CN1039851A - The technology of preparation porous metal - Google Patents

The technology of preparation porous metal Download PDF

Info

Publication number
CN1039851A
CN1039851A CN89106719A CN89106719A CN1039851A CN 1039851 A CN1039851 A CN 1039851A CN 89106719 A CN89106719 A CN 89106719A CN 89106719 A CN89106719 A CN 89106719A CN 1039851 A CN1039851 A CN 1039851A
Authority
CN
China
Prior art keywords
metal
technology
electrode
support material
deposition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN89106719A
Other languages
Chinese (zh)
Inventor
蒋振宗
蒋三平
陈衍珍
尤金跨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
City University Of Northampton Square
University of Essex
Original Assignee
City University Of Northampton Square
University of Essex
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by City University Of Northampton Square, University of Essex filed Critical City University Of Northampton Square
Publication of CN1039851A publication Critical patent/CN1039851A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/8853—Electrodeposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0442—Anodisation, Oxidation
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0454—Electrochemical coating; Electrochemical impregnation from melts
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • H01M4/29—Precipitating active material on the carrier by electrochemical methods
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0492—Chemical attack of the support material
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

But in the technology of the metal porous layer of a kind of preparation electrolytic deposition, a support material is immersed in the electrolytic medium that contains this metal ion species, and make this metal have a kind of oxidation (property) when material exists electrolytic deposition on this support material.This oxidation (property) material is a kind of metal reaction therewith and form a kind of material of the product that can be reduced under mode of deposition.In a kind of form of this technology, by oxygen being introduced in the medium from passing near the support material, with a kind of metal to be deposited on the support material in the aqueous electrolyte liquid that contains this metal ion.

Description

The technology of preparation porous metal
The present invention relates to a kind of technology for preparing porous metal, and have the goods of porous metal.The invention still further relates to a kind of method that forms metal oxide.
Porous metal have been widely used, as are used for battery pole plates, support of the catalyst, catalysis electrode, strainer, cat cracker.In these were used, with non-porous metallographic phase ratio, the bigger surface-area of porous metal provided higher performance.
Previously, porous metal prepare with powder metallurgy always.With thin metal-powder through pressed compact, then in reducing atmosphere through high temperature sintering.For behind sintering, increasing the number in the hole in the goods,,, before pressed compact, add in the powder as volatile salt usually with pore former.Yet in sintering process, because the particulate growth taken place, the average particle size particle size of the porous metal made from sintering process is generally greater than 5 μ, thereby the size in hole also is in the similar order of magnitude.
Porous electrode is to be coated on the wire netting by oxide compound or oxyhydroxide with metal always, carries out electrochemical reduction with that in the original place and makes.The particle size of the porous metal of Xing Chenging can be in the scope more than 3 μ like this.For obtaining gratifying electroconductibility, often,, mix in electrode as graphite with the powder of inert conduction.
In the time will being used for battery with the porous metal article that aforesaid method makes, in fact resulting effective energy density be lower than theoretical value significantly.
Electrodip process is that the preparation porosity of knowing is very low, or the method for very tiny metal level.Make the atoms metal deposition to form closely orderly atomic shell.In the application of galvanic deposit, as in plating, people wish to reduce to the atomic shell interference of formation in order very much as far as possible, are understandable so that the porosity of the metal level that is produced reaches minimum.
The invention provides a kind of method that on support material, produces electrodepositable metal porous layer, it comprises: support material is immersed contain in the electrolytic medium of this metal ion species, and provide a kind of and this metal reaction near the medium support material and when generating a kind of oxidizing substance of the product that under mode of deposition, can be reduced, with this metal electrodeposition on support material.
Method of the present invention can prepare the metal of high porosity, and the metal of making like this can have such as less than 3 μ, especially less than the average particle size particle size of 1 μ, thereby these particles is classified by the hole of similar size.
Owing to the higher porosity of the porous metallic layers for preparing by the present invention, compare with the product of prior art, just can obtain much bigger utilizable metal surface area.For example, when this metal is used to battery electrode, the performance of this battery has been compared tangible improvement with battery of the prior art, and particularly big surface-area means that this electrode has very high maximum current density, thereby can obtain very high momentary power density.And then when this metal was used as catalyzer, high porosity had improved the catalytic performance of metal.
Term as used herein " oxidation (property) material " broadly is used a kind of, and promptly this material can make the oxidation state of the metal that reacts with it be improved.
Can be sure of that in technology of the present invention, oxidation (property) material and sedimentary metal react and form a kind of metallic compound, this compound and be reduced into metal.The temporary transient existence of this metallic compound has prevented to form fine and close metal level in deposition process, thereby can generate the porous product.
During metal deposition, supply or generation oxidation (property) material are useful continuously.
Oxidation (property) is if a kind of oxidizing substance that contains aerobic of material is useful.Here employed " containing oxygen " refers to and contains one or more Sauerstoffatoms, and comprises molecular oxygen.
Oxygen containing oxidation (property) material can be, such as oxygen, or a kind of oxidation (property) material that under mode of deposition, produces by oxygen.Thereby oxidation (property) material can be, maybe can result to be imported in the electrolytic medium to make it to pass the gaseous oxygen of support material near zone.Under mode of deposition, result from oxygen to contain the oxygen oxidizing substance passable, such as being hydrogen peroxide, ozone, oxyhalogen negatively charged ion, particularly hypochlorous acid negatively charged ion.
Other oxidizing substance that can be used comprises, such as following substances, or results from the oxidizing substance of those materials under mode of deposition: hydrogen sulfide, halogen, especially chlorine.
It is favourable using at least two kinds of oxidizing substances, is oxygen containing oxidizing substance and preferably wherein have at least a kind of.As mentioned above, at least a oxidizing substance and metal reaction and generate a kind of product that under mode of deposition, can be reduced.Certainly, be understandable that, in some cases, a kind of unable to get up oxidizing substance effect under some occasion maybe can not produce the material of the oxidizing substance that meets the demands, if adjusting condition by rights, then can play this effect, or produce the oxidizing substance that meets the demands.Thereby such as, although another kind of oxidizing substance is being arranged, can be with the source of chloride ion when particularly oxygen or the oxidizing substance that results from oxygen under mode of deposition exist as oxidizing substance or oxidizing substance, but when lacking like this some other oxidizing substances, chloride ion will react not according to desired mode and this metal.
Therefore, in preferred mode according to technology of the present invention, a kind of oxygen containing oxidizing substance, for example oxygen or the oxidizing substance that results from oxygen under mode of deposition are supplied with second oxidizing substance.This second oxidizing substance preferably or results from halide ions, especially chloride ion or oxyhalide ion, especially hypochlorous acid negatively charged ion.A kind of existence of second oxidizing substance can improve the porosity of the porous metal that produced under many circumstances.
In type according to a particularly important of technology of the present invention, with a kind of technology porous metal are created on the support material, this technology comprises the support material immersion is contained in the ionic electrolytic medium of this metal, then, having mode to introduce under the condition of gaseous oxygen gaseous oxygen is passed through near the support material surface, with this metal deposition on support material.And contain halide ions in the electrolytic medium is desirable.Can by by row some conditions so that halogen gas overflow at opposite electrode, maybe this gas is blasted medium and gaseous halogen is infeeded medium, oxygen and chlorine are introduced in the medium respectively near the mode of passing separately the support material then in deposition process.What certainly can understand is under latter event, to require to take to give medium is left in anti-measure with control oxygen/chlorine gas mixture blast.
Employing is according to oxidizing substance of the present invention, to being that thin and thick particulate blended porous metal provide possibility basically on size thick, pore the grid close with particle size.The net of this thick, pore, as be widely used in the air electrode of metal-air battery and fuel cell, in the air electrode that can produce chargeable electrode, be useful especially.Under the situation that has oxygen to overflow, gross porosity will be drained, and the oxygen that results from the pore is overflowed effectively.Under the situation of hydrogen reduction, impose enough big air pressure in a side of the supply gas of electrode, so that the gross porosity of electrode exposes.Have only air pressure not to be high enough to discharge electrolytic solution in the pore, just can produce effective oxygen reduction reaction.
In the previous porous electrode that proposes, only work in the external region of electrode, this be because when gas when electrode interior is overflowed, bubble is with the electrolytic solution emptying in the hole.Previously using adherent polytetrafluoroethylstephanoporate stephanoporate electrode, in order that overflowed in the tetrafluoroethylene duct of gas through doing, so that can utilize the surface of resulting eelctro-catalyst biglyyer for avoiding in the trial that this problem does always.Yet, owing to exist non-conductive particle that electrode resistance has been improved.In the porous metal by method of the present invention preparation, the effect of gross porosity is similar to the tetrafluoroethylene duct, but the electroconductibility of electrode has had improvement, require high electric current (as:＞0.1 peace/centimetre 2) electrochemical applications in, this is very important performance.Though the performance of the electrode that the porous metal of being produced by method of the present invention are made is comparable to the performance of the poly-fluorine tetrem alkene electrode of adherent, concerning the gas evolution reaction, then the ohm voltage drop of being surveyed is to have reduced significantly.
The characteristic that it is believed that thin and thick particulate mixed structure can one or morely it is believed that the variable that can influence porosity and change by regulating.Those it is believed that the factor that can influence porosity comprises the characteristic of first oxidizing substance, the existence of second oxidizing substance, and if when having it to exist, the characteristic that it had, a kind of delivery rate of or every kind of oxidizing substance, the concentration of electrolytic medium and temperature, the atmosphere pressures of electrolytic solution top, and the pressure of oxidizing substance or its source this kind gas when being gas.Can be by changing, as changing the speed of introducing or producing oxidizing substance, or change the slewing rate of rotating support material and change a kind of delivery rate of oxidizing substance.
For example, for cobalt, by method of the present invention, blast oxygen and the porosity of the porous cobalt from cobalt chloride solution, produced near the mode support material of passing by solution, more much higher than the porosity of the cobalt of from cobaltous acetate or cobalt sulfate solution, being produced with similar approach.In addition, replace oxygen (air contains 20% oxygen approximately) with the air of identical flow velocity, porosity then significantly reduces.
In by the solution of ferrous chloride that is connected with oxygen, prepare under the situation of iron, discovery is in 3%(weight)-15%(weight) the strength of solution scope in, porosity raises with the rising of concentration, and find that best slewing rate is 300 rev/mins, and all be lower than porosity with 300 rev/mins the iron that speed was obtained with the porosity of the iron that speed was obtained higher or lower than this speed.
Electrolysis is situated between to separate and can contains two or more metal ions, and the porous metal of making so then contain two kinds of metals at least.And electrolytic medium can contain the ion of one or more metals, and wherein a kind of is that generating a kind of with the oxidizing substance reaction is unreducible product under mode of deposition.Thereby the present invention just might prepare the porous material of the oxide compound that contains first metal and second metal.
It is useful that support material is rotated.In a kind of optional suitable technology, available pump makes circulation of elecrolyte, gaseous oxygen is being introduced under the occasion of this medium, and the electrolyte flow direction is relative with the direction of Oxygen Flow.This has increased the residence time of bubble on electrode surface, and the metal of higher deposition is plated on the support material.And then replenish under the occasion of electrolytic solution when deposition, or under the sizable occasion of the volume of electrolytic medium, a kind of circulation of elecrolyte technology just can keep the composition of a metastable electrolytic solution.Opposite electrode and the metal that is deposited are that identical metal then is useful.This also helps to keep the metastable concentration of this metal ion in the medium.
If the concentration of the electrolytic medium of the metal of desiring to be deposited is low, then can obtain particularly advantageous result.When this medium was a kind of solution, then the ionic conductivity the pick of ground of this solution was provided by the ionogen that another kind can not be deposited on the support material under mode of deposition.
For example, in a kind of technology according to the present invention, this ionogen is a kind of aqueous ionogen, it preferably comprises a kind of first ionogen that contains the metal ion of desiring to be deposited, with a kind of sedimentary second ionogen does not take place on support material under mode of deposition, and the very big part of ionic conductivity is provided by second ionogen.Such as, a kind of cobalt electrode can by from rare cobalt chloride solution (as, 0.05-0.1M) in deposition and making.When using so a kind of dilute solution, with contain with the metallographic phase of desiring to be deposited with the electrode of metal be favourable as opposite electrode, do like this in order that keep that electrolytic solution forms relative stable.
During the dilute solution of the metal of desiring to be deposited when use, can not need rotate support material.
In general, support material is that lamelliform is desirable, and support can be, as nickel screen.Other available support material comprises, as titanium foil.In when deposition, can be by adding one or more materials, as adding a kind of salt of solvent, this metal, or a kind of salt of second metal changes the composition of electrolytic medium in medium, so the porous metallic layers of making so just has many different zones of forming.
But the metal of any electrochemical deposition can be used in the technology of the present invention, and this comprises, such as the lead that is widely used as electrode materials in lead-acid battery.This metal can be selected from transition metal, and selected metal is that cobalt, iron, nickel and cadmium then are useful.Other suitable transition metal comprises, as Zn, Ag, Mn and as the precious metal of Pt, Pd, Ir and so on.Exist by the prepared porous transition metal goods of the present invention,, superior performance is arranged in the application of fuel cell and catalytic material as gas battery.
For example, in agglutinating tetrafluoroethylene cobalt oxide/graphite air electrode, this cobalt oxide/graphite catalyst is for also original very high activity of oxygen in alkaline media.Yet the oxide compound of cobalt only is slightly soluble in basic solution, and when constantly changing alkaline electrolyte in application, and as at aluminium-air cell or in the application of chloro-alkali factory, the oxide compound of this cobalt is just leached gradually, so reduced the activity of electrode.According to the present invention, the porous cobalt that is deposited on the electrode can make electrode regenerate in the original place, remains on the gratifying level in long period to cause electrode performance.Thereby the present invention replaces cathode for hydrogen evolution with regard to making with cobalt/graphite air electrode as the oxygen reduction cathode in the chloro-alkali electrolyzer, and the result makes the low the most nearly 0.8V of groove pressure drop, that is to say that making energy consumption reduce nearly 25% becomes possibility.
For example also available a kind of cobalt electrode is as the anode in the Ni-Co battery.
A kind of ferroelectric utmost point can be used as the anode in the Ni-Fe battery.By the prepared a kind of Fe electrode of method of the present invention, compare with the porous iron electrode of making by sintering, have much higher significantly maximum current density, thereby also have high power density.
The NiOOH electrode is used as negative electrode in the alkaline charging store battery, this mainly is owing to its weather resistance, reliability and can bears the abilities that discharge and recharge for thousands of times.Yet NiOOH electroconductibility is poor comparatively speaking, and the electroconductibility that for example NiOOH is deposited on the electrode on the nickel screen is poor.Often NiOOH is added in the sintered compact of nickel porous to obtain electroconductibility preferably.The NiOOH material for preparing with the nickel porous of making by method of the present invention has fabulous electroconductibility, and a kind of application that has improved that makes the NiOOH material is achieved.Thereby, improved significantly by electroconductibility, particularly energy density and the power density of having used with the prepared NiOOH of method of the present invention, made the electrode that contains the NiOOH material that is deposited on the nickel screen.
Because formed nickel product only partly is reduced into nickel under mode of deposition, so the nickel electrode for preparing according to the present invention can be to have contained some NiOOH.This nickel electrode need not further processing and just can use.Yet, make it before use through the constant potential circular treatment to well.
In the Ni-Cd battery, use with porous cadmium anode.In electroconductibility of having improved and the porous cadmium made by technology of the present invention the improvement of resulting material utilising efficiency, improved the performance of this battery.
Electrolytic medium can be a kind of electrolytic medium of aquation.This medium is a kind of water-bearing media that contains transition metal ion preferably in the technology at one, thereby deposition current is no more than 300 milliamperes/centimetre 2, especially be not more than 100 milliamperes/centimetre 2
In another kind of technology according to the present invention, this electrolytic medium is a kind of fused salt, and this metal is a kind of refractory metal or rare earth metal, as La, Nb, W, Mo.
In another technology according to the present invention, this electrolytic medium is a kind of organic electrolyte, and this metal is a basic metal.Porous basic metal product is used in the organic electrolyte cell as the porous lithium product, and this battery is exigent momentary power density.The high porosity that obtains according to the present invention will make above battery in the prior art, and the momentary power density that has improved is reached.
Thereby technology of the present invention can be used to, as the preparation electrode, useful is, after forming electrode, through the constant potential circular treatment, this has the effect that improves resulting anode peak current when using this electrode with resulting electrode preparing metal level on the support.If desired, the organic or inorganic supplement can be suspended in the electrolytic medium during electrode in preparation, and with metal one synsedimentary, the electroconductibility that the electrode with the porous metallic layers that has comprised a kind of supplement can have a porosity that has been enhanced and/or be enhanced.
Method of the present invention also can be used for electrode is regenerated in position, so just prolonged its operation life.Like this, the present invention provides a kind of electrode regenerated method in battery that makes again further, and it comprises with above-mentioned any method of the present invention form one deck porous metallic layers on electrode.In some cases, the electrolytic solution that need not to change in the battery just can make electrode regeneration.For example, in the electrolytic solution of battery, contain under the ionic occasion of the metal of desiring to be deposited on the electrode, can
Oxygen is blasted in the battery electrolyte, and can introduce as the halogenide of metal playing second oxidizing substance on a small quantity and/or producing the active substance of the suitable source effect of second oxidizing substance.And under the other situation, battery electrolyte can be changed with the ionic electrolytic solution that contains the metal of desiring to be deposited on the electrode.
Like this, the present invention can make electrode, regenerates in position as the electrode of fuel cell and air-metal battery.Until today, still being unrealized regenerates air electrode in position.
The present invention also provides the another kind of technology that generates metal oxide on support material, it comprises: form porous metallic layers with above-mentioned any method of the present invention on support material, and then after producing this porous metallic layers, make this metal level carry out anodic oxidation to form the oxide compound of this metal.These porous metal can comprise two or more metals, and anodic oxidation is selectively to metal, and this selection makes the first all metals oxidized basically, and the second all metals still keeps the simple substance state basically.The mixture of a kind of like this oxide compound and metal is particularly useful as catalyzer.Two or more are oxidized and form the metal of blended oxide compound when anodic oxidation and porous layer can contain.Selecting metal is useful to make it being transformed into stupalith when the anodic oxidation.This stupalith can be, as perovskite oxide, as the lanthanum barium-copper oxide.Perovskite oxide has caused people's attention as superconductor.Support material can be a copper.
The present invention further provides a kind of on tubing, as on copper pipe, forming the technology of successive cramic coat, this comprises: tubing is inserted in the electrolytic medium, therein, on tubing, generate porous metal according to above-mentioned of the present invention any method, after this, this tubing is put into the zone that makes the porous metal anodizing and generate stupalith.So, the cost that the present invention can be low is made the tubing that is covered with ceramic layer in a kind of successive technology.Such as, can have successive perovskite oxide, the particularly copper pipe of lanthanum barium-copper oxide coating according to the present invention's preparation.In use, liquid nitrogen or other cryogen that suits can be fed in this copper pipe, so that oxide material is held under the temperature of superconductor at it.
The present invention also provides porous metal and a kind of goods with average particle size particle size less than the porous metal part of 3 μs of a kind of average particle size particle size less than 3 μ.Thin and the thick particulate mixture that the part of these porous metal is included in 0.05 μ to the 1 μ scope is desirable.These goods are favourable as pole plate, strainer, support of the catalyst or the catalysis electrode of battery.
The present invention general only is described in the mode of embodiment, referring to accompanying drawing, wherein:
Fig. 1 shows a kind of electrolytic cell device that is suitable for preparing the porous metal relevant with the present invention in the mode of partial cross section and partial schematic diagram.
Fig. 2 illustrates another kind of alternative with the form of partial cross section and partial schematic diagram, prepare the electrolytic cell device of the porous metal relevant with the present invention.
Fig. 3 shows a kind of electrolyte circulation system for preparing porous metal by the present invention that is applicable to.
Fig. 4 shows the device that is similar to Fig. 3, and difference is the layout difference of support material.
The porous iron anodic volt-ampere curve of Fig. 5 for preparing according to the present invention is respectively the NiCl that adds or do not add as additive in plating bath 2Two kinds of situations.
Fig. 6 shows the volt-ampere curve by the porous iron electrode of the present invention's preparation.
Fig. 7 shows the comparison by the present invention's anode performance of prepared porous cobalt electrode and the porous cobalt electrode for preparing when having oxygen to exist when lacking oxygen, the electrode for preparing when anoxic is used for comparison.
Fig. 8 shows the comparison of the cobalt electrode with higher deposition, and first kind of electrode is by prepared of the present invention, and second kind of electrode prepares with sintering method.
Fig. 9 shows constant potential circulation to the influence by the porous cobalt electrode anode cutting edge of a knife or a sword value electric current of the present invention's preparation.
Figure 10 shows the porous cobalt electrode stable state charge and discharge volt-ampere curve by the present invention's preparation.
Figure 11 shows the porous nickel electrode cathodic polarization curve by the present invention's preparation.
Shown in Figure 12 is the porous cadmium electrode anodic polarization curves for preparing by the present invention.
Shown in Figure 13 is the voltage-time curve that discharges under differing temps by the porous iron electrode that the present invention prepares.
Sintered iron electrode voltage-time curve that shown in Figure 14 is for comparing with Figure 13.
Figure 15 show the bonding tetrafluoroethylene of the ohm voltage drop compensation of hanging oneself and the porous NiCo of non-bonding tetrafluoroethylene 2O 4The comparison of the current density of electrode and the current density that is obtained from porous cobalt electrode by the various depositions of the present invention preparation.
Figure 16 shows the performance by the electrode of the cobalt electrode of the present invention's preparation and a kind of bonding tetrafluoroethylene, and the two does not all carry out the ohm voltage drop compensation.
Figure 17 shows the performance by two kinds of cobalt electrodes of the present invention's preparation, and one of them electrode is to prepare with a kind of rarer cobalt liquor, and
Figure 18 a and 18b show the discharge performance by the present invention's two kinds of prepared cobalt electrodes from the solution of different cobalt concentrations.
The preparation substrate
, the nickel wire point is welded in this substrate as current feed as base material with 60 purpose nickel screens, and with canned Lacomit, F65441 varnish is protected.At first this base material is dipped in the basic solution that is placed on the dilution in the ultrasonic bath, uses distilled deionized water rinsing then.This substrate of one square centimeter can be garden shape or quadrate.
The preparation electrode
Any electrochemical cell that employing is shown among Fig. 1-3 prepares porous metallic layers on support material.In each situation, support material 1 is hung in the electrolytic medium that is contained in the container 3.By the sintered glass plug 4 in the support material near zone oxygen is imported in this medium, support material 1 and opposite electrode 5 are electrically connected in known manner, these electrodes separate with level or vertical spaced relationship is arranged, vertically laying of working electrode (that is to say, when electrode is that level is when separating) have the level of advantage (Fig. 3) electrode that makes electrolyzer more compact to lay (Fig. 4) then to make oxygen bubbles that the longer residence time is arranged on electrode surface, 4 square centimeters platinum foil is used as opposite electrode, and uses saturated calomel electrode 6 as reference electrode in suitable location.Working electrode (support material 1) all is rotating in each case.In deposition process,, and plating tank imposed the constant electroplating current with plating tank constant temperature under a stable temperature.
Fig. 3 and Fig. 4 illustrate a kind of electrolytic solution can pass through pump 7 round-robin electrolyzers, and the direction of electrolyte flow is opposite with the direction of flow of oxygen.
For comparison purposes, the metal-powder that mixes volatile salt by the promising raising porosity of sintering zone in hydrogen prepares electrode.
Embodiment 1
(a) CoCl with 70 milliliters, 10%(weight) 2The aqueous solution places the electrolyzer as Fig. 1 or type shown in Figure 2.Electrolyzer constant temperature imposes 40 milliamperes/centimetre of constant in 25 ℃ to electrolyzer 2Electroplating current 30 minutes.Oxygen is fed this electrolyzer by the sintered glass plug, and flow rate control is at 40 centimetres 3/ minute, this support material is rotated with 300 rev/mins speed.
The porous cobalt layer color of making like this is furvous, and under similarity condition, but when not blasting oxygen sedimentary cobalt be light and reflectivity arranged.
(b) FeCl with 70 milliliters, 10%(weight) 2The aqueous solution places a kind of electrolyzer of Fig. 1 or type shown in Figure 2.This electrolyzer constant temperature is in 25 ℃ and to 60 milliamperes/centimetre of this electrolyzer feeding constant 2Electroplating current 40 minutes.Oxygen gas flow rate is controlled at 40 centimetres 3/ minute.Support material is rotated with 300 rev/mins speed.
(c) NiCl with 70 milliliters, 1%(weight) 2The aqueous solution places the electrolyzer of any class of Fig. 1-shown in Figure 3.This electrolyzer constant temperature is in 25 ℃.Feed constant, 10 milliamperes/centimetre to this electrolyzer 2Electroplating current 60 minutes.Oxygen gas flow rate is controlled at 50 centimetres 3/ minute.Working electrode is an immobilized.
(d) CdCl with 70 milliliters, 60%(weight) 2The aqueous solution places the electrolyzer of the arbitrary type shown in Fig. 1-3.This electrolyzer constant temperature is in 25 ℃ and to 6 milliamperes/centimetre of this electrolyzer feeding constant 2Electric current 2 hours.Oxygen is with 10 centimetres 3/ minute flow velocity be imported into this electrolyzer.Working electrode is an immobilized.
Embodiment 2
(a) to the influence of the electrode anode peak point current that obtains with different electrolyte solutions during with cadmium electrode at the preparation cobalt, illustrate by the result who is summarized in table 1.Prepare the condition of this metal electrode respectively as embodiment 1(a with metal chloride solutions) and (d) in defined.For from the acetate solution of the vitriol of metal and metal, preparing electrode, replace the chloride soln of metal respectively with the acetate solution of the sulfate liquor of metal and metal, and their concentration separately is identical with the concentration of metal chloride solutions.At 7M, the anode peak current of measuring in 25 ℃ the KOH aqueous solution, sweep velocity is 10 millivolts/second.
As shown in table 1, by measuring the performance that the anode peak current make electrode from metal chloride solutions records, all be better than in each case from the performance of the prepared electrode of metal sulfate and metal acetate solution.
Table 1
Metal (M) Anode peak current (Iap) milliampere/centimetre 2
MCl 2 MAc 2 MSO 4
Co 620 30 50
Cd 220 196 56
(b) as at embodiment 1(c) described in, from nickel chloride solution (NiCl 2) in the Performance of nickel electrode that makes be better than using the same method, but replace NiCl with nickelous acetate solution 2The performance of the prepared electrode of solution.With compare with the prepared electrode of nickelous acetate solution, in the ortho-acetic acid nickel solution, add some nickelous chlorides and the performance of the electrode that makes has been modified.Best performance by nickelous acetate, nickelous chloride and the prepared electrode of cobaltous acetate solution is listed.Under the situation of using nickel electrode, estimate the performance (seeing Table 2) of electrode by the electrode charge and discharge cycle number of times of measurement before significantly worsening appears in electrode.The electrode charge and discharge cycle is in 20 ℃ the 7MKOH aqueous solution, and sweep velocity is to carry out under 80 millivolts/second the condition.
Figure 891067191_IMG2
Embodiment 3
Cobalt, iron, nickel and cadmium electrode are pressed embodiment 1 described method preparation.The benchmark that provides one to compare with technology of the present invention is provided, except there not being gas to pass through the electrolyzer, under all identical situation of other condition, has prepared another set of electrode.By in the other method of the present invention, by embodiment 1(a) condition prepare cobalt electrode, but replace oxygen with air.The anode peak current value of each electrode is all at 7M, and during 25 ℃ KOH was water-soluble, sweep velocity was to record under 10 millivolts/second the condition.Measured result is listed in table 3.Can find out significantly that by table 3 it is measured to press anode peak current, be better than the performance of electrode prepared when shortage blasts gas significantly in the performance that the electrode for preparing when blasting oxygen is arranged.Under the situation that cobalt electrode prepared when blasting air is arranged, the performance of prepared cobalt electrode was good when this electrode performance blasted gas than nothing, but when blasting oxygen the performance of prepared cobalt electrode.
Table 3
Metal The anode peak current of electrode (milliampere/centimetre 2）
Prepare during no gas Blast oxygen Blast air
Co Fe Ni Cd 120 105 100 200 505 195 310 650 150 - - -
Embodiment 4
(a) by embodiment 1(a) described method prepares some cobalt electrodes, but each electrode adopts different deposition current preparations.Result by being summarized in following table 4a as seen, the optimal deposition current value is 40 milliamperes/centimetre 2This anode peak current (Iap) records with 10 millivolts/second sweep velocitys in 7M, 25 ℃ the KOH aqueous solution.
(b) except the deposition current difference, other condition is all by embodiment 1(b) some ferroelectric utmost points of preparation under the condition of defined.The gained result is summarized among the table 4b.Anode peak current (Iap) value is at 7M, in 25 ℃ the KOH aqueous solution, with 10 millivolts/second scan speed measurements.
Table 4a
Deposition current (milliampere/centimetre 2) 10 20 40 80 200
The anode peak current of electrode
(milliampere/centimetre 2) 375 520 620 510 70
Table 4b
Deposition current (milliampere/centimetre 2) 40 60 80 100
The anode peak current of electrode
(milliampere/centimetre 2) 280 90 310 310
(c) by with being similar to top embodiment 4(a) and (b) described experimental technique, find for Ni, in 1%(weight) NiCl 2Best electroplating current in the aqueous solution is 10 milliamperes/centimetre 2
Embodiment 5
Press embodiment 1(b) described method, but each working electrode adopts different velocities of rotation and prepares some porous iron electrodes.At 7M, in 25 ℃ the KOH aqueous solution, measure the anode peak current of each electrode with 10 millivolts/second sweep velocity.Gained as a result example in table 5.
Table 5
Velocity of rotation (rev/min) 0 200 300 400 600 900 1200
Anode peak current 195 220 270 223 198 210 219
（mA/cm 2）
Embodiment 6
(a) be 2.5%(weight in concentration range) to 15%(weight) the electrolytic solution (FeCl of different concns 2The aqueous solution) some ferroelectric utmost points of preparation in.Other condition is pressed embodiment 1(b) regulation.The anode peak current of finding prepared electrode raises with the concentration of deposited electrolyte to be increased: from 2.5%(weight) time 148 milliamperes/centimetre 2Rise to 15%(weight) 235 milliamperes/centimetre 2
(b) be 1.5%(weight in concentration range) to 10%(weight) the electrolytic solution (CdCl of different concns 2The aqueous solution) some cadmium electrodes of preparation in.Other condition such as embodiment 1(d) middle defined.The anode peak current of finding prepared electrode reduces with the reduction of the concentration of deposited electrolyte.
(c) be 0.7%(weight in concentration range)-5%(weight) the electrolytic solution (NiCl of different concns 2The aqueous solution) some nickel electrodes of preparation in.To the anode peak current with electrode is that the performance of sign is estimated, and the result of gained is summarized among the table 6a.Best performance is from 1%(weight) solution obtain in the prepared electrode.At different current densities and oxygen gas flow rate, and other condition and embodiment 1(c) influence of the metal pair performance of nickel electrodes of the situation deposit that the condition of defined is identical, illustrate by the result who is summarized in table 6b.
Figure 891067191_IMG3
Embodiment 7
(add 7 gram FeCl in 100 ml distilled waters at solution of ferrous chloride 2) middle some ferroelectric utmost points of preparation.Condition such as embodiment 1(b) middle defined, but used different types of additive of listing in the table 7.The concentration of additive also is changed.The anode peak current of the electrode that makes like this has been shown in the table 7.In the table 7 given data be corresponding to each additive and when the peak inrush current peak inrush current of the corresponding concentration value of additive.
At the nickelous chloride (NiCl that exists and do not exist as additive 2) time the prepared ferroelectric utmost point performance in Fig. 5, contrast, it shows at 7M, in 40 ℃ the KOH aqueous solution with the volt-ampere curve of the measured electrode of 10 millivolts/second sweep velocity.
Embodiment 8
As shown in table 8, in preparation during cadmium electrode, the anode peak current (Iap) of prepared electrode there are injurious effects by adding acidity that HCl improves electroplate liquid.
Table 7
Additive Optimum amount (milligram) The anode peak current milliampere/centimetre
Bi 2O 3CdCl 2KCl LiOH MnCl 2NiCl 2PbNO 3ZnCl 2N 2H 4·2HCl NiCl 2+N 2H 42HCl is additive-free 14 10 70 50 mg/ml, 7 210 552 210+2.5- 174 104 142 146 152 182 120 154 184 186 140
Embodiment 9
In the electrolyzer of type shown in Figure 2, adopt a nickel foil to replace platinum foil to prepare a ferroelectric utmost point as opposite electrode.The plating bath volume is 100 milliliters, plating bath composed as follows:
3%(weight) NiCi 2
0.03%(weight) N 2H 42HCl
10%(weight) FeCl 2
Used depositing current density is 100 milliamperes/centimetre 24(sees Fig. 2 by the sintering plug) oxygen is blasted in this solution.
Because Ni has very high chlorine deposition potential, thus the generation of no chlorine, and oxygen is product unique in this anodic reaction.Compare with the method for embodiment 1, so just pH value is remained on a metastable level, and thereby might obtain bigger iron deposition.The pure electric current efficiency of electrode (electric-electric efficiency) is higher than 80%.Fig. 6 shows nickeliferous, and deposition is 375 milligrams/centimetre 2The volt-ampere curve of the ferroelectric utmost point (in the KOH of 7M, 10 -3The Na of M 2Among the S, 40 ℃ of temperature, sweep velocity are to record under 10 millivolts/second the condition), and demonstrate this electrode and in the time of 40 ℃, provide very high electric current, 0.8 volt the time, electric current is 700 milliamperes/centimetre as the electropotential of relative Hg/HgO reference electrode 2
Embodiment 10
Fig. 7 shows the contrast of anode performance, and this performance represents with the current density of cobalt electrode, and this cobalt electrode is blasting oxygen preparation when existing according to the present invention, and another electrode prepares when nothing blasts oxygen.(by the performance estimated at 7M, in 25 ℃ the KOH aqueous solution, with 10 millivolts/second scan speed measurements; The deposition of cobalt is 60 milligrams).
Fig. 8 shows the similar contrast of the bigger cobalt electrode of some depositions, first electrode (153 milligrams/centimetre of depositions 2) by the present invention's preparation, second electrode is by sintering preparation (deposition: 486 milligrams/centimetre 2).(by the performance estimated at 7M, in 25 ℃ the KOH aqueous solution, with 2.5 millivolts/second scan speed measurements).Although sintered electrode has higher deposition, electrode of the present invention moves better significantly.
Embodiment 11
Make the cobalt electrode for preparing according to the present invention carry out the constant potential circulation.Anode peak current (Iap) improves with the increase of charge and discharge cycle number of times as shown in Figure 9, and this explanation recirculation helps to improve electrode performance.This anode peak current is at 7M, in 25 ℃ the KOH aqueous solution, with 80 millivolts/centimetre 2Sweep velocity record.In iron and nickel electrode, also observed similar results.
Embodiment 12
To what prepare by the present invention, the cobalt deposition is 249 milligrams/centimetre 2Cobalt electrode charge, then with 100 milliamperes/centimetre 2Discharging current discharge.What Figure 10 showed stable state discharges and recharges volt-ampere curve (at 7M, record in 25 ℃ the KOH aqueous solution), and explanation total pure electric current efficiency of this electrode under the condition of defined is high.
Embodiment 13
From nickelous acetate, nickelous chloride and cobaltous acetate solution, prepare a kind of nickel electrode (seeing Table method 2 in 2) according to the present invention.The cathodic polarization curve of this electrode is shown in Figure 11 and (at 7M, in 20 ℃ the KOH aqueous solution, records with 10 millivolts/second sweep velocitys; The deposition of electrode is 73 milligrams/centimetre 2).Because nickel electrode mainly is that people notice that with interest electrode according to the present invention is highly active from Figure 11, are 400 milliamperes/centimetre until current density as negative electrode in battery applications 2The time, polarization is seldom just arranged.After this, (descend～0.2V), and be accompanied by very little polarization, electrode continues to provide another 400 milliamperes/centimetre a very steep pressure drop in operating voltage 2Electric current, this shows and has two negative electrode steps.The step in back may comprise Ni(OH) 2Be reduced into Ni, and perhaps first step is that NiOOH is reduced into Ni(OH) 2In the nickel electrode of routine, because one size of particles and low electroconductibility and never observe the reduction process of this two steps.This fact may have practical advantages to the rechargeable cell that uses nickel cathode, because it can provide a kind of means that make things convenient for of complete charge.
Embodiment 14
Be shown among Figure 12 (in 7M, in 25 ℃ the KOH aqueous solution with 10 millivolts/second scan speed measurement) by the anodic polarization curves of the porous cadmium electrode of the present invention preparation.Figure 12 shows that cadmium anodic anode performance has been subjected to very low polarization, and this has shown high reactive behavior and good electrical conductivity.
Embodiment 15
KOH/10 at 7M -3The Na of M 2In the S aqueous solution, with 100 milliamperes/centimetre 2Discharging current, monitoring adapts with the present invention under 25～50 ℃ discharge temp, iron deposition is 375 milligrams/centimetre 2The variation of anode voltage time function of the ferroelectric utmost point.The results are shown in Figure 13, it has shown a very high utilization ratio.Figure 14 shows the performance of a kind of sintered iron electrode of the electrodeposition amount that almost decuples Figure 13 electrode, and this performance is by making this aquation electrode with 25 milliamperes/centimetre 3Current discharge, measured in 30%KOH and 5%LiOH solution.The sintered electrode of this high deposition demonstrates lower utilization ratio, although and discharge current density lower, find that its polarization surpasses the electrode by the present invention's preparation widely.
Embodiment 16
Current density to the cobalt electrode that is obtained from various depositions prepared in accordance with the present invention is measured.Figure 15 has provided the result of gained, for more together showing bonding tetrafluoroethylene and the non-bonding polytetrafluoroethylstephanoporate stephanoporate NiCo for preparing by thermolysis Ni-Co nitrate 2O 4The measuring result of electrode.The potential measurement of (this current density is at 5M, in 25 ℃ the KOH aqueous solution, with 1720 millivolts, with respect to the efficient hydrogen electrode of DHE().Do not do the ohmic loss compensation for the test result of this cobalt electrode, and to two kinds of NiCO 2O 4The test result of electrode has been done the ohmic loss compensation.Figure 16 represents, under the situation of not carrying out ohm compensation, is 7.5 milligrams/centimetre according to deposition of the present invention 2Cobalt electrode, current density be 1.1 the peace/centimetre 2In time, seems and is better than the NiCo of this bonding tetrafluoroethylene widely 2O 4Electrode.
Embodiment 17
From the 0.77M cobalt chloride solution, is 40 milliampere/centimetre in depositing current density according to the present invention 2Reach 1 hour deposition down and prepared a cobalt electrode (17A).A platinum is used as opposite electrode.Support material is with 500 revolutions per seconds of rotations.Oxygen is with 100 centimetres 3/ minute speed be provided in support material.Second cobalt electrode (17B) be according to the present invention from the cobalt chloride that contains 0.05M concentration with contain the potassium chloride solution of 0.5M, be 20mA/cm with the depositing current density 2, cobalt deposited on the immobilized support material in during 2.2 hours and makes.A slice cobalt paper tinsel is used as opposite electrode.Oxygen is with 100 centimetres 3/ minute speed supply with support material.Figure 17 shows that the anode peak current of electrode 17B is the anode peak current that is higher than electrode 17A significantly.
Adopt solid-state cobalt as opposite electrode following advantage to be arranged, promptly the strict composition of controlling electrolytic solution is separated out and be need not to no chlorine in this process.
Embodiment 18
The depth of discharge of electrode 17A is measured under different C lead.(C leads the discharge rate that is meant when C is theoretical electrical capacity; Referring to theoretical electrical capacity based on electrode as, C/3 is adjusted to discharge current value electrode was discharged in 3 hours.) discharge performance of electrode 17A is shown among Figure 18 a, and the discharge performance of the cobalt electrode for preparing from rare cobalt chloride solution is shown among Figure 18 b.The electrode of Figure 18 b is that the employing depositing current density is 40mA/cm from a kind of rare cobalt chloride solution (0.1M cobalt chloride, 0.5M Repone K) 2, the flow velocity of oxygen is 100cm 3/ minute, and make opposite electrode with the cobalt paper tinsel, on the immobilized support material, prepare.The deposition of this electrode is 219 milligrams of (6 centimetres of surface-area 2).Figure 18 a and Figure 18 b show by obtaining a kind of discharge performance that has improved from a kind of rare cobalt chloride solution metal refining, and wherein the Repone K in the solution is to exist as another kind of ionogen for the electric conductivity of keeping higher level.
For Figure 18 a and 18b, be at 7N KOH, temperature is measured depth of discharge down for 20 ℃.Related electric current is a total current among Figure 18 b.
Can think the improvement that obtains by deposit cobalt from a dilute aqueous soln performance may be owing to from the coordination cobalt compound different, deposited this metal with cobalt ion.Especially under low cobalt concentration, most of cobalt ions have formed coordination compound (as (Co(OH 2) 4Cl 2)) and cobalt metal sedimentary current potential from such compound is than from Co 2+It is more negative to carry out sedimentary current potential in the ion.Thereby think that more oxygen can be reduced, thus cause producing more hydroxide ion, and these hydroxide ions are the oxidation cobalt metal of vast scale more, thus the porosity that is deposited metal improved, and perhaps reduced the size of individual particle.

Claims (39)

1, a kind of technology that on a support material, produces a kind of porous layer of electrodepositable metal, it comprises: this support material is immersed in the electrolytic medium that contains this metal ion species, then under the condition of a kind of oxidation near the electrolytic medium the support material of being provided in is arranged (property) material, on this support material, this oxidation (property) material is to form a kind of material that can be reduced product under mode of deposition with this metal reaction with this metal electrodeposition.
2, a kind of technology according to claim 1 wherein, provides during metal refining continuously, or produces this oxidation (property) material.
3, a kind of technology according to claim 1 or 2, wherein this oxidation (property) material are a kind of oxygen containing oxidation (property) materials.
4, a kind of technology according to claim 3, wherein oxygen containing oxidation (property) material is an oxygen, or a kind of oxidation (property) material that results from oxygen under mode of deposition.
5, a kind of technology according to claim 4, wherein this oxygen containing oxidation (property) material is a gaseous oxygen, or results from and be introduced into electrolytic medium, to make it to pass near the support material gaseous oxygen.
6, a kind of according to technology one of any in the claim 3 to 5, wherein near the medium of this support material for have another kind of and this metal reaction form a kind of under mode of deposition oxidation (property) material of reducible product.
7, a kind of technology according to claim 6, wherein this another kind of oxidation (property) material is the negatively charged ion that is selected from halide ions, halogen and can be formed by halogen and halide ions under mode of deposition.
But 8, a kind of technology that on support material, produces the metal porous layer of electrolytic deposition, it comprises this support material immersed and contains in the electrolytic medium of this metal ion, and when the gaseous oxygen that imports this electrolytic medium in the mode of passing near this support material surface is arranged with this metal electrodeposition on support material.
9, a kind of technology according to Claim 8, wherein this electrolytic medium contains halide ions.
10, according to Claim 8 a kind of or 9 technology, wherein this electrolytic medium contains a kind of halogen.
11, a kind of one of any technology in 10 according to Claim 8, wherein this electrolytic medium contains oxyhalide ion.
12, a kind of according to one of any technology in the claim 1 to 11.Wherein contain the ion of two or more metals in this electrolytic medium, and contain two kinds of metals in the porous layer of making so at least.
It is 13, a kind of that wherein this electrolytic medium contains the ion of two or more metals according to one of any technology in the claim 1 to 11, wherein a kind of and this oxidation (property) substance reaction form a kind of under mode of deposition unreducible product.
14, a kind of according to one of any technology in the claim 1 to 13, wherein, support material is rotated during metal deposition.
15, a kind of according to technology one of any in the claim 1 to 14, wherein, the composition of this electrolytic medium changes by add one or more materials in electrolytic medium in deposition process, and the metal porous layer of making so just has several different particle structure area level.
16, a kind of according to technology one of any in the claim 1 to 15, wherein this porous layer comprises a kind of metal that is selected from transition metal.
17, a kind of technology according to claim 16, wherein this transition metal is selected from cobalt, iron, nickel and cadmium.
18, a kind of according to technology one of any in the claim 1 to 17, wherein this electrolytic medium is a kind of aqueous electrolytic medium.
19, a kind of technology according to claim 18, wherein this metal is a kind of transition metal, and deposition current is not more than 300 milliamperes/centimetre 2
20, a kind of technology according to claim 19, wherein this deposition current is not more than 100 milliamperes/centimetre 2
21, a kind of technology according to claim 18, wherein this electrolytic medium comprises ionic first ionogen that contains the metal of desiring to be deposited and do not produce sedimentary second ionogen under mode of deposition on support material, and the significant proportion of the ionic conductivity of this medium is provided by second ionogen.
22, a kind of technology according to claim 21, wherein by with the metallographic phase of desiring to be deposited with the electrode that metal constituted as opposite electrode.
23, a kind of wherein this electrolytic medium is a kind of fused salt according to one of any technology in the claim 1 to 15, and this metal is a kind of refractory metal.
24, a kind of wherein this electrolytic medium is a kind of organic electrolysis medium according to technology one of any in the claim 1 to 15, and this metal is a kind of basic metal.
25, a kind of technology that on support material, generates a kind of metal oxide, it comprises by generate the porous layer of this metal on support material according to technology one of any in the claim 1 to 22, and then after this porous metallic layers generates, make this porous layer anodic oxidation and form a kind of oxide compound of this metal.
26, a kind of technology according to claim 25, wherein this porous layer contains two or more metals, these metals are selected so that make first metal all oxidized basically when the anodic oxidation, and whole second metal keeps simple substance form basically.
27, a kind of technology according to claim 25, wherein this porous layer contains that two or more are oxidized and generate the metal of blended oxide compound when anodic oxidation.
28, a kind of technology according to claim 27, wherein these metals are selected like this, so that make it that these metals are converted into a kind of stupalith when anodic oxidation.
29, a kind of according to technology one of any in the claim 25 to 28, wherein this support material is made of copper.
30, a kind of technology that on tubing, forms a successive ceramic coat, it comprises that this tubing is passed in one of any technology of wherein using according in the claim 1 to 24 to be formed in the ionogen of a metal porous layer on tubing, then this tubing is inserted this porous metallic layers is formed in a kind of zone of stupalith by anodic oxidation.
31, a kind of technology that makes electrode regeneration in electrolyzer, it comprises by forming one deck porous metallic layers according to technology one of any in the claim 1 to 24 on electrode.
32, a kind of technology for preparing a kind of electrode, it comprises: use according to method one of any in the claim 1 to 24 to prepare one deck porous metallic layers to form an electrode on support material, make this electrode stand the constant potential circulation then.
33, a kind of technology of the preparation porous metallic layers described in one of any as this paper embodiment 1 to 9,17 and 18 basically.
34, a kind of every porous metal of being produced when using according to technology one of any in claim 1 to 24 or 33.
35, every a kind of goods of making according to one of any technology in the claim 1 to 33 of using.
36, a kind of goods with average particle size particle size less than the porous metal part of 3 μ.
37, a kind of goods according to claim 36, it comprises the thin and particle of thick of size in 0.05 μ to 1 μ scope.
38, a kind of according to one of any goods in the claim 35 to 37, wherein these goods are a kind of electrode pads, a kind of strainer, a kind of support of the catalyst or a kind of catalysis electrode.
39, a kind of battery that comprises according to the made a kind of electrode of technology one of any in claim 1 to 27 or 30 to 33.
CN89106719A 1988-06-29 1989-06-29 The technology of preparation porous metal Pending CN1039851A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888815494A GB8815494D0 (en) 1988-06-29 1988-06-29 Process for preparation of porous metal
GB8815494 1988-06-29

Publications (1)

Publication Number Publication Date
CN1039851A true CN1039851A (en) 1990-02-21

Family

ID=10639589

Family Applications (2)

Application Number Title Priority Date Filing Date
CN88106090A Pending CN1039073A (en) 1988-06-29 1988-07-22 The technology of preparation porous metal
CN89106719A Pending CN1039851A (en) 1988-06-29 1989-06-29 The technology of preparation porous metal

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN88106090A Pending CN1039073A (en) 1988-06-29 1988-07-22 The technology of preparation porous metal

Country Status (5)

Country Link
EP (1) EP0422094A1 (en)
CN (2) CN1039073A (en)
AU (1) AU3962389A (en)
GB (1) GB8815494D0 (en)
WO (1) WO1990000208A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367756A (en) * 2013-07-22 2013-10-23 山东大学 Preparation method of porous copper based lithium ion battery anode material

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9007105D0 (en) * 1990-03-29 1990-05-30 Dowty Electronic Components A battery
GB9405518D0 (en) * 1994-03-21 1994-05-04 Mupor Ltd Porous metal composite body
US6596187B2 (en) * 2001-08-29 2003-07-22 Motorola, Inc. Method of forming a nano-supported sponge catalyst on a substrate for nanotube growth
CN103422116B (en) * 2013-08-15 2016-08-17 重庆大学 A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode
CN106884190A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 A kind of preparation of classifying porous material and classifying porous material
US10991948B1 (en) * 2020-03-20 2021-04-27 Chang Chun Petrochemical Co., Ltd. Surface-treated copper foil for lithium-ion secondary batteries

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579385A (en) * 1970-04-13 1971-05-18 Westinghouse Electric Corp Method of impregnating metallic fiber battery electrodes
FR2481717A1 (en) * 1980-05-05 1981-11-06 Anvar Electrochemical prepn. method for solar surface - comprising forming grey nickel deposit and anodising
DE3307303A1 (en) * 1983-03-02 1984-09-06 Matthias 8757 Karlstein Faber Electrochemical process for producing active masses for the nickel or cadmium electrode, preferably in a nickel/cadmium storage battery
FI85060C (en) * 1985-11-11 1992-02-25 Mitsubishi Materials Corp Heat transfer material and process for making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103367756A (en) * 2013-07-22 2013-10-23 山东大学 Preparation method of porous copper based lithium ion battery anode material
CN103367756B (en) * 2013-07-22 2015-06-10 山东大学 Preparation method of porous copper based lithium ion battery anode material

Also Published As

Publication number Publication date
GB8815494D0 (en) 1988-08-03
WO1990000208A1 (en) 1990-01-11
CN1039073A (en) 1990-01-24
EP0422094A1 (en) 1991-04-17
AU3962389A (en) 1990-01-23

Similar Documents

Publication Publication Date Title
CN1089195C (en) Positive electrode active substance for alkali accumulator
CN1078389C (en) Nickel electrode active material, a nickel electrode and a nickel alkali storage cell using such nickel electrode active material, and production methods of such material electrode, and cell
CN105375039B (en) A kind of air electrode for lithium air battery and preparation method thereof
JP2013503257A (en) Compositions, electrodes, methods, and systems for water electrolysis and other electrochemical techniques
CN1178317C (en) Active materials for positive electrode in alkaline storage battery and manufacturing method of them
Nady et al. Ni–Cu nano-crystalline alloys for efficient electrochemical hydrogen production in acid water
CN100350667C (en) Hydrogen storage battery, positive nickel electrode, positive electrode active material and methods for making
CN110021758A (en) The Pt-M metal alloy catalyst that in organic system prepared by electro-deposition
WO1998022641A1 (en) Efficient electrowinning of zinc from alkaline electrolytes
CN111933961B (en) Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof
US20030099882A1 (en) Methods and materials for the preparation of a zinc anode useful for batteries and fuel cells
CN106868536A (en) The Carbon dioxide electrochemical reduction preparation of porous copper electrode and its electrode and application
JP2002536783A (en) How to perform an electrochemical reaction
Liu et al. Porous zinc anode design for zn-air chemistry
CN114525540A (en) Nano material with noble metal particles dispersed on surface of non-noble metal substrate, and preparation method and application thereof
CN1039851A (en) The technology of preparation porous metal
CN101740787B (en) Metal particle-amorphous diamond composite anode for fuel cell and preparation method thereof
Anani et al. Dispersion deposition of metal—Particle composites and the evaluation of dispersion deposited nickel—Lanthanum nickelate electrocatalyst for hydrogen evolution
Nikoloski et al. Addition of cobalt to lead anodes used for oxygen evolution—a literature review
JPS63900B2 (en)
McBreen et al. Electrodeposition of zinc on glassy carbon from ZnCl2 and ZnBr2 electrolytes
US4152224A (en) Inorganic additives for zinc-alkaline secondary batteries and alkaline zinc-plating baths
CN85106354A (en) The improvement technology of nickel hydroxide anode of alkaline accumulator
McBreen et al. Zinc electrode morphology in alkaline solutions: II. Study of alternating charging current modulation on pasted zinc battery electrodes
JP2008138282A (en) Anode for alkaline electrolysis

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent for invention or patent application
CB02 Change of applicant information

Address after: Colchester, England

Applicant after: University of Essex

Address before: London, England

Applicant before: The City University of Northampton Square

Co-applicant before: University of Essex

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: BEIAN PUDUN PLAZA OF THE CITY UNIVERSITY TO: ESSEX UNIVERSITY; CO-APPLICANT; FROM: ESSEX UNIVERSITY TO: NONE

C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication