JP2005520310A - Polymer matrix material and polymer matrix material incorporated in an electrochemical cell - Google Patents

Abstract

【Task】
A polymer matrix material comprising a polymerization product of one or more monomers selected from the group of water-soluble ethylenically unsaturated acids and acid derivatives, and a crosslinking agent, and a polymer matrix material are used. An electrochemical cell is disclosed herein. A certain amount of water is used in the polymerization so that the amount expands to a defined volume upon curing. Instead, water-soluble or water-swelling polymers and / or chemical polymerization initiators.

Description

  This specification includes US Provisional Application No. 60 / 301,558, filed June 28, 2001, entitled "POLYMER MATRIX", and Robert Augusta, Mark Stevens, and August 30, 2001 filed by Muguo Chen. No. 09 / 943,053, title of the invention “ELECTROCHEMICAL CELL INCORPORATION POLYMER MATRIX MATERIAL”, and US patent application No. 02/94, Aug. 30, 2001, by Robert Callahan, Mark Stevens, and Muguo Chen , 887, claiming priority based on the title of the invention "POLYMER MATRIX MATERIAL" Ri which is incorporated herein.

  The present invention relates to a polymer matrix material and an electrochemical cell using the polymer matrix membrane, and more particularly to a polymer matrix membrane suitable for solution support.

  Electrochemical devices typically incorporate an electrolyte source that provides the anions and cations required to cause an electrochemical reaction. These electrochemical devices include batteries, fuel cells, sensors, electrochemical gas separation systems, electrochromic devices, and protein separation devices.

  Batteries and fuel cells operate by electrochemical reactions of metals / air, metals / halogen compounds, metals / hydrides, hydrogen / air, or other materials capable of electrochemical reactions. For example, zinc / air systems require the diffusion of hydroxide anions and generally contain an aqueous potassium hydroxide solution as the electrolyte. However, the lifetime of this battery is limited for several reasons. First of all, the exposed zinc is corroded by both the liquid electrolyte and air. The second reason is that the air channel of the air cathode is gradually blocked by water from the electrolyte. The third reason is that the electrolytic solution is contaminated by the zinc oxidation product diffused from the anode.

  Various approaches have been attempted to solve many of the problems associated with electrolyte use in systems based on zinc anodes such as zinc / air fuel cells. For example, additives have been added to the electrolyte to extend life and protect the anode from corrosion. U.S. Pat. No. 4,118,551 discloses the use of inorganic additives such as mercury, indium, tin, lead, lead compounds, cadmium, or thallium oxide to reduce zinc electrolyte corrosion. However, many of these additives are expensive and, more importantly, very harmful. U.S. Pat. No. 4,378,414 discloses the use of a multilayer separator between positive and negative electrodes to reduce anode corrosion and electrolyte contamination by zinc oxidation products. In addition, hydrophobic materials have been introduced into the zinc-air device to prevent water from penetrating into the cathode air channel. However, the introduction of hydrophobic materials is a difficult process and can result in a decrease in cathode performance.

  In addition to the zinc / air system, other metal / air systems such as aluminum / air, lithium / air, cadmium / air, magnesium / air, and iron / air systems also theoretically have ampere-hour capacity, voltage, and specific energy. Since it is expensive, it has the potential to be used in many different applications. In practical use, these promising theoretical values are greatly impaired by corrosion of the metal anode in the electrolyte.

  US Pat. No. 5,688,613 discloses a solid electrolyte polybenzimidazole (PBI) film with hydroxide conductivity, which supports a polymer in which electrolyte active species are diffused. And the polymer structure is in intimate contact with both the anode and the cathode. However, since this PBI film does not absorb water, it does not retain water in the membrane and therefore dries quickly.

  U.S. Pat. No. 3,871,918 discloses an electrochemical cell using electrodes of zinc granules suspended in a gel consisting of methylenebisacrylamide, acrylic acid, and acrylamide. Potassium hydroxide contained in the gel serves as an electrolyte.

  Although much work has been done on devices based on cation conduction, most proton permeable membranes are very expensive to manufacture and usually do not function at room temperature. For example, in the 1970s, the fully fluorinated polymer membrane NAFION® (DuPont, Wilmington, DE USA) was released and became the basis for the subsequently developed proton permeable membrane.

  US Pat. No. 5,468,574 discloses a proton permeable membrane characterized by a highly sulfonated polymer membrane having a block copolymer of sulfonated polystyrene, blocks of ethylene and butylene. . In 1997 NASA's Jet Propulsion Laboratory announced the development of an improved proton permeable membrane made of sulfonated poly (ether ether ketone), commonly known as H-SPEEK.

  A separator in a cell or battery physically separates and electrically insulates electrodes having different polarities. The separator is required to serve as a barrier that prevents the movement of the active material between different electrodes and to provide ion permeation. Good ion permeation is necessary to ensure that the electrochemical cell or battery provides the amount of power that can be used in a particular application.

  In rechargeable electrochemical cells, separators are also used to prevent short circuits caused by penetration of metal dendrites during charging. For example, in a rechargeable zinc / air cell, zinc on the negative zinc electrode (anode) surface dissolves in the electrolyte as zincate ions during discharge. Then, during charging, depending on the particular anode used, if the charging current is generally less than 20 mA / cm 2, acicular dendritic zinc from the negative electrode in the direction of the charging electrode is formed from zincate ions. Unfortunately, these needle-like structures penetrate conventional separators and cause an internal short circuit. The service life of the cell ends as a result. In addition to preventing dendritic penetration, the separator needs to allow exchange of electrolyte ions during both cell discharge and charge.

  The most commonly used separator in rechargeable cells is a porous insulating film of polyolefin, polyvinyl alcohol (PVA), nylon, or cellophane. Acrylic acid compounds can be radiation grafted onto these separators to improve water absorption and increase electrolyte permeability. Much research has been done to improve the performance of the separator. However, in the above and other conventional separators, the problem of dendritic crystal penetration and reaction products such as metal oxides are present in other parts of the cell. Problems related to spreading often occur.

  In conventional separators, controlling the pore size of the separator is the only effective way to prevent dendritic penetration and product diffusion. Thereby, the ion permeability of a separator is also impaired significantly. This impedes high charge / discharge current density operation, which is an important consideration in applications such as electric vehicles.

US Pat. No. 5,549,988 (the '988 patent) discloses an electrolyte system separator disposed between the cathode and anode of a rechargeable electrochemical cell. The electrolyte system includes a polymer matrix made from polyacrylic acid or a derivative thereof. An electrolytic species such as KOH or H ₂ SO ₄ is then added to the polymer matrix to complete the system. However, as described in the '988 patent, the measured electrolyte conductivity of the disclosed electrolyte-polymer film is low, ranging from 0.012 S / cm to 0.066 S / cm.

  While these conductivities are sufficient, they are not sufficient for other advanced operations, including electric vehicles. Electrochemical reactions are also related to the function of the electrochromic device (ECD). Electrochromism is broadly defined as a reversible light absorption change induced in a material by an electrochemical redox process. In general, an electrochromic device has an electrochromic material (ECM) with two different complementary features, the first substance usually being reduced and from color (1) to color (2) while being reduced. A similar change occurs as the second material oxidizes and loses electrons.

  Basically, there are two types of electrochromic devices depending on where the electrochromic material is located in the device. In thin film type devices, two ECMs are coated on the two electrodes and remain there during the redox colored process. In a liquid phase device, both ECMs are dissolved in the electrolyte and remain there during the coloring cycle. Liquid phase devices are generally more reliable and have a longer lifetime, but external power must be constantly applied to maintain the color state. The thin film type device does not require external power to maintain its colored state, so that power consumption is greatly reduced, which is advantageous for energy saving applications such as smart windows. The problem with thin film type devices is their short lifetime. After a certain number of cycles, the ECM film loses contact with the electrode or no phase change is possible and the device expires.

  With respect to liquid phase devices, for example, US Pat. No. 5,128,799 discloses a method for reducing the current required to maintain a colored state involving adding gel to the device. This reduces energy consumption, but adding the gel into the device also significantly reduces the switching speed of the device. In connection with thin film equipment, attempts to extend the life of the equipment include changing the crystal structure of the film. Although such modifications have slightly extended the life of thin film devices, the standard life of such devices is still not sufficient.

  Due to the above problems, successful development and commercialization of electrochromic devices with green energy source fuel cell technology and several energy saving, decoration and information display applications such as smart windows and flat panel displays Is blocked. For the problems associated with rechargeable electrochemical cells, there is a high need for separators that can provide effective barriers to metal dendritic penetration and reaction product diffusion, as well as provide improved ionic conductivity. .

  The present invention provides a polymer matrix material that can support a solution. The solution can include, for example, any solution desired for the appropriate use of the material. For example, in systems operating with basic or acidic electrolytes, a suitable solution of ionic species may be provided in the polymer matrix material to be highly conductive to anions or cations. In systems where a neutral species is required, such a neutral solution may be provided within the polymer matrix material.

  The polymer matrix material includes a polymer of one or more monomers selected from the group of water soluble, ethylenically unsaturated acids and acid derivatives, and crosslinkers. A certain amount of water is used for the polymerization so that the polymer material expands to a predetermined size upon curing. Instead, water-soluble or water-swelling polymers and / or chemical polymerization initiators.

  In one embodiment, the polymer matrix material may be formed into a polymer matrix membrane that incorporates ionic species for use in electrochemical devices. For example, primary batteries, secondary batteries, and metals / air (eg, zinc / air, cadmium / air, lithium / air, magnesium / air, iron / air, aluminum / air) Zn / Ni, Zn / MnO2, Zn / AgO In fuel cells such as Fe / Ni, lead acid, Ni / Cd, and hydrogen fuel cells, the polymer matrix membrane may be introduced together with a suitable solution. Furthermore, the polymer matrix film may be used together with a suitable solution in electrochromic devices such as smart windows and flat panel displays. In secondary batteries (ie rechargeable), the polymer matrix membrane is particularly useful as an electrolyte source and as an anti-dendritic crystal separator between the charged electrode and the anode. In addition, the polymer matrix membrane described above can also be used in other electrochemical cell based devices such as electrochemical cell gas separators and sensors.

  For zinc / air fuel cell batteries, the anode and cathode can be protected, for example, using the conductive membrane of the present invention. In such a system, the ionic species are contained as a liquid phase in the polymer matrix membrane and can function as an electrolyte without the disadvantages described above. The polymer matrix membrane protects the anode from corrosion (by air or electrolyte) and prevents zinc oxide from the anode from fouling the electrolyte. For the cathode, the membrane itself is solid so that water does not block the cathode air channel. As a result, the lifetime of the system is extended.

  As used herein, the term “anode” refers to and can be interchanged with the term “minus electrode”. Similarly, “cathode” refers to and can be rephrased as the term “plus electrode”.

  The polymer matrix material has a first type polymer of one or more monomers selected from the group of water soluble ethylenically unsaturated acids and acid derivatives. The polymer matrix material also includes a second type of monomer, generally as a crosslinker. Furthermore, the polymer matrix material may comprise a water-soluble or water-swelling polymer that acts as a reinforcing element. Furthermore, an electropolymerization initiator may optionally be included. After polymerization, the ionic species may be incorporated into the polymer matrix by adding to the polymer matrix material.

  During polymerization, the monomer solution and the optional water-soluble or water-swelling polymer may comprise water, the type of solution ultimately desired within the polymer matrix material, or a combination thereof. Thus, the resulting polymer matrix material can contain a beneficial solution so that the polymer matrix material can be used in a particular application. When pure water is the only species added to the monomer solution, it acts as a space holder to increase the volume of the polymer after curing. By defining the volume of the polymer matrix together with a certain amount of water, the water will have an appropriate concentration of the desired ionic species without expansion or contraction of the material (or membrane, due to products from the material). (“Solution replacement process”). This is preferred because strength and ionic conductivity are greatly related to the volume and flexure of the ionic liquid phase. Large expansion of the polymer has the potential to reduce the mechanical strength of the final material. However, if the material does not expand sufficiently to be able to provide sufficient volume for the electrolyte, the conductivity is reduced. The solution replacement treatment can be performed in the form of dipping, soaking, spraying, contact with an ion exchange resin, or other techniques known to those skilled in the art.

  For example, in the case of an alkaline system, the hydroxide ionic species may be obtained from an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, or combinations thereof. Preferably, for example, the base in potassium hydroxide solution is at a concentration in the range of about 0.1% to 55% by weight, most preferably about 30% to 45% by weight. In the case of an acidic system, protons can be obtained from an acidic electrolytic aqueous solution of, for example, perchloric acid, sulfuric acid, hydrochloric acid, or combinations thereof. The concentration of perchloric acid is preferably, for example, from about 0.5% to 70% by weight, and most preferably from about 10% to 15% by weight. The polymer matrix membrane can also be used in a neutral system, and the solution supported by the polymer matrix membrane is a saturated neutral aqueous solution of ammonium chloride and potassium sulfate, a saturated solution of ammonium chloride, potassium sulfate, and sodium chloride, A saturated neutral solution of potassium sulfate and ammonium chloride is included, but is not limited thereto.

  The principles of the present invention may be applied to electrochromic devices. Here, since the electrochromic material of the device is contained within a polymer matrix, it provides the device with the reliability and longevity associated with a liquid phase EC system and the energy saving memory characteristics associated with a thin film EC system.

  Accordingly, yet another embodiment of the present invention is an electrochromic device in which the electrochromic material is contained within a polymer matrix membrane. Typically, such devices have two electrolytic substrates and an electrochromic material contained within a polymer matrix film sandwiched between them. The device may optionally have an aqueous or solid electrolyte between the polymer matrix membranes. The electrode substrate may be made of conductive glass such as platinum, gold, indium tin oxide, and the like.

  Hereinafter, description will be given with reference to the following drawings. FIG. 1 shows a typical zinc / air fuel cell, in which two polymer matrix membranes 1, 2 are disposed between a zinc anode 3 and an air cathode 4. The first film is the anode protective film 1, and the second film is the hydroxide conductive film 2. The membrane is not only a source of ionic species but also has a very high conductivity of that type, and provides a protective layer for the electrode to prevent the usual causes of cell failure. The membrane prevents diffusion of zinc oxidation products into the electrolyte phase, which prevents corrosion of the zinc anode by the electrolyte or air, and prevents water from the electrolyte from blocking the cathode air channel. The zinc / air system of FIG. 2 includes a protective, ionically conductive polymer matrix membrane 5, 6 on the surface of the zinc anode 3 and air cathode 4, and an aqueous electrolyte solution 7 between the two.

  Reference is now made to FIG. An aluminum / air fuel cell system incorporating a polymer matrix hydroxide conductive membrane 8 between an aluminum anode 9 and a cathode 10 is shown. Like the zinc / air system, the polymer matrix membrane of this example serves to prevent corrosion problems associated with the use of purely liquid electrolytes and also serves as an ion conducting medium.

  As illustrated in FIG. 4, when applied to hydrogen fuel cell technology, the polymer matrix membrane is simpler to manufacture, much cheaper than existing proton conducting membranes, and functions well at room temperature. It may be used to provide a material conductive membrane. Since the actual conducting medium is left in the aqueous solution within the polymer matrix membrane, the conductivity of the membrane corresponds to that of the liquid electrolyte and is quite high at room temperature. In this embodiment of the invention, a proton or hydroxide conducting polymer matrix membrane 11 is disposed between the hydrogen anode 12 and the air cathode 13, thereby separating hydrogen and air.

  As shown in FIG. 5, the principles of the present invention are also applicable to electrochromic systems. Here, the electrochromic material (ECM) is diffused into the solution phase retained within the polymer matrix. Since the ECM is in solution, the device exhibits the excellent reliability and long life of a solution phase device, and furthermore, since the ECM is physically confined, it does not diffuse into the electrolyte that is the bulk of the device. As a result, the device exhibits the superior memory of a thin film type device. As shown, the device comprises two electrode substrates 14, 15 having electrochromic material 16, 17 encapsulated by a polymer matrix membrane therebetween. As shown, the device optionally includes an aqueous solution or solid electrolyte 18 disposed between the polymer matrix membranes 16, 17.

  Reference is now made to FIG. A rechargeable electrochemical cell formed from three electrode assemblies 20, 30, 40 and housed in a housing 90 is illustrated. Electrode 20 represents a negative electrode or metal anode, electrode 40 is a positive electrode (ie, an air cathode), and electrode 30 is a porous charged electrode. In this embodiment, the cathode 40 and the charged electrode 30 are separate electrodes, and the charged electrode 30 is disposed between the cathode 40 and the polymer matrix film 60. As shown in the drawing, the three electrodes 20, 30, 40 are arranged parallel to each other with a space between them. The rechargeable electrochemical cell optionally includes a liquid (water soluble) electrode 80 that is typically in immersion contact with each electrode, polymer matrix membrane 60 and porous spacer 50 (if used).

The metal anode 20 is made of a metal that is easily oxidized, preferably zinc, cadmium, lithium, magnesium, iron or aluminum. For high current density applications, the air cathode 40 preferably has a current density of at least 200 mA / cm ² . An exemplary air cathode is disclosed in co-pending and commonly assigned US patent application Ser. No. 09 / 415,449, entitled “ELECTROCHEMICAL ELECTRODE FOR FUEL CELL” (filed Oct. 8, 1999). This reference is incorporated herein in its entirety. As will be apparent to those skilled in the art, other air cathodes can alternatively be used depending on their performance capabilities.

  As shown in FIG. 6, the porous charged electrode 30 is disposed between the metal anode 20 and the air cathode 40 in parallel. Any inactive conductive porous material can be used to form the porous charged electrode 30. Examples include, but are not limited to, platinum, nickel, nickel oxide, perovskite and its derivatives, carbon, and palladium. Further, openings or holes may be drilled or formed on the charged electrode 30 to assist ionic conduction. It is important that the electrodes are not in physical contact with each other, and a sufficient distance must be ensured to form a gap for the electrolyte.

  Furthermore, it may be desirable to place a porous spacer 50 between the charged electrode 30 and the air cathode 40 to ensure a sufficient distance between the two electrodes. When the porous spacer 50 is included in the rechargeable electrochemical cell 100, a gap is formed for the electrolyte on both sides of the porous spacer 50 and each electrode 30 and 40. However, the present invention is not limited to the structure including the porous spacer 50. Any means for preventing physical contact between the two electrodes can be used, such as securing the electrodes to the housing in a separated state. However, when the porous spacer 50 is used, the thickness is generally in the range of about 0.1 mm to about 2 mm because it is typically made of a porous plastic material such as nylon.

  As shown, the polymer matrix membrane 60 is spaced and parallel to the electrodes 20, 30, 40 and is located between the charged electrode 30 and the metal anode 20. The gap for the electrolyte is provided on both sides of the polymer matrix film 60. Alternatively, although not shown, when the polymer matrix membrane is radiation grafted onto one of the three electrodes, the electrode provides support to the polymer matrix membrane so that the polymer matrix membrane and it forms There is no gap between the electrodes to be applied. In accordance with the present invention, the polymer matrix membrane 60 functions in part to prevent a short circuit between the air cathode 40 and the metal anode 20.

  FIG. 7 shows the rechargeable electrochemical cell of the present invention, where the cathode and charged electrode form a single bifunctional electrode 41, i.e., the electrode is used both as a positive electrode and for charging the battery. Is done. Optionally, a liquid (aqueous) electrolyte 81 may be included in the cell housing. The polymer matrix film 61 is disposed between the anode 21 and the bifunctional electrode 41. The electrochemical cell also includes a housing 91.

  This electrode / separator binary structure shown in FIG. 7 can be used in several different types of rechargeable battery systems. For example, the anode 21 may be a metal that oxidizes, such as one in the list previously described in connection with FIG. 6 (preferably zinc), and the bifunctional electrode 41 is an air cathode as described above. May be. In another embodiment, anode 21 is zinc or zinc oxide. The bifunctional electrode 41 is nickel oxide, manganese dioxide, silver oxide or cobalt oxide. Alternatively, the anode 21 may be iron or cadmium and the single bifunctional electrode 41 is nickel oxide. In these systems, the ionic species contained in the polymer matrix membrane 61 is preferably from an aqueous alkali hydroxide solution and associated hydroxide concentration. However, in the rechargeable metal / air cell of the present invention, a neutral polymer matrix membrane 61 can be used instead if the ionic species is from a neutral aqueous solution.

  In an acidic system such as a rechargeable lead oxide battery in which the anode 21 is lead and the bifunctional electrode 41 is lead oxide, an acidic film may be used as the polymer matrix film 61. In this embodiment, the ionic species contained in the polymer matrix film 61 is from an aqueous solution of perchloric acid, sulfuric acid, hydrochloric acid, phosphoric acid or a combination thereof.

  In other rechargeable electrochemical cell structures not shown, the polymer matrix membrane is directly connected to the anode, charged electrode, cathode, or bifunctional electrode if a bifunctional electrode is used. It can also be grafted. In this case, an electrode substrate on which the polymer matrix film is formed provides support for the polymer matrix film.

  The shape of the electrolyte solution volume or housing (indicated by reference numeral 90 in FIG. 6 and reference numeral 91 in FIG. 7) is not limited to being square or rectangular. The shape may be circular, elliptical, polygonal, or any shape. Furthermore, the cell housing can be manufactured from any strong and chemically inert insulating material, such as plastics conventionally used in electrochemical cells and alkaline storage batteries.

  When in operation, conductors (not shown) are typically copper strips attached to the exposed portions of the metal anode, charged electrode, and cathode and / or bifunctional electrode. These conductors are used to apply an external voltage to the cell to recharge the anode. Insulating epoxies are commonly used to cover exposed seams.

  The polymer matrix material has a first type polymer of one or more monomers selected from the group of water soluble ethylenically unsaturated acids and acid derivatives. The polymer matrix material also includes a second type of monomer, generally as a crosslinker. Furthermore, the polymer matrix material may comprise a water-soluble or water-swelling polymer that acts as a reinforcing element. Furthermore, an electropolymerization initiator may optionally be included. After polymerization, the ionic species may be added to the polymer matrix material and remain in the polymer matrix.

  Water soluble ethylenically unsaturated acids and acid derivatives generally have the following formula:

  R1, R2 and R3 are each independently selected from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic, halogen, carboxylic acid derivative, sulfate and nitrate, Moreover, it is not necessarily limited to the above.

  R4 can be selected from the group consisting of halide, OR5, and carboxylic acid derivatives including but not limited to NR5, NHR5, NH2, OH, H, Cl and Br, but is not limited thereto. Where R5 can be selected from the group consisting of H, C, C2-C6 alkanes, C2-C6 alkenes, C2-C6 alkynes and aromatic compounds.

  Such ethylenically unsaturated acids and derivatives having the general formula (1) are methylene bisacrylamide, acrylamide, methacrylic acid, acrylic acid, fumaramide, fumaric acid, N-isopropylacrylamide, N, N-dimethylacrylamide, Including, but not limited to, 3,3-dimethylacrylic acid, maleic anhydride and combinations of at least one of the aforementioned ethylenically unsaturated acids and derivatives.

  Depending on the desired characteristics, other ethylenically unsaturated acids and derivatives monomers with readily polymerizable groups can be used as the first type of monomer. Monomers of this type include, but are not limited to, combinations of 1-vinyl-2-pyrrolidinone, sodium salt of vinyl sulfonic acid, and at least one of the aforementioned ethylenically unsaturated acids and derivatives. It is not a thing.

In general, the first type of monomer comprises about 5% to 50%, preferably about 7% to 25%, more preferably 10% to 20% by weight of the total monomer solution before polymerization.
Furthermore, the second type of monomer or monomer group is generally provided as a crosslinking agent during polymerization. The general formula for such monomers is:

Where i = 1 → n and N ³ 2,
R2, i, R3, i, and R4, i are from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic, halogen, carboxylic acid derivative, sulfate and nitrate Each is independently selected, but is not limited to the above.

  R1 can be selected from the group consisting of N, NR5, NH, O, and a carboxylic acid derivative, but is not limited thereto, wherein R5 is H, C, C2-C6 alkane, C2 -C6 alkene, C2-C6 alkyne and an aromatic compound can be selected.

  Monomers generally suitable for use as general crosslinkers of general formula (2) above are methylene bisacrylamide, ethylene bisacrylamide, any water-soluble N, N′-alkylidene bis (ethylenically unsaturated amide), and 1,3,5-triacryloylhexahydro-1,3,5-triazine. In general, such crosslinking monomers comprise from about 0.01% to 15%, preferably from about 0.5% to 5%, more preferably from 1% to 3% by weight of the total monomer solution prior to polymerization.

  The water-soluble or water-swelling polymer that serves as a reinforcing element is polysulfone (anionic), poly (sodium-4-styrenesulfonate), carboxymethylcellulose, polysulfone (anionic), poly (styrenesulfonic acid-co-malein) Acid) sodium salt, corn starch, any other water-soluble or water-swelling polymer, or a combination of at least one of the aforementioned polymers. The addition of reinforcing elements improves the ionic conductivity and mechanical strength of the separator. In general, such water soluble or water swelled polymers comprise from about 0% to 30%, preferably from about 1% to 10%, more preferably from 1% to 4% by weight of the total monomer solution prior to polymerization.

  It may also contain a polymerization initiator such as ammonium persulfate, alkali metal persulfates and peroxides, other initiators, or a combination of at least one of the aforementioned initiators. This type of initiator generally accounts for about 0% to 3% of the solution before polymerization. In addition, initiators may be used in combination with free radical generation methods such as radiation including ultraviolet light, X-rays, gamma radiation and the like. However, if radiation alone is strong enough for initiation of polymerization, it is not necessary to add a chemical initiator. Specific examples of suitable polymerization initiators include 1-phenyl-2-methyl-2-hydroxypropanone, ammonium persulfate, 4,4′-diazidostilbene-2,2′-disulfonic acid disodium salt, Benzenediazonium 4- (phenylamino) -sulfuric acid (1: 1) polymer with formaldehyde, 2- (2- (vinyloxy) ethoxy) -ethanol), but is not limited thereto. These initiators may be combined with charge transfer compounds such as triethanolamine that enhance activity.

  In addition, an acidity or alkalinity modifier may be included to neutralize the monomer solution. For example, if the monomer solution is acidic, an alkaline solution such as KOH may be added to neutralize the solution.

  The polymerization is generally carried out in the range from room temperature to about 130 ° C. In certain embodiments, the polymerization is heat induced, where high temperatures ranging from about 75 ° C. to about 100 ° C. are preferred. Depending on the situation, the polymerization may be carried out using radiation together with heating. Alternatively, depending on the intensity of the radiation, the polymerization can be carried out using only radiation without increasing the temperature of the components. Examples of radiation types useful for the polymerization reaction include, but are not limited to, ultraviolet light, gamma rays, X-rays, electron beams, or combinations thereof.

  In certain embodiments, water can be used as the substantially only liquid species that is added to the monomer solution. The water serves to create a matrix structure and acts as a space holder to increase the polymer volume after curing. Thus, the volume of the polymer matrix can be defined by a specific amount of water. Usually, water accounts for about 50% to 90%, preferably about 60% to 80%, more preferably about 62% to 75% of the weight of the polymeric matrix material.

  The polymer matrix membrane or material can be provided to the end user as is, or alternatively, the water can be replaced by a solution of the appropriate concentration of the desired ionic species. Since the initial water defines the volume of the polymer matrix material, it depends on the solution properties to be exchanged (ie acidity or alkalinity and concentration), but is appropriate for the desired ionic species with minimal swelling or reduction. It is possible to replace water with a solution of a different concentration. This is preferred because strength and ionic conductivity are greatly related to the volume and flexure of the ionic liquid phase. Large expansion of the polymer can reduce the strength of the final material. However, if the material does not swell enough to provide sufficient volume for the electrolyte, the conductivity is reduced. Typically, the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than about 50%, preferably less than about 20%, more preferably less than about 5%. It is. The solution replacement treatment can be performed in the form of dipping, soaking, spraying, contact with an ion exchange resin, or other techniques known to those skilled in the art.

  In one method of forming a polymeric material, the monomer solution, and optionally a polymerization initiator, is polymerized by heating or irradiation with ultraviolet light, gamma rays, X-rays, electron beams, or combinations thereof. When the ionic species are included in the polymerized solution, hydroxide ions (or other ions) remain in solution after polymerization. Further, to replace or add a desired solution to the polymer matrix, it can be added to the polymer matrix by immersing the polymer matrix in the desired solution.

  The polymer matrix membrane formed from the polymer matrix material can have a support material or substrate in one, which is preferably a polyolefin such as nylon, a woven or non-woven fabric such as polyvinyl alcohol, cellulose or polyamide. Alternatively, the substrate / support may be an anode, a charged electrode or a cathode (not illustrated).

  In another method of forming a polymer matrix membrane, a selected fabric may be immersed in a monomer solution (with or without the desired solution species), the solution-coated fabric is cooled, and a polymerization initiator is optional. To be added. The monomer solution can be polymerized by heating or by irradiation with ultraviolet light, gamma rays, X-rays, electron beams, or a combination thereof, thereby producing the polymeric material. When the desired ionic species is included in the polymerized solution, the ionic species remain in solution after polymerization. Further, when the polymer material does not contain an ionic species, for example, the polymer material may be added by immersing it in an ion solution.

  In order to control the thickness of the film, the monomer solution or the monomer solution coated on the cloth may be placed in a suitable mold prior to polymerization. Alternatively, the fabric coated with the monomer solution may be placed between a suitable film such as glass and polyethylene terephthalate (PET) film). The thickness of the film may vary and will be apparent to those skilled in the art based on the effect in a particular application. In certain embodiments, the membrane or separator may have a thickness of about 0.1 mm to about 0.6 mm, for example to sequester oxygen from the air. Since the actual conducting medium remains in the aqueous solution within the polymer backbone, the conductivity of the membrane is comparable to that of the liquid electrolyte and is quite high at room temperature.

  The polymer matrix material may be in the form of a hydrogel material having high conductivity, especially at room temperature. The material has a well defined macrostructure (ie form or shape). Furthermore, even if a portion of the polymer matrix material is cut or removed, for example, the material does not recombine, simply does not physically recombine by contact between the parts, It remains. This is in contrast to gelatinous materials (eg, Carbopol®-based materials), which are usually fluid and do not have independent macrostructures and can be distinguished when multiple separations are recombined. It becomes a lump of material that is not connected.

  Typically, the ionic conductivity is greater than about 0.1 S / cm, preferably greater than 0.2 S / cm, more preferably greater than about 0.4 S / cm. Its unexpectedly high ionic conductivity (currently up to 0.45 S / cm was not seen in conventional systems, but said polymer in the electrochemical cell described herein. It is important to note that this is achieved using a matrix membrane, in part because the electrolyte remains in a liquid phase within the polymer matrix. It also prevents penetration of the membrane by dendritic metal and protects the negative electrode from dendrite formation, especially during charging of rechargeable cells.The polymer matrix membrane further includes a metal oxidation product in the electrolyte. By preventing diffusion, cell destruction is also prevented.

EXAMPLES Preferred embodiments of the present invention are described in more detail below by way of the following examples provided by way of illustration, but are not limited thereby. The reactants and reagents used in the reaction are readily available materials. Such materials are conveniently prepared according to conventional preparative procedures, or are available from commercial sources.

  The following procedure is used to produce a strong polymer membrane for use in the present invention. 3.5 grams (g) of methylenebisacrylamide, 5.3 g of acrylamide, 2.6 g of 1,3,5-triacryloylhexahydro-1,3,5-triazine, 42.9 g of methacrylic acid, 6. 3 g of poly (sodium 4-styrenesulfonate), 1.8 g of 1-phenyl-2-methyl-2-hydroxypropanone and 7.0 g of triethanolamine were dissolved in 224.6 ml of water, Then 56.1 g of 50% KOH was added to the resulting solution and then kept at room temperature. A piece of fabric was immersed in the resulting monomer solution and then sandwiched between a piece of glass and a piece of PET transparent film. This was irradiated for 1 minute under intense UV light, thereby forming a strong polymer film. This film was then immersed in 45% KOH for 24 hours.

  The resulting film has very high hydroxide ion conductivity (0.45 S / cm) and is suitable for use in alkaline zinc / air cells. The conductivity was measured by Parico Battery Separator System Model 9100-2 (Palico Battery Separator Test System Model 9100-2, sold by Parico Instrument Laboratories, Circle Pines, Minnesota). Here, the membrane film is sandwiched between an air cathode and a zinc anode to separate air and zinc while allowing hydroxide ions to diffuse.

  While the preferred embodiment has been illustrated and described, various modifications and alternatives can be made without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the above description is illustrative and not restrictive.

Many other advantages and features of the present invention will become apparent upon reading the following detailed description of the embodiments with reference to the accompanying drawings. put it here
FIG. 1 is a schematic diagram of a zinc / air fuel cell incorporating the anode protective polymer matrix membrane and hydroxide conductive polymer matrix membrane of the present invention. FIG. 2 is a schematic diagram of a zinc / air fuel cell incorporating the polymer matrix membrane for anode and cathode protection of the present invention. FIG. 3 is a schematic diagram of an aluminum / air fuel cell incorporating the hydroxide conductive polymer matrix membrane of the present invention. FIG. 4 is a schematic diagram of a hydrogen / air fuel cell incorporating the proton or hydroxide conducting polymer matrix membrane of the present invention. FIG. 5 is a schematic view of an electrochromic device in which an electrochromic material is contained in a polymer matrix film of the present invention. FIG. 6 is a schematic diagram of a rechargeable metal / air battery according to the present invention having three electrodes, a porous spacer, and a polymer matrix membrane incorporated as a separator. FIG. 7 is a schematic diagram of a rechargeable metal / air battery according to the present invention having a polymer matrix membrane incorporated as an anode, a bifunctional electrode, and a separator.

Claims (95)

A polymer matrix material,
A polymerization product of one or more monomers that are water soluble and selected from the group of ethylenically unsaturated acids and acid derivatives;
A crosslinking agent, wherein a certain amount of water is used for the polymerization, said amount being selected such that upon curing the polymeric material expands to a defined volume.   The polymer matrix material according to claim 1 further comprises a water-soluble or water-swelling polymer.   The polymer matrix material according to claim 1 further includes a chemical polymerization initiator.   The polymer matrix material according to claim 1 further includes a water-soluble or water-swelling polymer and a chemical polymerization initiator.   The polymer matrix material according to claim 1 further has a neutralizing agent.   2. The polymer matrix material of claim 1, wherein the water is replaced with a solution of the desired species.   7. The polymer matrix material according to claim 6, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 50%.   7. The polymer matrix material according to claim 6, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 20%.   7. The polymer matrix material according to claim 6, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 5%.   7. The polymer matrix material of claim 6, wherein the species is selected from the group of an anion conducting species, a cation conducting species, a neutral species, an electrochromic species and a combination comprising at least one of the aforementioned species.   The polymer matrix material of claim 1, wherein water accounts for about 50% to about 90% of the polymer matrix material by weight.   The polymer matrix material of claim 1, wherein water accounts for about 60% to about 80% of the polymer matrix material by weight.   The polymer matrix material of claim 1, wherein water comprises from about 62% to about 75% of the polymer matrix material by weight. The polymer matrix material of claim 1, wherein the water soluble ethylenically unsaturated acid and acid derivative have the general formula:

Here, R1, R2 and R3 are each independently from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic compound, halogen, carboxylic acid derivative, sulfate and nitrate. Selected
R4 is selected from the group consisting of NR5, NHR5, NH2, OH, H, halide, OR5, and a carboxylic acid derivative, wherein R5 is H, C, C2-C6 alkane, C2-C6 alkene, C2 -C6 alkyne and selected from the group consisting of aromatic compounds.   The polymer matrix material according to claim 1, wherein the water-soluble ethylenically unsaturated acid and derivative are methylene bisacrylamide, acrylamide, methacrylic acid, acrylic acid, fumaramide, fumaric acid, N-isopropylacrylamide, N, N -Selected from the group consisting of dimethylacrylamide, 3,3-dimethylacrylic acid, maleic anhydride, and combinations having at least one of the aforementioned ethylenically unsaturated acids and derivatives.   The polymer matrix material according to claim 1, wherein the water-soluble ethylenically unsaturated acid and derivative are 1-vinyl-2pyrrolidinone), a sodium salt of vinyl sulfonic acid, and the aforementioned ethylenically unsaturated acid and derivative. Selected from the group of combinations comprising at least one of the objects.   2. The polymer matrix material of claim 1, wherein the ethylenically unsaturated acid or derivative comprises about 5% to 50% by weight relative to the total monomer solution prior to polymerization.   2. The polymer matrix material of claim 1, wherein the ethylenically unsaturated acid or derivative comprises about 7% to 25% by weight relative to the total monomer solution prior to polymerization.   2. The polymer matrix material of claim 1, wherein the ethylenically unsaturated acid or derivative comprises about 10% to 20% by weight relative to the total monomer solution prior to polymerization. The polymer matrix material of claim 1, wherein the general formula of the cross-linking agent is:

Where i = 1 → n and n ≧ 2.
R2, i, R3, i, and R4, i are from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic, halogen, carboxylic acid derivative, sulfate and nitrate Each selected independently,
R1 is selected from the group consisting of N, NR5, NH, O, and a carboxylic acid derivative, wherein R5 is H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne and aromatic compound Selected from the group consisting of   2. The polymer matrix material of claim 1, wherein the cross-linking agent is methylene bisacrylamide, ethylene bisacrylamide, any water soluble N, N′-alkylidene-bis (ethylenically unsaturated amide), and 1,3 , 5-triacryloylhexahydro-1,3,5-triazine, and a combination having at least one of the cross-linking agents.   2. The polymer matrix material of claim 1, wherein the cross-linking agent comprises about 0.01% to 15% by weight relative to the total monomer solution prior to polymerization.   The polymer matrix material of claim 1, wherein the cross-linking agent comprises about 0.5% to 5% by weight with respect to the total monomer solution prior to polymerization.   2. The polymer matrix material of claim 1, wherein the crosslinker comprises about 1% to 3% by weight with respect to the total monomer solution prior to polymerization.   7. A polymer matrix material according to claim 6, wherein the desired species comprises an alkaline solution.   26. The polymer matrix material of claim 25, wherein the alkaline solution comprises KOH.   27. The polymer matrix material of claim 26, wherein the conductivity is greater than about 0.1 Siemens / cm.   27. The polymer matrix material of claim 26, wherein the conductivity is greater than about 0.2 Siemens / cm.   27. The polymer matrix material of claim 26, wherein the conductivity is greater than about 0.4 Siemens / cm.   3. The polymer matrix material according to claim 2, wherein the water-soluble or water-swelling polymer is polysulfone (anionic), poly (sodium-4-styrenesulfonate), carboxymethylcellulose, polysulfone (anionic), poly (styrenesulfone). Acid-co-maleic acid) sodium salt, corn starch, any other water-soluble or water-swelling polymer, or a combination having at least one of the aforementioned polymers.   3. The polymer matrix material of claim 2, wherein the water soluble or water swelled polymer comprises less than about 30% of the polymer matrix material by weight.   3. The polymer matrix material of claim 2, wherein the water soluble or water swelled polymer comprises about 1% to 10% of the polymer matrix material by weight.   3. The polymer matrix material of claim 2, wherein the water soluble or water swelled polymer comprises about 1% to 4% of the polymer matrix material by weight.   5. The polymer matrix material according to claim 4, wherein the water-soluble or water-swelling polymer is polysulfone (anionic), poly (sodium-4-styrenesulfonate), carboxymethylcellulose, polysulfone (anionic), poly (styrenesulfone). Acid-co-maleic acid) sodium salt, corn starch, any other water-soluble or water-swelling polymer, or a combination of at least one of the aforementioned polymers.   5. The polymer matrix material of claim 4, wherein the water soluble or water swellable polymer comprises less than about 30% of the polymer matrix material by weight.   5. The polymer matrix material of claim 4, wherein the water soluble or water swelled polymer comprises about 1% to 10% of the polymer matrix material by weight.   5. The polymer matrix material according to claim 4, wherein the water-soluble or water-swelling polymer comprises 1% to 4% of the polymer matrix material by weight.   4. The polymer matrix material of claim 3, wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, or a combination having at least one of the foregoing initiators. The   4. The polymer matrix material of claim 3, wherein the chemical polymerization initiator comprises less than about 3% of the polymer matrix material by weight.   5. The polymer matrix material of claim 4, wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, or a combination having at least one of the foregoing initiators. The   5. The polymer matrix material of claim 4, wherein the chemical polymerization initiator is less than about 3% of the polymer matrix material by weight.   A method for producing a polymer matrix material, comprising water-soluble, polymerization of an aqueous solution of one or more monomers selected from the group of ethylenically unsaturated acids and acid derivatives, a crosslinking agent, and a curing agent A certain amount of water is selected so that the polymer matrix material expands to a predefined volume.   43. The method of claim 42, wherein the polymerization is carried out in a temperature range from room temperature to about 130 ° C.   43. The method of claim 42, wherein the polymerization is carried out in a temperature range from 75 ° C to about 100 ° C.   43. The method of claim 42, wherein the polymerization is performed using radiation together with heating.   43. The method of claim 42, wherein the polymerization is performed using radiation.   47. The method of claim 46, wherein the radiation source is selected from the group consisting of ultraviolet light, gamma rays, X-rays, electron beams or combinations thereof.   The method according to claim 46, wherein the aqueous solution further contains a chemical polymerization initiator.   45. The method of claim 42, comprising replacing the water with a desired species.   50. The method of claim 49, wherein the amount of the desired species is such that the difference between the volume of the polymer matrix material after seed replacement and the volume of the polymer matrix material before seed replacement is less than about 50%. And the concentration is selected.   50. The method of claim 49, wherein the amount and concentration of the desired species is such that the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than about 20%. Is selected.   50. The method of claim 49, wherein the amount of the desired species is such that the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than about 5%. And the concentration is selected. An electrochemical cell,
A first electrode;
A second electrode;
An electrolyte ionically conducting with the first electrode and the second electrode, wherein the electrolyte comprises a polymer matrix material, the polymer matrix material being water soluble and a group of ethylenically unsaturated acid and acid derivatives A polymerization product of one or more monomers selected from: and a crosslinking agent, wherein a certain amount of water is used for the polymerization, said amount expanding the polymer material to a predefined volume upon curing The water in the polymer matrix material is replaced with the desired solution.   54. The electrochemical cell according to claim 53, wherein the polymer matrix material further comprises a water soluble or water swellable polymer.   54. The electrochemical cell according to claim 53, wherein the polymer matrix material further comprises a chemical polymerization initiator. 54. The electrochemical cell according to claim 53, wherein the polymer matrix material further comprises a water soluble or water swellable polymer and a chemical polymerization initiator.   54. The electrochemical cell according to claim 53, wherein the polymer matrix material further comprises a neutralizing agent.   54. The electrochemical cell according to claim 53, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 50%.   54. The electrochemical cell according to claim 53, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 20%.   54. The electrochemical cell according to claim 53, wherein the difference between the volume of the polymer matrix material after seed substitution and the volume of the polymer matrix material before seed substitution is less than 5%.   54. The electrochemical cell according to claim 53, wherein the species replaced with water in the polymer matrix material is an anion conducting species, a cation conducting species, a neutral species, an electrochromic species, and at least one of the foregoing species. Selected from the group of combinations consisting of   54. The electrochemical cell according to claim 53, wherein water comprises from about 50% to about 90% of the polymer matrix material by weight before species replacement.   54. The electrochemical cell according to claim 53, wherein water comprises from about 60% to about 80% of the polymer matrix material prior to species replacement.   54. The electrochemical cell of claim 53, wherein water comprises from about 62% to about 75% of the polymer matrix material prior to species replacement. 54. The electrochemical cell of claim 53, wherein the water soluble ethylenically unsaturated acid and acid derivative have the general formula:

R1, R2 and R3 are each independently selected from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic, halogen, carboxylic acid derivative, sulfate and nitrate,
R4 is selected from the group consisting of NR5, NHR5, NH2, OH, H, halide, OR5, and a carboxylic acid derivative, wherein R5 is H, C, C2-C6 alkane, C2-C6 alkene, C2 -C6 alkyne and selected from the group consisting of aromatic compounds.   54. The electrochemical cell of claim 53, wherein the water soluble ethylenically unsaturated acid and derivative are methylene bisacrylamide, acrylamide, methacrylic acid, acrylic acid, fumaramide, fumaric acid, N-isopropylacrylamide, N, N -Selected from the group of combinations consisting of at least one of dimethylacrylamide, 3,3-dimethylacrylic acid, maleic anhydride and the aforementioned ethylenically unsaturated acids and derivatives.   54. The electrochemical cell of claim 53, wherein the water soluble ethylenically unsaturated acid and derivative are 1-vinyl-2-pyrrolidinone, sodium salt of vinyl sulfonic acid, and the ethylenically unsaturated acid and derivative described above. Selected from the group of combinations consisting of at least one of the objects. 54. The electrochemical cell of claim 53, wherein the ethylenically unsaturated acid and derivative are
It accounts for about 5% to 50% by weight of the total monomer solution before polymerization. 54. The electrochemical cell of claim 53, wherein the ethylenically unsaturated acid and derivative are
It accounts for about 7% to 25% by weight of the total monomer solution before polymerization. 54. The electrochemical cell of claim 53, wherein the ethylenically unsaturated acid and derivative are
It accounts for about 10% to 20% by weight of the total monomer solution before polymerization. 54. The electrochemical cell of claim 53, wherein the cross-linking agent has the general formula:

Where i = 1 → n and n ≧ 2.
R2, i, R3, i, and R4, i are from the group of H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne, aromatic, halogen, carboxylic acid derivative, sulfate and nitrate Each selected independently,
R1 is selected from the group consisting of N, NR5, NH, O, and a carboxylic acid derivative, wherein R5 is H, C, C2-C6 alkane, C2-C6 alkene, C2-C6 alkyne and aromatic compound Selected from the group consisting of   54. The electrochemical cell of claim 53, wherein the cross-linking agent is methylene bisacrylamide, ethylene bisacrylamide, any water soluble N, N'-alkylidene-bis (ethylenically unsaturated amide), 1,3,5. -Selected from the group consisting of triacryloylhexahydro-1,3,5-triazine and at least one combination of the aforementioned crosslinking agents.   54. The electrochemical cell of claim 53, wherein the crosslinking agent comprises about 0.01% to 15% by weight of the total monomer solution prior to polymerization.   54. The electrochemical cell of claim 53, wherein the cross-linking agent comprises about 0.5% to 5% by weight of the total monomer solution prior to polymerization.   54. The electrochemical cell of claim 53, wherein the crosslinking agent comprises about 1% to 3% by weight of the total monomer solution prior to polymerization.   54. The electrochemical cell according to claim 53, wherein the desired species comprises an alkaline solution.   77. The electrochemical cell according to claim 76, wherein the alkaline solution comprises KOH.   78. The electrochemical cell of claim 77, wherein the conductivity is greater than about 0.1 Siemens / cm.   78. The electrochemical cell of claim 77, wherein the conductivity is greater than about 0.2 Siemens / cm.   78. The electrochemical cell of claim 77, wherein the conductivity is greater than about 0.4 Siemens / cm.   55. The electrochemical cell according to claim 54, wherein the water-soluble or water-swelling polymer is polysulfone (anionic), poly (sodium-4-styrenesulfonate), carboxymethylcellulose, polysulfone (anionic), poly (styrenesulfone). Acid-co-maleic acid) sodium salt, corn starch, any other water-soluble or water-swelling polymer, or a combination having at least one of the aforementioned polymers.   55. The electrochemical cell of claim 54, wherein the water soluble or water swelled polymer comprises less than about 30% of the polymer matrix material by weight.   55. The electrochemical cell of claim 54, wherein the water soluble or water swellable polymer comprises about 1% to 10% of the polymer matrix material by weight.   55. The electrochemical cell of claim 54, wherein the water soluble or water swelled polymer comprises about 1% to 4% of the polymer matrix material by weight.   57. The electrochemical cell according to claim 56, wherein the water-soluble or water-swelling polymer is polysulfone (anionic), poly (sodium-4-styrenesulfonate), carboxymethylcellulose, polysulfone (anionic), poly (styrenesulfone). Acid-co-maleic acid) sodium salt, corn starch, any other water-soluble or water-swelling polymer, or a combination having at least one of the aforementioned polymers.   57. The electrochemical cell of claim 56, wherein the water soluble or water swelled polymer comprises less than about 30% of the polymer matrix material by weight.   57. The electrochemical cell of claim 56, wherein the water soluble or water swellable polymer comprises about 1% to 10% of the polymer matrix material by weight.   57. The electrochemical cell of claim 56, wherein the water soluble or water swellable polymer comprises about 1% to 4% of the polymer matrix material by weight.   56. The electrochemical cell of claim 55, wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, or a combination having at least one of the foregoing initiators. Is done.   56. The electrochemical cell of claim 55, wherein the chemical polymerization initiator comprises less than about 3% of the polymer matrix material by weight.   57. The electrochemical cell according to claim 56, wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, or a combination having at least one of the foregoing initiators. Is done.   57. The electrochemical cell of claim 56, wherein the chemical polymerization initiator comprises less than about 3% of the polymer matrix material by weight.   54. The electrochemical cell according to claim 53, wherein the first electrode is a metal fuel and the second electrode is an air diffusion electrode.   54. The electrochemical cell according to claim 53, wherein the first electrode has a hydrogen releasing electrode and the second electrode has an air diffusion electrode.     54. The electrochemical cell according to claim 53, wherein the first electrode is a metal fuel, the second electrode is an air diffusion electrode, and is electrically conductive with the first electrode, the second electrode. And a third electrode that is electrically insulated from each other.

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