining containing manganese transition metal is as electroplate liquid, in electroplate liquid, contain manganese sulfate, nickelous sulfate, cobaltous sulfate and ammonium sulfate, in electroplate liquid, the concentration of manganese ion is 0.5～1 mol/L, the ion mol ratio of manganese ion and other transition metals is 100～700, in electroplate liquid, the concentration of ammonium sulfate is 1～2 mol/L, the pH value scope of electroplate liquid is 2～5, with one through surface finish and cleaned current collector material as negative electrode (work electrode), with an inert anode (titanium, graphite etc.) as anode, adopt electrochemical deposition method in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, the electrochemical deposition method adopting comprises pulsed deposition, constant voltage deposition or constant current deposition, it is 3～9V that tank voltage when pulsed deposition or constant voltage deposition is controlled, and it is 80～300 mA/cm that cathode-current density during constant current deposition is controlled
2, after having deposited, obtain composite coating anode, when carrying out electrochemical deposition, manganese in electroplate liquid and transition metal ions reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and transition metal ions in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again, therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode,
(2) composite coating anode above-mentioned steps (1) being made is as anode, inert electrode (stainless steel substrates or other sheet metal) is as cathode, using electrolytic solution for super capacitor (as the metabisulfite solution of 0.5mol/L) as electrolyte, carry out anodized, obtain containing manganese compound transition metal oxide electrode; Anodic current density scope control when carrying out anodized is 0.1～5 mA/cm
2.
For the ease of understanding the present invention, below in connection with preferred embodiment, the present invention is done more comprehensively, described meticulously, but protection scope of the present invention is not limited to following specific embodiment.
embodiment 1:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal nickel (Ni), in active material, Ni content is about 1%.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, NiSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, being mixed with containing manganese ion 0.6 mol/L, ammonium root concentration is that 2 mol/L, nickel ion concentration are the mixed solution of 0.001 mol/L, regulates the pH value to 2 of electroplate liquid, and stir after 30 minutes standby with ammoniacal liquor and sulfuric acid.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, nickel and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant current electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, it is 300 mA/cm that cathode-current density during constant current deposition is controlled
2, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal nickel ion reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and nickel ion in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 0.5 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode, with XRF analysis, find that in composite oxides, nickel content is about 1%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 313 F/g.
embodiment 2:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal cobalt, in active material, Co content is about 1%.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, CoSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, being mixed with containing manganese ion 0.6 mol/L, ammonium root concentration is that 2mol/L, concentration of cobalt ions are the mixed solution of 0.001 mol/L, regulates the pH value to 4 of electroplate liquid, and stir after 30 minutes standby with ammoniacal liquor and sulfuric acid.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, cobalt and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant current electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, it is 200 mA/cm that cathode-current density during constant current deposition is controlled
2, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal cobalt ions reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and cobalt ions in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 0.5 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode, with XRF analysis, find that in composite oxides, cobalt content is 1%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 281 F/g.
embodiment 3:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal nickel (Ni), in active material, Ni content is about 2.5%.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, NiSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, the concentration being mixed with containing manganese ion 1mol/L, ammonium sulfate is that 1.5mol/L, nickel ion concentration are the mixed solution of 0.003 mol/L, regulates the pH value to 2 of electroplate liquid, and stir after 30 minutes standby with ammoniacal liquor and sulfuric acid.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, nickel and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant current electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, it is 150 mA/cm that cathode-current density during constant current deposition is controlled
2, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal nickel ion reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and nickel ion in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 1 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode.With XRF analysis, find that in composite coating, nickel content is 2.5%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 237 F/g.
embodiment 4:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal nickel (Ni), in active material, Ni content is about 3.8%.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, NiSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, being mixed with containing manganese ion 0.5mol/L, ammonium root concentration is 2 mol/L, NiSO
4concentration be the mixed solution of 0.005 mol/L, with ammoniacal liquor and sulfuric acid, regulate the pH value to 2 of electroplate liquid, and stir after 30 minutes standby.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, nickel and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant current electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, it is 100 mA/cm that cathode-current density during constant current deposition is controlled
2, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal nickel ion reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and nickel ion in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 5 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode, with XRF analysis, find that in composite oxides, nickel content is 3.8%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 213 F/g.
embodiment 5:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Comprise manganese metal and transition metal nickel (Ni) and cobalt (Co) containing manganese transition metal, in active material, to be about the content of 3.2%, Co be 0.8% to Ni content.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, NiSO
47H
2o, CoSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, the concentration being mixed with containing manganese ion 0.8 mol/L, ammonium sulfate is that 1.2mol/L, nickel ion concentration are that 0.004 mol/L, concentration of cobalt ions are the mixed solution of 0.001 mol/L, with ammoniacal liquor and sulfuric acid, regulate the pH value to 2 of electroplate liquid, and stir after 30 minutes standby.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, nickel, cobalt and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant current electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, it is 150 mA/cm that cathode-current density during constant current deposition is controlled
2, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal nickel ion, cobalt ions reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and nickel and cobalt ions in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 1 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode.With XRF analysis, find that in composite oxides, nickel content is 3.2%, cobalt content is 0.8%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 242 F/g.
embodiment 6:
Containing a manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, active material is mainly the oxide containing manganese transition metal, and does not contain Binder Composition in active material.Containing manganese transition metal, comprise manganese metal and transition metal cobalt, in active material, Co content is about 1%.
The above-mentioned preparation method containing manganese compound transition metal oxide electrode, comprises the steps:
(1) take a certain amount of MnSO
4h
2o, CoSO
47H
2o and (NH
4)
2sO
4be dissolved in deionized water, being mixed with containing manganese ion 0.6 mol/L, ammonium root concentration is that 2mol/L, concentration of cobalt ions are the mixed solution of 0.001 mol/L, regulates the pH value to 4 of electroplate liquid, and stir after 30 minutes standby with ammoniacal liquor and sulfuric acid.
(2) 304 stainless steel foils being cut into area is 4 * 1 cm
2stainless steel band, as collector, carries out ultrasonic washing with 10% aqueous sulfuric acid and acetone to this collector successively, and final rinse water is also dried.With 4 * 4 cm titanium nets, be anode electrode, with the above-mentioned mixed solution containing manganese, cobalt and ammonium radical ion, as electroplate liquid, as negative electrode, (work area is 1 * 2 cm to the collector after surface clean
2), adopt constant potential electrodeposition process in current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, tank voltage during potentiostatic electrodeposition is 4V, electrodeposition time is 2 minutes, after having deposited, obtains composite coating anode; When carrying out electrochemical deposition, manganese in electroplate liquid and transition metal cobalt ions reduce and form alloy on negative electrode, and separate out hydrogen on negative electrode, make the pH value near the liquid layer of this electrode increase, part manganese and cobalt ions in solution are hydrolyzed, and then at electrode surface, generate corresponding high price hydroxide again; Therefore the composite coating of gained mainly reduce by manganese and transition metal ions the hydroxide that the metal that forms and these ions occur to be hydrolyzed in electrode surface generation and forms on negative electrode.
(3) composite coating anode above-mentioned steps (1) being made is as anode, stainless steel substrates (area 4 * 4 cm
2) be cathode, saturated calomel electrode is reference electrode, with the aqueous sodium persulfate solution of 0.5 mol/L, as electrolyte, carries out constant current anodized, it is 0.5 mA/cm that the anodic current density when carrying out anodized is controlled
2, after reaching 0.8 V, anode potential finishes oxidation, obtain containing manganese compound transition metal oxide electrode, with XRF analysis, find that in composite oxides, cobalt content is 1%.
With the aqueous sodium persulfate solution of 0.5 mol/L, be electrolyte, above-mentioned preparation containing manganese compound transition metal oxide electrode be work electrode, area is 4 * 4 cm
2platinum electrode be that auxiliary electrode is assembled into three-electrode system, carry out cyclic voltammetry, test potential scope is 0～0.8 V (with respect to saturated calomel electrode), sweep speed is 5 mV/s.The ratio electric capacity that calculates electrode active material according to cyclic voltammetry curve is 274 F/g.
Claims (10)
1. one kind contains manganese compound transition metal oxide electrode, comprise current collector material and be attached to the active material in current collector material, it is characterized in that: described active material is mainly containing the oxide of manganese transition metal and/or hydroxide, and do not contain Binder Composition in described active material.
2. according to claim 1 containing manganese compound transition metal oxide electrode, it is characterized in that: the described oxide containing manganese transition metal at least comprises MnO
2and comprise NiO, CoO, Co
3o
4in at least one; The described hydroxide containing manganese transition metal comprises Ni (OH)
2, Co (OH)
2, at least one in NiOOH, CoOOH.
3. according to claim 1 and 2 containing manganese compound transition metal oxide electrode, it is characterized in that: the described manganese transition metal that contains comprises manganese metal and transition metal, described transition metal is Ni and/or Co, and in described active material, the quality percentage composition of transition metal is less than 5%.
4. the preparation method containing manganese compound transition metal oxide electrode as described in claim 1 or 2 or 3, comprises the steps:
(1) the soluble-salt solution of usining containing manganese transition metal is as electroplate liquid, by a current collector material as negative electrode, with an inert anode, as anode, adopt electrochemical deposition method in described current collector material, to prepare containing manganese transition metal and hydroxide composite coating thereof, obtain composite coating anode;
(2) composite coating anode above-mentioned steps (1) being made is as anode, and inert electrode, as cathode, is usingd electrolytic solution for super capacitor as electrolyte, carries out anodized, obtains containing manganese compound transition metal oxide electrode.
5. preparation method according to claim 4, is characterized in that: the described manganese transition metal that contains comprises manganese metal and transition metal, and described transition metal is Ni and/or Co; Described soluble-salt refers to the sulfate of respective metal element.
6. preparation method according to claim 5, is characterized in that: in described electroplate liquid, the concentration of manganese ion is 0.5～1 mol/L, and in described electroplate liquid, manganese ion is 100～700 with the ratio of the ion molal quantity of other transition metals.
7. according to the preparation method described in claim 4,5 or 6, it is characterized in that: in described electroplate liquid, except containing the soluble-salt of manganese transition metal, be also added with and be only added with ammonium sulfate, in electroplate liquid, the concentration of ammonium sulfate is 1～2 mol/L, and the pH value scope of electroplate liquid is 2～5.
8. according to the preparation method described in claim 4,5 or 6, it is characterized in that: in described step (1), the electrochemical deposition method of employing comprises pulsed deposition, constant voltage deposition or constant current deposition;
It is 3～9V that tank voltage when described pulsed deposition or constant voltage deposition is controlled, and it is 80～300 mA/cm that cathode-current density during described constant current deposition is controlled
2.
9. according to the preparation method described in claim 4,5 or 6, it is characterized in that: in described step (2), the anodic current density scope control when carrying out anodized is 0.1～5 mA/cm
2.
One kind as described in claim 1 or 2 or 3 containing manganese compound transition metal oxide electrode in the application for the preparation of in electric chemical super capacitor.
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