CN100365855C - Oxygen reduction electrode and electrochemical element using same - Google Patents

Oxygen reduction electrode and electrochemical element using same Download PDF

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Publication number
CN100365855C
CN100365855C CNB2004800016199A CN200480001619A CN100365855C CN 100365855 C CN100365855 C CN 100365855C CN B2004800016199 A CNB2004800016199 A CN B2004800016199A CN 200480001619 A CN200480001619 A CN 200480001619A CN 100365855 C CN100365855 C CN 100365855C
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oxygen
carbon
electrode
carbide
infrared absorption
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CN1717825A (en
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铃木正明
山田由佳
铃木信靖
森永泰规
佐佐木英弘
外邨正
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode

Abstract

To effectively utilize waste matters containing yeasts remaining after the utilization of the yeasts, it has been a practice to carbonize the waste matters and thus employ, together with other carbonized materials, in adsorbents, desiccants, soil conditioners, catalysts, etc. To enlarge the industrial applicability thereof, it is needed to search for new uses. An electrode enabling electrochemical oxygen reduction can be obtained by carbonizing a yeast-containing material and loading the thus obtained particulate or powdery carbide on an electrically conductive and air permeable substrate. When located at the cross-point of an ion pathway and an oxygen pathway, this carbide makes it possible to induce electrochemical oxygen reduction under a low overvoltage (resistance) and thus provide a large electromotive force. Thus, a novel use which has not been proposed hitherto can be provided.

Description

Electrode for use in oxygen reduction, the electrochemical element that uses it and manufacture method thereof
Technical field
The present invention relates to be used for electrochemical element that oxygen is carried out the electrode for use in oxygen reduction of reduction reaction and uses this electrode for use in oxygen reduction.
Background technology
Make oxygen (O by cell reaction as everyone knows 2) under the situation of reduction, the reduction of an electron reduction, two-electron reduction or the quadrielectron can take place.Generate peroxide during one electron reduction.Generate hydrogen peroxide during two-electron reduction.And when the quadrielectron is reduced, then generate water (" electro-catalysis " of compiling such as JacekKipkowski, Philip N.Ross (Electrocatalysis), Wiley-VCH publishes, 1998 years, 204～205 pages).
When the reduction reaction with oxygen was used as the positive pole reaction of battery, requirement obtained the battery of big capacity, high voltage and High Output Current etc.In the case, in the reduction reaction of oxygen, require a) mobile electron as much as possible; B) make current potential high as far as possible (positive); C) suppress overvoltage as far as possible.For this reason, preferably use the catalyst that under high potential, carries out quadrielectron reduction with little overvoltage.As one of such catalyst platinum (Pt) is arranged.
But platinum has following problem.(1) platinum is expensive noble metal, and is unfavorable to cost; (2) platinum not only can make hydrogen reduction, and owing to the oxidation reaction to fuel materials such as ethanol, hydrogen also demonstrates activity, so to the reaction lack selectivity.Therefore, when actual the utilization, must carry out the place of oxidation reaction and reduction reaction and separate with barrier film etc.; (3) surface of platinum is difficult to keep the catalyst activity than higher easily by carbon monoxide or hydroxyl passivation.
Therefore, in order to develop the catalyst that substitutes platinum, carried out multiple cooperation so far.
For example, known motion in fair 2-030141 communique of spy and special fair 2-030142 communique is by carrying the electroconductive powder of metal chelate compounds such as having held FePC with reduction oxygen ability, Cobalt Porphyrin and the catalyst that the porous formed body of fluororesin is formed.In addition, the dimer (two nuclear complex compounds) by using metal chelate compound can reach high oxygen reducing ability (quadrielectron reducing power), is expected to be applied to the air cell of big output.
For example, disclose as Cobalt Porphyrin two and examined complex compounds etc., with transition metal such as Cr, Mn, Fe, Co technology (" electro-catalysis " that JacekKipkowski, Philip N.Ross compile of oxygen reduction catalyst of the big ring complex compound of central metal, Wiley-VCH publishes, 1998,232～234 pages).
Open in the flat 11-253811 communique the spy, disclose the manganese complex catalyst that is used for hydrogen reduction.This complex compound becomes and is used for carrying out with high selection rate the catalyst of the quadrielectron reduction reaction of oxygen.In the document, put down in writing and say that manganese atom is got the valence mumber of divalent to 7 valency, in the reduction reaction of-0.5V Catalytic Oxygen to the potential range of+2V.
When reality is used these catalyst, be that catalyst is carried on the carrier that is held in excellent in stability mostly.Under the situation of the electrode reaction that is used for electrochemical element, be extensive use of carbon materials as carrier with conductivity.Such as using carbon materialses such as carbon black, active carbon, graphite, conductivity carbon element, vitreous carbon.Known these carbon materialses cause the two-electron reduction reaction usually when oxygen is carried out electroreduction, produce hydrogen peroxide.
Summary of the invention
But, if, need have the metal complex of high valence mumber central metal atom by using aforesaid catalyst to obtain high potential.And because the reactive height of such metal complex, the material that can be contacted with metal complex (seeing through film etc. such as electrolyte, electrode connection, collector body, battery container, barrier film, gas-selectively) reacts, and the shortcoming that causes these material aging one classes is arranged again.
In addition, about the carbon materials as carrier, known activated coco nut charcoal, wooden carbide etc. have the effect of decomposition of hydrogen peroxide.Such as, the active carbon that has open conduct to have high performance hydrogen peroxide decomposition catalyst has (spy open flat 7-024315 communique, the spy opens 2003-001107 communique etc.) such as the carbides of Dralon carbide, brewex's grains.
But,, generally only know electrode reaction (being the two-electron reduction reaction) about the catalytic action that carbon materials self has.And for as the catalytic action and the validity thereof that make the electrode catalyst of hydrogen reduction, then not special open.
Main purpose of the present invention provides and a kind ofly oxygen is being carried out give in the reduction reaction quadrielectron reduction reaction with the electrode for use in oxygen reduction of high selectivity more.
Another object of the present invention provides a kind of to dissolving in the stable electrode for use in oxygen reduction that electrolytical fuel material shows oxidation activity hardly.
That is to say the electrochemical element that the present invention relates to electrode for use in oxygen reduction as described below and use this electrode.
First aspect present invention is a kind of manufacture method that is used for oxygen is carried out the electrode for use in oxygen reduction of quadrielectron reduction, this method comprises: (1) contains first operation that material obtains carbide by the charing yeast, and (2) use the electrode material that contains above-mentioned carbide to make second operation of above-mentioned electrode for use in oxygen reduction.
In its preferred execution mode, yeast contains material, be brewer's yeast, wine yeast, saccharomyces sake, whiskey yeast, Saccharomyces cerevisiae, fodder yeast, brewex's grains, pure mellow wine poor, make the grape juice squeezing that grape wine uses poor, make at least a that the wheat juice squeezing that whiskey uses is poor, the corn juice squeezing is poor and soy sauce is poor.
In its preferred execution mode, in first operation, under the atmosphere below the oxygen concentration 10 volume %, contain material at the above-mentioned yeast of charing below 1200 ℃ more than 300 ℃.
In its preferred execution mode, in first operation, under the atmosphere below the oxygen concentration 10 volume %, contain material at the above-mentioned yeast of charing below 1000 ℃ more than 500 ℃.
In its preferred execution mode, above-mentioned atmosphere is inert gas atmosphere.
In its preferred execution mode, in first operation, carbide is further carried out activation processing.
In its preferred execution mode, in second operation, after the shape that above-mentioned electrode material is configured as regulation obtains formed body, by with above-mentioned formed body lamination or be crimped on the conductive base body and make above-mentioned electrode for use in oxygen reduction.
In its preferred execution mode, in second operation,, above-mentioned paste is coated on makes above-mentioned electrode for use in oxygen reduction on the conductive base by after above-mentioned electrode material being made paste and being obtained containing the paste of electrode material.
In its preferred execution mode, in above-mentioned yeast contains at least a in material, carbide and the electrode material, add at least a inorganic compound that contains in phosphorus (P) and the calcium (Ca).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C).
In its preferred execution mode, above-mentioned carbide is at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry.
In its preferred execution mode, above-mentioned carbide is at about 1700cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of oxygen (O).
In its preferred execution mode, above-mentioned carbide is at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C), at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry, at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon (C)=oxygen (O) and at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, in above-mentioned yeast contains material, carbide and electrode material at least a, add at least a of metal and oxide thereof.
In its preferred execution mode, oxide is to use formula M nO yThe rudimentary manganese oxide of (here, y is the oxygen atomicity with the valence mumber decision of manganese (Mn), less than 2) expression.
Second aspect present invention is a kind of electrode for use in oxygen reduction, and this electrode contains the carbide that the charing yeast contains the material gained, and is used for oxygen is carried out quadrielectron reduction.
In its preferred execution mode, comprise at least a inorganic compound that contains in phosphorus (P) and the calcium (Ca).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C).
In its preferred execution mode, above-mentioned carbide is at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry.
In its preferred execution mode, above-mentioned carbide is at about 1700cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of oxygen (O).
In its preferred execution mode, above-mentioned carbide is at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C), at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry, at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon (C)=oxygen (O) and at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, contain at least a in metal and the oxide thereof.
In its preferred execution mode, above-mentioned oxide is the rudimentary manganese oxide with MnOy (here, y is the oxygen atomicity with the valence mumber decision of manganese (Mn), less than 2) expression.
In its preferred execution mode, above-mentioned carbide is a graininess, and the electrode material that contains above-mentioned carbide is carried to be held on the conductive base.
In its preferred execution mode, conductive base has gas permeability.
In its preferred execution mode, be used for molecularity oxygen being carried out electrochemical reduction at the neutral electrolyte aqueous solution.
Third aspect present invention is a kind of electrochemical element, and this element comprises: the positive pole, the b that a) oxygen are carried out quadrielectron reduction) negative pole and c) electrolyte, and above-mentioned positive pole contains the carbide that the charing yeast contains the material gained.
In its preferred execution mode, above-mentioned positive pole comprises: at least a inorganic compound that contains phosphorus (P) and calcium (Ca).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C).
In its preferred execution mode, above-mentioned carbide is at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry.
In its preferred execution mode, above-mentioned carbide is at about 1700cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of oxygen (O).
In its preferred execution mode, above-mentioned carbide is at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C), at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry, at about 1700cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of oxygen (O), at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned positive pole contains at least a in metal and the oxide thereof.
In its preferred execution mode, above-mentioned oxide is to use MnO yThe rudimentary manganese oxide of (here, y is the oxygen atomicity with the valence mumber decision of manganese (Mn), less than 2) expression.
In its preferred execution mode, above-mentioned carbide is a graininess, and the electrode material that contains above-mentioned carbide is carried to be held in and constitutes above-mentioned positive pole on the conductive base.
In its preferred execution mode, conductive base has gas permeability.
In its preferred execution mode, electrolyte is a neutral aqueous solution.
In its preferred execution mode, negative reaction is the oxidation reaction of electrochemically taking out electronics from dissolve in electrolytical fuel material.
In its preferred execution mode, in above-mentioned electrolyte, contain at least a of carbohydrate and alcohols.
Fourth aspect present invention is a kind of method of reducing, and this method is the method for oxygen being carried out quadrielectron reduction, comprising:
Provide to have and a) contain the positive pole that the charing yeast contains the carbide of material gained; B) negative pole and c) battery that contains electrolytical battery provides operation, and
By oxygen being carried out the oxygen supply operation that the quadrielectron is reduced to the above-mentioned anodal oxygen of supplying with.
In its preferred execution mode, above-mentioned positive pole comprises: contain at least a inorganic compound in phosphorus (P) and the calcium (Ca).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C).
In its preferred execution mode, above-mentioned carbide is at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry.
In its preferred execution mode, above-mentioned carbide is at about 2100cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of oxygen (O).
In its preferred execution mode, above-mentioned carbide is at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned carbide about 1000 to 1200cm -1Scope in demonstrate carbon (C)-oxygen (O)-flexible INFRARED ABSORPTION of carbon (C), at about 1600cm -1The place demonstrates carbon (C)=flexible INFRARED ABSORPTION of carbon (C) symmetry, at about 2100cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon (C)=oxygen (O) and at about 3000cm -1The place demonstrates oxygen (O)-flexible INFRARED ABSORPTION of hydrogen (H).
In its preferred execution mode, above-mentioned positive pole contains at least a in metal and the oxide thereof.
In its preferred execution mode, above-mentioned oxide is to use MnO yThe rudimentary manganese oxide of (here, y is the oxygen atomicity with the valence mumber decision of manganese (Mn), less than 2) expression.
In its preferred execution mode, above-mentioned carbide is a graininess, and the electrode material that contains above-mentioned carbide is carried to be held in and constitutes above-mentioned positive pole on the conductive base.
In its preferred execution mode, conductive base has gas permeability.
In its preferred execution mode, electrolyte is a neutral aqueous solution.
In its preferred execution mode, negative reaction is the oxidation reaction of electrochemically taking out electronics from dissolve in electrolytical fuel material.
In its preferred execution mode, in above-mentioned electrolyte, contain at least a in carbohydrate and the alcohols.
Description of drawings
Fig. 1 represents is in test electrode 1 and 2 and each voltage (electromotive force)-current characteristics figure of the oxygen reduction reaction in electrode relatively.
What Fig. 2 represented is for comparing the figure of voltage (the electromotive force)-current characteristics of the oxygen reduction reaction in the electrode at test electrode 3,4,5,6 and each.
The sectional view of three utmost point electrode batteries that Fig. 3 represents when being the mensuration of one embodiment of the present of invention.
Fig. 4 is the sectional view of the generating battery of an alternative embodiment of the invention.
Symbol description:
1 air pole, 1a air pole mixture, 1b fluororesin porous plate, 1c electrode connection, 2 pairs of utmost points, 3 reference electrodes, 4 electrolyte, 5 glass chambers, 6 glass substrates, 7 ito thin films, 8 TiO 2The particulate film, 9 pigment molecular layers, 10 electrolyte, fuel fluid, 11 air pole, 12 oxygen permeability hydrophobic membrane, 13a electrolyte, fuel fluid inlet, 13b electrolyte, fuel fluid outlet, 14a, 14b Liquid valve, 15 negative pole wiring, 16 anodal wiring, 17 encapsulants.
Embodiment
1. electrode for use in oxygen reduction and manufacture method thereof
Electrode for use in oxygen reduction of the present invention is by comprising: (1) charing yeast contains first operation that material obtains carbide; (2) manufacture method of using the electrode material that contains above-mentioned carbide to make second operation of electrode is made.
(1) first operation
In first operation, contain material by the charing yeast and obtain carbide.
The yeast class
Containing material as yeast, except yeast self, also can be the material from yeast poor and so on as the squeezing of yeast.They can use a kind of or two or more.
As yeast, can use such as each primary yeasts such as brewer's yeast, wine yeast, saccharomyces sake, whiskey yeast, Saccharomyces cerevisiae, fodder yeasts.
Poor as squeezing, can enumerate beer vinasse, pure mellow wine poor, make the grape juice squeezing that grape wine uses poor, make that the wheat juice squeezing that whiskey uses is poor, the corn juice squeezing is poor, soy sauce is poor etc.Using under the poor situation of these squeezings, can obtain advantages such as efficent use of resources, reduction cost of material.
Contain in the material at these yeast, and under situation, preferably contain many phosphorus and calcium its charing.Under the situation of using such yeast, can obtain higher hydrogen reduction effect.Such as, can suitably use at least a in poor of brewer's yeast and squeezing thereof.
In the present invention, can contain other additive of cooperation in the material at yeast as required.Its addition can be according to the suitably decisions such as kind of additive.
Such as, in order to improve the operability of carbide, can add the adhesive of organic adhesion agent (polyvinyl alcohol, polyvinyl butyral resin etc.) or inorganic adhesive (silicon dioxide etc.).
In addition, contain in the material at yeast and can also cooperate solvent.Such as using phenol or phenol derivatives organic solvents such as (such as single nitrophenol, dinitrophenol, trinitrophenol, resorcinol, 1,4-dihydroxy benzenes, metacresol, paracresol etc.).
Charing processing and activation processing
Contain material by the above-mentioned yeast of charing and make carbide.Usually, can heat-treat and obtain carbide by yeast being contained material.Heat treated condition can contain the composition of material, the characteristic of desirable carbide etc. according to the yeast that uses and suitably set.
Scope about heat treated temperature generally can be set in more than 300 ℃ below 1200 ℃.Owing to surpassing under 1200 ℃ the situation, graphitization can take place, preferably the temperature below this is handled.More preferably in the scope below 1000 ℃ more than 500 ℃.By being set in more than 500 ℃, can give good electrical conductivity more.In addition, by being set in below 1000 ℃, can be in the carbon content remaining above-mentioned C-O-C key that the reaction of giving the hydrogen reduction activity effectively carries out etc. that makes.
Heat treatment period, as long as charing is fully carried out, the kind, amount etc. that can contain material according to the yeast of heat treated temperature, use are suitably set.
As heat treated atmosphere, in order to be heated to approximately more than 300 ℃ the time, the yeast class can not burnt, the preferred very low or non-existent in fact state of oxygen of oxygen concentration.Concrete is that preferably setting oxygen concentration is the following atmosphere of 10 volume %, more preferably the following atmosphere of 1 volume %.Particularly preferably be the atmosphere of inert gas (nitrogen, argon gas, helium etc.) or be vacuum.
After charing is handled, wish the carbide that obtains is carried out activation processing.By activation processing, thereby the specific area that increases carbide can improve its activity, also improve its with by the compatibility of reactant, improve in the compatibility of carrying when holding with other material, regulate surperficial acidity.
The method of activation processing can be carried out according to known method.Can use such as 1) method of the gas activation undertaken by steam, carbon dioxide etc.; The method of the medicine activation of 2) being undertaken by ammonium chloride, zinc chloride, potassium hydroxide etc.The temperature of activation processing is different and different according to processing method.Such as in the gas activation method, preferably handle the temperature of same degree with above-mentioned charing.In the medicine activation method, can at room temperature handle, or reach later on to handle in the temperature range of same degree and handle exposing medicine to the open air with above-mentioned charing.
(2) second operations
In second operation, use the electrode material that contains above-mentioned carbide to make electrode.
Carbide
Carbide contains and generally has the organic principle that contains the structure of material (from the cellulosic of yeast class, the structure of saccharic etc.) from yeast.
Above-mentioned carbide, wave number is 1000cm in infrared absorption spectroscopy -1To 1200cm -1Scope in, especially preferably demonstrate about 1100cm -1Flexible the absorption and/or about 1600cm of carbon (C)-oxygen (O)-carbon (C) -1Unsaturated carbon (C)=carbon (C) symmetry absorb.This is the feature of not seeing in the active carbon, carbon black etc. at other, is the peculiar feature of the present invention.
In addition, though carbide, in infrared absorption spectroscopy and the indeterminate carbon content inorganic constituents that comes from, but preferred the demonstration result from about 1700cm of possess hydrophilic property carbonyl -1Carbon (C)=oxygen (O) flexible absorb and/or result from hydroxyl at about 3000cm -1Near oxygen (O)-hydrogen (H) is flexible to be absorbed.
Contain the carbide that shows these absorption compositions by use, can more effectively help to improve electrode characteristic.As the composition of such carbide, generally contain carbon content and inorganic constituents.
Carbon content can be crystalline or noncrystalline, but particularly preferably is noncrystalline.In addition, the general preferred conductivity that has of above-mentioned carbon content.
Inorganic constituents contains difference differences such as material because of the yeast that uses, but general as the composition from yeast, contains phosphorus (P), calcium (Ca), potassium (K), magnesium (Mg) etc.More preferably contain P and Ca as main component.These inorganic constituentss also can exist with forms such as oxide, phosphate, carbonate.The total content of inorganic constituents in carbide, difference contains more than the 10 quality % usually though also contain the kind difference of material according to the yeast that uses, and preferably contains more than the 20 quality %.In this, be different with the total content of inorganic constituents for the active carbon of number quality %, carbon black etc.
The content of inorganic constituents, available ash determination when carbide is carried out the CHN elementary analysis can be used mensuration such as fluorescent X-ray elementary analysis, ion chromatography about amount of element.
In the present invention, in order to replenish above-mentioned inorganic constituents, can add the compound that contains these inorganic constituentss by other approach.Particularly, suitable use contains inorganic compound at least a in phosphorus and the calcium.Except using phosphoric acid, sodium phosphate, potassium phosphate, dibastic sodium phosphate, calcium monohydrogen phosphate, calcium carbonate, calcium oxide, calcium hydroxide, can use in phosphate, the inorganic calcium salt etc. one or more.
In addition, contain the compound of inorganic constituents,, especially preferably contain material and cooperate with yeast though can contain any cooperation in material or the carbide with above-mentioned yeast.
The form of carbide just has no particular limits as long as have above-mentioned rerum natura, but usually preferred granular or Powdered (powder body).At carbide is under the situation of powder body, preferably makes by the granularity more than Tyler screen 200 orders.More preferably make maximum particle diameter (diameter) below 20 μ m, especially preferably make below the above 20 μ m of 1 μ m.Because general reduction reaction is to take place on the surface of powder body, if may reduce with respect to the efficient of use amount above 20 μ m.Can use known pulverizer, grader to wait and regulate granularity.
Electrode material
Use contains the electrode material manufacturing electrode of above-mentioned carbide.In order to improve electrode characteristic etc., can in electrode material, cooperate various materials as required.In the scope that does not hinder effect of the present invention, these materials can be engaged in above-mentioned yeast in advance and contain in the material.
Such as, in order further to improve the ability (oxygen exchange capacity) of getting oxygen or emitting, can complexed metal and oxide at least a.Can enumerate such as Mn 2O 3, Mn 3O 4, Mn 5O 8, γ-MnOOH (Mn 3O 4And Mn 5O 8Mixture) etc. rudimentary manganese oxide MnO y(y is the oxygen atomicity by the valence mumber decision of manganese, less than 2), ruthenium-oxide, Cu X-1Sr xTiO 3(x=0～0.5), La xSr 1-xMnO 3(x=0～0.5), SrTiO 3Beyond the perovskite oxide, can also enumerate palladium oxide, platinum black etc.
Wherein, from the degrading activity height of hydrogen peroxide, the aging minimizing, and also cheaply these aspects are considered, preferred rudimentary manganese oxide.So-called rudimentary manganese oxide, the chemical valence that is manganese atom is less than 4 manganese oxide.This is because the manganese dioxide positive pole such as the manganese dry cell after using directly can be used, and perhaps uses the later goods of sintering, so from the viewpoint of efficent use of resources, preferred especially.
The addition of above-mentioned metal or its oxide, can suitably determine according to metal or the kind of its compound, the desirable electrode characteristic etc. used, to make in the electrode that finally obtains be more than the 1 weight % below the 50 weight %, particularly preferably in more than the 5 weight % and below the 20 weight % but preferably set.
In addition, in electrode material, also can cooperate other various additives.Use additive can reach following purpose: such as 1) regulate the compatibility with other material; 2) acidity on adjusting surface (electrode surface); 3) give catalyst activity; 4) provide co-catalyst; 5) reduce overvoltage etc.As such additive, can be according to above-mentioned adding purpose, use any in organic material, inorganic material, their composite material, their mixture etc.More specifically be to use carbon materialses such as metal or alloy, graphite, active carbon such as platinum, cobalt, ruthenium, palladium, nickel, gold, silver, copper, platinum cobalt alloy, platinum-ruthenium alloys, cupric oxide, nickel oxide, cobalt oxide, ruthenium-oxide, tungsten oxide, molybdenum oxide, manganese oxide, lanthanum-manganese-metal oxides such as copper perovskite oxide, FePC, phthalocyanine cobalt, CuPc, manganese phthalocyanine, Phthalocyanine Zinc etc. to have metal complexs such as the metal phthalocyanine of porphyrin ring or metalloporphyrin, ruthenium ammino-complex, cobalt ammonia complex, cobalt ethylenediamine complex compound etc.
Central metal element to above-mentioned metal complex is unqualified, but at least a in preferred especially platinum, ruthenium, cobalt, manganese, iron, copper, silver and the zinc.By using these metallic elements, can carry out the reduction reaction of oxygen with littler overvoltage.In addition, the valence mumber of preferable alloy element is below 4.By making valence mumber, can suppress the oxidability of catalyst effectively below 4.Its result can prevent effectively that the inscape of electrochemical element is (such as electrolyte.Electrode connection, collector body, battery container, barrier film, gas-selectively see through film etc.) owing to wearing out that oxidation produces.
The addition of above-mentioned additive can suitably determine according to the kind of materials used, desirable electrode characteristic etc., accounts in the electrode that finally obtains more than the 1 weight % below the 80 weight % but preferably make, below the above 60 weight % of preferred especially 20 weight %.
Above-mentioned electrode material also can contain: the material that is added in known electrode material.Such as, can suitably add conductive auxiliary agents such as resin adhesives such as fluororesin adhesive, polyvinyl alcohol, polyvinyl butyral resin such as polytetrafluoroethylene, high fluoride resin, graphite, electrical conductivity Carbon black, hydrophilic carbon black, hydrophobicity carbon black etc. as required.
Make electrode
About making electrode,, get final product according to known electrode manufacturing method manufacturing so long as use above-mentioned electrode material.Such as formed body lamination that can be by the electrode material that will make in advance or be crimped on method on the conductive base (collector body), coating contains the method for the paste of electrode material on conductive base, and with the making such as method of conductive material and electrode material hybrid shaping.
Above-mentioned conductive base can use effectively: copy the carbon paper that the paper method is made carbon fiber such as using; Wire nettings such as stainless steel cloth, nickel wire net; Be processed into the conductive composite material sheet of sheet etc. with the bonding carbon dust of adhesive made of synthetic resin such as fluororesin adhesive, metal dust etc.
In addition, when the above-mentioned paste of modulation, can obtain paste by dissolving adhesive in appropriate solvent.Such as using under the situation of polytetrafluoroethylene as adhesive, can use alcohols such as ethanol as solvent.The concentration of adhesive can be according to the suitably decisions such as kind of the adhesive that uses.
The redox electrode
The present invention also comprises the redox electrode that obtains with manufacture method of the present invention.That is to say, comprise and contain the charing yeast and contain the carbide that material obtains, be used for oxygen is carried out the electrode for use in oxygen reduction of quadrielectron reduction.So, in electrode of the present invention,, adopted disclosed in front material to get final product as long as above-mentioned yeast contains inscapes such as material, carbide.
In electrode for use in oxygen reduction of the present invention, to the content of above-mentioned carbide without limits, can suitably set according to the purposes of electrode, the purpose of use etc.Particularly preferably in the content of above-mentioned carbide in the electrode below 80 weight % more than the 1 weight %, below 60 weight % more than the 20 weight %.By being set within this scope, can access more excellent quadrielectron reducing property.
In electrode for use in oxygen reduction of the present invention, under with its situation about using as the positive pole of battery, following reaction takes place.
In electrode for use in oxygen reduction of the present invention, use O 2+ H 2O+2e -→ OH -+ HO 2-The two-electron reduction reaction (1) of the oxygen of (in akaline liquid) expression generates hydrogen peroxide (H 2O 2, in akaline liquid, use HO 2-The hydrogen peroxide ions of expression).And the hydrogen peroxide ions that generates is used 2HO again 2-→ O 2+ 2OH -The decomposition reaction (2) of expression generates oxygen once more.This oxygen is accepted two-electron reduction and is generated hydrogen peroxide ions.
An oxygen molecule is by the hydrogen peroxide ions of 1 molecule of two-electron reduction reaction (1) generation.The hydrogen peroxide ions of 1 molecule that generates provides the oxygen of 1/2 molecule by decomposition reaction (2).The oxygen molecule of 1/2 molecule is by the hydrogen peroxide ions of 1/2 molecule of two-electron reduction reaction (1) generation.The hydrogen peroxide ions of 1/2 molecule that generates, the oxygen by 1/4 molecule of decomposition reaction (2) generation again.The oxygen molecule of 1/4 molecule is by the hydrogen peroxide ions of 1/4 molecule of two-electron reduction reaction (1) generation.The hydrogen peroxide ions of 1/4 molecule that generates is passed through the oxygen that decomposition reaction (2) provides 1/8 molecule again.Carry out two-electron reduction reaction (1) and decomposition reaction (2) so repeatedly.
That is to say, reduction for an oxygen molecule, used 2 electronics, 1 electronics, 1/2 electronics, 1/4 electronics, 1/8 electronics ...., total 4 electronics of (1/2) n electronics (n be tending towards infinitely great), in fact oxygen molecule on the current potential of two-electron reduction reaction with to accept quadrielectron reduction reaction identical.In other words, with generation O 2+ 2H 2O+4e -→ 4OH -Reaction and display go out same result.
Contain the effect of the carbide of material about yeast, can think, when the two-electron reduction reaction takes place in oxygen molecule on carbon content, inorganic constituents is immediately with the hydrogen peroxide decomposes that generates, again the oxygen that generates is carried out immediately the two-electron reduction reaction, by carrying out so repeatedly, quadrielectron reduction reaction has taken place in fact.Can think such reaction, be owing to taking place existing inorganic constituents with the very near place of carbon content.Can think perhaps, have the state of oxidation of various kinds in each, improve the oxygen exchange capacity and promoted the decomposition of hydrogen peroxide owing to mixes the elements such as phosphorus, calcium of the main inorganic constituents of existence with carbon content.
In addition, can think, because they near carbon content, except improving the compatibility to oxygen, have also improved the compatibility to water, thereby promoted the two-electron reduction reaction.Can also think that further carbon content itself has C-O-C key or C=O key, OH base etc., all improve to the compatibility of oxygen and hydrogen peroxide with to the compatibility of water, thereby can carry out effective reduction reaction.In addition, can think,, may play a part to promote the co-catalyst of reaction because other inorganic constituentss such as silicon also exist with the state of oxidation.In a word, can think, because the synergy quadrielectron reduction reaction of various compositions is optionally carried out.
As mentioned above, electrode for use in oxygen reduction of the present invention, the electrochemical catalyst effect of the carbide by containing material by yeast, given the reduction passage of oxygen for the electrochemical reduction that with oxygen is the electrode reaction material, can quadrielectron reduction reaction take place with very high selection rate (selection rate) near 100%.
(2) electrochemical element
Electrochemical element of the present invention is characterized in that, comprising: a) positive pole that reacts as positive pole with the reduction reaction of oxygen; B) negative pole, and c) electrolyte, and above-mentioned positive pole contains the charing yeast and contains the carbide that material obtains.
That is to say, in electrochemical element of the present invention, use electrode of the present invention basically as above-mentioned positive pole.As negative pole, can use such as known electrodes such as platinum, zinc, magnesium, aluminium, iron.
Electrochemical element of the present invention except using electrode for use in oxygen reduction of the present invention as the positive pole, also is fit to use the inscape of known electrochemical element.Such as, can use known or commercially available electrolyte, barrier film, container, electrode connection etc.
Particularly, as electrolyte, electrolyte or solid electrolyte all are fine, but are particularly suitable for using electrolyte.Under the situation of using electrolyte, its solvent can be a water, also can be organic solvent.Wherein, preferably use the aqueous solution as electrolyte.The pH value of electrolyte without limits, but especially preferably from the neutral range of pH6 to pH9.In the present invention, from obtaining the viewpoint of higher activity, preferably use neutral aqueous solution as electrolyte.
In electrolyte, preferably contain fuel material.Preferred dissolved fuel material in neutral aqueous solution particularly.Preferably electrochemically take out the oxidation reaction of electronics as negative reaction with the fuel material from be dissolved in electrolyte this moment.As above-mentioned fuel material, so long as in used electrolyte (particularly neutral aqueous solution) soluble material, just have no particular limits, but at least a in preferred carbohydrate and the alcohols.As carbohydrate, for example can enumerate glucose, fructose, mannose, starch, cellulose etc.As alcohols, can enumerate such as methyl alcohol, ethanol, propyl alcohol, butanols, glycerol etc.
The content of fuel material (concentration) in electrolyte will be determined according to the kind of the fuel that uses, solvent types etc., but general preferred about below the 100 weight % more than the 0.01 weight %, particularly below 20 weight % more than the 1 weight %.
In electrochemical element of the present invention, the redox electrode is preferably such as 1) oxygen containing gas; 2) liquid that constitutes by electrolyte solution; 3) these three place that phase the contacted configurations of solid that are made of electric conducting material are used.So, by electrode of the present invention (the particularly carbide of yeast class) is configured on the crosspoint of ion channel and electron channel, just can under little overvoltage (impedance) electrochemical reduction of oxygen take place successfully, thereby obtain big current value.
Electrode for use in oxygen reduction of the present invention is to showing oxidation activity hardly as the carbohydrate or the alcohols that dissolve in electrolytical fuel.Therefore, can use electrode of the present invention, use carbohydrate or alcohol solution, be used for making the negative pole of carbohydrate or oxidation of alcohols, just can constitute the battery of generating by manufacturing as electrolyte as positive pole.In the case, even isolate side of the positive electrode and negative side without barrier film, even directly contact with anodal as carbohydrate that is dissolved in electrolytical fuel or alcohols, the voltage of generating battery can not reduce yet.Certainly, in electrochemical element of the present invention, also can use barrier film as required.
In electrochemical element of the present invention, yeast is contained carbide that the material charing obtains as positive pole, so as the illustrated in front quadrielectron reduction reaction that causes oxygen owing to used to contain.In other words, the electrochemical element of the application of the invention can carry out the quadrielectron reduction reaction of oxygen.
The invention effect
In the present invention, because redox has used yeast to contain the carbide of material with electrode, can access the electrode that can carry out electrochemical reduction effectively to oxygen.
That is to say that electrode of the present invention is unknown, demonstrates the effect of substantial quadrielectron reduction reaction in the traditional carbon class material of the two-electron reduction of existing Catalytic Oxygen molecule reaction.
By with electrode of the present invention, be configured in the crosspoint of ion channel and oxygen passage, can cause the electrochemical reduction of oxygen with smaller overvoltage (impedance) smoothly.Its result can provide the electrochemical element that obtains big electromotive force and big current value.
Particularly, electrode of the present invention owing to carry out the reduction reaction of oxygen molecule in fact with the quadrielectron, just becomes the substitute of existing noble metal catalysts such as platinum as quadrielectron reducing catalyst.Thus, can provide the electrode that has following feature concurrently, 1) low price; 2) place that there is no need will to carry out oxidation reaction and reduction reaction with barrier film etc. separately; 3) can suppress because the catalysqt deactivation that catalyst poisoning etc. cause.
In addition, contain carbide that material the obtains carrier as catalyst by use the charing yeast in electrode in redox, because carrier self carries out catalysis with electrochemical means to reduction reaction, this can reduce the use amount of noble metal catalysts such as platinum again.
Also have, think the effect that may also have the reduction performance that inhibition causes because of noble metal catalyst poisonings such as platinum etc., can seek further to improve performance.
The possibility of utilizing on the industry
According to the present invention, can provide electrochemical reduction, to give the electrode for use in oxygen reduction of the excellent in stability of substantial quadrielectron reduction reaction near 100% selection rate to oxygen.Can be with this electrode for use in oxygen reduction, be used for the reduction reaction of oxygen as the oxygen utmost point of the electrochemical element of positive pole reaction, air pole etc.Such as, applicable to air cells such as zinc-air battery, aluminium-air cell, sucrose-air cells; Fuel cells such as oxygen hydrogen fuel cell, methanol fuel cell; In the electrochemical sensor such as enzyme sensor, lambda sensor.
As mentioned above, electrode of the present invention and manufacture method thereof are to be suitable for the method for producing with commercial scale, have very high practicality.
Embodiment
Below provide embodiment and comparative example, the present invention is described in more details.But scope of the present invention is not limited to embodiment.
(embodiment 1)
Make test electrode 1,2
After the beer vinasse charing that will contain brewer's yeast under 800 ℃ the nitrogen atmosphere, use and under 900 ℃, carry out the carbide manufacturing test electrode 1,2 that steam activation obtains.
Fixedly carbon element in the carbide that obtains is approximately 64 quality %.Carry out the wherein about 30 quality % of ash content of elementary analysis.To inorganic constituents wherein, by x-ray fluorescence analysis as can be known phosphorus (P) be approximately 30 quality %, calcium (Ca) is 23 quality %, magnesium (Mg) is 7 quality %, potassium (K) is 3 quality %, silicon (Si) is approximately 20 quality %, P and Ca are main components.In addition, by infrared spectroscopic analysis, observe as characteristic absorption at the about 1110cm of wave number -1The C-O-C that the place has absworption peak absorbs, at about 1570cm -1The C=C that the place has absworption peak absorbs, at about 1705cm -1The C=O that the place has an absworption peak absorbs and at 3000cm -1Near wide O-H absorbs.The carbide completely that these are not only carbon element also derives from the molecular structure that the preceding yeast of charing contains material.
The carbide that obtains pulverized obtain the powder of maximum gauge below 10 μ m.With the such powder of 25 μ g, be dispersed in the 5 μ l ethanolic solutions of the high fluoride resin (trade name high fluoride resin 112 (Nafion 112), company of Du Pont (Du Pont) makes, and is as follows) that has dissolved 0.05 quality % proton-conducting.By the dispersant liquid drop that will obtain to ventilative conductive base and it is covered go up whole surface, carrying out the air-dry dry ethanol evaporation that makes of temperature again falls, and then the same dispersion liquid that drips, evaporate ethanol and produce the test electrode that contains carbide and high fluoride resin.
As the conductive base of gas permeability, the carbon paper of used thickness 0.36mm (ProductName TGPH-120, eastern Li manufacturing, below with).The mixture that use will be made up of the polytetrafluoroethylene (PTFE) adhesive of the carbon black particle of 1 weight portion and 0.1 weight portion is with 2.25mg/cm 2Remain on the carbon paper and the water proofing property carbon paper substrate that obtains and the carbon paper substrate of not carrying out water-proofing treatment.
On the surface of water proofing property carbon paper substrate, be coated with 4.2mg/cm according to the method described above 2Carbide obtain test electrode 1.In addition, on carbon paper substrate, form 2mg/cm according to the method described above 2Carbide, obtain test electrode 2.
(embodiment 2)
Make test electrode 3
After the beer vinasse charing that will contain brewer's yeast under 800 ℃ the nitrogen atmosphere, under 900 ℃, carry out steam activation.With carbide 4 weight portions (the about 5 μ m of average grain diameter) that obtain, rudimentary manganese oxide (Mn 3O 4And Mn 5O 8Mixture, the about 10 μ m of average grain diameter) 4 weight portions, carbon black 1 weight portion, fluororesin adhesive (PTFE) 0.2 weight portion mix.Make sheet with this mixture and with the nickel plating stainless steel cloth (thickness 0.15mm, 25 orders) of gas permeability conductive base as core.Then, crimping fluororesin porous chips on a face of this sheet (porosity about 50%, thickness 0.2mm) is made the test electrode 3 of the about 3mm of thickness.
(embodiment 3)
Make test electrode 4
In 0.1 weight portion silicon dioxide adhesive, mix 5 weight portion brewer's yeasts and 0.1 weight portion calcium monohydrogen phosphate and make it to form solid.Under 900 ℃ nitrogen atmosphere with the mixture charing that obtains.The carbide that pulverizing obtains makes that to become maximum gauge be the following powder of 20 μ m.With the powder 25 μ g that obtain, be dispersed in the 5 μ l ethanolic solutions that are dissolved with 0.05 quality % high fluoride resin.On the matrix of the carbon paper by process water-proofing treatment that this dispersant liquid drop is used in embodiment 1 and make and cover whole surface, the air-dry dry test electrode 4 that ethanol evaporation is made contain carbide and high fluoride resin of temperature.In addition, form 2mg/cm 2Carbide.
(embodiment 4)
Make test electrode 5
Under 800 ℃ the nitrogen atmosphere with the brewer's yeast charing after, under 900 ℃, carry out steam activation and obtain carbide.This carbide is crushed to powder below the maximum gauge 10 μ m.In the ethanolic solution of the chloroplatinic acid of 3mmol/L, make it to carry platinum salt by the powder impregnation that will obtain.At room temperature adding sodium borohydride reduction therein carries and holds platinum.The platinum of this moment carries holdup and is approximately 10 quality %.25 μ g have been added this carbide of platinum, be dispersed in the 5 μ l ethanolic solutions of the high fluoride resin that is dissolved with 0.05 quality % proton-conducting.Make it to cover whole surface on the carbon paper substrate by process water-proofing treatment that this dispersant liquid drop is used in embodiment 1, the air-dry dry ethanol evaporation that makes of temperature, this dispersion liquid that drips once more evaporates ethanol, makes the test electrode 5 that contains carbide and high fluoride resin.In addition, in this test electrode 5, form 2mg/cm 2Carbide, this moment platinum content approximately be 0.2mg/cm 2
(embodiment 5)
Make test electrode 6
After the manufacturing whiskey that will contain yeast under 800 ℃ the nitrogen atmosphere was with the poor charing of wheat juice squeezing, use was carried out steam activation and is obtained carbide manufacturing test electrode 6 under 900 ℃.Above-mentioned carbide is ground into the powder of maximum gauge below 10 μ m.With 25 these powder of μ g, be dispersed in the 5 μ l ethanolic solutions of the high fluoride resin that is dissolved with 0.05 quality % proton-conducting.By with this dispersant liquid drop on by the gas permeability conductive base of the carbon paper manufacturing of thickness 0.36mm and make and cover whole surface, the air-dry dry ethanol that evaporates of temperature, this dispersion liquid that drips once more evaporates ethanol, makes the test electrode 6 that contains carbide and high fluoride resin.In addition, upload in carbon paper substrate and hold 2mg/cm 2Carbide.
(comparative example 1)
Make relatively electrode 1,2,3,4 and 5
25 μ g platinum are carried the hydrocarbon black powder that holdup is 50 quality %, be dispersed in the 5 μ l ethanolic solutions that are dissolved with 0.05 quality % proton-conducting high fluoride resin.By at the mixture of forming by carbon black particle 1 weight portion and polytetrafluoroethylene (PTFE) adhesive 0.1 weight portion of gas permeability conductive base with 2.25mg/cm 2Amount remain on this dispersion liquid and make and cover whole surface of dripping on the water proofing property carbon paper substrate of making on the carbon paper of thickness 0.36mm, the air-dry dry ethanol evaporation that makes of temperature, the same dispersion liquid that drips again makes ethanol evaporation again, makes platinum content and is approximately 0.35mg/cm 2Comparison electrode 1.
At this moment, replace carrying out almost same processing the above-mentioned hydrocarbon black powder, make platinum content and be approximately 0.2mg/cm except using hydrocarbon black powder that platinum carries holdup 30 quality % 2Comparison electrode 2.
In addition, make comparison electrode 3, only make comparison electrode 4, use the high fluoride resin ethanolic solution of the proton-conducting that does not contain above-mentioned carbide on carbon paper substrate, to form relatively electrode 5 with carbon paper with above-mentioned water proofing property carbon paper substrate.
(embodiment 6)
The electrode characteristic evaluation of test electrode 1,2
Constitute 3 utmost point batteries as shown in Figure 3, with the reduction characteristic of the oxygen of voltage-current characteristic evaluation on test electrode.In Fig. 3, the 1st, air pole, 1a is test electrode or comparison electrode, and 1b is the fluororesin porous plate, and 1c is an electrode connection, the 2nd, to the utmost point, the 3rd, reference electrode, the 4th, electrolyte, the 5th, be used for disposing the aquarium with diameter 16mm peristome of air pole.As shown in Figure 3, air pole 1 is configured in the peristome of aquarium 5, is positioned at the face exposed to weather of fluororesin porous plate 1b one side, and another side contacts with electrolyte 4.The 0.1M phosphate buffer solution that uses pH value 7.0 is as electrolyte 4.The utmost point 2 is used platinum, and reference electrode 3 uses Ag/AgCl (saturated KCl) electrode.In addition, test electrode or comparison electrode 1a and fluororesin porous plate 1b tight bond.
In Fig. 1, relatively and demonstrate with test electrode 1 and 2, and each voltage-current characteristic when relatively electrode is as air pole 1.In addition, keep the electric current that applies and measured at least 10 minutes, electromotive force is that benchmark is represented with the standard hydrogen electrode (NHE) with the battery impedance correction.With respect to the comparison electrode of being made by carbon black 3, test electrode 1 and 2 can obtain high electromotive force with little overvoltage, obtains and the comparison electrode of being made by platinum catalyst 1 and the electromotive force of 2 same degree.This just can think, the traditional carbon material carries out two-electron reduction to oxygen relatively, and the carbide that uses in test electrode carries out quadrielectron reduction in fact, so obtain the characteristic that is equal to mutually with the quadrielectron reduction reaction of carrying out with platinum.
(embodiment 7)
Test electrode 3,4,5 and 6 electrode characteristic evaluation
The same with embodiment 6, constitute 3 utmost point batteries as shown in Figure 3, with the hydrogen reduction characteristic of voltage-current characteristic evaluation test electrode.
In Fig. 2, relatively and shown with test electrode 3,4,5 and 6 and each voltage-current characteristic when relatively electrode is as air pole 1.To the comparison electrode of being made by carbon black 3, coexisting mutually with embodiment 6 obtains high electromotive force under the smaller overvoltage in each test electrode, has played making the catalytic action of oxygen near quadrielectron reduction reaction as can be seen.
In test electrode 3, because rudimentary manganese oxide contained in air pole has very strong decomposition to the hydrogen peroxide that generates in the two-electron reduction reaction of oxygen molecule, obtained the effect of very high quadrielectron reduction reaction in fact, obtained the electromotive force almost equal with the comparison electrode made by platinum 1.
In test electrode 4, even in through the carbide that is solidified to form that is shaped, obtain very high electromotive force as the electrochemical catalytic effect under pulverulence.Thus, do not make electrode etc. and be expected to improve operability yet even do not form formed body that the powder body forms carbide.
In test electrode 5, the comparison electrode 2 identical with respect to the platinum amount of adding in carbide obtains higher electromotive force.This be because, in the platinum that adds, add charing the carbide of yeast, strengthened its reduction, effective reduction reaction takes place.By using such carbide, can reduce the use amount of expensive noble metal catalyst as catalyst carrier.
In addition, with retention time of the electromotive force in the air pole of service test electrode 5 when relatively electrode 1 compares, confirm that the retention time of the electromotive force of test electrode 5 is long more than 5 times than electrode 1 in electromotive force is reduced to time of 10% frequently.One of essential factor of the maximum that this electromotive force reduces is because as the catalyst poisoning of the platinum of catalyst.Because the platinum content of test electrode 5 is fewer, so the reduction of electromotive force is also just little, but just since surpassed the platinum content difference (test electrode 5: electrode 1=0.2 relatively: 0.35) produce effect, can not only illustrate with catalyst poisoning, think other effect also in action.Also fuzzy for this effect, but can think that carbide makes oxygen carry out the effect of quadrielectron reduction reaction in fact, has also played the effect that suppresses the catalyst poisoning of platinum.
In test electrode 6, can obtain the effect of quadrielectron reduction reaction as can be seen in the carbide of the yeast beyond coming from brewer's yeast equally.
(embodiment 8)
The generating battery evaluating characteristics
To comprise embodiment 1 test electrode 1 air pole as anodal, with to the platinum of the utmost point as negative pole, the pH value of having dissolved 100mM glucose is that 6.8 0.1M phosphate buffer is as electrolyte formation generating battery a.Use positive pole, the negative pole identical with generating battery a, the 0.1M phosphate buffer that has dissolved the pH value 6.8 of 3 quality % methyl alcohol constitutes generating battery b as electrolyte.In addition, except with the platinum plate be air pole as the positive pole, constitute generating battery c and generating battery d with same structure.Be displayed in Table 1 out the open circuit voltage of these generating batteries and the voltage that generating battery was discharged 10 hours with the constant current value of 1mA.
Table 1
Generating battery Anodal Fuel Open circuit voltage (V) Voltage (V) after 10 hours discharges
a Air pole Glucose 0.86 0.78
b Air pole Methyl alcohol 0.72 0.66
c The platinum plate Glucose 0.43 0.28
d The platinum plate Methyl alcohol 0.33 0.28
Use and contain carbide of the present invention and be the air pole of active ingredient generating battery a, b, compare, can access the open circuit voltage that exceeds 0.2～0.4V with the generating battery c, the d that use the platinum plate as positive pole as positive pole.This shows, by containing the positive pole that carbide that the charing brewer's yeast the obtains air pole as active ingredient constitutes, even directly contact also with glucose or methyl alcohol and oxidation reaction can not take place, what give is current potential by the oxygen reduction reaction decision, so generating battery provides high voltage.In contrast, can think and when directly contacting, can play oxidation reaction by the positive pole that constitutes because of by the platinum plate, provide electronegative potential, so generating battery provides low voltage by glucose or oxidization of methanol reaction and oxygen reduction reaction decision with glucose or methyl alcohol.
In addition, though in electrolyte, used glucose or methyl alcohol as soluble fuel material, but the carbohydrate (such as fructose, mannose, starch, cellulose etc.) beyond the use glucose, or the alcohols (such as ethanol, propyl alcohol, butanols, glycerol etc.) beyond the methyl alcohol also can obtain same result.In addition, the salt solution that uses the KOH aqueous solution of 0.1N as electrolyte or dissolved 3 quality %NaCl replaces the 0.1M phosphate buffer of pH value 6.8 also can obtain same result.
(embodiment 9)
The assembling generating battery
The generating battery A and the generating battery B of assembling structure as shown in Figure 4.
In Fig. 4, the air pole 11 that plays anodal effect among the generating battery A is to use the test electrode 1 that obtains in embodiment 1 to make.In Fig. 4, the 15th, negative pole wiring, the 16th, anodal wiring, the 17th, the encapsulating material that constitutes by transparent silicon rubber.
Playing the photochemical catalyst electrode of negative pole effect in Fig. 4, is by glass substrate 6, ito thin film 7, titanium oxide (TiO 2) particulate film 8 and pigment molecular layer 9 constitute.Preparation forms sheet resistance 10 Ω/cm on the glass substrate 6 of thickness 1mm 2The photopermeability conductive board of indium tin oxide (ITO) film 7, with the TiO of average grain diameter 10nm 2Particle is dispersed in the polyethylene glycol with 11 quality %, will contain the acetonitrile solution of this polyethylene glycol 30 quality %, is coated on the ito thin film by infusion process, after 80 ℃ of following dryings, burns till under 400 ℃ 1 hour in air, forms the TiO that thickness is approximately 10 μ m 2Particulate film 8.Then, by with TiO 2The particulate film, in dissolving as follows flood in the ethanolic solution of 10mM ruthenium metal complex pigment molecular 9, at TiO 2Add pigment molecular 9 in the particulate film 8.In the 4-tert .-butylpyridine, flood again, carry out drying again with the acetonitrile washing then and just obtain above-mentioned photochemical catalyst electrode.
Figure C20048000161900301
As electrolyte, fuel fluid 10, use is dissolved with the solution of the hydrogenlyase (FDH) of the aldehyde dehydrogenase (AlDH) of alcohol dehydrogenase (ADH), 1.0U/ml of coenzyme nicotinamide nucleotide (NADH), the 16.0U/ml of fuel methanol, the 5mM of 5 quality % and 0.3U/ml in the 0.1M of pH value 7.0 phosphate buffer.With electrolyte, fuel fluid 10, inject from electrolyte, fuel fluid inlet 13a, after generating, discharge from outlet 13b.Air supplies to generating battery inside by oxygen flow hydrophobic membrane 12 from the outside.
Structure at the generating battery described in Fig. 4 is described.The negative side of this generating battery mainly is made of glass substrate 6, at the surperficial lamination ito thin film 7 of this glass substrate 6.On ito thin film 7, negative pole wiring 15 is set.The side of the positive electrode of generating battery mainly is made of tabular air pole 11, in the surperficial lamination oxygen flow hydrophobic membrane 12 of air pole 11.Anodal wiring 16 is stretched out from the inside of air pole 11.The surface of such glass substrate 6 and the inside of tabular air pole 11 are closed up in opposite directions, by encapsulating material 17 glass substrate 6 and air pole 11 are fitted between them, this has just formed generating battery.
Between glass substrate 6 and air pole 11, electrolyte (or fuel fluid) 10 is positioned at air pole 11 1 sides, has disperseed then to be positioned at glass substrate 6 one sides by the atomic particulate film 8 that titanium oxide constitutes.And, between electrolyte (or fuel fluid) 10 and particulate film 8, clip pigment separating layer 9.
In addition, on encapsulating material 17, be provided with electrolyte, fuel fluid inlet 13a and the electrolyte, the fuel fluid outlet 13b that connect encapsulating material 17.On electrolyte, fuel fluid inlet 13a and electrolyte, fuel fluid outlet 13b, be respectively equipped with liquid valve 14a and 14b.It is designed to make that electrolyte (or fuel fluid) 10 can be via electrolyte, fuel fluid inlet 13a and electrolyte, fuel fluid outlet 13b, is injected between glass substrate 6 and the air pole 11 from the outside and is discharged to the outside.
In addition, generating battery B except using the air pole of being made by the test electrode 3 that obtains among the embodiment 2, makes identically with generating battery A structure.
The characteristic of generating battery action
After being full of generating battery with electrolyte, fuel fluid, from the irradiation of glass substrate 6 sides from solar simulator (AM1.5,100mW/cm 2) light, measure the electromotive force (OCV) of generating battery and with the constant current of 100 μ A voltage to the generating battery of generating battery discharge in the time of 20 minutes.The OCV of generating battery A is 0.80V, and generating battery B is 0.65V.In addition, the voltage of the generating battery after 20 minutes that discharges, generating battery A is 0.75V, generating battery B is 0.55V.When obtaining so high electromotive force, even when discharge, also can keep and compare higher voltage.
In addition, in the present embodiment, shown and used the negative pole of photochemical catalyst electrode as generating battery, the battery that acts as a fuel with methyl alcohol, but as negative pole, even use metals such as zinc, magnesium, aluminium, by making up with electrode for use in oxygen reduction of the present invention, the battery of the high cell voltage in the time of also accessing the high electromotive force that has as electrochemical element and discharge.

Claims (56)

1. the manufacture method of an electrode for use in oxygen reduction is characterized in that: described electrode for use in oxygen reduction is used for oxygen is carried out quadrielectron reduction, and this method comprises:
(1) by the charing yeast contain material obtain carbide first operation and
(2) use the electrode material that contains described carbide to make second operation of described electrode for use in oxygen reduction.
2. manufacture method as claimed in claim 1 is characterized in that:
Yeast contains material, is brewer's yeast, wine yeast, saccharomyces sake, whiskey yeast, Saccharomyces cerevisiae, fodder yeast, beer vinasse, pure mellow wine vinasse, makes grape juice vinasse that grape wine uses, makes that the wheat juice squeezing that whiskey uses is poor, the corn juice squeezing is poor and at least a in poor of soy sauce.
3. manufacture method as claimed in claim 1 is characterized in that:
In first operation, under being atmosphere below the 10 volume %, oxygen concentration contains material at the described yeast of charing below 1200 ℃ more than 300 ℃.
4. manufacture method as claimed in claim 3 is characterized in that:
In first operation, under the atmosphere below the oxygen concentration 10 volume %, contain material at the described yeast of charing below 1000 ℃ more than 500 ℃.
5. manufacture method as claimed in claim 3 is characterized in that:
Described atmosphere is inert gas atmosphere.
6. manufacture method as claimed in claim 1 is characterized in that:
In first operation, further carbide is carried out activation processing.
7. manufacture method as claimed in claim 1 is characterized in that:
In second operation, after the shape that described electrode material is configured as regulation obtains formed body,, make described electrode for use in oxygen reduction by with described formed body lamination or be crimped on the conductive base body.
8. manufacture method as claimed in claim 1 is characterized in that:
In second operation,, described paste is coated on makes described electrode for use in oxygen reduction on the conductive base by after described electrode material being made paste and being obtained containing the paste of electrode material.
9. manufacture method as claimed in claim 1 is characterized in that:
In described yeast contains material, carbide and electrode material at least a, add at least a inorganic compound that contains in phosphorus and the calcium.
10. manufacture method as claimed in claim 1 is characterized in that:
Above-mentioned carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon.
11. manufacture method as claimed in claim 1 is characterized in that:
Described carbide is at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry.
12. manufacture method as claimed in claim 1 is characterized in that:
Described carbide is at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen.
13. manufacture method as claimed in claim 1 is characterized in that:
Described carbide is at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
14. manufacture method as claimed in claim 1 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon, at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry, at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen, and at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
15. manufacture method as claimed in claim 1 is characterized in that:
In described yeast contains at least a in material, carbide and the electrode material, add at least a in metal and the oxide thereof.
16. manufacture method as claimed in claim 7 is characterized in that:
Oxide is to use formula M nO yThe rudimentary manganese oxide of expression, here, y is the oxygen atomicity by the valence mumber decision of manganese, less than 2.
17. an electrode for use in oxygen reduction is characterized in that:
This electrode contains the charing yeast and contains the carbide that material obtains, and is used for oxygen is carried out quadrielectron reduction.
18. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that: comprising:
At least a inorganic compound that contains phosphorus and calcium.
19. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon.
20. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide is at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry.
21. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide is at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen.
22. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide is at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
23. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon, at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry, at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen, and at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
24. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Contain at least a of metal and oxide thereof.
25. electrode for use in oxygen reduction as claimed in claim 24 is characterized in that:
Described oxide is to use MnO yThe rudimentary manganese oxide of expression, here, y is the oxygen atomicity by the valence mumber decision of manganese, less than 2.
26. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Described carbide is a graininess, and the electrode material that contains described carbide is carried to be held on the conductive base.
27. electrode for use in oxygen reduction as claimed in claim 26 is characterized in that:
Conductive base has gas permeability.
28. electrode for use in oxygen reduction as claimed in claim 17 is characterized in that:
Be used for the oxygen of molecularity being carried out electrochemical reduction at the neutral electrolyte aqueous solution.
29. an electrochemical element is characterized in that:
This element comprises: oxygen is carried out positive pole, negative pole and the electrolyte that the quadrielectron is reduced, and described positive pole contains the charing yeast and contains the carbide that material obtains.
30. electrochemical element as claimed in claim 29 is characterized in that:
Described positive pole comprises, contains at least a inorganic compound of phosphorus and calcium.
31. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon.
32. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide is at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry.
33. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide is at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen.
34. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide is at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
35. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon, at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry, at about 1700cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen, and at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
36. electrochemical element as claimed in claim 29 is characterized in that:
Described positive pole contains at least a of metal and oxide thereof.
37. electrochemical element as claimed in claim 36 is characterized in that:
Described oxide is to use MnO yThe rudimentary manganese oxide of expression, here, y is the oxygen atomicity by the valence mumber decision of manganese, less than 2.
38. electrochemical element as claimed in claim 29 is characterized in that:
Described carbide is a graininess, and the electrode material that contains described carbide is carried to be held in constitutes described positive pole on the conductive base.
39. electrochemical element as claimed in claim 38 is characterized in that:
Conductive base has gas permeability.
40. electrochemical element as claimed in claim 29 is characterized in that:
Electrolyte is a neutral aqueous solution.
41. electrochemical element as claimed in claim 29 is characterized in that,
Negative reaction is the oxidation reaction of electrochemically taking out electronics from dissolve in electrolytical fuel material.
42. electrochemical element as claimed in claim 29 is characterized in that:
In described electrolyte, contain at least a of carbohydrate and alcohols.
43. a method of reducing is characterized in that:
This method is that oxygen is carried out quadrielectron reduction, comprising:
Provide to have and contain the positive pole that the charing yeast contains the carbide that material obtains, negative pole, and the battery of the battery formed of electrolyte provides operation, and
By oxygen being carried out the oxygen supply operation that the quadrielectron is reduced to the described anodal oxygen of supplying with.
44. method of reducing as claimed in claim 43 is characterized in that:
Described positive pole comprises, contains at least a inorganic compound of phosphorus and calcium.
45. method of reducing as claimed in claim 43 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon.
46. method of reducing as claimed in claim 43 is characterized in that:
Described carbide is at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry.
47. method of reducing as claimed in claim 43 is characterized in that:
Described carbide is at about 2100cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen.
48. method of reducing as claimed in claim 43 is characterized in that:
Described carbide is at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
49. method of reducing as claimed in claim 43 is characterized in that:
Described carbide, about 1000 to 1200cm -1Scope in demonstrate the flexible INFRARED ABSORPTION of carbon-oxygen-carbon, at about 1600cm -1The place demonstrates carbon=flexible INFRARED ABSORPTION of carbon symmetry, at about 2100cm -1The place demonstrates the flexible INFRARED ABSORPTION of carbon=oxygen, and at about 3000cm -1The place demonstrates the flexible INFRARED ABSORPTION of oxygen-hydrogen.
50. method of reducing as claimed in claim 43 is characterized in that:
Described positive pole contains at least a of metal and oxide thereof.
51. method of reducing as claimed in claim 50 is characterized in that:
Described oxide is to use MnO yThe rudimentary manganese oxide of expression, here, y is the oxygen atomicity by the valence mumber decision of manganese, less than 2.
52. method of reducing as claimed in claim 43 is characterized in that:
Described carbide is a graininess, and the electrode material that contains described carbide is carried to be held in constitutes described positive pole on the conductive base.
53. method of reducing as claimed in claim 52 is characterized in that:
Conductive base has gas permeability.
54. method of reducing as claimed in claim 43 is characterized in that:
Electrolyte is a neutral aqueous solution.
55. the method for reducing as claim 43 is characterized in that,
Negative reaction is the oxidation reaction of electrochemically taking out electronics from dissolve in electrolytical fuel material.
56. method of reducing as claimed in claim 43 is characterized in that:
In described electrolyte, contain at least a of carbohydrate and alcohols.
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