CN102625957A

CN102625957A - Metal-air battery with siloxane material

Info

Publication number: CN102625957A
Application number: CN2010800375178A
Authority: CN
Inventors: 特吕格弗·伯查特; 若菲奥·阿尔格拉尼-希盖蒂; 卡特林·维耶·迪特·比勒
Original assignee: REVOLT Tech Ltd
Current assignee: REVOLT Tech Ltd
Priority date: 2009-06-30
Filing date: 2010-06-30
Publication date: 2012-08-01
Also published as: WO2011001287A2; EP2449613A2; WO2011001287A3

Abstract

A metal-air battery includes an air electrode and a siloxane material proximate to or incorporated within the air electrode. A method is also disclosed that includes providing a siloxane material, providing a transfer layer, and co-extruding the siloxane material with the transfer layer to form a siloxane membrane. The siloxane membrane may be used in a metal-air battery.

Description

The metal-air battery that contains silicone compositions

The cross reference of related application

The application requires to enjoy the U.S. Provisional Patent Application No.61/230 that submitted on July 31st, 2009,550 priority and rights and interests.The application also requires to enjoy the U.S. Patent application No.12/826 that submitted on June 29th, 2010; Priority and the rights and interests of International Application PCT/US10/40445 that on June 29th, 383 and 2010 submitted to; Wherein each said application all requires to enjoy the U.S. Provisional Patent Application No.61/221 that submitted on June 30th, 2009; The U.S. Provisional Patent Application No.61/340 that on March 15th, 998 and 2010 submitted to, 293 priority and rights and interests.Whole disclosures of each application described in this section are all incorporated the application into citation form.

Technical field

The application relates to the field of battery and battery component basically.More specifically, the application relates to the purposes of technology, material and structure/composition, in order to the inside chemical reaction of metal-air battery and the interaction between the external environment condition are managed.Disclosed idea also further is applied to metal-air fuel cell among the application.

Background technology

Metal-air battery comprises negative metal electrode (for example, zinc, aluminium, magnesium, iron, lithium etc.) and has the positive electrode (being considered to be used for the air electrode of said battery usually) that oxygen reaction is had the loose structure of catalytic performance.Electrolyte is used for keeping the high ionic conductivity between said two electrodes.For the metal-air battery (promptly having alkaline electrolyte) of alkalescence, said air electrode is processed by thin, polymeric material porous and that combine carbon-coating (for example, polytetrafluoroethylene) usually.In order to prevent battery short circuit, between anode and negative electrode, assemble separator.

In said metal-air battery discharge process, in air electrode, be converted into hydroxide ion from the oxygen in the atmosphere.Reaction in said air electrode comprises the generation of oxygen reduction, electronics consumption and hydroxide ion.To the migration of metal negative electrode, the metal of negative electrode forms oxide and discharges electronics in said metal negative electrode generation oxidation said hydroxide ion through electrolyte.In secondary (being rechargeable) metal-air battery, charging process is meant that hydroxide ion is converted into oxygen in said air electrode, discharges electronics.In said metal electrode, metal oxide or ion reduction form metal, simultaneously consume electrons.

Metal-air battery provides huge energy storage benefit.For example, the energy storage density of metal-air battery is the several times of lithium ion battery, and uses on the earth abundant and metal (for example, zinc) cheaply as energy-accumulating medium.This technology comparatively safe (non-combustible) and environmental friendliness (nontoxic and can use recyclable materials).All be prone to material and the method obtained in the U.S. and other area because this technology has been used, therefore can alleviate dependence scarce resource (like oil).

Metal-air battery is the part open system, and wherein air electrode uses the oxygen from surrounding environment.A challenge about such open system is environmental condition (like humidity) and carbon dioxide (CO ₂) existence possibly impact said battery, and possibly seriously shorten the useful life of said battery in this case.Possibly limit the possible application that to use common metal-air cell like this.

Observed humidity low relatively in the surrounding environment (for example, relative humidity is less than 45%) and possibly cause that electrolyte can not expectedly kill.Killing of said metal-air battery causes Ohmic resistance to increase, and the loss that thereupon brings power of battery density and efficient.And, to follow to be exposed to relatively for a long time in the dry environment, electrolyte possibly killed fully, thereby causes irremediable batteries lose.

Further observed when the humidity in surrounding environment when high relatively (relative humidity is higher than 45%), electrode possibly overflow.For example, under the high relatively situation of humidity, moisture possibly get in the metal-air battery, cause concentration of electrolyte decline and volume is increased.Therefore the discharge performance of said metal-air battery will descend, and electrolyte possibly leak simultaneously.

Reported CO ₂Existence negative effect that the performance of metal-air battery and life-span are caused.CO has been proposed ₂Possibly cause closing of air electrode pore space structure, and CO ₂The loss that also possibly cause electrical conductance is (for example through using CO ₃ ^2-Replace OH ^-(hydroxide) ion).Though CO ₂Possibly get into the metal-air battery from external environment condition, but also propose CO ₂Maybe by said metal-air battery itself within it portion produce the oxidation of carbon loaded article (for example, through).

In order to handle about the problem to metal-air battery and the undesirable environmental condition of fuel cell, other technical scheme has advised using external system (for example, fan, valve, humidifier, CO ₂Washer etc.), to be used for controlling the influence that external environment condition possibly brought.The conspicuous shortcoming of such scheme comprises the complexity that increased cost and system, increased size (therefore providing lower effective energy density) and such scheme can not be suitable for the fact (for example, an example is not hope to use the external fan that is used for the hearing aids battery) in some purposes, used.

Summary of the invention

Structure/feature for the battery that the improvement of handling one or more the problems referred to above is provided and this battery is benefited.Assembling is used for managing the inside chemical reaction of said battery and interactional material and the structure between the external environment condition also benefited in metal-air battery.Provide and have more the metal-air battery of long life and also benefit.The metal-air battery that is provided for various uses (including but not limited to extensive and small-scale application) is benefited equally.Other advantageous characteristic of disclosed this battery will be conspicuous for those those skilled in the art that read disclosure text in this application.

Description of drawings

Fig. 1 is the perspective view according to the metal-air battery of the button cell monomeric form of an exemplary embodiment;

Fig. 2 is the cutaway view along the line 2-2 of the metal-air battery shown in Fig. 1;

Fig. 3 is the cutaway view that is similar to the metal-air battery shown in Fig. 1;

Fig. 4 is the cutaway view that is similar to the metal-air battery shown in Fig. 1;

Fig. 5 is the cutaway view that is similar to the metal-air battery shown in Fig. 1;

Fig. 6 is the perspective view according to the metal-air battery of the prismatic battery monomeric form of another exemplary embodiment;

Fig. 7 is the cutaway view along the line 7-7 of the metal-air battery shown in Fig. 6;

Fig. 8 is the detailed section view along the line 8-8 of the metal-air battery shown in Fig. 7;

Fig. 9 is the part decomposition diagram according to the flow battery of an exemplary embodiment;

Figure 10-the 18th shows the curve chart like a plurality of result of experiment of the application's description, and it is intended to be presented at and uses the benefit of selecting material like the oxygen of siloxanes in the metal-air battery.

Embodiment

According to an exemplary embodiment, metal-air battery or battery cell are assembled into demonstration as other compositing factor (for example, the CO that is exposed to steam (for example, relative humidity) and its surrounding environment ₂) time the stability and the performance of raising.Said metal-air battery is configured to keep moisture basically when ambient humidity is hanged down, stop when ambient humidity is high and overflow and do not sacrificing basically under the situation of these benefits, effectively conversion between low-humidity environment and high humidity environment.Also said metal-air battery being configured to reduce simultaneously maybe be by being exposed to CO ₂The unexpected effect that causes.According to an exemplary embodiment; Can one or more materials and structures/assemblies be incorporated in the metal-air battery; In order to be provided the useful life of prolongation under the situation of the high current density of not abandoning said battery, thereby said battery is being used widely in the purposes.

Said metal-air battery can have the configuration of any expection; Include but not limited to coin (coin) or button cell monomer (button cell), prismatic battery monomer, cylindrical battery monomer, elliptical cells monomer, flow battery monomer etc., maybe can have the configuration of fuel cell.Further, said metal-air battery can be once (disposable, single uses) or secondary (rechargeable) battery.

With reference to Fig. 1-2, according to an exemplary embodiment, diagram the metal-air battery 10 of coin or button cell monomeric form.According to an exemplary embodiment, said battery 10 comprises oxygen selective membrane (being meant " silicone film " among the application), electrolyte 18, the separator 20 of metal electrode 12, air electrode 14, silicone film 16 forms and is shown as the closing structure of housing 22.

According to an exemplary embodiment, said battery 10 is zinc-air batteries.According to other exemplary embodiment, said battery 10 can use other metal to replace zinc, includes but not limited to aluminium, magnesium, iron, lithium, cadmium and/or metal hydride.The example of metal hydride material comprises AB ₅Or AB ₂Type structure, wherein AB _xForm is meant the ratio of elements A and element B.For AB ₅Type, A can be the composition of La, Ce, Pr and Nd, for AB ₂Type, A can be the composition of Ti, Zr or Ti and Zr.For above-mentioned these two kinds of structure types, B can be the composition of Ni, Mn, Co, Al and Fe.

Further with reference to Fig. 2, according to an exemplary embodiment, said housing 22 (for example, casing, container, body etc.) be shown as comprise at the bottom of the shell 23 with cap 24.Make seal 25 (for example, the sealed nylon pad of moulding etc.) basically form in or be arranged on shell at the bottom of between 23 (for example, open jar etc.) and the cap 24 (for example, shell cap, valve jacket, overhead guard etc.), in order to help to keep at the bottom of the shell 23 and the relative position of cap 24.Seal 25 also helps prevent unexpected contact (for example, causing short circuit) and/or reveals.Said cap 24 comprises one or more openings 26 (for example, hole, aperture, slit, passage etc.), and it is positioned at the relative first 27 of second portion 28 of basic and housing 22.Said metal electrode 12 is shown as and in housing 22, is positioned at or is in close proximity to second portion 28.Said air electrode 14 is shown as and is positioned at or is in close proximity to first 27, and with metal electrode 12 segment distance is arranged.Said opening 26 makes between the oxygen (for example, air) in air electrode 14 and the environment and interacts.Said environment can be that extraneous air maybe can import or one or multiply air stream through opening 26.According to other exemplary embodiment, said housing can have any a plurality of shape and/or configuration.According to other exemplary embodiment, can use any a plurality of opening with any multiple shape, size and/or configuration.

According to an exemplary embodiment, separator 20 is basic setup film or films (for example, plastic film, ion-selective membrane etc.) thin, porous between metal electrode 12 and air electrode 14.Said separator 20 is configured to through between metal electrode 12 and air electrode 14, providing electricity to isolate the short circuit that prevents battery 10.In the embodiment of certain exemplary, said separator 20 comprises or processed by polypropylene or polyethylene, wherein said polypropylene or polyethylene has been treated to have to be configured to be used for the hydrophilic pores of filling electrolyte 18.In other exemplary embodiment, said separator can be suitable for preventing battery 10 short circuits and/or be comprised that the material of hydrophilic pores processes by any.

In an exemplary embodiment, said electrolyte 18 is shown as and is set at basically between metal electrode 12 and the air electrode 14.Electrochemical reaction in battery 10 does not consume electrolyte 18 (for example, potassium hydroxide (" KOH ") or other ionic conduction medium hydroxy), but said electrolyte is configured in discharge process, make hydroxide ion (OH ^-) be transported to the metal electrode 12 from air electrode 14, and be under the situation of electrical secondary system at battery 10, hydroxide ion is transported to the air electrode 14 from metal electrode 12.Electrolyte 18 is arranged in some holes of some holes and air electrode 14 of metal electrode 12.According to an exemplary embodiment, said electrolyte can partly be absorbed into said air electrode, in order to the three phase region that has the high-specific surface area that is used for air electrode catalyst (three-phase zone) to be provided.Can also with said electrolyte uniform distribution in said metal electrode,, help prevent the inhomogeneous CURRENT DISTRIBUTION in the metal electron carrier along with the surface of reaction from said zinc electrode moves through.According to other exemplary embodiment, the distribution of said electrolyte and position can change.According to the embodiment of certain exemplary, the composition of said electrolyte can help prevent and/or manage the CO in said battery cell ₂Generate.

According to an exemplary embodiment, said electrolyte 18 is the alkaline electrolytes that are used for keeping high ionic conductivity between said metal electrode and the said air electrode.According to the embodiment of certain exemplary, said electrolyte can be any electrolyte (for example, NaOH, LiOH, KOH etc.) that has high ionic conductivity and/or oxygen reduction/separate out and burning/reduction reaction had high reaction rate.According to other exemplary embodiment, said electrolyte can comprise that salt solution or other provide the salt based sols (for example, being used for navigation/military applications etc.) of sufficient conductivity for the target purposes.Other exemplary embodiment according to another, said electrolyte can be organic group, water base or organic group and water base combination.

According to an exemplary embodiment, said metal electrode and electrolyte are combined (for example, mixing, stirring etc.).The combination of said metal electrode and electrolyte can form thickener, powder, particle, slurry etc.

Said air electrode 14 comprises and has one or more layer of different nature and current-collector (for example, wire netting, it also helps to stablize said air electrode).In the embodiment of certain exemplary, a plurality of air electrodes can be used for a battery.In some of these exemplary embodiments, at least two scheme and/or compositions in the said air electrode with different interlayers.In other exemplary embodiment, current-collector is not wire netting current-collector (for example, a foam current-collector).

With reference to Fig. 2, according to an exemplary embodiment, said air electrode 14 comprises gas diffusion layers 30 (being abbreviated as " GDL " sometimes) and active layer 32 (being abbreviated as " AL " sometimes).

Said gas diffusion layers 30 is shown as the opening 26 that is arranged on the second portion 28 that is in close proximity to housing 22, basically between active layer 32 and gas diffusion layers 30.According to an exemplary embodiment, said gas diffusion layers 30 comprises a plurality of holes 33.With said gas diffusion layers 30 be configured to porous with hydrophobic, make gas flow through described hole as being used for preventing the barrier that flow of liquid is crossed.In the embodiment of certain exemplary, oxygen reduction and evolution reaction occur in the close-connected one or more air electrode layer of this layer in.

According to an exemplary embodiment, with active layer 32 basic setups between the opening 26 of the second portion 28 of metal electrode 12 and housing 22.Said active layer 32 has the diplopore hole structure that comprises hydrophobic hole 34 and hydrophilic hole 36.Said hydrophobic hole helps to realize the oxygen diffusion of two-forty, and hydrophilic hole 36 makes sufficient electrolyte permeability to the conversion zone that is used for oxygen reaction (for example, through capillary force).According to other exemplary embodiment, said hydrophilic hole can be arranged in the layer of separating with said active layer, and for example, oxygen is separated out layer (being abbreviated as " OEL " sometimes).Further, can other layer or material be included in the said air electrode/go up or coupled.For example, gas selects material to be included in the pore space structure.

Said air electrode 14 can comprise the combination of pore-forming material (pore forming material).In the embodiment of certain exemplary; The hydrophily hole of said air electrode is configured to be provided for catalyst or catalyst composition carrier material (for example; Through help catalyst is anchored in the material (reaction site material) of reactive site) (for example, the cobalt on the carbon, the silver on the carbon etc.).According to an exemplary embodiment, pore-forming material comprises that the carbon of activation or graphite (for example, have greater than 100m ²G ^-1The BET surface area).According to other exemplary embodiment, can use pore-forming material or other material like the high-specific surface area pottery.The CO that causes by those carrier materials when more specifically, using the carrier material (support material) (or pore-forming material) of non-carbon back to avoid discharging with high voltage (for example, being higher than 2V) ₂Form.An example is to use the silver (Ag) of high-specific surface area; Said silver can be blue Buddhist nun Ag, and wherein said high-specific surface area becomes the element of alloy to obtain by elimination from silver alloy (for example, Ag-Zn alloy).Other exemplary embodiment according to another, any material stable in aqueous slkali, conductivity and that can form the pore space structure that is configured to make electrolyte and oxygen infiltration can be used as the pore-forming material of air electrode.According to an exemplary embodiment, the internal structure of said air electrode can be used for managing humidity and CO ₂

Further,, current-collector 39 is arranged between the gas diffusion layers 30 and active layer 32 of air electrode 14 according to an exemplary embodiment with reference to Fig. 2.In the exemplary embodiment that shows, the position of said current-collector 39 has promoted the assembling of silicone film 16 and air electrode 14.According to another exemplary embodiment, can said current-collector be arranged on (for example, when comprising non-conductive layer in the said air electrode or not containing gas diffusion layers) on the said active layer.Said current-collector 39 can be formed by any suitable electrical conductance material.

Said air electrode 14 also comprises composition 42 and/or other additive (for example, ceramic material, metal in height ratio surface area or in alkaline medium stable alloy etc.) of composition 40, catalyst or the catalyst of adhesive or adhesive.According to an exemplary embodiment, adhesive 40 is included in said active layer 32 and the gas diffusion layers 30, catalyst 42 is included in the said active layer.According to other exemplary embodiment, can said adhesive, catalyst and/or other additive-package be contained in any layer or all layers of said air electrode, or be not comprised in any layer of said air electrode.In other exemplary embodiment, said air electrode can not comprise composition and/or other additive of composition, catalyst or the catalyst of one or more adhesives or adhesive.

Said adhesive 40 is intended to provide for air electrode 14 mechanical strength of enhancing, and keeps the high relatively diffusion rate (for example, comparing with the air electrode of more traditional common use polytetrafluoroethylene (" PTFE ")) of oxygen.Said adhesive 40 can also produce hole in order to realize hydrophobicity in air electrode 14.According to an exemplary embodiment, said adhesive comprises the PTFE with other adhesive bond.According to other exemplary embodiment; The polymeric material that also can use other (for example; Thermoplastic; Like polybutylene terephthalate or polyamide, Kynoar, silica-based synthetic rubber, like dimethyl silicone polymer or elastomeric material, like ethylene-propylene rubber and/or its composition).

According to an exemplary embodiment, said adhesive 40 provides is enough to mechanical strength that air electrode 14 is formed in many ways, includes but not limited to push, press mold, punching press, use electric hot plate, calendering etc. a kind of or combine.The mechanical strength of this enhancing also makes air electrode 14 form any multiple shape (for example, tubular form etc.).The ability that makes air electrode form any kind of shape can aid in like bluetooth earphone and use or require to use the manufacturing of the metal-air battery (for example, AA type battery, AAA type battery, D type battery etc.) of tubular cell aspect.

Catalyst 42 is configured to be used to improve the reaction rate of oxygen reaction.According to the embodiment of certain exemplary, used reactive metal or oxygen metal salt (for example, Pt, Pd, Ag, Co, Fe, the MnO of catalysis ₂, KMnO ₄, MnSO ₄, SnO ₂, Fe ₂O ₃, CoO, Co ₃O ₄Deng).According to an exemplary embodiment, can use combination more than a kind of active material of catalysis.

In an exemplary embodiment, said battery 10 is secondary cell (for example, rechargeable), and said air electrode 14 is bifunctional air electrodes.In this exemplary embodiment, except the composition of above-mentioned catalyst and/or catalyst, the catalyst or the carbon monoxide-olefin polymeric that can also use extra having the ability that oxygen is separated out.According to the embodiment of certain exemplary, catalyst can include but not limited to WC, TiC, CoWO ₄, FeWO ₄, NiS, WS ₂, La ₂O ₃, Ag ₂(promptly one group of general formula is AB for O, Ag, spinelle ₂O ₄Oxide, wherein A represents bivalent metal ion such as magnesium, iron, nickel, manganese and/or zinc, B represents trivalent metal ion, like aluminium, iron, chromium and/or manganese) and the perovskite material (promptly one group of general formula is AXO ₃Oxide, wherein A is a bivalent metal ion, like cerium, calcium, sodium, strontium, lead and/or various rare earth metal, X is the tetrahedron metal ion, like titanium, niobium and/or iron, wherein all ions in this group all with the XO that forms interconnective octahedra framework ₃Atom has same basic structure).According to other exemplary embodiment, said battery 10 can be primary cell (for example, single use, disposable use etc.).

According to an exemplary embodiment, said air electrode 14 forms in three step process.Each layer of multi-layer air electrode 14 forms respectively.The first step mixes the element of every layer expection.Under the influence of mechanical energy, heat energy or mechanical energy and heat energy, said pore-forming material, catalyst, jointing material and/or other additive are mixed.In this step process, be contemplated to said material is distributed well.If said mixture contains hydrophobic adhesive, this then adhesive forms the three-dimensional netted thing that powder is connected to agglomerate.Usually extruding of said mixture or agglomerate and/or calendering are become the stratiform thing then.In second step, utilize heat and/or pressure (for example, through calendering and/or punching press) will have one or more layers (for example said gas diffusion layers and said active layer) of different nature usually and combine.The 3rd step, with said current-collector punching press or roll into said combination layer (for example, become active layer, become gas diffusion layers, between active layer and gas diffusion layers etc.).According to other exemplary embodiment, can utilize other technology that said air electrode is formed.

According to an exemplary embodiment, in order to form said air electrode 14 the layer the first step in used dried hybrid technique.In dried hybrid technique, the form of said layer all the components with dry powder mixed.According to an exemplary embodiment, drying process has the PTFE that particle size is lower than 1mm with use and separates out layer as adhesive and additional pore-forming auxiliary agent (like carbonic hydroammonium) in order to structure gas diffusion layers and/or oxygen.

According to other exemplary embodiment, can use wet-mixed technology to substitute.In wet-mixed technology, one or more solvents are added in the incipient stage or in mixed process, or replacedly, can use one or more compositions with the form of disperseing or suspending.Usually subsequently said solvent is removed (for example, after said hybrid technique directly or in the preparation technology of back) (for example, through use heating/drying process).According to an exemplary embodiment, the wet processing use is suspended in PTFE waterborne and separates out layer as adhesive with like the pore-forming auxiliary agent of carbonic hydroammonium in order to structure oxygen.

Other exemplary embodiment according to another can utilize diverse ways to prepare various single layers.For example, plurality of layers can be utilized dried hybrid technique preparation, and other the wet processing that utilizes prepares.According to another other exemplary embodiment; Announce WO 2005/004260 (its disclosure is incorporated the application into citation form) according to PCT; Can dry process and wet processing combined to be used for different layers, and this preparation can be carried out on continuous production line.

Can oxygen be separated out layer is included in the said air electrode.According to an exemplary embodiment, said oxygen is separated out layer can comprise the adhesive of 2-15% by weight and the catalyst of 25-65% by weight.The residue that said oxygen is separated out layer possibly comprise other additive of high specific area carbon and/or graphite material and some.

The exemplary embodiment of utilizing dried hybrid technique to form the method for air electrode will be discussed below.According to this method; The preparation of said active layer has used by weight 15% PTFE (for example; As adhesive, available from (the Lawrence Industries of Thomasville of Lao Lunsi factory of North Carolina state Thomas Wei Er; NC) and particle size less than the powder type of 1mm), 70% high specific area carbon is (for example by weight as pore former; XC 500 available from card Bert (Cabot)) and as catalyst by weight 15% manganese sulfate (for example, available from the MnSO of French Prolabo ₄) mixture.With said adhesive, pore former and catalyst mix together (for example, in single-axle turning formula mixer with the rotating speed of about 1000rpm) to form basic mixture uniformly.Said mixture is heated to the temperature of expection.When said mixture of powders reaches desired temperature, this powder is milled into agglomerate.For example, can said mixture be heated to desired temperature and its rotating speed with about 1000rpm was milled 1 hour with 90 ℃ or about 90 ℃, perhaps said mixture is heated to lower initial temperature, but mills (for example, 10000rpm) with high rotating speed.Said agglomerate is struck out fragment of brick (for example, the thick fragment of brick of about 2mm) and it is rolled flakiness (for example, the about 0.5mm of thickness).According to other exemplary embodiment, can be according to certain material that uses and other factors different, can change temperature, the speed of milling and number of times and other parameter.

The formation of said gas diffusion layers used as adhesive by weight 25% PTFE mixture (for example; Available from the Lao Lunsi factory of North Carolina state Thomas Wei Er, particle size powder type less than 1mm) and as pore former 75% sodium acid carbonate is (for example by weight; Available from Sigma Ao Ruiqi company (Sigma-Aldrich, Inc.) and particle size be lower than 10 μ m).In single-axle turning formula mixer, (for example, carried out 2 hours), said adhesive and pore former are mixed to form agglomerate with desired temperature (for example, being usually less than 40 ℃ maximum temperature) with 1500rpm.Said agglomerate is struck out fragment of brick (for example, about 2mm thickness) and rolls flakiness (for example, thickness is about 1mm) then.

The exemplary embodiment of utilizing wet-mixed technology to form the method for air electrode will be discussed below.According to this method; The preparation of said active layer has utilized that 15% PTFE (being dispersed in the water by weight in the suspension of 60% PTFE containing) is (for example by weight as adhesive; Available from (the Sigma-Aldrich of Sigma Ao Ruiqi company; Inc.)), as pore former by weight 65% the high specific area carbon XC 500 of card Bert (for example, available from) and as catalyst by weight 20% manganese sulfate (for example, available from the MnSO of French Prolabo ₄).With two kinds of catalyst mix in said high specific area carbon and the water.Respectively, said PTFE suspension is mixed with water.Then, join said PTFE suspension in the said carbon suspension liquid and mix and form the pulpous state agglomerate.Afterwards, said slurry is mixed (for example, in ultrasonic bath 30 minutes) and subsequent drying (for example, under 300 ℃, carrying out 3 hours) to remove any surfactant.The naphtha Shellsol D40 of London shell chemical (for example, available from) that makes said dried mixture caking then and add the low boiling hydrogen treat is to form thickener.At last, said thickener is rolled straticulation to form active layer.

According to an exemplary embodiment, can sharp use the same method forms hydrophobic gas diffusion layers.In this layer, only use high specific area carbon (by weight 65%) and PTFE (by weight 35%).Final layer relative thin (for example, the about 0.8mm of thickness).

Then, said active layer and said gas diffusion layers are combined (for example, through calendering) to form said air electrode (for example, gross thickness is 0.8mm).At last, current-collector (for example, nickel screen) is stamped between the active layer and gas diffusion layers in the air electrode (for example, under 70 crust (bar) and about 80-320 ℃, and being preferably 300 ℃).Can said air electrode dry (for example, under 70 ℃, carrying out 8 hours) be used for constructing the weep hole of gas diffusion layers and be used for therefrom shifting out carbonic hydroammonium then.

According to the exemplary method of other formation and structure air electrode and its layer, said layer can form has all thickness and/or composition.And, can said layer be combined through any multiple method well known in the art.

Return with reference to Fig. 2; According to an exemplary embodiment; The film that is shown as silicone film 16 (for example, film, layer etc.) is set to be adjacent to air electrode 14 (promptly being positioned at the gas diffusion layers 30 that is adjacent to air electrode 14 basically, between the opening 26 of gas diffusion layers 30 and housing 22).Said silicone film 16 is selective membranes, and it makes the gas like oxygen pass through this film, but as the damp-proof layer (moisture barrier) that stops moisture to get into said battery and therefrom leave.Help to keep the water balance in the battery 10 so conversely.

Through preventing or killing of the said electrolyte that slows down and overflowing of said air electrode, can silicone film 16 be constructed performance and the useful life that is used for improving battery 10.Silicone film 16 is configured to prevent that the moisture from electrolyte 18 from (for example leaving battery 10; When relative humidity be lower than 45% relative humidity or some other will cause the relative humidity of water loss the time), the power density of the said battery that takes place when therefore helping to have avoided electrolyte to kill and the loss of efficient.Simultaneously also with silicone film 16 be configured to prevent the overflowing of battery 10 (for example, when relative humidity be higher than 45% or some other will cause overflowing relative humidity the time), help prevent electrolyte 18 therefrom to reveal.When said electrolyte was revealed from said battery, the concentration of said electrolyte (ratio between electrolyte and the Zn) reduced, and has caused the serious decline of the ability of discharge performance and longer-term storage metal-air battery.In this method, said silicone film 16 helps to have stablized battery 10, improved its performance and prolonged its life-span, has opened up the potential commercial use of metal-air battery widely.

Simultaneously also silicone film 16 is configured to prevent CO ₂Opening 26 through said housing gets into.Known CO ₂Consumed the OH in the electrolyte ^-, increased evaporation of water and formed non-hygroscopic crystal.Through preventing CO ₂Get into housing 22, silicone film 16 helps to have safeguarded electrolyte 18 and has kept the water balance in the battery 10.

Said silicone film 16 thickness are about 0.1-200 μ m (but can be bigger according to other this thickness of exemplary embodiment; For example; The thickness of this film also can be for 1-50 μ m, be less than or equal to 10 μ m, be less than or equal to 6 μ m, be less than or equal to 3 μ m or other any as under this environment, can suit suitable thickness); And having suitable mechanical strength, manufacturing approach realizes its production in order to use widely.The thickness of said silicone film is big more, and its expection prevents CO ₂Be transported in the battery 10 with steam and/or the performance that from battery 10, transports out good more (for example, because long the evolving path).Can change the thickness of silicone film 16 according to the desired use difference of said battery, because it is directly proportional with the current density that can be used for battery to be contemplated to the thickness of film/film of use.For example, for the application of using low relatively current density (for example, lower power application, as be used for the battery of wrist-watch, transducer, RFID label (tag) etc.), can the big relatively film of used thickness (for example, maximum current density being provided is 2mA/cm ²The film of 100 μ m).Require in the application (for example, high power applications is like camera, bluetooth applications, mobile phone etc.) of high current density at other, possibly hope to use the silicone film of low thickness (for example, to be higher than under the voltage of 1V, can to provide maximum current density greater than 50mA/cm ²The film of 3 μ m).

Different application has different current density requirements, and therefore can select the current density of thickness to realize expecting of selective membrane.This names a person for a particular job and is described in more detail below with reference to Figure 17.According to other exemplary embodiment, can use any have be enough to the selective membrane material that stable metal-air cell keeps the thickness of estimated performance level/diffusion coefficient combination simultaneously.

According to an exemplary embodiment, the surface area that increases said air electrode can use thicker but still silicone film that make said battery realization prospective current density.In a word, bigger surface area produces higher chemical speed, because current density (mA/cm ²) confirm through the thickness of silicone film, and electric current (mA) is confirmed by the surface area of current density that can be used for this purposes and air electrode.These ideas can be used for the cell designer of raising of purposes of the selective silicon siloxane film of said battery through the battery performance utilization that reaches out for certain level and come balance.

Said silicone film 16 also allows to use than to do to change the opening 26 on the bigger and/or more housing 22 of also passable normal conditions (for example to be used for the oxygen entering; Because 16 pairs of silicone films are killed and are overflowed useful protection, when using silicone film 16, more air are got in the said battery).Make battery 10 operate in higher electric current like this, do not have oxygen diffusion restriction and the situation of killing speed that improves under carry out.Like an embodiment, a coin battery monomer (for example, 675 types) zinc-air battery can show diffusion restriction at about 30mA owing to limited oxygen inlet.Provide hole to provide the pulsating current that does not have under the diffusion restriction situation greater than 100mA greater than the 5mm diameter.Further, in the design of housing 22 (for example, body, container etc.), obtain greater flexibility and the oxygen better uniformity that distributes like this and (be accompanied by O ₂Dividing potential drop spreads all over whole surface, and reaction rate equates, and reaction more uniformly provides Zn and air electrode better stable).Through allowing the bigger and/or more opening of said housing, the current density of said battery does not receive the restriction through the oxygen entering of said opening, but receives the restriction through the oxygen delivery of said selective membrane.Along with said selective membrane has high transportation performance for oxygen, so also opened the possibility that metal-air battery is used for higher power application (for example, notebook computer, car etc.).

According to an exemplary embodiment, said silicone film 16 does not comprise carrier layer (for example, pore film, non-woven etc.), because silicone film 16 thickness own are that given purposes provides enough stability and structural intergrities.Operability of improving in the battery production process and the repellence that pin hole is formed also are provided so simultaneously.For thin silicone film (for example, thickness is lower than the film of about 20 μ m), use carrier layer possibly have some advantages.

The mechanical strength of the raising of said silicone film also provides and has formed and methods for using them widely.As will carry out in greater detail below, the formation technology of said silicone film can comprise press mold, punching press and/or other technology or with the combination of technology out of use or that use with thin and/or more weak film or film.And the formation and methods for using them of said raising is used in widely in the purposes battery 10.

According to an exemplary embodiment, said silicone film 16 is processed by the siloxanes Geniomer

80 available from the Wa Ke group (Wacker Chemie AG) of Munich, Germany.Geniomer

the 80th, silicones and the product of gathering silica liquid, it has formed waterproof mould release membrance (water-repellent release film).These films have the better compatibility that can obtain than dimethyl silicone polymer and with a lot of organically-modified comparable viscosity of silica liquid of gathering.For Geniomer

80, be about 6.2 * 10 for the oxygen diffusion coefficient of the thick film of 10 μ m ^-11m ²/ s.According to other exemplary embodiment, can use other silicone compositions (for example, available from Folex Imaging, Celfa AG, the siloxanes of CM Celfa Membranes etc.).For example, the oxygen diffusion coefficient for the thick film of the 20 μ m that prepared by the siloxanes available from Celfa is about 5.7 * 10 ^-11m ²/ s.

Although described a particular using the battery of silicone film,, can make amendment to the composition and/or the location of silicone film according to other exemplary embodiment.For example, according to an exemplary embodiment, conduction in the time of can the top that said silicone film is formed in said gas diffusion layers being used.According to an exemplary embodiment, can material (for example, particle form) be joined in the silicone film so that silicone film plays a role as the current-collector of cell cathode.Exemplary material includes but not limited to carbon (for example, graphite) particle and metallic particles.According to an exemplary embodiment, can be through the gas diffusion layers dip-coating be processed conduction with silicone film in the siloxane solution.When electrically conductive carrier material (carbon) and current-collector electrically contact, produce silicone film in the pore space structure of gas diffusion layers.

According to another exemplary embodiment, as shown in Figure 2, can said silicone film be placed on the outside (rather than inside of said housing) of said housing.Fig. 3 diagram the exemplary embodiment of a metal-air battery 10, this battery comprises and is placed on the outside silicone film 116 of housing 122.Said silicone film 116 is shown as to be set on the porous carrier film 144 and to be placed as basic covering and is contained in the opening 126 in the housing 122.This configuration possibly especially hope, for example, has than Battery case more in the housing of high surface area if battery 110 is placed on.According to another exemplary embodiment, can use siloxanes (it can fill some holes of said carrier material) to apply porous carrier materials (for example, processing), and this porous support materials is placed as the covering described hole by polymer like PTFE.According to the embodiment of certain exemplary, can the porous carrier materials that comprise silicone additives be placed as the covering described hole.Should be noted that when said silicone film was arranged on said outside, the conductivity of said silicone film was incoherent basically, because do not need transmission electronic basically.

According to another exemplary embodiment, said silicone film and said housing are become one.For example, the battery that has soft capsule bag form housing can be incorporated siloxanes in the capsule bag material into.In another exemplary embodiment, can silicone film be assembled into said air electrode or the portion within it of being in close proximity to.

According to another exemplary embodiment, said silicone film can replace or as gas diffusion layers.For example, Fig. 4 diagram another comprise the exemplary embodiment of the metal-air redox flow battery 210 of air electrode 214 and silicone film 216.Said air electrode 214 comprises active layer 232 and does not have continuous gas diffusion layers.On the contrary, said siloxane layer 216 is shown as and is adjacent to active layer 232 settings.This configuration provides a plurality of advantages; Include but not limited to provide the long-life stability and the fail safe that suppresses to reveal of raising; Because said siloxane layer 216 is basic solid films, said solid film does not allow liquid infiltration and selective in order to prevent CO to oxygen simultaneously ₂Get into said battery cell.

According to another exemplary embodiment, can be with the material mixing of siloxanes and gas diffusion layers to form single siloxanes rete of conduction.For example, Fig. 5 shows the exemplary embodiment of another metal-air redox flow battery 310, and this battery comprises silicone compositions 316 and air electrode 314.Said air electrode 314 is shown as and comprises active layer 332 and gas diffusion layers 330.Said silicone compositions 316 is included in the gas diffusion layers 330.According to an exemplary embodiment, the said gas diffusion layer material of said silicone compositions and other is mixed, be formed in the gas diffusion layers then.

According to an exemplary embodiment, can in monometallic-air cell, assemble many metal electrodes and air electrode.Further, the purpose that said silicone film and air electrode is independent of disclosure text is discussed, but is to be appreciated that and can thinks that said silicone film is one deck of said air electrode.

According to an exemplary embodiment; Can silicone film 16 and additional layer (for example, porous plastic materials one or more layers, one or more metal levels etc.) be used in combination to realize selectivity, the management of steam and the management of carbon dioxide to the oxygen that is used for battery 10.For example, through forming thin (sub-micron is between the nanometer) solid-state atresia silvery layer (for example, using vapor deposition or similar techniques) on the said siloxanes, can improve O ₂The transmission selectivity and stoped steam and CO ₂Passage.Since oxygen is slow through the transmission rate of silver, this additional layer just needs carrier material extremely thin and that will therefore need be used to deposit so.Siloxanes can be used as this carrier material, and advantage ground has the high oxygen transport properties.

The illustrative methods of preparation silicone film 16 will be discussed below.Idea for silicone film preparation technology comprises: for example, guarantee to have low tolerance silicone film uniform thickness ability, accurately control the ability of silicone film thickness, the ability of guaranteeing the ability of the basic free of pinholes of said silicone film, in mass preparation, handling said silicone film and undamaged ability and assemble said silicone film and metal-air battery.

According to an exemplary embodiment that satisfies above-mentioned idea; To become the film (for example, film, thin slice etc.) of two-layer Compound Extrusion available from the silicone film 16 (Geniomer

80) of Wa Ke with low density polyethylene (LDPE) (LDPE) conversion layer Compound Extrusion.According to an exemplary embodiment; Said silicone film be at least part Geniomer

80 films that cover the 10 μ m of (for example, being arranged on top etc.) 60 μ m LDPE films to make the gross thickness of the film 70 of Compound Extrusion be 70 μ m.Further, can obtain to have the silicone film (for example, less than the thickness of the combination of 50 μ m, greater than thickness of the combination of 50 μ m etc.) of wide region thickness by this method.

Said compound hot extrusion process assists in ensuring that the uniform thickness of the layer of said silicone film and/or other extruding.Said compound hot extrusion process helps to make the relatively easy delamination of one or more layers like this, thereby makes the layer of said silicone film also can it be assembled into said air electrode for extensible.

Confirm the uniformity of said film subsequently and guarantee wherein to appear few relatively hole or do not have hole (for example, through test air permeability).Can control process parameters, like temperature, pressure, thickness, extrusion speed and feeding screw rod type, in order to the uniformity that assists in ensuring that said silicone film and assist in ensuring that the hole that existence is few relatively on said silicone film or do not have hole.

The film of said Compound Extrusion is placed on the side of gas diffusion layers of said air cell, thereby makes said silicone film 16 towards said air electrode 14.The edge (rand) of the adhesive that will in assembled battery 10, use (for example, 5mm) is not left by silicone film 16 coatings.Then, with the calendering of air electrode 14 and Compound Extrusion silicone film so that adhering to each other being in the same place (for example, two steps made the thickness of its combination reach 1.62cm between two sand paper in two step calendering technologies and two cellulose papers).Shift out top LDPE conversion layer then, stay the air electrode of the silicone film that has a side that at least partly covers its gas diffusion layers.

Be similar to above-mentioned preparation method's exemplary method, according to an exemplary embodiment, with said silicone film Compound Extrusion on backing member (backing) or conversion layer (for example, like plastics of LDPE etc.).With the process of said air electrode assembling in, said conversion layer is used to improve the processing property of said silicone film and is reduced in the pin hole and damaged danger on the said silicone film.The layer that will comprise the Compound Extrusion of siloxanes and conversion layer is placed on the said air electrode, and said silicone film is towards said gas diffusion layers simultaneously.Then, utilize lamination and/or calendering technology that the silicone film and the air electrode of said Compound Extrusion is adhering to each other.After with said silicone film and air electrode adhesion,, therefore can said conversion layer relatively easily be shifted out because the adhesion between said air electrode and the silicone film is very strong.According to other exemplary embodiment, the technology through any amount of use heating and/or pressurization can be connected to each other said silicone film and air electrode/adhere to.

According to an exemplary embodiment, with said silicone film Compound Extrusion to conversion layer.Then, the layer of one or more said air electrodes (for example, all layers of active layer, gas diffusion layers, said air electrode etc.) is deposited on the said silicone film.After layer deposition, can use lamination and/or calendering technology to reduce thickness with one or more said air electrodes.Even described the compound hot extrusion process of multilayer above, but said extrusion process can be the individual layer extrusion process.Further, the compound hot extrusion process of said multilayer can comprise layer more than two Compound Extrusion components, material etc.

According to another exemplary embodiment, said silicone film is deposited on the conversion layer.Said depositing operation can include but not limited to that casting (solvent or water), spraying (solvent or water), contact print (screen template, aniline printing, intaglio printing, hectographic printing etc.), contactless printing (for example, ink-jet), rotation apply and chemical vapor deposition.Then, can append the technology of using heating and/or pressurization (for example, lamination, calendering etc.) to remove pin hole, to make said structure smooth and/or realize the ideal thickness of said silicone film for this depositing operation.In case said silicone film is deposited on the said conversion tunic, just can connects or stick to then (for example, through calendering and/or laminating technology) on the said air electrode.

According to another exemplary embodiment, said silicone film is directly deposited on the said air electrode.Said depositing operation can include but not limited to that casting (solvent or water), spraying (solvent or water), contact print (screen template, aniline printing, intaglio printing, hectographic printing etc.), contactless printing (for example, ink-jet), rotation apply and chemical vapor deposition.Then, can append the technology of using heating and/or pressurization (for example, lamination, calendering etc.) to remove pin hole, to make said structure smooth and/or realize the ideal thickness of said silicone film and/or air electrode for this depositing operation.

According to other exemplary embodiment, said silicone film is connected or adheres on the housing of said metal-air battery.Can said silicone film be connected or adhere to the inside or the outside of said casing.Said silicone film can or can further not adhere on the said air electrode.According to the embodiment of certain exemplary, can the technology that comprise heating and/or pressurization (for example, lamination, calendering etc.) be used for said silicone film is connected or adheres to said housing.According to other exemplary embodiment, can depositing operation be used for said silicone film is adhered to said housing.Said depositing operation includes but not limited to that casting (solvent or water), spraying (solvent or water), contact print (screen template, aniline printing, intaglio printing, hectographic printing etc.), contactless printing (for example, ink-jet), rotation apply and chemical vapor deposition.

According to an exemplary embodiment, can use encapsulate moulding (overmolding) technology.According to an exemplary embodiment, the material (for example, porous material) that can pass through to form said housing is with said silicone film encapsulate moulding.According to other exemplary embodiment, can use other distortion about the encapsulate moulding technology.

According to another exemplary embodiment, can use any being enough to that silicone film (perhaps not being the selective membrane of silicone compositions) is connected or adheres to the air electrode of said metal-air battery and/or the technology on the housing.These technologies all do not require the use carrier layer.Further; In the exemplary technology of any of these, use the technology of heating and/or pressurization to be included in and remove pin hole, make that said structure is smooth, the ideal thickness that obtains said silicone film and/or air electrode and/or other Ideal Characteristics that obtains to be used for said silicone film and/or air electrode with one or many.For example, can heating/radioactive source (for example, ultraviolet radioactive source, infrared radioactive source etc.) be used for said silicone film is cured to said air electrode, bring out crosslinked betwixt and/or the initiated polymerization thing " cave in " with the change transportation performance.In a further embodiment, heating source (for example, ultraviolet radioactive source) is provided as said silicone film is cured on the said air electrode.Then, wash said silicone film and air electrode patternless to remove (curing) zone.

Although battery 10 has been described as the form of coin or button cell monomer above; But should be noted that also and can silicone film be applied to also battery with other configuration be complementary (for example, prism property battery cell, cylindrical battery monomer, elliptical cells monomer, flow battery monomer, fuel cell etc.).According to an exemplary embodiment; The position of the silicone film in isomorphism type battery not can be used for the coin battery monomer similar (for example; Be placed between said battery cell housing and the said air electrode, be connected to said housing, or as the outer surface of other configuration of the application description or position on).

With reference to Fig. 6-8,, shown prismatic metal-air (being zinc-air) battery 410 according to an exemplary embodiment.Fig. 7 has shown the cutaway view of battery 410, and Fig. 8 has shown the detail drawing of the battery 410 among Fig. 7 along the end of line 8-8.Metal electrode 412, the air electrode 414 that said battery 410 comprises housing 422, extend along the length direction of said battery cell and be assemblied in metal electrode 412 and air electrode 414 between the electrolyte 418 of position.Said electrolyte 418 is put to stay in the hole of metal electrode 412 and partly and is in the hole of air electrode 414.Silicone film 416 (be similar to and be used for the description of silicone film 16 related contents of above-mentioned coin battery monomer embodiment) is assemblied in the top of air electrode 414/be adjacent to air electrode 414.The thickness of said silicone film 416 is greater than 0.1 μ m, and is provided for the humidity and the CO of the improvement of battery ₂Manage, the desirable speed of oxygen diffusion also is provided simultaneously.The top of said housing 422 comprises the opening 426 (for example, slit, aperture etc.) that makes air get into battery 410.

Can with said air electrode 414 and silicone film 416 fixing (for example, through gluing) to the cap of said housing in case stopping leak reveal.One side of the gas diffusion layers of said air electrode is to the opening 426 of battery container 422, and silicone film 416 is placed between the opening 426 of said gas diffusion layers and housing 422 basically.Utilize metal (for example, zinc) thickener that said battery 410 is filled.Can utilize contact pin (contact pin) to be connected, and it covered (for example, utilizing adhesive) in case the gas in the battery cell is overflowed through the current-collector that electric resistance welding, Laser Welding or other method well known in the art will be used for air electrode and metal electrode.Then with said housings close (except air openings) (for example, through ultrasonic bonding).

Said battery 410 provides the commercial available prismatic battery that can aspect much, use; Wherein use and maybe can use prismatic battery; Because battery 410 is except providing high current density; Also provide for these purposes (for example, mobile phone, camera, MP3 player, portable electric appts etc.) sufficient and/or expected life.

Also can silicone film be used for the U.S. Patent application No.12/826 like International Application PCT/US10/40445 and submission on June 29th, 1 simultaneously; In those kinds flow battery of describing in 383; Each is all submitted on June 29th, 2010, and with citation form its whole disclosures is incorporated among the application.Fig. 9 diagram the exemplary embodiment of flow battery 510.

With reference to Fig. 9, according to an exemplary embodiment, metal-air redox flow battery is shown as the zinc-air redox flow battery 510 of the silicone film 516 that comprises demonstration.Term " flow battery " is intended to refer to that reactant is transfused to and exports the battery system of said battery.For metal-air redox flow battery system, mean from said battery system, shifting out in metal anode thickener and electrolyte introducing (for example, pump suction) said battery and with metal oxide.Similar with fuel cell, said flow battery system requirements reactant in use flows through said system.

Said zinc-air redox flow battery 510 is shown as closed-circuit system; The reactor 546 that it comprises zinc electrode 512, electrolyte 518, is shown as one or more storage devices of storage tank or storage chamber 544 and has one or more reaction tubes 548, each reaction tube 548 comprises air electrode 514.

According to an exemplary embodiment, zinc electrode 512 is combined with electrolyte 518 to form zinc thickener 550, it is as the reactant that is used for zinc-air redox flow battery 510.Said reactant (for example, active material etc.) is configured to carry (for example, feed, pump are taken out, promotion, the application of force etc.) in said reaction tube 546 and therefrom transport out.When said zinc-air redox flow battery 510 discharges; Zinc thickener 550 is transported in the reaction tube 546 also through reaction tube 548; And after said zinc thickener 550 and hydroxide ion react, zinc oxide thickener 552 is transported out from reaction tube 546, wherein said hydroxide ion produces behind air electrode 514 and the oxygen reaction from air.When 510 chargings of said zinc-air redox flow battery, be transported in the reaction tube 546 zinc oxide paste 552 and through reaction tube 548, and after said hydroxide ion transforms back oxygen, zinc thickener 550 transported out from reaction tube 546.Be transferred through before the reaction tube 546 with afterwards thickener 550,552 is stored in the storage tank 544, zinc thickener 550 is stored in first cavity 554 of storage tank 544, zinc oxide paste 552 is stored in second cavity 556 of storage tank 544.

As above-described, each reaction tube 546 comprises the air electrode 514 that is arranged between at least two protective layers.According to an exemplary embodiment, Fig. 9 in more detail diagram the reaction tube 548 (it decomposites from zinc-air redox flow battery) of zinc-air redox flow battery 510.According to an exemplary embodiment, reaction tube 548 is shown as has the stratiform configuration, pipe or base portion 558, separator 560, air electrode 514 and outer tube or protective sleeve 562 in it comprises.Said base portion 558 is shown as the innermost layer of reaction tube 546, outermost layer and other layer that protective sleeve 562 is shown as reaction tube 546 be shown as basic setup between base portion 558 and protective sleeve 562 and with the two concentric.

According to the exemplary embodiment that shows, the composition of said air electrode 514 generates the tubulose air electrode according to an exemplary embodiment.Said air electrode 514 comprises a plurality of adhesives 564.Said adhesive 564 provides the mechanical strength that strengthens for air electrode 514, has kept the high relatively diffusion rate (for example, comparing with more traditional air electrode) of oxygen simultaneously.Said adhesive 564 can provide enough mechanical strengths, so that air electrode 514 forms in many ways, includes but not limited to push, a kind of in the press mold, punching press, use heating plate, calendering etc. or combine.The mechanical performance of this enhancing also can make air electrode 514 form the shape (for example, tubulose etc.) of any kind ofs.

The tubular configuration of said reaction tube 546 and corresponding air electrode 514 is relatively easily assembled air electrode 514 and is not had a leakage.The current-collector that is used in air electrode 514 with the tubular configuration of the gas diffusion layers coupling of conduction is positioned on the outside of reaction tube 546, prevents any leakage from said air electrode current-collector basically.Further, said tubular configuration is used in the current-collector of zinc electrode 512 to be incorporated in the reaction tube 546 basically, has eliminated the contact pin leakage.

In addition, the tubular configuration of said air electrode 514 provides pressure, corrosion (for example, in the course of conveying of zinc thickener 550 and zinc oxide thickener 552) and the repellence of overflowing.For example, the tubular configuration of said air electrode makes the zinc thickener flow through the passage 560 of its qualification with littler friction (said air electrode being configured to tabular such as fruit), thereby causes its inner littler friction relatively.Simultaneously, the cylindrical reaction tubes 546 that has a stratiform configuration allows to incorporate into the element/layer that mechanical stability is provided and helps to provide the crushing resistance of enhancing.

According to an exemplary embodiment, said silicone film 516 is shown as the outside of the gas diffusion layers 530 and the active layer 532 of the air electrode 514 that is arranged in the reaction tube 546.Through in zinc-air redox flow battery 510, comprising silicone film 516, in storage tank 522, need less electrolyte 518 to adapt to the loss of the water of following by operation (for example, because evaporation etc.).Further, through reducing CO ₂Negative effect on zinc-air redox flow battery 510, said silicone film 516 have reduced ancillary equipment and have safeguarded (for example, CO ₂Washer etc.) needs.According to other exemplary embodiment, can said air electrode and silicone film be configured to other form.For example, said silicone film can replace said gas diffusion layers or be placed on the outside of said protective sleeve 562.Other exemplary embodiment according to another can be being not that the form of film is incorporated siloxanes in the said reaction tube into.For example, can silicone compositions be incorporated in one or more layers of said air electrode.

According to an exemplary embodiment, can the silicone film 516 of metal-air redox flow battery 510 be squeezed into tubulose and also then it be rolled to the gas diffusion layers 530 of air electrode 514.According to an exemplary embodiment, can said silicone film be squeezed into flat thin slice, said thin slice is also adhered to (for example, through lamination or calendering) on it then around said air electrode setting or parcel.According to the embodiment of certain exemplary, about any one technology of silicone film 516 descriptions or the combination of technology, said silicone film can form and adhere to or be connected on the air electrode and/or housing of flow battery monomer through top.

According to an exemplary embodiment, the operation of zinc-air redox flow battery 510 in the discharge process will be described below.

In discharge process, it is distributed between the reaction tube 546 with zinc thickener 550 feeds and through feeding system 572 from first cavity 554 through the zinc inlet/outlet.According to the exemplary embodiment that shows, said feeding system 572 comprises a plurality of Archimedes's screw rods 574.Said screw rod 574 is carried zinc thickener 550 from the first end section 576 that is in close proximity to each reaction tube 546 with the first direction rotation to second end section 578.Flow 580 air current system 582 (be shown as and comprise fan 584) through a plurality of air stream channel 586 guiding air that between reaction tube 546, limit.Like a plurality of path 590 that show, the said air stream 580 a plurality of openings 588 through protective sleeve 562 are housed in the reaction tube 546 and towards passage 566 at least in part.Oxygen from air stream 580 is converted into hydroxide ion in air electrode 514; This reaction generally includes in order to produce the oxygen reduction and the electronics consumption of hydroxide ion.Then, 512 migrations of the zinc electrode in the zinc thickener 550 of said hydroxide ion in the passage 566 of reaction tube 546.Said hydroxide ion causes the zinc oxidation, discharges electronics and energy is provided.

Because the interaction of itself and said hydroxide ion, zinc thickener 550 changes into zinc oxide thickener 552 and discharges electronics in reaction tube 546.Along with said screw rod 574 is rotated further with first direction, continue zinc oxide thickener 552 is carried to second end section 578.Finally, zinc oxide thickener 552 is carried through the zinc oxide inlet/outlet from reaction tube 546, and it is deposited in second cavity 556 of storage tank 544.

According to an exemplary embodiment, the operation of zinc-air redox flow battery 510 in the charging process will be discussed below.

As above-described, zinc-air redox flow battery 510 is rechargeable.In charging process, zinc oxide thickener 552 transforms or the zinc thickener 550 of regenerating back.Zinc oxide thickener 552 is distributed between the reaction tube 546 from second cavity, 556 feeds and through feeding system 572.Said screw rod 574 with second direction rotation (promptly with discharge process in its direction of rotation opposite), zinc oxide thickener 552 is carried to first end section 576 from the second end section 578 that is in close proximity to each reaction tube 546.Along with electronics consumption and storage, 552 reduction of zinc oxide thickener form zinc thickener 550.Hydroxide ion is converted into oxygen in air electrode 514, and oxygen is joined in the air stream 580.Like the path 590 that shows, the opening 588 through protective sleeve 562 outwards flows out this Oxygen Flow to be in close proximity to passage 566 from reaction tube 546.

The existing metal-air battery of silicone film that do not use receives environmental condition (for example, CO ₂Existence, humidity etc.) restriction, said environmental condition has limited battery life and performance (for example, standby life-span (standby lifetime)).Metal-air coin or button cell monomer are the metal-air batterys that present only large-scale commercial applications can be used/use.The most normally, these metal-air batterys are used for hearing aids.These batteries are owing to closed air duct encapsulation has long relatively shelf-lifeing; But (for example killing in the short time relatively; Remove the housing hole that covers said metal-air coin battery monomer adhesive tape about five the week in); Because in use, ambient environmental conditions causes the capacitance loss at a slow speed of said metal-air coin battery cell.Because these restrictions, these batteries only can be used in the Battery Market of fraction coin battery monomer model.For existing coin metal-air battery, the metal of 675 types-current density that reaches 20-25mA of air coin battery monomer and the cut-out voltage of 1-1.1V are enough to be used in hearing aids usually.Simultaneously, the energy density of 1400Wh/l can be shown as and be used for existing coin metal-air battery.The coin battery monomer that is used for other electronic installation be based on can not with Ag/Zn, the MnO of the energy density coupling of metal-air (for example, zinc-air) battery ₂/ Zn or lithium.

To show experimental data below, operation, function and CO that its expression provides through silicone film (for example silicone film 16) and/or silicone additives (for example, in the gas diffusion layers or active layer of said air electrode) ₂Management benefit.

Figure 10-the 13rd, expression CO ₂Curve chart with the effect that makes the trend that electrolyte kills, this figure are also represented to change along with the weight percent of time changing electrolyte.Known potassium hydroxide (KOH) is a kind ofly possibly be used for the material of metal-air battery electrolyte and be hygroscopic.In theory, KOH should be unable to kill more than the relative humidity at certain.

Figure 10 and 11 is illustrated in relative humidity and is about in 35% the environment CO ₂Absorption is to the influence that changes along with the weight percent of time of KOH electrolyte.At no CO ₂Environment under (Fig. 3) and contain CO ₂Environment under, in surface plate, taken up the various KOH/ aqueous solution (7.7M, 10.2M, 12.8M), and monitored said electrolyte along with the weight percent of time changes.As can be observed in Figure 10, at no CO ₂Environment under; At first according to concentration; Adjusting various KOH solution through suction or dehydration makes it be suitable for the relative humidity of environment; Afterwards, its weight remain unchanged basically/stablize (do not have at first the weight of adjusted 12M KOH solution to a great extent because its with 35% relative humidity balance).Under the contrast, show, contain CO in that KOH solution is placed on like Figure 11 ₂Following time of environment, even do not have CO ₂Environment under KOH in the time after solution-stabilized, the weight of these KOH solution still continues to descend, and has represented containing CO ₂Environment under, KOH solution will be tending towards killing.Finally, these solution at least partially crystallizable form K ₂CO ₃Crystal.This crystal generates basic owing to CO in the environment ₂Existence make CO ₂Suffer carbonating.Carbonating has caused evaporation of water in the KOH electrolyte basically.Different with initial KOH, resulting K ₂CO ₃Crystal does not have the character of moisture absorption basically.

Figure 12 and 13 has showed the identical behavior that shows in basic and Figure 10 and 11, and different is that result displayed is to utilize the prismatic battery monomer sample acquisition (replaced as using surface plate in Figure 10 and 11) that has air electrode but do not have metal electrode in Figure 12 and 13.Be accompanied by 7.7M KOH concentration of electrolyte, use various air electrodes to prepare the test battery monomer.Extend below expression said electrolyte weight like the alignment that shows in the curve chart by Figure 13 and continue the proof of loss, containing CO ₂Environment under KOH solution be tending towards again killing in time.

The result that Figure 10-13 is described representes that KOH changes in time and is containing CO ₂Environment under continue to kill (be shown as in time weight and continue loss, the said loss in weight is lost owing to current), and contain CO when KOH is positioned on the contrary ₂Environment in the time, the weight of said electrolyte is represented in time constant basically (showing as said electrolyte does not kill).Stressed to prevent CO like this ₂Get into the importance in the metal-air battery, and proved optionally delivering oxygen and stop CO ₂The benefit that the film that is transferred (like silicone film 16) can provide far reaching to increase the service life for metal-air battery.

Figure 14 and 15 graphical representation be intended to detect along with the time changes CO ₂Experimental result to hydroxide concentration influence in the metal-air battery of prismatic sample.This result representes because CO ₂Exist said hydroxide concentration to descend.At no CO ₂Environment in, Figure 14 signify hydrogen oxide concentration keeps constant relatively in time, and is containing CO ₂Environment in, Figure 15 shows that change hydroxide concentration in time significantly descends.Like what write down in Figure 14 and 15, at no CO ₂Environment in, K ₂CO ₃Concentration keep constant relatively in low-down value, and at CO ₂When existing, K ₂CO ₃Grow with time and increase.

Hydroxide concentration also influences the capacity of metal-air anode simultaneously.Along with hydroxide concentration descends, the capacity of this battery is tending towards descending.Therefore, through reducing the hydroxide concentration in the metal-air battery, CO ₂Not only made metal-air battery kill but also reduce the capacity of metal-air battery.Represented to prevent CO so again ₂Get into the importance of battery.

Before applicant's investigation, available technical literature also do not occur and describe owing to temperature, relative humidity and airborne CO ₂The mechanism that the effect of concentration is lost the current in the zinc-air battery.Like what show, do not have or low CO when being exposed to by above-mentioned experiment ₂In the time of in the air of gas concentration, observe a small amount of or do not have current to lose to take place for KOH solution.Yet, when being exposed to higher relatively CO ₂In the time of in the air of gas concentration, the speed that current lose is obviously higher.Be not that hope necessarily belongs to any particular theory, what the applicant believed this current mistake is that it is by CO because KOH suffers carbonating ₂Cause, be described as through following equation:

KOH+CO ₂←→K ₂CO ₃

Following mechanism can be described the phenomenon that metal-air (for example, zinc-air) battery is killed and overflowed: CO ₂(g) be converted into CO ₂(aq), subsequently because high OH ^-Concentration (this reaction consumes 2OH ^-), CO ₂(aq) be converted into CO ₃ ^2-(aq).Then, this OH ^-Lowering of concentration, and along with OH ^-Lowering of concentration is because K ₂CO ₃(aq) having the agent of low hygroscopicity steam partial pressure raises.Be accompanied by because current lose the concentration that increases, when reaching solubility product, can observe K ₂CO ₃(s) deposition.Because KOH is hygroscopic and K ₂CO ₃Has agent of low hygroscopicity, along with at CO ₂Existing down, KOH is converted into K ₂CO ₃, the stability decreases of battery (for example, killing, shorten its useful life).

Should be noted that although known KOH (with other hydroxide solution) is moisture absorption, the top test result of discussing has shown at CO with this mechanism empirically ₂KOH is tending towards killing under existing, and it was not shown as before effort of the inventor and is established.Because the result of this understanding reduces CO ₂Transfer rate and to O ₂Has the material standed for that the selectivity material of (but stoping steam) (like silicone film 16) was shown as for the life-span of improving metal-air battery.

The graphical representation of Figure 16 silicone film can have to slow down above-mentioned CO ₂The benefit of negative effect.Prepared prismatic metal-air cell sample (not comprising metal electrode); The some of them sample comprises the thick silicone film of 50 μ m on the gas diffusion layers that is arranged on air electrode (using the siloxanes available from Celfa) (other sample of preparation under the situation that does not contain silicone film, and conduct " blank sample " in data).9M KOH electrolyte solution is used for said battery cell.

At the CO that is exposed under 35% relative humidity, 25 ℃ the temperature ₂Situation under, monitor said sample battery cell in time.The metal-air battery of the said prismatic sample that comprises silicone film showed as hydroxide concentration after more than 800 hour only have small reduction, and the sample that those do not comprise silicone film drops to and is lower than 1M (K in this process being shown as hydroxide concentration under the same time range ₂CO ₃Concentration rise).In a word, in metal-air battery, slowly take in CO ₂Help to keep hydroxide concentration to stablize and reduced formation K ₂CO ₃Trend.Therefore, the result who is accompanied by the remarkable rising of using the silicone film hydroxide concentration is shown among Figure 16, and it representes that said silicone film has slowed down CO ₂Be transported in the metal-air battery.Through more stable hydroxide concentration is provided, said silicone film helps to have slowed down killing of metal-air battery.These results are also very important, because the battery that its expression does not contain silicone film receives the influence of environment significantly.

Data presented representes that also it is relevant that the carbonization of said electrolyte is lost with current among Figure 16.This data show that KOH is far longer than (for example, less than 45% the relative humidity of killing boundary) of early stage hypothesis to the stable amplitude of water.Be accompanied by carbonate and in electrolyte, form, the moisture absorption forfeiture of KOH is also killed.Therefore, be expressed as report in the prior art kill speed at least part because CO ₂Effect.

Figure 17 shows the data that detect relation between the silicone film thickness be used for the test battery monomer and the oxygen diffusion restriction.The sample metal-air battery is prepared as the silicone film of incorporating all thickness (3,6 and 10 μ m) into, and in discharge process monitoring current density and compare with the sample battery that does not use silicone film.All are tested in the half-cell monomer that all under 25 ℃, has 7M KOH electrolyte and carry out.The air electrode surface that exposes is 3cm ²Silicone film is placed on the porous polypropylene carrier material with the layer that separates, and is placed on towards the top of the gas diffusion layers of said air one side.As above-described,, and,, said carrier material is shifted out along with silicone film being transported on the porous support materials as above-described with silicone film and support materials Compound Extrusion.

Shown in figure 17, said silicone film is thin more, and is high more to the oxygen diffusion limit of sample battery cell.The battery cell that does not have silicone film has shown higher oxygen diffusion limit, owing to do not exist siloxanes to limit the amount that oxygen gets into said battery cell.As above-described, because humidity and CO ₂Influence on the assembly of said battery cell has obviously more limited useful life with being contemplated to the battery cell that does not contain silicone film than those battery cells that contain silicone film.In being designed for the battery cell in the field of providing, there are balance in the running current amplitude and the battery cell that are contemplated at battery cell between the life-span.The designer of said battery will have right to choose and (provide simultaneously from the advantage (humidity and the CO that for example, are used for the improvement of said battery cell that use siloxanes selecting to have the silicone film that makes the thickness that said battery cell moves in the suitable current scope ₂Management)).

According to an exemplary embodiment; Replaced using the film that contains siloxanes; Can utilize siloxane solution to apply said air electrode (through ready air electrode being immersed in the siloxane solution or all parts of air electrode through siloxane solution being coated to other means of use or the outside of a part), so that said air electrode is used siliconc-impregnated.

In order to test the effect of said silicone compositions, apply air electrode with silicone compositions through the immersion process.After the said air electrode of preparation; Said electrode (is for example immersed siloxane solution; 5.8% siloxanes ethanolic solution) time (about in this case 1s is although apply time possibility difference according to other exemplary embodiment) short relatively in is to apply said air electrode.

Then said air electrode was placed in the vacuum storage chamber about 10 minutes, anyly is absorbed in the air in the said air electrode structure and forces said siloxanes to get in the hole of said air electrode in order to remove.After said vacuum treatment, paper towel is removed excessive solution (according to other exemplary embodiment, can use dry or other method that is fit to of air) from said air electrode.Then, with said air electrode dry in baking oven (for example, under 70 ℃, carrying out 15h) although maybe be different according to other exemplary embodiment temperature and time.In the said oven drying stage, with the placement that faces up of said gas diffusion layers, dry to accomplish rear film be visible on said gas diffusion layers.

In order to estimate the effect of siloxanes, use untreated air electrode (i.e. the air electrode of a uncoated siloxane solution) as blank sample.The air electrode of said blank sample and said siloxane treated is prepared in same batch.This experiment is repeated several times.Be surprised to find with dip-coating not and compare to the air electrode in the siloxane solution, the initial charge of the air electrode of dip-coating and discharge curve are superior in siloxane solution.For example represent that like this Figure 18 has shown at 20mA/cm ²Down, have the original charge and the discharge curve of the battery cell of 6M KOH electrolyte, said electrolyte has been incorporated air electrode said processing or untreated into.As for example live part through this curve is higher than the 2.0V level and representes up to the fact of its normalization in the 2.0V left and right sides along with each charging cycle descends gradually; For untreated air electrode (dotted line); Voltage spended time in charging and discharge process comes normalization (for example, about 120h).By contrast, the air electrode of said processing (gray line) runs through said test in constant voltage range circulation, and the time that do not require is used in the horizontal normalization of 2.0V.

These results represent through utilizing siloxane solution to handle air electrode; Possibly reduce or eliminate carrying out initial cells medelling operation (battery formation operation) so that the needs of the charging of said air electrode and discharge behavior (for example, the said air electrode of activation) normalization.Carry out the battery mode operation and be commonly used to guarantee that battery presents standard and foreseeable charging and discharge cycles.If utilize untreated air electrode can not carry out such battery mode operation, will be difficult to set up accurate cell charging demonstration (algorithm) so more, because the response of said battery is unknown up to this battery normalization.Through using siloxane solution to apply all parts or the part of said air electrode; Can eliminate said battery mode process; Time and the cost that can reduce preparation air electrode and metal-air battery on the contrary are (for example; If the needs to carrying out junior one group charge/discharge cycle have been eliminated, can from the preparation process, eliminate tediously long initial charge and discharge operation, save time and resource).

In another experiment, said siloxane solution only is coated in gas diffusion layers one side of first air electrode and is coated in active layer one side (for example, through said solution brush is being divided on other layer) of another air electrode.The untreated samples of chemical property does not have any different significantly in the sample that said gas diffusion layers one side has siloxanes has demonstration and relates to charging and discharge process.Yet the sample of handling in active layer one side of said air electrode is shown as and the air electrode similar performance improvement of immersing fully in the said siloxane solution.This expression is handled initial charge/discharge curve that active layer can help improve said air electrode with siloxane solution; Yet applying said gas diffusion layers one side possibly not provide any remarkable advantage that is used to improve said battery activity (although possibly have other advantage, as antagonism water and CO to be provided ₂Carry second barrier; Further, should be noted that and to hope in some cases in the preparation process, to use dipping process, rather than only brush or apply a side) with solution.

In order to confirm it is that siloxanes rather than solvent in the siloxane solution caused active raising, with the dip-coating of air electrode sample in the neat solvent of the siloxanes that does not wherein contain any dissolving.This air electrode sample shown and the similar chemical property of untreated sample, shows as on said solution scribbles siloxane solution in raising the initial charge/discharge performance of air electrode inoperative.

Therefore the present inventor has unexpected discovery: except sealing and CO are prevented in relate to relevant with siloxanes ₂Get into outside the said battery cell advantages associated (as describing about the purposes of silicone film top; But be applied to similarly in the air electrode that scribbles siloxane solution), the siloxanes that in the immersion process, uses also has advantage for the activity that improves said air electrode.This point is different from and relates to traditional idea that battery forms, and thinks that wherein cell activation requires slow wetting said active layer in long-term battery mode charge/discharge cycle process.

In an exemplary embodiment, the various combinations of the material of discussing among the application, structure, application method, preparation method and application can be used in the scope of disclosure text.And although battery is pointed in the description that the application comprises basically, disclosed idea also is applied to fuel cell and has the electrochemical conversion device of desirable configuration with other.

Like what use among the application, term " about ", " approximately ", " basically " and similarly term be intended to have and cooperate common and wide in range implication by the those of ordinary skill acceptance relevant with disclosure text subject field.Reading those skilled in the art should understand that to: these terms of disclosure text is intended under the situation that scope of these characteristics is not restricted to the accurate number range that provides, the special characteristic of describing with requiring described.Therefore, with being construed as within the scope of the present invention that expression thinks in the claim of liking enclosed, to enumerate to these terms of the unsubstantiality of the theme describing and require or non-important modification or variation.

Should be noted that: the term " exemplary " that is used for describing various embodiments in this application is intended to represent such embodiment: reasonably embodiment, expression and/or the reasonably explanation of embodiment (and such term does not represent that such embodiment is necessary uncommon or best embodiment).

For the purpose of present disclosure, term " connection " is meant that two parts are connected with each other directly or indirectly.Like this link to each other can be in essence fix or movably.The realization that links to each other like this is to make up with any extra intermediate member (intermediate member) and be integrally formed each other or two parts or two parts are attached to any extra intermediate member each other through two parts or two parts.Like this link to each other can be fixing in essence maybe can be in essence movably or releasable.

Should be noted that according to other exemplary embodiment the situation of various elements can be different, and such variation is intended to be included in the disclosure text.

Be important to note that structure and configuration at the metal-air redox flow battery shown in the various exemplary embodiments are exemplary.Although in disclosure text, just describe some embodiments in detail; But read under the situation that the person skilled in the art will easily understand the advantage that does not substantially depart from the theme of enumerating in novel teachings and the claim of disclosure text; The a lot of modification is reasonably (for example, ratio, parameter value, the device to size, size, structure, shape and various elements disposes, the change of the use of material, color, direction etc.).For example, being shown as integrally formed element can be made up of a plurality of parts or element, and the position of said element can put upside down or change, and the character of discrete element or number or position also can be changed or changed.According to alternate embodiment, the order of any technology or method step or sequence can change or reorder.Under the situation that does not depart from the scope of the invention, in design, ruuning situation and the configuration of various exemplary embodiments, also can make substituting, revise, change and omitting of other.

Claims

1. a metal-air battery comprises

Air electrode; With

Be in close proximity to or be merged in the silicone compositions in the said air electrode.

2. metal-air battery according to claim 1 is characterized in that, said silicone compositions is transported in the said metal-air battery for reducing carbon dioxide by body plan.

3. metal-air battery according to claim 1 is characterized in that said silicone compositions fitted to be silicone film.

4. metal-air battery according to claim 3; It is characterized in that; Said metal-air battery also is included in the housing that wherein assembles at least one opening, and wherein said silicone film is set at said air electrode and is adjacent between the housing of said at least one opening.

5. metal-air battery according to claim 3 is characterized in that said metal-air battery also is included in the housing that wherein assembles at least one opening, and wherein said silicone film is adjacent to the opening setting of the outer surface of said housing.

6. metal-air battery according to claim 3 is characterized in that said air electrode comprises active layer and gas diffusion layers, and wherein said silicone film is connected with first side of said gas diffusion layers.

7. metal-air battery according to claim 3 is characterized in that, said air electrode comprises active layer and the silicone film that replaces gas diffusion layers to use.

8. metal-air battery according to claim 3 is characterized in that the thickness of said silicone film is about 3-50 μ m.

9. metal-air battery according to claim 3 is characterized in that said silicone film comprises the additive of conduction.

10. metal-air battery according to claim 3 is characterized in that said silicone film is used to replace the current-collector of said air electrode.

11. metal-air battery according to claim 1 is characterized in that, said silicone compositions fitted to be at least one lip-deep coating of said air electrode.

12. metal-air battery according to claim 1 is characterized in that, said air electrode comprises active layer and gas diffusion layers, and wherein said silicone compositions is incorporated in the said gas diffusion layers.

13. metal-air battery according to claim 1; It is characterized in that; Said metal-air battery is that flow battery and said air electrode are basic tubular configuration; Wherein said silicone compositions fitted to be the film of basic tubular form, and this film fitted to be and is adjacent to said air electrode.

14. a portable electron device comprises the metal-air battery of enumerating in above-mentioned arbitrary claim.

15. a method comprises:

The assembling silicone compositions;

The assembling conversion layer; With

With said silicone compositions and said conversion layer Compound Extrusion to form silicone film.

16. method according to claim 15 is characterized in that, also comprises said silicone film is separated from said conversion layer.

17. method according to claim 15 is characterized in that, said conversion layer comprises low density polyethylene (LDPE).

18. method according to claim 15 is characterized in that, also comprises the silvery layer is connected on the silicone film.

19. method according to claim 15 is characterized in that, also comprises applying a kind of of heating and pressurization at least, in order to said silicone film is connected on the air electrode of metal-air battery.

20. method according to claim 15 is characterized in that, also comprises applying a kind of of heating and pressurization at least, in order to said silicone film is connected on the housing of metal-air battery.