CN86105478A - Porous electrode and manufacture method thereof - Google Patents
Porous electrode and manufacture method thereof Download PDFInfo
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- CN86105478A CN86105478A CN86105478.4A CN86105478A CN86105478A CN 86105478 A CN86105478 A CN 86105478A CN 86105478 A CN86105478 A CN 86105478A CN 86105478 A CN86105478 A CN 86105478A
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- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
Porous electrode is common to the lead acid accumulator of no support plate or support grid.This electrode is a porous self-bearing type overall structure, and electrical property is continuous.The lead-acid battery that kind electrode is housed is compared with the lead-acid battery of routine, its characteristic be improved significantly.The preparation method of this electrode comprises: the molten mixture that forms metal (for example plumbous) and pore-creating component (for example cadmium); The solid electrode that its cooling and formation is had above-mentioned pore-creating component; From this electrode, remove the pore-creating component, stay the hollow net of determining hole; With the metal inner surface oxidation in the hole, so that on the hole inwall, form a kind of coating (for example brown lead oxide) of electrochemical active material.
Description
The present invention relates generally to the electrode of battery, particularly relate to the self-bearing type porous electrode in the storage battery.A concrete aspect of the present invention is at being used for the improved self-bearing type porous electrode of plumbic acid formula secondary accumulator battery.
The present invention also comprises the method for making this self-bearing type porous electrode simultaneously.
The early history of battery technology can be traced to the invention of primary cell before 1800 at least.From that time, in order to develop the electrode that is applicable to all kinds of batteries, numerous researchers has carried out extensive studies and experiment in electrochemistry or battery chemistries field.Really, most of novel battery electrodes, its advantage has obviously surpassed the electrode invented of Pulan spy (G.Plant é) in 1859, adopts the battery of novel electrode to compare with early stage battery, has tangible advantage, and its characteristic is improved.
Though lead acid accumulator has obtained tangible improvement for many years, they still are subjected to some great limitation, and especially in actual use, battery stands violent charging one discharge cycle to be changed.Violent charging one discharge cycle means battery at high rate discharge, promptly surpasses the extreme discharge of bearing repetition in 4 hours under discharge rate (C/4), almost near a hundred per cent of its nominal capacity.For make conventional not or have small rotten lead acid accumulator to recharge effectively, charging current must be lower than the value that the rated capacity of this battery is allowed.But,, just need reach 8 hours or longer time could sufficient conventional battery with low like this current charges.Even under charging one discharging condition of the most accurate control, in the useful life of present lead acid accumulator, under suitable discharge rate, have only a hundreds of cycle at most.
In the lead-acid battery of routine, intrinsic above-mentioned limitation and other limitation are because the influence of the electrode type that is adopted in this battery causes basically, and wherein the positive electrode influence is bigger, and the negative electrode influence is less.The lead-acid battery electrode of routine techniques level, its anodal and negative pole all is to be made by the sedimentary deposit of electrochemical active material, for example, on a carrier board or the lead oxide on the cell structure.Because the electrolyte (sulfuric acid) in the lead acid accumulator has very strong corrosivity, this electrode (particularly positive electrode) is slowly corroded, it surperficial oxidized, a kind of electronic barrier layer of formation between carrier board and the active material above it.Electric current during the formation meeting limit battery charge or discharge on this barrier layer.When grid is corroded gradually along with the increase in battery useful life (oxidized), the current strength of charging and discharge further is restricted, thereby the gross efficiency of battery obviously reduces.If battery uses under this condition, the result will make positive plate obviously corrode, and the barrier layer obviously forms, so that the fully charge or discharge again under any condition of this battery.
The corrosion of carrier board also damages the mechanical integrity of this electrode structure, and electrode is broken.In addition, even in the starting stage of carrier board corrosion, active material is peeled off, and particularly peels off from positive pole, and this phenomenon is called as sulfation.This electrochemical active material from the electrode peel off with sulphation be irreversible, therefore, along with the continuity in useful life, battery will irreversibly be lost its capacity gradually.
Because lead acid accumulator often is in the harsh conditions, the carrier board that uses in this battery must be enough big and solid to reach necessary mechanical strength.Therefore, this carrier board has increased the weight of battery greatly, and to its capacity (amp hr) do not improve.In addition, the increase of this weight often reduces the accessible energy density of battery (watt-hour/pound or watt-hour/cubic inch).
Since the special carrier board in invention Pulan more than one in century, numerous researchers has carried out a large amount of experiments at the electrode of lead acid accumulator or the improvement of manufacture method, and delivers in many patents and publication.Yet a kind of production method that is used for the porous crystalline attitude metallic plate of lead acid accumulator that proposes as far back as Gidon Kremer Te Peien on November 19th, 1889 (Clement Payen) is awarded patent right.The method of Penn comprises melts some metallic salt and certain metal together, pours melted material into mold then, makes the crystalline state structural chemistry be reduced to certain metallic state, again with electrolysis removal impurity wherein.
Another early stage patent is the method that to authorize James's Hart Robert's inferior (James Hart Robertson) relevant manufacturing porous plate on September 24th, 1895 be porous electrode, according to this patent, certain metal (for example plumbous) is heated to molten state, then to artificial porous mass that wherein adds granular or powdery or natural porous mass, float stone for example, brick dust, kaolin, materials such as coral.Then, stir the cementitious mixtures that is produced, so that particulate matter is fully admixed and uniformly dispersing in integral material.Then, with this material die casting or extrusion modling in the mould of specified size.Subsequently, with mold heated, make the air bubble expansion in the porous material of adding, thereby in the body of casting, produced the gas compartment, promptly a kind of " porous " body of casting.When this mixture is still stayed in the mould, the mould and the body of casting are heated up a little, to obtain more level and smooth plate, again the porous plate that is produced is shifted out mould.If this plate is intended for an electrode in the battery, it may be necessary effect that the patent description that the Robert is inferior, made plate can be subjected to, and electrolysis for example spreads all over generation " active material " of hole in the plate.
Above-mentioned Penn and the inferior patent of Robert be numerous with improve two patents making in the relevant patent of battery terminal.Below be that some comparatively representational patent lists (being not whole) wherein have U.S. Patent number No.415,330; 415,331; 415,348; 415,349; 415,683; 434,458; 440,267; 440,268; 440,269; 440,270; 440,272; 440,273; 440,274; 440,275; 440,276; 440,277; 538,628; 760,561; 1,749,819; 2,640,864; 2,969,414; 3,113,048; 3,496,020; 3,558,359; 3,582,403; And 3,796,607.
Today after electrode technology is studied and explored more than 100 year, the electrode that lead acid accumulator still adopts routine techniques to make, this battery still can not be broken away from above-mentioned several intrinsic shortcoming.In order to improve the performance of lead-acid battery, (Rudolf R.Hradcovsky and Otto R.Kozak are in U.S. Patent No. 4,143,261(1979 announced March 6) in delivered the positive electrode that applies the lead oxide of polycrystalline attitude and crystalline state as the carrier board manufacturing of electrolysis active material with a kind of.Compare with the lead-acid battery of routine techniques level, adopt the storage battery of kind electrode to have lower internal resistance, improved charging-discharge rate, have lower sulfation, have higher capacitance of storage and the exportable bigger magnitude of current in the quite short time.
The present invention attempts to provide a kind of battery, and this battery has whole or most improved characteristics that battery is showed in above-mentioned Hradcovsky-Kozak patent, still, when making electrode without support grid or carrier board.
Therefore, an object of the present invention is to provide improved electrode for storage battery.
Another object of the present invention is to make self-bearing type porous electrode anodal and that negative pole all is suitable for, and this electrode is applicable to storage battery, particularly the lead-acid battery.
A further object of the invention provides battery, lead-acid accumulator particularly, because the self-bearing type porous electrode that battery has been packed into and made by the present invention, so it has improved characteristic.
Another object of the present invention provides a kind of method of making the self-bearing type porous electrode, and this electrode is applicable to the positive pole and the negative pole of lead-acid accumulator.
Above-mentioned purpose of the present invention and other purpose, the present invention hereinafter detailed description and accompanying drawing in will do more fully to explain.
Description of drawings;
Fig. 1 is a binary alloy phase diagram of being made up of cadmium (Cd) and plumbous (Pb).
Fig. 2 is a binary alloy phase diagram of being made up of zinc (Zn) and plumbous (Pb).
This phase Graph Character will be explained in following detailed description of the present invention.
The invention provides a kind of novel and unique porous electrode, it mainly is applicable to lead-acid accumulator, and this electrode is that self-bearing type is integrally-built, and electrical property is continuous. Owing to when making kind electrode, do not adopt support plate or grid, resulting battery is more light than conventional lead-acid battery. In addition, as what describe in detail in the present invention's detailed description hereinafter, the lead-acid battery that has filled this novel electrode has better characteristic than conventional lead-acid battery.
Electrode of the present invention is to make with unique method, and its method is summarized as follows:
(a) certain metal (for example plumbous) and certain pore-creating component (for example cadmium) are formed molten mixture, in this molten mixture, these two kinds of components distribute mutually equably.
(b) with this molten mixture cooling, and with solid state electrode of its formation (for example with casting or die casting mode), this electrode has size and the external form of setting.
(c) remove the pore-creating component from this solid state electrode, to form a kind of porous electrode, this electrode has equally distributed relatively, spreads all over the hole net of this metallic matrix.
(d) handle this porous electrode in an oxidation environment, in this environment, the inwall of hole is oxidized and form one deck electrochemical active material (for example aluminium dioxide).
The invention provides a kind of self-bearing type porous electrode of uniqueness, it is used for lead acid accumulator, below is also referred to as lead-acid battery.Because electrode of the present invention do not adopt carrier board or grid, compare with the electrode of the lead-acid battery of state-of-the art, it has dwindled volume, has alleviated weight greatly, and aspect structural integrity or mechanical strength of electrodes without any harmful effect.
Another advantage of porous electrode of the present invention is that electrochemical active material forms in the hole of this electrode on the spot, and constitutes an integral body with the metal that forms electrode structure (usually being plumbous).Thereby, at the same time as between the metallic lead of mechanical support body and collector body surface and the active material that in hole, forms on the plumbous surface, machinery and continuity electrical property are arranged.Thereby this active material always keeps contacting closely with plumbous surface (it plays collector body), and in hole, active material all constitutes an integral body with the hole inwall.This structure makes the resistance loss between active material and the plumbous surface reduce to minimum (IR falls).Thereby, even the additional surfaces oxidation produces, also can cause the increase of battery capacity and the continuity of unlikely forfeiture electrical property, the formation that takes the form of the additional activity material that this oxidation increases.Therefore, the lead-acid battery of the kind electrode of packing into is compared with the lead-acid battery of routine, presents very high discharge rate and quick charge capability.From the preparation method's of following this electrode narration, can further recognize other advantage of the present invention and improve characteristic.
In a word, in order to form novel self-bearing type porous electrode of the present invention, plumbous or certain lead alloy that is suitable for are heated with second component, to form a kind of liquid melts, this second component is called as " pore creating material " or " pore-creating " component here, then, fully stir this liquid melts, this pore creating material is distributed in selected lead or lead alloy equably.For the ease of explaining and explanation that the present invention will explain at lead.Press down, this molten mixture is cast in the mould or cavity of a setting shape, then the molten mixture in the mould is cooled off rapidly, it is solidified, to form the electrode of setting size and profile.Molten mixture is processed into solid electrode, adopts conventional casting, die casting die casting to suit.
Another kind of mode is, this molten mixture can be cast into solid blank, and this blank is rolled into the thickness of electrode of setting, and then strikes out the shape and size of final electrode.Any remaining material can be by the lay equal stress on formation electrode of new casting of refuse.
No matter adopt what mode to form solid electrode, resulting electrode will comprise an integral body, continuous metallic lead matrix, and wherein pore creating material has relatively uniformly and distributes, forming continuous empty net.By mode described below, from the metallic lead matrix, to remove pore creating material, thereby formed a kind of porous electrode of self-bearing type, it is applicable to the lead-acid battery with above-mentioned improvement characteristic.
The use of second component (pore creating material) has constituted of the present invention one big characteristics, thereby in order to reach required purpose, second component must carefully be selected.A very important experience is, the selected second suitable component, and the solubility in metallic matrix must be very little or insoluble fully.Making the used lead of electrode, the material that higher solubility is arranged in lead alloy or any other metal, perhaps can with above-mentioned lead, the material that lead alloy or any other metal form the intermetallic complex compound all is not suitable for as pore creating material, should not be used as second component with them.
This second component must easily be mixed with metallic matrix when being heated mutually, and to form a kind of liquid melts, the electrode size and the shape of setting can be cast or be molded into to this melt easily.
Select another criterion of second component to be, it must be eliminated from it is distributed in wherein metallic matrix, producing empty net, and forms a kind of porous electrode.To be described hereinafter about several case methods of from metallic matrix, removing second component.
This second component itself can be a metal, also can be nonmetal or organic substance.The example of metal pore creating material includes, but is not limited to cadmium, gallium, thallium, zinc, and their mixture.
This second component also can be some inorganic salts, for example alkali-metal carbonate or bicarbonate, for example sodium carbonate, sodium acid carbonate, potash and saleratus.In addition, ceruse and basic lead carbonate also are practical pore creating material in the present invention.Though above-mentioned inorganic salts does not melt under normal condition, they really form a kind of liquid melts with lead or lead alloy, and distribution therein easily.These salts are removed from the solid metal matrix easily, and stay empty net therein, and this net has been established the hole in final electrode structure.
Except above-mentioned metal and inorganic metal salt, some organic compound also can be used as pore creating material, and these organic compounds comprise camphor, the derivative of urea and camphor or urea, perhaps their any mixture.
Pore creating material there is no need to be restricted to single component, and it can be the mixture of any two or more second components of top introduction.The second specific components selection and its relative amount in melt depend on the distribution of desired bore hole size and capacity in the final electrode.When lead is metallic matrix, when cadmium is desired pore creating material, can be in order to the quantity of the cadmium that forms molten mixture by selected in the present patent application accompanying drawing 1.This figure is the phasor of cadmium-lead alloy, the melting point curve of marking and drawing this alloy according to the atomic percentage conc and the weight percentage of cadmium in the Cd-Pb alloy among the figure.
As indicating, Fig. 1 (saw " lead and lead alloy; character and technology " Wilhelm Hofman, Springer-Verlag, New York-Heideberg-Berlin 1970), no matter how many lead in the liquid melts and relative amounts of cadmium be, the solid solubility of cadmium is limited in about 8% in the lead.This limited solid solubility of cadmium helps removing cadmium (pore creating material) greatly in the lead from the lead base body.
Ideally, second component (pore creating material) should not have solid solubility in lead.(see " zinc and its alloy " as shown in Figure 2, Circular of The Bureau of Standards No.395, issued November 6,1931 by the United States Government Printing Office, Washington, D.C.) the approaching second desirable component of zinc, and in practical application of the present invention, can be used as effective pore creating material.The similar phasor of other alloy in various literature and publications is valuable, and for each molten mixture of making electrode of the present invention, the selected of its second component quantity can these phasors be criterion.
In order to keep the mechanical integrity of electrode, must avoid producing excessive hole the harsh and unforgiving environments of lead-acid battery in order to avoid electrode can not be resisted.Usually, the consumption of second component is selected like this, and the empty volume (pore volume) that it causes is about 10% to 50% of entire electrode.Obviously, to a certain extent, suitable hole volume depends on second component, makes the metallic matrix and the electrode necessary mechanical strength of electrode.
Although the metallic matrix of the electrode that this is novel can be selected lead or lead alloy (for example lead-calcium and aluminium-antimony alloy) for use, also can select other metal or their alloy for use, as long as these metal or alloy and above-mentioned second component formation molten mixture, and make the electrode that obtains, in lead-acid battery, present needed mechanical integrity.
From above-mentioned explanation of the present invention, a people who is familiar with the one's own profession technology can prepare the molten mixture that is used to cast or be molded into electrode easily.Thereby, behind selected a kind of metallic matrix, just can from the catalogue of above-mentioned second component, choose a kind of suitable pore creating material, to form the molten mixture of making electrode,, obtain the self-bearing type porous electrode then by the removal of pore creating material.The electrode of making is a self-bearing type, and is integrally-built, and not as existing lead-acid battery electrode normally used support grid of institute or support plate.
For average bore hole size and the hole that obtains to set distributes, formed solid electrode (imperforate) can be further by heat treatment.Heat treatment makes second component form nucleus, and precipitation or diffusion after pore creating material is removed, can form different hole dimensions and pore size distribution in metallic matrix.And then estimate accurate heat-treat condition again, this condition depends on metallic matrix, second component and the hole dimension and the pore size distribution that set.Average cell size in the final electrode structure can be set in about 0.1 micron usually and arrive between the hundreds of micron.Should understand, in the practical application of the present invention, accurate heat-treat condition and final hole dimension and distribution itself are not very strict.
After above-mentioned solid (atresia) electrode structure formed, second component must therefrom be removed, to form required porous self-bearing type electrode structure.The removal of second component can realize with different modes according to the character of second component, for example, and thermal release, Chemical Decomposition (for example lixiviation process) or electrochemistry separate mode.No matter adopt any mode, must deal carefully with, do not damage the mechanical strength and the structural intergrity of metallic matrix.Method according to example, when metallic matrix is plumbous, when second component is gallium, this second component available heat partition method is removed, in this case, solid electrode structure be heated to exceed about more than 30 ℃, under this temperature, gallium can melt from this electrode structure and separate out, and available mechanical system or decant mode are removed.If zinc is second component, available lixiviation process in a suitable leaching agent, is removed it from electrode structure, and this leaching agent leaches zinc and can not influence the lead base body.For example, found that hydrochloric acid is the leaching agent that is fit to do this purposes.When using cadmium to make second component, this electrode structure sulfuric acid treatment, sulfuric acid can leach cadmium from the lead base body.In order to quicken to remove cadmium, this electrode as anode, is linked to each other with an electromotive force power supply that adds, and passes to suitable electric current.
If second component adopts carbonate or bicarbonate, their available heat water loggings go out or leach with certain acid that is suitable for, for example sulfuric acid.
Select certain organic substance (for example, camphor or urea) for use when second component, they can separate these organic substances with the thermal release mode, perhaps leach with certain solvent that is suitable for, for example ethers or alcohols.
Thereby, can find out obviously that from above-mentioned explanation available different mode is removed second component from metallic matrix.Certainly, for those skilled in the art, along with the metallic matrix that forms electrode and the change of second component, themselves also can propose other removing method and leaching agent.Must be pointed out that in addition no matter adopt any second component that removes of heat, chemistry or electrochemical means.All can adopt conventional equipment, the condition of use can be improved to obtain optimum efficiency.
Second component is once removal, and this electrode structure will be the porous self-bearing type, mechanical strength big and have integrally-built, the metallic matrix that electrical property is continuous.(for example plumbous, lead alloy etc.).This porous electrode must be for further processing, to form a kind of electrochemical activity electrode that uses in the lead-acid battery that is predefined in.This can make the metallic interior surface in the hole in the lead base body form electrochemical active material with chemical conversion or electro-chemical conversion mode on the spot, lead oxide for example, brown lead oxide, vulcanized lead, or their any composition.The conversion on the spot on plumbous surface is that this lead surface is exposed in the oxidation environment in this hole.No matter adopt chemical method or electrochemical method, formed electrochemical active material closely contacts with the surperficial maintenance of the metallic lead in the hole, thereby has guaranteed electrochemical active material, electrolyte, and the electricity continuity between the impressed electromotive force power supply.
Must be noted that the over oxidation of avoiding plumbous surface in the hole.Ideal situation is that continuous electrochemical active material layer of oxidized surface formation, its thickness approximately are to several microns from the several molecule layer.When oxidated layer thickness increased, its internal resistance was also along with increase, thereby, should avoid the blocked up of electroactive substance.
The plumbous surface in oxidation hole comprises the mixture process porous electrode of using hydrogen peroxide and sulfuric acid so that form the case method of electrochemical active material in the above; Perhaps under the situation that sulfuric acid and oxygen are arranged, water Steam Heating electrode; Perhaps, electrode is carried out electrochemical oxidation chloride ion being arranged or not having in the sulfuric acid of chloride ion.These processing procedures can independently, be carried out according to priority or synthetically according to the economic condition of technology and the electrode property that sets.
After above-mentioned electrochemical active material forms, electrode is packed battery into as positive electrode before, clean and drying it.If electrode uses as negative pole, then Shang Mian electrochemical active material can be reduced into lead with it with the method for routine.
Thereby, according to the present invention, can provide a kind of self-bearing type porous integral structure, the electrode structure that electrical property is continuous.When forming electrode, do not adopt grid or support plate; Therefore, the battery that kind electrode is housed lead-acid battery than conventional on weight is light significantly.In addition, the battery that novel porous electrode of the present invention is housed has shown lower internal resistance, peels off less or does not have peeling phenomenon, and charging and discharging rate height has higher capacitance of storage, in a word, compares with the lead-acid battery of routine, and it has more superior characteristic.
Though the present invention is described to some particularity, also be described at lead as the electrode metal matrix, the person skilled in the art can recognize that the guidance content of this paper is extensively to be suitable for.Therefore, they also belong within the scope of the present invention some tangible changes and modification that the present invention's narration is proposed.
Errata
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Claims (26)
1, a kind of method that forms the continuous electrode of porous self-bearing type overall structure and electrical property, this method comprises:
(a) form the molten mixture of a kind of conducting metal and pore-creating component, wherein, this pore-creating component is that the form with dispersed particles shape material is dispersed among the whole molten mixture.
(b) with this molten mixture cooling, and form a kind of solid electrode structure with preliminary dimension and shape, pore-creating component wherein is dispersed among the whole solid metal electrode.
(c) remove granular pore-creating component from solid electrode, thereby form porous electrode structure on this electrode, each hole is all limited by metallic walls.
(d) electrode structure with porous places a kind of oxidation environment, to form one deck electrochemical active material on the metallic walls in hole on the spot.
2, according to the process of claim 1 wherein that described metal is lead or lead alloy.
3, according to the process of claim 1 wherein that described oxidation environment is the hydrogen peroxide in the sulfuric acid.
4, according to the process of claim 1 wherein that described oxidation environment has been included in water vapour, this electrode of heating under the situation of oxygen and sulfuric acid.
5, according to the process of claim 1 wherein that described oxidation environment is included under the situation of sulfuric acid this porous electrode is carried out electrochemical anodic oxidation.
6, according to the method for claim 2, wherein said oxidation environment is the hydrogen peroxide in the sulfuric acid.
7, according to the method for claim 2, wherein said oxidation environment has been included in water vapour, this porous electrode of heating under the situation of oxygen and sulfuric acid.
8, according to the method for claim 2, wherein said oxidation environment is included under the situation of sulfuric acid, and this porous electrode is carried out electrochemical anodic oxidation.
9, a kind of method that forms porous self-bearing type overall structure and continuous electric performance electrode is arranged, this electrode is used for lead acid accumulator, and this method comprises;
(a) form the molten mixture that comprises a kind of metal and a kind of pore-creating component, wherein, this pore-creating component is dispersed in dispersed particles shape form among the whole molten mixture, and this metal is selected from the material group of being made up of plumbous and lead alloy, and this pore-creating component is selected from following material group;
1) cadmium, gallium, thallium, zinc, and their mixture.
2) alkali carbonate, alkali metal hydrogencarbonate, ceruse and basic lead carbonate and composition thereof.
3) camphor, urea, and their mixture.
(b) with this molten mixture cooling, and form the solid electrode structure with predetermined size and dimension, pore-creating component wherein is dispersed in the whole resulting solid metal electrode;
(c) from this electrode, remove granular pore-creating component, thereby form porous electrode.
(d) this porous electrode structure is placed an oxidation environment, so that on the metal inner surface of hole, form one deck electrochemical active material on the spot.
10, according to the method for claim 9, wherein said electrochemical active material is lead oxide or lead sulfate.
11, according to the method for claim 9, wherein said metal is plumbous.
12, according to the method for claim 11, wherein, described electrochemical active material is a brown lead oxide.
13, according to the method for claim 9, wherein, the pore-creating component is to be selected from such one group of material, and this group material comprises cadmium, gallium, thallium, zinc, and composition thereof.
14, according to the method for claim 10, wherein, described pore-creating component is to be selected to comprise cadmium, gallium, thallium, zinc, and composition thereof such one group of material.
15, according to the method for claim 11, wherein, described pore-creating component is selected from and comprises cadmium, gallium, thallium, zinc, and composition thereof such one group of material.
16, according to the method for claim 12, wherein, described pore-creating component is selected from and comprises cadmium, gallium, thallium, zinc, and composition thereof such one group of material.
17, according to the method for claim 9, wherein said metal is plumbous, and described second component is a cadmium.
18, according to the method for claim 9, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid perhaps there is being under the situation of sulfuric acid with this porous electrode electrochemical anodic oxidation this porous electrode of heating.
19, according to the method for claim 10, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, is perhaps having under the situation of sulfuric acid the porous electrode electrochemical anodic oxidation.
20, according to the method for claim 11, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, this porous electrode of heating under the situation of oxygen and sulfuric acid, or having under the situation of sulfuric acid this electrode electro Chemical anodic oxidation.
21, according to the method for claim 12, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, or is having under the situation of sulfuric acid this electrode electro Chemical anodic oxidation.
22, according to the method for claim 13, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid perhaps there is being under the situation of sulfuric acid with this electrode electro Chemical anodic oxidation this porous electrode of heating.
23, according to the method for claim 14, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, or is having under the situation of sulfuric acid this porous electrode electrochemical anodic oxidation.
24, according to the method for claim 15, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, or is having under the situation of sulfuric acid this porous electrode electrochemical anodic oxidation.
25, a kind of method according to claim 16, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, or is having under the situation of sulfuric acid this porous electrode electrochemical anodic oxidation.
26, a kind of method according to claim 17, wherein, described oxidation environment is the hydrogen peroxide in the sulfuric acid, and water vapour is being arranged, and under the situation of oxygen and sulfuric acid, heats this porous electrode, or is having under the situation of sulfuric acid this porous electrode electrochemical anodic oxidation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76067385A | 1985-07-30 | 1985-07-30 | |
| US760,673 | 1985-07-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86105478A true CN86105478A (en) | 1987-05-27 |
| CN1010633B CN1010633B (en) | 1990-11-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86105478A Expired CN1010633B (en) | 1985-07-30 | 1986-07-29 | Porous electrodes and method of making same |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0231348A4 (en) |
| JP (1) | JPS63500481A (en) |
| KR (1) | KR880700478A (en) |
| CN (1) | CN1010633B (en) |
| AU (1) | AU581339B2 (en) |
| BR (1) | BR8606786A (en) |
| DK (1) | DK159887A (en) |
| ES (1) | ES2000786A6 (en) |
| FI (1) | FI871382A0 (en) |
| GR (1) | GR862003B (en) |
| IL (1) | IL79533A (en) |
| PH (1) | PH22687A (en) |
| PT (1) | PT83087B (en) |
| WO (1) | WO1987000973A1 (en) |
| ZA (1) | ZA865535B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248547B (en) * | 2005-08-01 | 2010-05-19 | 托马斯·约翰·迈耶 | An electrode and a method for forming an electrode |
| CN103056366A (en) * | 2013-01-28 | 2013-04-24 | 昆明理工大学 | Preparation method for porous stainless steel |
| CN112095118A (en) * | 2020-09-03 | 2020-12-18 | 广东臻鼎环境科技有限公司 | Composite lead dioxide anode and preparation method thereof |
| CN113258039A (en) * | 2021-04-28 | 2021-08-13 | 风帆有限责任公司 | Method for improving porosity of positive plate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050040714A (en) * | 2003-10-28 | 2005-05-03 | 티디케이가부시기가이샤 | A porous functional membrane, a sensor, a method for manufacturing a porous functional membrane, a method for manufacturing a porous metal membrane and a method for manufacturing a sensor |
| CN101949031A (en) * | 2010-10-18 | 2011-01-19 | 中南大学 | Composite porous electrode for sulfuric acid system and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE86459C (en) * | ||||
| US440267A (en) * | 1890-11-11 | Process of producing porous crystallized metal plates | ||
| FR523294A (en) * | 1919-04-26 | 1921-08-16 | Henri Tailleferre | Manufacturing process for lead-acid battery plates |
| US1641241A (en) * | 1924-08-23 | 1927-09-06 | Strasser Albert | Manufacture of lead electrode for accumulators |
| FR634032A (en) * | 1926-05-07 | 1928-02-08 | Ig Farbenindustrie Ag | Process for the preparation of highly porous lead aggregates |
| GB284352A (en) * | 1927-01-28 | 1928-08-09 | Ig Farbenindustrie Ag | Manufacture of accumulator plates |
| FR655340A (en) * | 1927-05-24 | 1929-04-17 | Ig Farbenindustrie Ag | Manufacturing process for lead electrodes for accumulators |
| DE476344C (en) * | 1927-06-01 | 1929-05-15 | I G Farbenindustrie Akt Ges | Process for the production of accumulator plates |
| US1919730A (en) * | 1929-06-11 | 1933-07-25 | Ig Farbenindustrie Ag | Porous metal and metal oxide |
| US2969414A (en) * | 1958-09-30 | 1961-01-24 | Fleischer Arthur | Manufacture of cadmium and nickel plates for batteries of the nickelcadmium type |
| AU439977B2 (en) * | 1970-04-08 | 1973-09-03 | Dunlop Australia Limited | Improved electrode for an electro-chemical device |
| SE360952B (en) * | 1970-12-21 | 1973-10-08 | Suab | |
| US3929505A (en) * | 1971-04-23 | 1975-12-30 | Mcculloch Corp | Formation of battery plates |
| US4131515A (en) * | 1977-08-26 | 1978-12-26 | Samuel Ruben | Method for making positive electrode for lead-sulfuric acid storage battery |
| US4251603A (en) * | 1980-02-13 | 1981-02-17 | Matsushita Electric Industrial Co., Ltd. | Battery electrode |
-
1986
- 1986-07-24 ZA ZA865535A patent/ZA865535B/en unknown
- 1986-07-25 WO PCT/US1986/001554 patent/WO1987000973A1/en not_active Application Discontinuation
- 1986-07-25 BR BR8606786A patent/BR8606786A/en unknown
- 1986-07-25 JP JP61504331A patent/JPS63500481A/en active Pending
- 1986-07-25 EP EP19860905031 patent/EP0231348A4/en not_active Withdrawn
- 1986-07-25 PH PH34064A patent/PH22687A/en unknown
- 1986-07-25 AU AU61930/86A patent/AU581339B2/en not_active Ceased
- 1986-07-28 IL IL79533A patent/IL79533A/en unknown
- 1986-07-29 ES ES868600700A patent/ES2000786A6/en not_active Expired
- 1986-07-29 GR GR862003A patent/GR862003B/en unknown
- 1986-07-29 PT PT83087A patent/PT83087B/en unknown
- 1986-07-29 CN CN86105478A patent/CN1010633B/en not_active Expired
-
1987
- 1987-03-05 KR KR870700189A patent/KR880700478A/en not_active Application Discontinuation
- 1987-03-30 FI FI871382A patent/FI871382A0/en not_active IP Right Cessation
- 1987-03-30 DK DK159887A patent/DK159887A/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248547B (en) * | 2005-08-01 | 2010-05-19 | 托马斯·约翰·迈耶 | An electrode and a method for forming an electrode |
| CN103056366A (en) * | 2013-01-28 | 2013-04-24 | 昆明理工大学 | Preparation method for porous stainless steel |
| CN112095118A (en) * | 2020-09-03 | 2020-12-18 | 广东臻鼎环境科技有限公司 | Composite lead dioxide anode and preparation method thereof |
| CN113258039A (en) * | 2021-04-28 | 2021-08-13 | 风帆有限责任公司 | Method for improving porosity of positive plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010633B (en) | 1990-11-28 |
| DK159887D0 (en) | 1987-03-30 |
| ES2000786A6 (en) | 1988-03-16 |
| FI871382A (en) | 1987-03-30 |
| JPS63500481A (en) | 1988-02-18 |
| IL79533A0 (en) | 1986-10-31 |
| EP0231348A1 (en) | 1987-08-12 |
| GR862003B (en) | 1986-12-23 |
| IL79533A (en) | 1989-10-31 |
| PT83087B (en) | 1987-12-23 |
| EP0231348A4 (en) | 1990-01-24 |
| WO1987000973A1 (en) | 1987-02-12 |
| PH22687A (en) | 1988-11-14 |
| AU6193086A (en) | 1987-03-05 |
| DK159887A (en) | 1987-03-30 |
| ZA865535B (en) | 1987-03-25 |
| BR8606786A (en) | 1987-10-13 |
| PT83087A (en) | 1986-08-01 |
| FI871382A0 (en) | 1987-03-30 |
| KR880700478A (en) | 1988-03-15 |
| AU581339B2 (en) | 1989-02-16 |
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