CN103814463A - LPCS formed composite current collector and methods therefor - Google Patents

LPCS formed composite current collector and methods therefor Download PDF

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Publication number
CN103814463A
CN103814463A CN201280034366.XA CN201280034366A CN103814463A CN 103814463 A CN103814463 A CN 103814463A CN 201280034366 A CN201280034366 A CN 201280034366A CN 103814463 A CN103814463 A CN 103814463A
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lead
lead alloy
foil
grid
composite insulating
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弗兰克·勒夫
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AIC BLAB Co
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AIC BLAB Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/18—Lead-acid accumulators with bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • 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
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • 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
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H01M10/0418—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes with bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/029—Bipolar electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Contemplated lead acid batteries include a monolithic lead/lead alloy composite foil that is preferably formed by cladding mechanically unstressed lead and lead alloy foils. In such batteries, a light-weight non-conductive grid is placed onto the lead alloy side of the composite foil, which is most preferably pre-treated with a lead-containing adhesive that improves retention of the grid and improves retention and intimate electric contact of the positive active material.

Description

Composite collectors and method thereof that LPCS forms
The application requires the U.S. Provisional Application sequence the 61/485th of submitting on May 13rd, 2011, the priority of No. 984.
Technical field
The field of the invention is the composite construction for the dipole elements of bipolar lead-acid battery, and is in particular the current-collector (current collector, current collector) for bipolar lead-acid battery.
Background technology
Although extremely simple, but Bipolar Membrane battery provides multiple significant advantages.For example,, because internal path length is shorter and because electrode area is relatively large, so internal resistance is conventionally very low, make to generate minimum heat in the time of quick charge and discharge cycles.And due to its bipole arrangement, battery weight reduces, and at least conceptive, production is simplified.But some shortcomings have hindered being widely used of bipolar lead-acid battery at present.In addition, because lead can distortion (creep) (be that lead flake can collapse under the weight at himself, unless be attached to stronger strutting piece under load, for example steel), so lead is the construction material of being on duty mutually, and needs extra material to support lead conventionally, cause weight to increase.In addition, plumbous distortion causes face checking and crack to form conventionally, and this in most cases can accelerated corrosion (stress corrosion).
Well-known in lead-acid battery manufacturing technology, due to the PbSO being formed in electrolyte 4/ PbO x(1<x<2) insulating barrier, pure lead has relatively high corrosion resistance comprising in electrolytical sulfuric acid.Therefore and at least prima facie, due to PbSO 4/ PbO xlayer is as semi-permeable membrane and stop SO 4 2-and/or HSO 4 -the conveying of material, thereby seem it is desirable to form the positive plate with the current collector grid structure of being made by pure lead in excide battery.In most of the cases, PbSO 4/ PbO xlayer has the thickness of about 4 microns, and region keeps this value within the operating period of lead acid storage battery pool unit, and the battery of being made up of pure lead grid does not in most of the cases experience corrosion in the time of floating charge.
In the situation that lead-acid battery is bipolar lead-acid battery, especially it is desirable to have durable and corrosion resistant substrate.Therefore, considered the main material as this substrate by pure lead, to utilize PbSO 4/ PbO xthe protective value of layer.From United States Patent (USP) the 3rd, be known that for 806, No. 696, pure lead grid and pure stereotype can weld together to provide composite collectors structure, in this composite collectors structure, the weld part producing has lower internal driving, and relatively thick in improving non-oxidizability and corrosion resistance.This method has advantageously reduced the resistance in grid/plumbous interface.But, due to the PbSO forming in operating process 4/ PbO xlayer is also as the insulator (this and then cause the too early capacitance loss of battery) with very high resistance, thereby the lead grid structure of pure lead is unsuitable for dark cycle applications unfortunately.For fear of these shortcomings, nearly all production battery grid are made (for example, comprising at least Odyssey(Odyssey of 0.7%Sn in lead alloy) lead-acid battery by the various not lead alloys of welding).
And, from United States Patent (USP) the 6th, be known that for 620, No. 551 lead-acid battery current-collector can by the bottom of pure leadwork and extra superficial layer form, this superficial layer comprises the lead alloy composition (comprising alkali metal or alkaline-earth metal in the most common situation) without Sb.By quoting as proof this and every other extrinsic material discussed herein with its overall combination.The definition of the term in comprised list of references or use inconsistent with the definition of the term that provided in this article or contrary, be suitable for the definition of the term that provided herein and the definition of term in inapplicable list of references.Although this current-collector can reduce or avoid forming PbSO even completely 4/ PbO xlayer, but still there are other shortcomings.For example, manufacturing this composite construction will need lamination, plating or welding conventionally, and this is tending towards the high-intensity work of needs and high production cost.
Therefore, even if become known for a lot of apparatus and method in substrate and/or current-collector, but still need to provide improved substrate and/or current-collector, and be particularly useful for bipolar lead-acid battery.
Summary of the invention
The present invention relates to have the bipolar lead-acid battery of monolithic lead/lead alloy composite insulating foil, this composite insulating foil is preferably by the lead foil that is not subject to mechanical stress with lead alloy-foil is coated or form by low pressure cold is spray deposited.The grid that grid are most preferably the non-conductive grid of lightweight or are formed by lead alloy by low pressure cold spray deposited (LPCS).In another preferred aspect, active material of positive electrode and/or grid for example, are engaged to composite insulating foil by leaded adhesive (being made up of the red lead Pb3O4 powder that mixing with water and carboxymethyl cellulose), to improve the contact of active material of positive electrode and the adhesion of grid and composite insulating foil.
Of theme of the present invention preferred aspect, a kind of dipole elements for bipolar lead-acid battery is provided, this dipole elements comprises monolithic lead/lead alloy composite insulating foil, and this monolithic lead/lead alloy composite insulating foil has first surface and second surface and the lead/lead alloy fused interface between first surface and second surface.In the most common situation, first surface is formed by lead, and second surface is formed by lead alloy.Aspect particularly preferred, non-conductive grid be set on second surface, or use lead alloy to form grid by second surface.
Some preferred aspect, lead/lead alloy composite insulating foil is the coated lead foil of lead alloy, and most preferably, the thickness that lead/lead alloy composite insulating foil has is equal to or less than 0.2mm.In these areas, particularly preferably be polymer grid as non-conductive grid.Aspect other designs, second surface is the spray deposited layer of palisade low pressure cold, and in another preferred aspect, this sedimentary deposit comprises Ti in first surface and/or second surface 4o 7particulate.Regardless of the structure of composite insulating foil, all preferably monolithic lead/lead alloy composite insulating foil is engaged to polymer frame by strengthened sealing agent conventionally.
In another preferred aspect, manufacture comprises a step that builds monolithic lead/lead alloy composite insulating foil for the method for the dipole elements of bipolar lead-acid battery, this monolithic lead/lead alloy composite insulating foil has first surface and second surface and the lead/lead alloy fused interface between first surface and second surface.In a preferred method, first surface is formed by lead, and second surface is formed by lead alloy.In another step, make in the following manner grid be engaged to lead/lead alloy composite insulating foil: on second surface, arrange non-conductive grid, or by being formed grid by lead alloy to form at least partly second surface.
In particularly preferred method, the plumbous lead foil as having the first thickness is provided, and provide lead alloy as the lead alloy-foil with the second thickness, wherein, the first thickness and/or the second thickness are realized by the operation except the rolling that it is carried out (being most preferably casting).In these methods, the step of structure is by realizing with the coated lead foil of lead alloy-foil, and/or non-conductive grid are engaged to second surface, and wherein, the opening in grid is equipped with paste applying device.Alternatively, the step of structure also can realize by the spray deposited lead of low pressure cold and/or lead alloy.In these methods, lead and/or lead alloy further comprise Ti 4o 7particulate.No matter use which kind of mode to build composite insulating foil, all preferably monolithic lead/lead alloy composite insulating foil uses strengthened sealing agent to be installed in polymer frame (conventionally not need extra material for support structure).
Therefore, and from another perspective, the bipolar lead-acid battery of design comprise anode end plate and cathode end plate and be arranged on anode end plate and cathode end plate between multiple bipolar plates (preferably by laser welding together with).In the most common situation, at least one in bipolar plates comprises framework, monolithic lead/lead alloy composite insulating foil is installed in this framework hermetically by strengthened sealing agent (preferably including silica flour and/or silane), wherein, monolithic lead/lead alloy composite insulating foil has first surface, second surface and the lead/lead alloy fused interface between first surface and second surface.Active material of positive electrode is set on second surface, and active material of cathode is set on first surface.In the most common situation, first surface is formed by lead, and second surface forms by lead alloy, and non-conductive grid are set on second surface, or uses lead alloy to form grid by second surface;
In the time that lead/lead alloy composite insulating foil is the coated lead foil of lead alloy, the thickness that preferably composite insulating foil has be conventionally equal to or less than 0.2mm(and conventionally preferably in the time using composite insulating foil without other structural supports in framework).In the most common situation, these devices comprise that polymer grid is as non-conductive grid.Alternatively, second surface can be the spray deposited layer of palisade low pressure cold and (comprises alternatively Ti 4o 7particulate, this particle also can be present in first surface).
By following detailed description and the accompanying drawing of preferred implementation, each target, feature, aspect and the advantage of theme of the present invention will become more apparent, in the accompanying drawings the similar element of similar numeral.
Accompanying drawing explanation
Fig. 1 is the illustrative diagram of bipolar lead-acid battery assembly according to the inventive subject matter;
Fig. 2 is the illustrative diagram with monolithic lead/lead alloy composite insulating foil of non-conductive grid, adhesive and PAM;
Fig. 3 is the illustrative diagram with monolithic lead/lead alloy composite insulating foil of grid, adhesive and the PAM of LPCS formation;
Fig. 4 A show by use cast the monolithic composite insulating foil that terne metal paper tinsel covering and casting lead foil forms cross section amplify the microphoto of (polarised light) with 20x;
Fig. 4 B shows the microphoto amplifying with 20x on the lead surface of the monolithic composite insulating foil of Fig. 4 A;
Fig. 4 C shows the microphoto amplifying with 20x on the terne metal surface of the monolithic composite insulating foil of Fig. 4 A.
Embodiment
Ladies and gentlemen inventor finds, can be for the preparation of the composite bipolar assembly of bipolar lead-acid battery (BLAB), and wherein, the advantage of Pb-Sn alloy Gate combines with economical and technical desirable mode with the advantage at the bottom of pure leadwork.In further preferred aspect, grid also can be formed by lightweight non-conducting material.Composite bipolar assembly will advantageously comprise monolithic lead/lead alloy composite insulating foil (not needing structural support plumbous and that lead alloy is coupled thereon in the most common situation), the thickness that this composite insulating foil has is less than 1mm, more typically less than 0.5mm, and be the most conventionally less than 0.2mm.
In addition ladies and gentlemen inventor finds, in the time using traditional rolling mill practice to be used in the lead of dipole elements and/or lead alloy material to be formed as film or paper tinsel, the film forming like this or paper tinsel are with far away higher than stand sulfuric acid degraded/be oxidized with the speed that reduces or avoid completely film prepared by the mode of the mechanical stress of lead and/or lead alloy material or paper tinsel.In not wishing to be subject to the restriction of any specific theory or hypothesis, ladies and gentlemen inventor conceives lead and/or lead alloy material rolling or is stamped into needed thickness and will pressurize and amplify crystal boundary crystal boundary, thus and surface reduction and/or larger that provides sulfuric acid subsequently to be stood to degrade/be oxidized.
Therefore, the especially preferred manufacture method of lead and/or lead alloy material will comprise that the method that can not make grainiess obviously be out of shape (for example, makes the single size after manufacturing be increased to desired thickness, compared with before manufacturing, this thickness is more than 2.5 times, is more typically more than 3 times).Therefore, especially preferred manufacture method is by spray deposited the low pressure cold that comprises forming paper tinsel or composite insulating foil, and with desired thickness cast lead and/or lead alloy-foil and can be before paper tinsel be incorporated in composite construction in rolling or further reduce the thickness (at least reduce 20%, more generally at least reduce 50%) of paper tinsel in pressing operation.In the situation that lead and/or lead alloy-foil are cast into desired thickness, these paper tinsels can be in coated operation each other fusion be monolithic composite insulating foil.
Due to preferred manufacture method, ladies and gentlemen inventor it has also been found that, this operation advantageously allows the formation of monolithic composite construction, these monolithic composite constructions are especially desirable, and this is because delamination (delaminate) can not occur this structure as conventionally run in laminated composite structures.In addition, should be appreciated that, monolithic composite construction also provides desirable conductivity between lead and/or lead alloy.Term " monolithic " and composite construction are in conjunction with being combined into for representing that this structure comprises at least two kinds of different materials that form continuous interfacial, these materials form intermetallic combination in this interface conventionally, and wherein, this interface does not comprise the independent bond material being arranged between different materials.Therefore, monolithic composite construction will can not present delamination along this interface.In the most common situation, these two kinds of different materials have the structure (macroscopic be flat substantially in appearance) of sheet or paper tinsel, wherein sheet or paper tinsel have the corresponding apparent surface vertical with the thickness of sheet or paper tinsel, and surface of one of them sheet or paper tinsel and a surface conjunction of another sheet or paper tinsel.
In Fig. 1, schematically show an exemplary bipolar lead-acid battery assembly, wherein, battery component 100 has anode end plate (positive end plate) 102 and cathode end plate (negative end plate) 104 and is arranged on the multiple bipolar plates (n) between anode end plate and cathode end plate.Each bipolar plates has framework 106, uses strengthened sealing agent 108(to preferably include silica flour and/or silane) monolithic lead/lead alloy composite insulating foil 110 is arranged in this framework hermetically.Monolithic lead/lead alloy composite insulating foil 110 has the first surface 112 being formed by lead foil, the second surface 114 being formed by lead alloy-foil and the lead/lead alloy fused interface 116 between first surface and second surface.Non-conductive grid 140 are arranged on second surface, or grid 140 form by the second surface with lead alloy, as described further below.Active material of positive electrode (PAM) 130 is arranged on second surface, and active material of cathode (NAM) 120 is arranged on first surface.The withstand voltage separator 150 that comprises gel electrolyte (not shown) is arranged on PAM and NAM.
Fig. 2 has schematically shown an execution mode, and wherein the compound lead/lead alloy-foil of monolithic is the coated lead foil of lead alloy, and wherein grid are non-conductive lightweight polymeric grid.Here, dipole elements 200 comprises the compound lead/lead alloy-foil 210 of monolithic, and it has the first surface 212 being made up of lead foil and the second surface 214 being made up of lead alloy-foil.Here, lead foil and lead alloy-foil are the casting paper tinsel of each thickness all with about 0.254mm.After coated, the compound lead/lead alloy-foil of monolithic has the thickness of about 0.152mm.Aspect particularly preferred, PAM230 is kept by grid 240, and leaded adhesive 218 forms layer on second surface 214, for helping the grid 240 adhesively to remain on second surface and for improvement of the electric and Mechanical Contact of PAM230 and second surface 214.
Alternatively, as being schematically shown in Fig. 3, the compound lead/lead alloy-foil of monolithic is formed by LPCS.Here, dipole elements 300 has the frame part 1 that keeps lead foil 2, and grid 4 are formed on this lead foil by LPCS.Therefore, this assembly will have the first surface being formed by lead foil 2 and the second surface being formed by lead alloy grid 4.Be supported in solid carrier (for example metal or plastic plate) when upper where necessary or at lead foil, by conductive contact 3(, it also can be formed by LPCS) electric current is collected in lead foil 2 from PAM6, thus the high resistivity PbSO effectively on bypass substrate 4/ PbO xlayer.In this composite insulating foil, lead/lead alloy preferably further comprises Ti 4o 7particulate (not shown).As previously mentioned, can use leaded adhesive that PAM is arranged on grid.Be apparent that, use the expection method proposing to allow to manufacture the composite collectors with multiple ideal performance herein, for example, be even also like this lead foil and grid thinner (0.15mm) in the situation that.In addition, the grid in this device are connected to paper tinsel equably, and this current-collector being difficult to especially by having the thin substrate being coupled with grid is realized.
With regard to lead material, ladies and gentlemen inventor notices, the data of weight saving can represent to be subject to the alloy lead alloy of desired thickness (and be especially rolled into by materials in storage) of mechanical stress/mechanical deformation all to corrode sooner than casting alloy at all temperature.Therefore, and use larger mechanical stress/distortion to cause higher corrosion rate and more expose the hypothesis of crystal boundary, ladies and gentlemen inventor's research is not subject to the applicability of lead and the lead alloy-foil of mechanical stress in the time of preparation dipole elements.Ladies and gentlemen inventor and then discovery, be not subject to the lead of mechanical stress and lead alloy-foil to be especially of value to manufacture dipole elements.Aspect preferred, this material is especially included in the lead and the lead alloy-foil that on the commercially available casting machine of business, are cast into desired thickness, wherein in the +/-25% of the directly final thickness before formation composite construction of desired thickness in lead or lead alloy-foil, be more typically in +/-10%, and the most conventionally in +/-5%.From different angles, plumbous and lead alloy-foil is preferably cast into certain thickness in the case of not being rolled into the thickness that further reduces paper tinsel.Therefore, should be appreciated that, metal grain will have the size stress reducing, and conventionally making longest dimension is below 4 times of minimum dimension, is more typically below 3 times, is generally most below 2.5 times.Lead and the lead alloy-foil of preparation are used to form composite construction like this, and most preferably form monolithic composite construction.
As it is evident that from Fig. 4 A-Fig. 4 C, lead/lead alloy composite insulating foil has evenly interface closely, this interface display the intermetallic combination that does not have delamination between paper tinsel layer, and this lead/lead alloy composite insulating foil has further been shown clearly in the form that is not subject to mechanical stress of crystal grain.Fig. 4 A show by use cast the monolithic composite insulating foil that terne metal paper tinsel covering and casting lead foil forms cross section amplify the microphoto of (polarised light) with 20x.Fig. 4 B shows the microphoto amplifying with 20x on the lead surface of the monolithic composite insulating foil of Fig. 4 A, and Fig. 4 C shows the microphoto amplifying with 20x on the terne metal surface of the monolithic composite insulating foil of Fig. 4 A.In this composite insulating foil, show being conventionally at least 95%, being more generally at least 97% and be the most conventionally at least in 99% length of interface, plumbous and lead alloy is bonded to each other along the interface with the cross section of choosing at random.This very high associativity produces excellent machinery and electrical performance characteristic.
For example, of theme of the present invention preferred aspect, lead foil and lead alloy-foil are coated togather to form the compound lead/lead alloy-foil of monolithic.In this operation, coated plumbous particulate under the contact of about 600psi, plumbous fusing and the combination of generation intermetallic under this pressure.Certainly, should be appreciated that, contact can marked change in the limit of coating layer.Therefore, at the temperature between about 4 ℃ and 150 ℃, typical contact at about 500psig in the scope of 900psig.Although theme of the present invention is not limited, carry out coated operation but also conceive with Tory Crane type coated mode casting lead foil and lead alloy-foil, and the thickness of the such monolithic lead/lead alloy composite insulating foil producing of design is less than the additional thickness of lead foil and lead alloy-foil.
For example cast paper tinsel by the thickness conventionally having between 0.01mm and 10mm, be more typically in 0.1 and 1.0mm between, and the most conventionally 0.2 and 0.3mm between.When coated, the thickness of monolithic lead/lead alloy composite insulating foil be equal to or less than plumbous and lead alloy-foil additional thickness 80%, more generally be equal to or less than plumbous and lead alloy-foil additional thickness 50%, and be generally equal to most or be less than lead and lead alloy-foil additional thickness 25%.For example, plumbous and lead alloy-foil is about 0.254mm in the preferred thickness before coated, and the final thickness that monolithic lead/lead alloy composite insulating foil has is about 0.1524mm.Should also be noted that lead foil and lead alloy preferably have identical thickness (before coated).But aspect replaceable, comparable another paper tinsel of paper tinsel is thicker or thinner.Further, conceiving plural paper tinsel can be coated togather, and suitable extra foils comprises the paper tinsel of such as, for example, being made up of metal material (copper, silver, aluminium etc.) and nonmetallic materials (conducting polymer).But conventionally preferably, stabilized zone or other functional layers are not set between the lead in coated prod and lead alloy-foil.
With regard to the purity of lead foil, conventionally preferably plumbous have high purity, and will comprise 99wt% at least and be more typically the metallic lead of 99.9wt%.But aspect not quite preferred, lead foil also can comprise extra material, these extra materials can be used as ' impurity ' and for example exist or can be added to, for plumbous preparation (mug(unit of measure) alunite profit phase low oxide).Equally, it should be noted, lead alloy-foil can comprise known alloying metal in a large amount of these technology.But especially preferred alloying metal comprises tin and calcium.With regard to tin, it should be understood that the corrosion rate of terne metal depends on the content of tin.Ladies and gentlemen inventor is definite, and the best tin content in lead alloy-foil is 1.8wt%, and it provides minimum corrosion rate.Pb-1.8%Sn has the corrosion resistance lower than pure lead, but advantageous particularly for dark circulation.Use the tin of 1.8wt% by relatively limited surface corrosion is provided, only there is fragmentary pitting attack.But in the time that sulfuric acid infiltrates fragmentary hole, corrosion is by because the formation of Pb paper tinsel passivation layer stops.
By be coated to manufacture monolithic lead/lead alloy composite insulating foil in the situation that, preferably grid are made and are arranged in by non-conducting material on first and/or second surface of monolithic lead/lead alloy composite insulating foil conventionally.In the situation that grid are arranged on first surface, grid are configured to provide incompressible NAM distance piece conventionally.In the situation that grid (going back) are arranged on second surface, grid are structured as the light-duty low footprint similar to traditional lead grid (low foot print) carrier, to promote the electrode of pasting.In this respect, should be appreciated that, these grid can be configured to allow on traditional automatic adhesion equipment, paste and solidify.The benefit of the method is, manufactures aspect anode and cathode electrode that this is relative simple and have a cost efficiency on existing high power capacity equipment.Therefore, suitable non-conductive grid material will comprise thermoplasticity and thermosetting polymer, and especially comprise polyethylene (PE), high density polyethylene (HDPE) (HDPE), acrylonitrile-butadiene-styrene (ABS) (ABS), various polyacrylate (PA), Merlon (PC) and polypropylene (PP), poly-(methyl methacrylate) (PMMA), polystyrene (PS) and polybutylene terephthalate (PBT).
In another example, also can manufacture monolithic lead/lead alloy composite insulating foil by LPCS technique, so that not only at the upper deposit lead alloy-layer of lead layer (this lead layer also can be formed by LPCS), and realize single chip architecture and build grid.Therefore, should be appreciated that, can deposit to form bipolar composite construction by the LPCS of electric conducting material at least partly, the composite collectors that wherein spraying forms is combined with the advantage of higher non-oxidizability and lower manufacturing cost.
The composite collectors of particularly preferred apparatus and method is fabricated to the gate part (being generally Pb-Sn alloy most) that makes current-collector have alloying, at the bottom of this part and pure leadwork, in structure and conductivity, has continuity.At the bottom of leadwork, can comprise an extra sandwich layer (being most preferably copper), for improving the conductivity of current-collector.Be apparent that, use the contemplated methods proposing to allow to manufacture the composite collectors with multiple desirable performances herein, for example, be even also like this lead foil and grid thinner (0.15mm) in the situation that.In addition, the grid in this device are connected to paper tinsel equably, and this current-collector being especially difficult to by having thin substrate and grid is realized.
Based on the experiment of carrying out with the commercially available LPCS equipment of business, ladies and gentlemen inventor finds, (be for example less than 300 ℃ at low temperature, more typically less than 250 ℃, the most conventionally be less than 200 ℃) lower use Pb-Sn alloy powder (for example 1.5wt%Sn, 98.5wt%Pb) to spray pure leadwork at the bottom of for example, when (purity is at least the thin lead foil of 99wt%), seem intensive and present good combination/adhesive property through the alloy-layer of deposition.Do not exist be oxidized, the sign of torsion, residual stress and/or undesirable metallurgy conversion, and the deposit producing has enough mechanical strengths and conductivity between substrate and the material of deposition.By scaling type Laval nozzle, Pb-Sn metal powder mixture is entrained in the air-flow of acceleration and is incident upon and in target substrate, manufacture coating.By compressed-air actuated air-flow, particulate is accelerated as supersonic speed.Aspect most preferred, these particulates were solid-state (not fusing) before clashing into substrate.Therefore, due to the compression stress obviously reducing between coating and substrate, thereby LPCS deposition can be used for manufacturing the thick and close coating with high-adhesion.
On the surface of being devoted at substrate, manufacture suitable grid structure aspects, ladies and gentlemen inventor prevents that with various masking materials metal spraying from adhering to the undesirable region of substrate, and is preferred masking material standard to the applicability of high power capacity manufacture.The shelter template of being made up of the self-adhesion vinyl adhesive tape of commercially available 5 mil thick of business by application is received relatively good result, this has not only been avoided making grid and the coupling of substrate conduction by effort and expensive conventional processes, but also allows to form composite construction in increasingly automated and simple mode in multiple structure.Producing with the LPCS of grid and/or substrate the term " formation (formed) " being combined with represents, in progressive interpolation operation, manufacture grid and/or substrate, wherein material is joined in newborn grid and/or substrate, thereby realize final grid and/or substrat structure.
Therefore, will be appreciated that, the various bipolar electrode assemblies of ladies and gentlemen inventor's design for using at bipolar lead-acid battery, and will be appreciated that, this assembly advantageously comprises one or more composite collectors, in this current-collector, conductive substrates is formed by the first metal ingredient (being generally pure lead), and grid structure is formed by the second metal composites (being generally Pb-Sn lead alloy) in this current-collector.Most preferably, under the help of low temperature spraying process, manufacture the device of design, wherein sprayed on material not fusing in spray gun, but with United States Patent (USP) the 6th, 139, No. 913 with No. 2003/0077952Alth, U.S. Patent application described in the similar operation of operation in, be deposited on substrate to dynamics at low temperatures.The deposit that produces is intensive and have good combination/adhesion strength, but has relatively slow Pb-Sn powder deposition speed.In addition, this material does not mechanically bear pressure, and will present excellent performance characteristics.
Based on multiple experiments, ladies and gentlemen inventor recognizes, deposition rate is subject to a great extent nozzle and is subject to the impact of stopping up, and this need to clear up often.Add softer powder to produce needed cleaning effect to nozzle harder particulate (for example aluminium oxide) although conventionally known, but known additive is not suitable in current collector structure conventionally at present, this is for example, because these materials often affect machinery and/or electric parameter (reducing the overall conductivity of deposition materials) negatively.After passing through the great many of experiments of various materials, ladies and gentlemen inventor finds Ti in a small amount 4o 7(Ebonex) powder adds Pb and/or Pb-Sn powder can reduce the obstruction of nozzle, keeps the impedance of depositing metal layers to be only slightly higher than the material that there is no additive simultaneously.Also further find Ti 4o 7particulate preferably has the size of 1-150 micron (maximum size) and the aspect ratio between about 10:1 and 1:1.Also conventionally preferably, these particulates exist with the amount of 0.05 to 5% percentage by weight of Pb and/or Pb-Sn particulate.
With regard to Pb or Pb-Sn particulate, preferably these particulates have the average-size between about 10-200 micron (maximum size) conventionally, and aspect ratio is approximately between 20:1 and 4:1.Based on above considering and method, ladies and gentlemen inventor can be high productivity ratio (for example average deposition speed is about 0.82kg/h) on pure lead or lead alloy substrate, effectively deposit Pb and/or Pb-Sn material, realize the maximal phase of about 200 microns of deposition materials to uniform height (thickness) simultaneously.The adhesion strength of deposition materials is rendered as 20 in the ideal range of 80MPa.In fact, ladies and gentlemen inventor's discovery, in the time carrying out tension test, in most of the cases, Pb paper tinsel breaks sooner than the material layer of cold spraying.And it is intensive that sprayed coating seems, has low porosity.For example, the 5 × 5mm section package of the Pb-Sn through deposition on the thick Pb paper tinsel of 0.15mm, in epoxy resin, and carries out polishing for checking.Porosity is rendered as in 2-3%.Therefore, comprise Ti 4o 7additive is rendered as the mechanical quality that does not damage deposition materials.
With regard to substrate, design be that this substrate comprises lead or is made up of lead completely, and there is the structure of substantitally planar shape and relative thin.Therefore,, aspect theme of the present invention most typical, substrate is the thickness that has at the about pure lead foil between 2mm and 0.05mm.At the bottom of leadwork, also can be revised as the parts that comprise except lead to increase oxidation resistant stability, or at the bottom of this leadwork, can be lead alloy so that desirable characteristic to be provided.It should be noted, for example, at lead foil very thin (being equal to or less than 0.1mm) or there is the 200cm of exceeding 2the situation of the area of plane under, can realize conduction and/or non-conductive carrier so that this Stability Analysis of Structures.For example, suitable carrier comprise non-conductive and oxidation resistant polymeric material (for example synthetic polymer, such as PC, HDPE and in battery technology known other polymer).Regardless of the character of carrier, this carrier relative thin (for example, between 0.1 to 100 times that the thickness all having is substrate thickness) and can keep substrate preferably conventionally.Therefore, suitable carrier layer can be pressed onto in substrate and (see for example United States Patent (USP) the 5th, 510, No. 211, bipolar cell substrate as composite collectors has been described, it comprise by lead flood to form porous non-conductive (for example pottery) substrate through the multichannel conductive path of substrate).Therefore, the whole bag of tricks is suitable for producing conductive path, comprises the leads that molten lead is saturated, electrolyte precipitates or comprises the massive parallel with molten polymer.Should be noted that, all these methods can be used for conductor to embed reliably in the matrix of non-conductive and electrochemical stability, wherein this matrix has the conductive plane on the opposition side that is positioned at matrix, and wherein multiple conductors are made and be electrically connected to conductive plane by lead or lead alloy.Ladies and gentlemen inventor further finds, in following situation, produce desirable result: for example, by polymeric material and (be preferably thin glass fibre paper tinsel, its thickness is between 0.1 to 3.0mm) the non-conductive and oxidation resistant carrier made is with multiple small diameter bore, and these holes allow to comprise that pure lead is to be delivered to opposite side by electronics from a side of carrier.Most preferably, realize these holes with the ratio in every square centimeter of about two holes of bearer plane, wherein these holes have the average diameter of about 100 to 150 microns.Be apparent that, the plumbous combination zone comprising like this have can be suitable with the best battery grid of traditional design or than its better conductivity, but have advantages of more light than most of known devices and may be more cheap.It should be noted, ladies and gentlemen inventor is also surprised to find that, the plumbous particulate of spraying embeds in plastic material fully, thereby for carrier provides reliable adhesiveness, this has eliminated the needs for lamination completely.
Other of theme of the present invention preferred aspect, design be can be on carrier the conductive plane of (cold) spraying composite collectors.Additionally or alternatively, also can use valuably cold spray deposition, to fill pure lead in the hole of outputing, and in the negative side of carrier, deposit the pure lead of one deck and on its side of the positive electrode, deposit one deck Pb-Sn alloy.In this and other devices, negative electrode layer is about 50 to 75 microns by the thickness having, and anodal layer is about 75 to 150 microns by the thickness having, thereby sufficient conductivity and corrosion deposit are provided.In addition, it should be understood that in the time there is no non-conductive carrier, also can deposit the pure lead of one deck and then on this lead layer, form Pb-Sn grid structure.It should be noted, regardless of the design of composite collectors, be binary lead alloy for the most preferred material of grid or positive planar conductor, it comprises the Sn that arrives 0.9wt% with pure Pb in 0.4 of balance.
And at least partly according to the selection of material, further preferably, grid structure and/or the whole conductive structure without carrier can form to produce monolithic composite construction by LPCS therefore.The exact configuration of conductive structure depends on size and the structure of substrate, and will further depend on the application-specific of battery.Regardless of specific structure, conventionally preferably substrate has at least 3mm(and is preferably 5mm) wide flange (there is no the region of grid), be used for allowing to be encapsulated in (being generally plastics) framework, as previously determined described in WO2010/135313 in our common generation.
No matter monolithic lead/lead alloy composite insulating foil (for example, the coating layer of LPCS or casting paper tinsel) manufacture how, preferably composite insulating foil is installed in preferably non-conductive framework, most preferably make composite insulating foil and the two half-unit of the framework that engages of the periphery of composite insulating foil between.With regard to suitable frame material, should be appreciated that, it is suitable that various materials are all regarded as, and particularly preferred material comprises and can be or can not be the light material of conductivity type.For example, preferred light material comprises various polymeric materials, carbon composite, light ceramics etc.But particularly preferred material comprises the material that is suitable for carrying out thermoplasticity laser welding.For example, the thermoplastic of design comprises acrylonitrile-butadiene-styrene (ABS) (ABS), various polyacrylate (PA), Merlon (PC) and polypropylene (PP), gather (methyl methacrylate) (PMMA), polystyrene (PS) and polybutylene terephthalate (PBT), these materials can be strengthened by various materials and especially glass fibre.
At these frameworks, by laser welding together time, material is in this case selected to be only subject in welding and/or assembling procedure at least at certain some place the restriction of plastics that can laser penetration.In addition, it should be noted, in the situation that polymer is completely transparent, can uses pigment (inner or outside) to carry out absorbing laser energy, thereby be convenient to weld.But the mode of framework fusion is not necessarily limited to laser welding, but can change significantly, and comprises spot welding and seam weldering, ultra-sonic welded, the welding of use activating surface (for example plasma etching surface) chemistry and use one or more adhesives.
Aspect theme of the present invention further preferred, use reinforced adhesive to make composite insulating foil and frame seal.Can prepare particularly preferred reinforced adhesive by the commercially available epoxy adhesive of the business that is added with viscosity intensifier.In other suitable selections, especially preferred viscosity intensifier comprises the silica flour of the commercially available SiO2 smog of business.By percentage by weight is approximately 2% to 8% and percentage by weight be more typically 4% to 5% this powder and add in the commercially available epoxy component of business, ladies and gentlemen inventor has manufactured a kind of sealer compound, under the initial capacity of the DOD to 70% that sealer compound proves at C/2 to 80%, through 390 circulations, electrolyte and electrolysis shunt is had to impermeability.By coupling agent is added into adhesive, even can further improve combination and sealability between composite insulating foil and framework.In other preparations, ladies and gentlemen inventor finds, the commercially available silane performance bins of business is outer good, and the preferred amounts of coupling agent 0.1 and 5wt% between, most preferably 1 and 3wt% between.Therefore, should be appreciated that, interface between monolithic composite insulating foil and framework can seal reliably with reinforced adhesive, in this strengthened sealing agent, traditional adhesive for example, carrys out modification by one or more additives (epoxy adhesive), with increased viscosity and the adhesion to substrate.This reinforced adhesive proved within the extremely long time has impermeability and conventionally more lasting than the designed life of battery to electrolytical movement.
With regard to suitable PAM, it should be noted, all known PAM are all regarded as being suitable for the use that combines with the instruction content that proposed in this article.Therefore, plumbous oxide is the most common selection of PAM.In addition, ladies and gentlemen inventor has produced adhesive composition, and said composition comprises red lead (Pb3O4) powder mixing with water and as the carboxymethyl cellulose of adhesive.The adhesive of manufacturing like this has the viscosity as honey, and is deposited on lead alloy surface before placing the non-conductive electrode of anode.In addition, this adhesive is also for increasing adherence and provide comprehensive engagement between positive electrode material and composite insulating foil.Ladies and gentlemen inventor is surprised to find that, and CMC adhesive (adhesive that is for example 0.05% by percentage by weight is added into oxide mixture) provides enough adhesion to keep the comprehensive engagement of electrode material and dry paper tinsel.As everyone knows, red lead is known due to its quality being shaped in order to improvement, and is only conventionally added into lead oxide slurry due to this object.On the contrary, the PAM slurry in existing battery will not comprise red lead, and with solidify after be dry paper tinsel and coordinate.In current known battery, although and electrode fully compressed, be difficult to wish comprehensive engagement between paper tinsel and electrode, be even also like this make paper tinsel by electrolyte after saturated.On the contrary, the red lead adhesive proposing in this article provides the close contact between electrode and paper tinsel, and electrode is held in place and is prevented paper tinsel from delamination occurring in the time of assembling.Therefore, use lead oxides adhesive, reduced shaping starting voltage, this so that reduce the electrochemical corrosion of paper tinsel at shaping.
After recognizing the key effect at grid-PAM interface under dark circulating load, set up PAM weight (W pAM) with the gate region (S contacting with PAM grid) between optimization relation, wherein β is defined as the W in half positive battery pAM/ S grid.Among other grid of manufacturing, the β value that especially suitable experiment grid have is at about 0.5-1.3g/cm 2between, more preferably at about 0.65-1.1g/cm 2between, and most preferably at about 0.8-1.0g/cm 2between, and typical SLI(starts, lights a fire, ignites) the battery β value that is regarded as having is approximately 2.5g/cm 2.In other especially preferred experiments, the gate part of current collector structure is designed to about 0.95g/cm 2β value (use the PAM of 42g and the 44cm of grid line 2the gross area contacting with PAM).Be apparent that, in this and above-mentioned grid and substrate, to there is enough large current collection surfaces of area, to realize being uniformly distributed of the PAM that contacts with grid line, to improve the utilization of PAM and to improve cycle life, especially for carrying out dark cycling.As used in this article, term " approximately " combines with numeral, represents to comprise the scope of this digital +/-10%.In addition, unless and context represent on the contrary, otherwise all scopes of setting forth are herein understood to include its end points, and open scope is interpreted as only comprising the value of commercially practical.Similarly, enumerating of all values should be regarded as comprising median, unless context represents on the contrary.
Similarly, with regard to suitable active material of cathode (NAM), should be appreciated that, all known NAM are all regarded as being suitable for use herein.Therefore, the NAM of special design comprises the various slurries based on plumbous.Use most preferably is withstand voltage non-conductive carrier (grid) and comes preferably NAM to be remained on substrate place.Although theme of the present invention is not construed as limiting, but non-conductive grid are preferably manufactured by synthetic polymer acidproof and resistance to oxidation corrosion.Preferably, this grid (for example skeleton structure) will advantageously have the height identical with the thickness of NAM under complete charged state.Therefore, can be depressed into desirable pressure by bipolar in both sides, and not affect negatively electrode performance.But, it should be noted, conductive gate also can be regarded as being suitable for use herein.
Particularly preferred battery also will comprise withstand voltage separator; electrolyte is remained gel form by this separator; this not only allows the significantly compression (coming off thereby eliminated active material of positive electrode) of battery pile, and allows to move relevant problem while failing to have any sealing that protection opposing solvent moves (even in the case of bipolar) battery is operated to electrolyte not occurring.In particularly preferred method and apparatus, the separator of battery comprises the material that makes electrolyte gel, and therefore prevents bipolar leakage around.Most preferably, this separator is configured to bear compression stress, further to improve the operating parameter of battery.
Therefore, should be appreciated that, can manufacture so bipolar (being most preferably valve-regulated bipolar) lead-acid battery, wherein by withstand voltage separator separately, wherein electrolyte keeps the form of gel for the first bipolar electrode assembly and the second bipolar electrode assembly.From different angles, the battery of design will have the first withstand voltage separator and the second withstand voltage separator that engage with anode active material layers and the cathode active material bed of material respectively, and wherein the first withstand voltage separator and the second withstand voltage separator comprise the electrolyte of gel form.
The term " withstand voltage separator " using in this article represents to bear the mechanical compress of at least 30kPa in battery pack and does not produce loss thickness or its thickness loss is equal to or less than 10% separator.But in the most common situation, the pressure in the battery pack that preferred withstand voltage separator bears is at least 50kPa, and be even more generally at least 100kPa, wherein thickness loss is equal to or less than 10%, is more preferably equal to or less than 5%, and is most preferably equal to or less than 3%.Therefore, preferred separator will comprise the pottery or the polymeric material that are suitable for bearing this pressure.
In addition the separator particularly preferably being according to the inventive subject matter, can also keep electrolyte in contacting with the active material of battery.This ability preferably realizes by the form that electrolyte is remained to gel, and wherein all known gel preparations are all considered to be suitable for use herein.For example, suitable gel can be organic polymer or inorganic material.Of theme of the present invention particularly preferred aspect, electrolyte is fixed in the separator that forms micropore gel, thereby prevent the conductive bridge between bipolar positive pole and negative side, and it is suitable with cycle life (calendar and cyclic life) with the calendar of traditional lead-acid battery or than its better calendar and cycle life therefore to make bipolar cell have.
Among other suitable separators, ladies and gentlemen inventor finds, AJS(acid gelling (jelling) separator) (for example can business buying from Daramic Co., Ltd) not only can bear compression stress, and can stop electrolyte to be moved beyond boundary electrode.In fact, ladies and gentlemen inventor finds, uses this electrolyte to fix, can manufacture can continued operation (for example, in several charge/discharge cycle) and can not cause the bipolar lead-acid battery of the sealing of any unit in battery.Daramic AJS is synthetic microporous material, and this material is filled with 6 to 8wt% dryness pyrolysis silicon.At AJS by 1.28s.g.(proportion) electrolyte and when saturated, its silicon composition and the latter react and form gel.Therefore, design be that electrolyte becomes fixing by the Van der Waals force of Hydrogenbond or gel and/or by the hole in separator, make even in air, also not have seepage.The limited mobility of gel electrolyte prevents from occurring conductive bridge between bipolar positive pole and negative side.At United States Patent (USP) the 6th, other suitable materials are described in 124, No. 059, by quoting as proof incorporated herein this patent.But, aspect theme of the present invention replaceable, it should be noted, the material of dimensionally stable (can thickness loss be less than 10% and bear the material of the compression stress of 100kPa be more preferably less than 5% in the situation that) use in being all regarded as being suitable for herein with all combinations of gel electrolyte.
Should be appreciated that especially, another important advantage of AJS material is, under the bipolar compression stress conventionally imposing in lead-acid battery (and particularly VRLA), it has very limited size surrender (dimensional yield).From the conventional AGM(fiber heat absorbing glass felt of conventionally surrendering under compression stress) separator is different, and AJS material allows active material to be compressed to 30 to 100kPa and even higher desired pressure.
Although this compression is ideally for active material of positive electrode (PAM, conventionally being combined to form by plumbous oxide and basic lead sulphate) come off to slow down it, but unfavorable owing to having reduced the porosity of active material of cathode and thickness thereby target active material (NAM).In order to avoid at least some problems relevant to NAM compression, ladies and gentlemen inventor has been combined with skeleton structure, and NAM is with this structural engagement and have and contact with negative electrode surface.
Aspect theme of the present invention particularly preferred, skeleton structure comprises the grid of being made up of fiberglass gridding, and the thickness of grid equals the thickness of NAM.Then, cathode size is filled into even towards separator in the situation that on its surface in the cavity of grid (not having the excessive pasting (over-paste) of grid line).The compression stress that this design can protect NAM to avoid being applied by AJS.Although AJS and NAM have good interface, be stopped in and on NAM, apply power.Certainly, it should be noted, multiple replaceable skeleton structures are also suitable for, and these skeleton structures comprise material perforated panel and other porous and constitutionally stable (being generally non-conducting material).Most preferably, skeleton structure is made up of material stable in sulfuric acid and is had a required mechanical performance (for example thermoplastic, such as ABS, PP or PC).Under 100% charged state, framework material will have identical thickness with NAM conventionally, thereby as separator and be included in the supporter between the NAM in the void space of framework material.
With regard to suitable valve, it should be noted, all known valves and valve gear are all regarded as being suitable for use herein.For example, but particularly preferred valve and valve gear comprise unidirectional valve (duckbill valve), provide unidirectional release characteristic with the unit to single (preferably entering in ventilation collection channel), do not allow to enter in other unit from the gas of this unit or passage simultaneously.This valve has improved significantly the balance of voltage of unit between charge period.
Therefore, will be appreciated that, can simply and there is the VRLA that cost-benefit technique is manufactured bipolar cell and especially had high power density, this technique will not only significantly reduce the use of weight metal, and significantly eliminates electrolyte and climb (creep) and/or loss and the problem relevant to delamination and oxidative damage of oozing.
In addition, should be specifically noted that, the apparatus and method of design will not need reprocessing or special equipment conventionally, but can use the existing production equipment of great majority (if not all) and operation to manufacture.Once through assembling, battery can be filled electrolyte and experience forming process, this forming process can " in container " (for example, for bipolar relatively little VRLA battery being arranged in housing) or " in cell body " (in the situation that grid and active material form respectively in electrolysis tank) carry out.But, should be appreciated that, the battery proposing is in this article applicable to this two operations.Therefore, can simple and economic mode come manufacturing property and the obviously battery of raising of reliability.
In addition, should be appreciated that, due to the structure of lightweight, thereby can manufacture the battery that specific energy significantly improves.For example, use the apparatus and method of design, can manufacture valve regulation formula lead-acid battery, the content of the metallic lead of this battery and/or metallic lead alloy is equal to or less than 10g/Ah, more generally be equal to or less than 8g/Ah, and be generally equal to most or be less than 6g/Ah(under the state of electric discharge completely), and the specific energy content of this battery is 45Wh/kg at least, be more typically at least 50Wh/kg, and be generally at least 54Wh/kg most.Among the battery of other types, particularly preferred VRLA battery comprises that universal battery, SLI(start, light a fire, ignite) battery, UPS(uninterrupted power supply) battery and the battery (hybrid electric vehicle or battery of electric vehicle etc.) for transporting.In International Patent Application WO 2010/019291, WO2010/135313 and the WO2011/109683 determining in our common generation, disclose and be suitable for and the instruction content other aspects, structure and the method that use in combination that propose in this article, by quoting as proof incorporated herein all these patent applications.
It will be apparent to one skilled in the art that in the case of not deviating from inventive concept herein, except the modification of having described, also can have more modification.Therefore, theme of the present invention is not restricted except in the spirit of appended claims.In addition,, in the time interpreting both the specification and the claims book, all terms should be explained in wide in range as far as possible mode consistent with the context.Particularly, term " comprises (comprises) " and " comprising (comprising) " should be interpreted as mentioning parts, element or step in the mode of nonexcludability, represents that mentioned parts, element or step can exist or be utilized or combine with not specifically mentioned miscellaneous part, element or step.In the time that specification and claims are mentioned at least one in some object in the group of selecting free A, B, C.... and N composition, be interpreted as herein only needing parts in this group, but not A adds N or B adds N etc.

Claims (20)

1. for a dipole elements for bipolar lead-acid battery, comprising:
Monolithic lead/lead alloy composite insulating foil, has first surface and second surface and the lead/lead alloy fused interface between described first surface and described second surface;
Wherein said first surface is formed by lead, and wherein said second surface is formed by lead alloy; And
Be arranged on the non-conductive grid on described second surface, or the grid that use lead alloy to be formed by described second surface.
2. dipole elements according to claim 1, wherein, described lead/lead alloy composite insulating foil is the coated lead foil of lead alloy.
3. dipole elements according to claim 1, wherein, the thickness that described lead/lead alloy composite insulating foil has is equal to or less than 0.2mm.
4. dipole elements according to claim 1, wherein, described second surface is the spray deposited layer of palisade low pressure cold.
5. dipole elements according to claim 1, wherein, at least one in described first surface and described second surface further comprises Ti 4o 7particulate.
6. dipole elements according to claim 1, further comprise plumbous oxide skin(coating), the oxide skin(coating) of described lead comprises adhesive, and the oxide skin(coating) of described lead is arranged between at least one and the described second surface in described non-conductive grid and active material of positive electrode.
7. dipole elements according to claim 1, further comprises polymer frame (106), and described monolithic lead/lead alloy composite insulating foil is engaged to described polymer frame by strengthened sealing agent.
8. manufacture, for a method for the dipole elements of bipolar lead-acid battery, comprising:
Build monolithic lead/lead alloy composite insulating foil, described monolithic lead/lead alloy composite insulating foil has first surface and second surface and the lead/lead alloy fused interface between described first surface and described second surface;
Wherein said first surface is formed by lead, and wherein said second surface is formed by lead alloy; And
Make in the following manner grid be engaged to described lead/lead alloy composite insulating foil: on described second surface, arrange non-conductive grid, or by being formed described grid by lead alloy to form at least partly described second surface.
9. method according to claim 8, wherein, the described plumbous lead foil as having the first thickness is provided, wherein, provide described lead alloy as the lead alloy-foil with the second thickness, and wherein, at least one in described the first thickness and described the second thickness realized by the technique except being rolled this at least one.
10. method according to claim 9, wherein, the step of structure is by realizing with the coated lead foil of lead alloy-foil.
11. methods according to claim 8, further comprise the step that forms plumbous oxide skin(coating), the oxide skin(coating) of described lead comprises adhesive, between at least one and the described second surface of the oxide skin(coating) of described lead in described non-conductive grid and active material of positive electrode.
12. methods according to claim 8, wherein, the step of structure realizes by low pressure cold is spray deposited.
13. methods according to claim 8, wherein, at least one in described lead and described lead alloy further comprises Ti 4o 7particulate.
14. methods according to claim 8, further comprise and use strengthened sealing agent that described monolithic lead/lead alloy composite insulating foil is installed to the step in polymer frame.
15. 1 kinds of bipolar lead-acid batteries, comprising:
Anode end plate (102) and cathode end plate (104) and be arranged on described anode end plate and described cathode end plate between multiple bipolar plates (n);
Wherein, at least one in described bipolar plates comprises framework (106), monolithic lead/lead alloy composite insulating foil (110) is installed in described framework hermetically by strengthened sealing agent (108), wherein, described monolithic lead/lead alloy composite insulating foil has first surface (112), second surface (114) and the lead/lead alloy fused interface (116) between described first surface and described second surface;
Wherein said first surface is formed by lead, and wherein said second surface is formed by lead alloy;
Be arranged on the non-conductive grid (140) on described second surface, or the grid (140) that use lead alloy to be formed by described second surface;
Wherein, described strengthened sealing agent comprises at least one in silica flour and silane; And
Be arranged on the active material of positive electrode (130) on described second surface and be arranged on the active material of cathode (120) on described first surface.
16. bipolar lead-acid batteries according to claim 15, wherein, described lead/lead alloy composite insulating foil is the coated lead foil of lead alloy, the thickness that the coated lead foil of described lead alloy has is equal to or less than 0.2mm.
17. bipolar lead-acid batteries according to claim 16, further comprise plumbous oxide skin(coating), the oxide skin(coating) of described lead comprises adhesive, and the oxide skin(coating) of described lead is arranged between at least one and the described second surface in described non-conductive grid and active material of positive electrode.
18. bipolar lead-acid batteries according to claim 15, wherein, described second surface is the spray deposited layer of palisade low pressure cold.
19. bipolar lead-acid batteries according to claim 18, wherein, at least one in described lead and described lead alloy further comprises Ti 4o 7particulate.
20. bipolar lead-acid batteries according to claim 15, wherein, described strengthened sealing agent comprises silica flour and silane, and wherein, described framework and the framework laser welding that at least one is extra.
CN201280034366.XA 2011-05-13 2012-05-11 LPCS formed composite current collector and methods therefor Pending CN103814463A (en)

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