TW201228081A - Electrodes and production and use thereof - Google Patents

Abstract

Electrodes, comprising (A) a solid medium through which gas can diffuse, (B) at least one electrically conductive, carbonaceous material, (C) at least one organic polymer, (D) at least one compound of the general formula (I) M1aM2bM3cM4dHeOf (I) in particulate form, where the variables are each defined as follows: M1 is selected from Mo, W, V, Nb and Sb, M2 is selected from Fe, Ag, Cu, Ni, Mn and lanthanoids, M3 is selected from B, C, N, Al, Si, P and Sn, M4 ist selected from Li, Na, K, Rb, Cs, NH4, Mg, Ca and Sr, a is in the range from 1 to 3, b is in the range from 0.1 to 10, c is in the range from zero to one, d is in the range from zero to one, e is in the range from zero to 5, f is in the range from 1 to 28, and wherein compound of the general formula (I) has a BET surface area in the range from 1 to 300m<SP>2</SP>/g.

Description

201228081 VI. Description of the Invention: [Technology of Invention] Field of the Invention The present invention relates to an electrode comprising: (A) a solid medium through which a gas can diffuse, (B) at least one conductive carbonaceous material, (C) at least An organic polymer, (D) at least one compound of the formula (1) M1aM2bM3cM4dHe〇f (I) in the form of particles, wherein the variables are each defined as follows: M1 is selected from the group consisting of Mo, W, V, Nb and Sb, and Μ2 is selected From Fe, Ag, Cu, Ni, Μη and lanthanide metals, M3 is selected from B, C, N, A, Si, P and Sn, and M4 is selected from Li, Na'K, Rb, Cs, NH4, Mg , Ca and Sr, a are in the range of 1 to 3, b is in the range of 0.1 to 10, C is in the range of 0 to 1, d is in the range of 0 to 1, and e is in the range of 0 to 1. Within the range of 5, f is in the range of 1 to 28, and the compound of the formula (I) thereof has a coffee surface area in the range of i to 3 〇〇 m 2 /g. Ding electro-acupuncture, for example, in metal-air battery packs, for example, in cadmium-air battery packs, Shao. Pool Group or iron-air battery packs, and especially Zn•air battery packs; 156873.doc 201228081. The invention further relates to a method of making an electrochemical cell of the invention' and a method of making the electrode of the invention. [Prior Art] An alternative to conventional electrochemical cells has been studied for many years. In conventional electrochemical cells, charge transport is carried out to some extent by hydrated protons, and thus the maximum voltage is limited. One of the alternatives to the storage medium for electrical energy is a lithium ion battery pack in which charge transport is ensured by lithium ions in a non-aqueous solvent. However, many of these battery packs are sensitive to air and moisture, which in the worst case can cause spontaneous combustion of the defective lithium ion battery. Furthermore, electrochemical cells are expected to have high energy density. An improvement is provided by a metal-air battery pack (e.g., a word battery). In a common embodiment, the metal (e.g., rhodium) is oxidized by atmospheric oxygen in the presence of an inert electrolyte to form an oxide or hydroxide. The release of the pound is electrochemically utilized. Such a battery pack can be recharged by resuming metal ions formed in the discharge. For this purpose, it is known to use a gas diffusion electrode (GDE) as a cathode. The gas diffusion electrode is porous r and has a dual function. The metal_air battery must be capable of reducing atmospheric oxygen to hydroxide ions during discharge and oxidizing hydroxide ions to oxygen during charging. For this purpose, for example, it is known that the gas diffusion electrode is located on a carrier material composed of finely dispersed carbon, the carrier material comprising a catalyst for catalyzing oxygen reduction or oxygen evolution &amp; or poly(tetra). The choice of catalyst here is very important. In this paper, the following distinctions are described: pure discharge catalysts, for example, metal oxides, for example, on 〇 2, 156873.doc 201228081

Co304, La203, LaNi〇3, NiC〇2〇4, LaMn〇3 and LaNi〇3; metals such as Ag; metal complexes such as CoTMMP (tetramethoxyphenyl porphyrin) and FeTMMP-Cl Metal nitrides such as Mn4N, CrN, Fe2N; metal carbides such as TaC, TiC and WC; and bifunctional catalysts, for example, about titanium ore, such as La〇.8Sr〇.2B〇3 (see, V· Neburchilov et al. 'J. Power Scources, 2010, 195, 1271) or La 〇. 6 Ca 〇 . 4 Co 〇 3 (see WO 2003/54989). WO 2007/065899 discloses a dual function catalyst for a secondary metal-air battery, wherein the active layer of the electrode comprises an oxygen reduction catalyst and a dual function catalyst selected from the group consisting of La203, Ag20 and spinel. No. 5,3,8,862 discloses an electrode material consisting of agglomerated mixtures of graphite, NiS, FeW〇4 and WC which have been coated with cobalt. All materials known from the prior art cited above may still be modified for at least one of the following properties: electrocatalytic activity, chemical chemistry, electrochemical corrosion resistance, mechanical stability, good adhesion to carrier materials, and Conductive carbon black, binder and, if present, low interaction of the discharge catalyst. SUMMARY OF THE INVENTION Therefore, the electrodes defined above have been found. An electrode as defined above (also referred to herein as an electrode of the invention) comprises: (A) a solid medium through which a gas can diffuse, also referred to herein as medium (A) or carrier (A), (B) at least A conductive carbonaceous material, (C) at least one organic polymer, 156873.doc 201228081 (D) at least one compound of the formula (1) in the form of particles

MiaM2bMWdHeOf (I) wherein the variables are defined as follows: M1 is selected from the group consisting of Mo, W, V, Nb and Sb, Μ2 is selected from the group consisting of Fe, Ag, Cu, Ni, Μ and lanthanide metals, and M3 is selected from lanthanum, C, Ν, SiSi, Ρ and Sn, M4 is selected from the group consisting of Li, Na, K, Rb, Cs, NH4, Mg, Ca and Sr, a is in the range of 1 to 3, and b is in the range of 0.1 to 10. Within the range, c is in the range of 0 to 1, d is in the range of 0 to 1, e is in the range of 0 to 5, f is in the range of 1 to 28, and its formula (I The compound has a BET surface area in the range of from 1 to 300 m2/g. [Embodiment] In the present invention, a solid medium through which a gas can diffuse (also referred to as medium (A) for short) is preferably also considered to be a porous body through which oxygen or air can diffuse even if no high pressure is applied, for example, a metal mesh and a gas diffusion medium composed of carbon (especially activated carbon) and a carbon-coated metal mesh. For example, the gas permeability can be measured by the Gurley method similar to the measurement of the gas permeability of paper or paperboard. In an embodiment of the invention. Medium (A) has between 20 and 1000 seconds/10 156873.doc 201228081

The Cm3 air' is preferably a porosity in the range of 40 to 120 seconds/10 cm3. In this article, 'seconds' means "Geli seconds." In one embodiment of the invention, flow through the medium (A) is impeded. In one embodiment of the invention, air or atmospheric oxygen may be substantially unimpeded. Medium (A) is a medium that conducts electrical current. In a preferred embodiment of the invention, the medium (A) is chemically inert with respect to the reaction in an electrochemical cell during standard operation (i.e., during charging and during discharge). In one embodiment of the invention, the medium is selected from carbon having a bet surface area (preferably referred to as an apparent bet surface area) in the range of from 2 Torr to 1500 m2/g. In one embodiment of the invention, the medium (A) is selected from a metal mesh, such as a nickel mesh or a button mesh. The metal mesh can be thick and thin. In another embodiment of the invention, the medium is selected from the group consisting of a fabric comprising a wire, a mat, a felt or a non-woven fabric. In one embodiment of the invention, the medium is selected from the group consisting of a gas diffusion medium, for example, activated carbon, oxidized aluminum-doped, tin-doped tin oxide or porous carbide or nitride 'eg 'wc, M〇2c , m〇2n, TiN, ZrN or TaC. The electrode of the present invention further comprises at least one electrically conductive carbonaceous material (B) (also referred to herein as electrically conductive carbon (B)). The conductive carbon (B) may be selected from, for example, graphite, activated carbon, carbon black, carbon nanotubes, graphene or a mixture of at least two of the foregoing. In one embodiment of the invention, the electrically conductive carbon (B) is carbon black. Carbon black (eg, 156873.doc 201228081) is selected from the group consisting of lamp black, furnace carbon black, flame carbon black, hot carbon black, B fast black, and industrial carbon black. The carbon black may contain impurities such as hydrocarbons, especially aromatic and, or oxygenates or oxygen-containing groups, such as hydrazine H*. In addition, sulfur or iron-containing impurities may also be present in the carbon black. In the case where the medium (A) and the conductive carbon (B) are selected as activated carbon, the matrix (A) and the conductive carbon (B) may be chemically different or preferably identical. The conductive carbon (B) may, for example, be present in the form of particles having a diameter in the range of (^ to 丨(10) mm, preferably 2 to 2 〇μηη. In one variation, the conductive carbon (Β) is a partially oxidized carbon. In one embodiment of the invention, the conductive carbon (cerium) comprises a carbon nanotube. Carbon nanotubes (abbreviated as CNT), such as single-wall carbon nanotubes (sw CNT), are preferred. Wall carbon nanotubes (MW CNT). Its manufacturing method and some properties (for example) are described by A_ jess et al. in Chemie “讧...

Technik 2006, 78, 94-100. In an embodiment of the invention, the carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm. In one embodiment of the invention, the carbon nanotubes have a length in the range of mm, preferably 100 11111 to 5 〇〇 nm. The carbon nanotubes can be prepared by well-known methods. For example, a carbon-containing compound (eg, 'methyl or carbon monoxide, acetylene, or ethylene) may be present in the presence of one or more reductions such as 'hydrogen' and/or another gas (eg, nitrogen). (eg 'synthetic gas'). Alternatively - a suitable mixture of carbon monoxide and ethylene. The suitability for decomposition is, for example, within the scope of (10) generations. 156873.doc 201228081 Suitable pressure conditions for decomposition are, for example, within a range of 100 bar, preferably 1 bar. Single or multi-walled carbon nanotubes can be obtained, for example, by decomposing carbonaceous compounds in the arc of light, specifically in the presence or absence of a decomposition catalyst. In the embodiment, the decomposition of the volatile carbon-containing compound or the carbon-containing compound is carried out in the presence of a decomposition catalyst (e.g., Fe, Co or preferably Ni). In the context of the present invention, graphene is meant to mean a nearly ideal or ideal two-dimensional hexagonal carbon crystal having a structure similar to a single graphite layer. In the embodiment of the invention, the electrically conductive carbon (8) and in particular the carbon black have a BET surface area in the range from 20 to 1500 m2/g as measured by ISO 9277. The electrode of the present invention comprises at least one organic polymer 'abbreviated as polymer (C) or binder (C). As used herein, the term "organic polymer" also includes organic copolymers, and means that the main chain contains predominantly carbon atoms (ie, at least 5 mole %) and can be polymerized by free radical polymerization, anionic, cationic or catalytic polymerization. Or a polymeric compound prepared by addition polymerization or condensation polymerization. Particularly suitable polymers (C) may be selected, for example, from (co)polymers obtainable by anionic, catalytic or free radical (co)polymerization, especially selected from the group consisting of polyethylene, polyacrylonitrile, polybutylene a copolymer of a diene, a polystyrene, a polyethyleneimine, and at least two comonomers selected from the group consisting of ethylene, propylene, styrene, (meth)acrylonitrile, and i,3-butadiene. Polypropylene is also suitable. Polyisoprene and polyacrylates are also suitable. The most preferred one is polyacrylonitrile. As used herein, &quot;polyacrylonitrile&quot; is understood to mean not only a polyacrylonitrile homopolymer&apos; but also a copolymer of acrylonitrile and 1,3-butadiene or styrene. Preferred are polyacrylonitrile homopolymers. 156873.doc 10· 201228081 In the context of the present invention, polyethylene is understood not only to mean homopolyethylene, but also to mean at least 50 mol% of copolyethylene and up to 5 mol% of at least one other co-monomer (for example, _-olefins such as propylene, butene (butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, pentene and isobutylene; vinyl aromatic hydrocarbons, for example, styrene And (indenyl) acrylic acid, vinyl acetate, vinyl propionate, Ci_Ci decyl (meth) acrylate, especially methyl acrylate, methacrylate, ethyl acrylate, ethyl methacrylate, An ethylene copolymer of n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate; and maleic acid, maleic anhydride, and itaconic acid. The polyethylene can be HDPE or LDPE. In the context of the present invention, 'polypropylene is understood to mean not only homopolypropylene, but also means at least 50 m〇l% of copolypropylene and at most 5〇m〇1% of at least one other co-monomer (for example, ethylene and α_). A propylene copolymer of an olefin such as butene, hexylene, hydrazine, hydrazine, 1 undoxene and pentylene. Polypropylene is preferably isotactic or substantially isotactic polypropylene. In the context of the present invention, polystyrene is understood to mean not only a homopolymer of styrene but also an alkyl group with acrylonitrile, hydrazine, 3-butadiene, (meth)acrylic acid, (meth)acrylic acid. Copolymer, divinylbenzene, especially copolymer of i,3-divinylbenzene, 1,2-diphenylethylene and fluorene-methylstyrene. Another preferred binder (polymer (c)) is polybutadiene. Further suitable polymers (c) are selected from the group consisting of polyethylene oxide (pE), cellulose, carboxymethyl cellulose, polyimine and polyvinyl alcohol. In one embodiment of the invention, the polymer (c) is selected from the group consisting of having a range of from 5〇〇(9) to 1 000 〇〇〇g/m〇i, preferably up to 5〇〇〇〇〇g/m〇l The average score within the 156873.doc •11·201228081 sub-quantity of the goods of the (co)polymer. The polymer (c) may be a crosslinked or uncrosslinked (co)polymer. In a particularly preferred embodiment of the invention, the polymer (6) is selected from a halogenated (co)polymer, which is selected, inter alia, from a (co)polymer or a fluorinated (co)polymer: a (co)polymer comprising at least one (co)polymerized (co)monomer having at least one (four) or at least one atomic atom per molecule, preferably at least two tooth atoms per molecule or at least two fluorine atoms . Examples are polyvinyl chloride, polyvinylidene oxide, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropene copolymer, vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) ), a vinylidene fluoride-tetrafluoroethylene copolymer, a terpene-based ethylene-based copolymer, an ethylene-tetrafluoroethylene copolymer, a vinylidene fluoride-gas difluoroethylene copolymer, and an ethylene-gas fluoroethylene copolymer. Things. Suitable polymers (C) are, in particular, polyvinyl alcohols and halogenated (co)polymers, such as polyethylene or polyvinylidene chloride, especially fluorinated (co)polymers, such as polydivinyl and especially polypyridyl Vinyl fluoride and polytetrafluoroethylene. The present invention (4) further comprises at least one compound M1aM2bM3cM4dHeOf (|) of the formula (1) of the formula (4), which is also simply referred to as the compound (D) ' wherein the variables are defined as follows: ^ is selected from the group consisting of Mo, W, V, Nb and Sb, preferably v, M〇 and w, Μ2 is selected from the group consisting of Fe, Ag, Cu, Ni, Μ and lanthanide metals, preferably Fe, Ag and especially lanthanide metals La and Ce, Μ3 Self-Μ 4 is selected from the group consisting of Li, Na, K, Rb, Cs, NH4, Mg, and Cawr^ 156873.doc 12 201228081 The best is NH4, Li, K and Na, a is in the range of 1 to 3, preferably 1, b is in the range of 0.1 to 1 ,, preferably 0.3 to 3, c is in the range of 〇 to 1 'preferably to 0.2, and d is in the range of 〇 to 1, preferably to 0.2, e It is in the range of 5' to io, f is in the range of 1 to 28, and the compound of the formula (I) thereof has 1 to 3 〇〇m2/g, preferably 1 to 1 〇. 〇m2/g, more preferably BET surface area in the range of 1 to 5 〇 m 2 /g. In one embodiment of the invention, the variable f is selected such that the compound (D) is uncharged. In another embodiment of the invention, the variable f is selected such that the compound (D) is non-charged, e.g., the band is less than 〇 to _2. When the variable 4 is selected to be not equal to 〇, hydrogen is preferably present in the compound (D) _ with the oxy-ion ion. In the embodiment of the present invention, m1, m2, and m^4 in the compound (D) are selected from a mixture of at least two elements. For example, it is selected from a mixture of Fe and Ag. For example, M丨 can be selected from a mixture of v_〇. In the examples of the present invention, the compound (d) is selected from the group consisting of mixed oxides and isopolyacids and salts thereof. The compound (9) is preferably selected from the group consisting of mixed oxides. In an embodiment of the invention, the compound (9) is selected from IFe_Ag_x_〇,

Fe-v-X-〇, Ag x 〇, wherein X is selected from the group consisting of cranes and preferably molybdenum. 156873.doc •13·201228081 In an embodiment of the invention, the Fe-Ag-Χ-Ο system in the compound (1) from the compound of the formula (II)

XeFebiAgb2〇f 00 wherein the sum of the variables bl and b2 is 〇.丨 to 1〇 and its covariates are as defined above. In one embodiment of the present invention, Fe_v_x_〇 is selected from the group consisting of preferably 0.3 to 3, and the formula (III)

ValXaiFebOf (III) wherein the sum of the variables al and a2 is defined by the remainder of the remainder. In the range of the compositions 1 to 3 and preferred in the embodiment of the present invention, and the 'Ag-V-Χ-Ο system is selected from the group consisting of the formula (IV)

VaiXa2Agb〇f wherein the variables are as defined above in an embodiment of the invention (IV)

Ce-x-0 is selected from the group consisting of the formula (V) ^ (V) wherein the variables are as defined above. Compound (D) is in the form of particles. « Ml, 'In this case, the particles may be regular or irregular in shape and have a regular shape. For example, a spherical shape, a small plate shape, a needle shape or not according to the present invention - the embodiment IS e , the yttrium compound (1)) has a + average primary particle diameter within 10 to 50 nmg of solid. Etiquette, _ by # X π sentence primary particle size can be determined by microscope, for example, fine and tracing electrons *' brother or by transmission electron microscope 156873.doc •14·201228081 (TEM). In the embodiment of the present invention, the compound (9) is in the form of coalesced particles: in this case, the agglomerates may have 2. Give 1 〇〇 之 平 :. In this case, the agglomerates may have an appearance in which the particles of the compound (9) are, for example, at least two to several thousands of primary particles. In one embodiment of the present invention, the compound (D) has a 表面积τ surface area of from 1 to 30 〇 m 2 / _ in accordance with IS0 9277. In the embodiment of the present invention, the compound (9) has a bimodal particle size distribution. In an embodiment of the invention, the electrode of the invention comprises a mixture of at least two different compounds (D). In an embodiment of the invention, the electrode of the invention comprises based on the total electrode: conductive carbon (8) in the range of 20 to 50% by weight, preferably 35 to 45% by weight, in 5 to 45% by weight, preferably 3 to Polymerization _ in the range of 4% by weight, and compound (1) in the range of 55 to 25% by weight, preferably 5 to 15% by weight. In one embodiment of the invention, the electrode of the invention further comprises at least one discharge catalyst (E). Examples of suitable discharge catalysts (E) are, for example, La2〇3, Ag2〇, spinel, for example, LiMn204, Mn02, Ag, CoTMMP (tetrakis-p-methoxybenzamine), FeTMMP-Cl , Mn4N, CrN, Fe2N, TaC, TiC, WC, Co304, La203, LaNi〇3, NiCo204, LaMn03,

LaNi〇3, especially Ag and Ag/C. The discharge catalyst (E) is preferably in the form of particles. In this case, the particles may be regular or irregular in shape, and have, for example, a spherical shape, a small plate shape, a needle shape or an irregular shape. The average diameter of the discharge catalyst particles can be in the range of 2 nm to 100 μm. The particles of Ag (also referred to herein as Ag particles) may, for example, have an average diameter in the range of 2 to 200 nm, preferably 10 to 50 nm. If it is desired to use Ag-coated carbon as a discharge catalyst, the Ag particles may have a diameter in the range of 2 to 200 nm, and the carbon particles have a diameter in the range of 〇1 to 1 〇〇 μπι. In an embodiment in which the electrode of the present invention comprises at least one discharge catalyst (Ε), the electrode of the present invention comprises a total of a conductive carbon (Β), a polymer ((:), and a compound (D) a ten in the range of 5 to 80 Discharge catalyst (E) in the range of weight / 〇. In a preferred embodiment in which the electrode of the present invention comprises Ag particles as a discharge catalyst (E), the electrode of the present invention comprises conductive carbon (B), a polymer and a compound. The sum of (D) is in the range of 55 to 15% by weight, preferably 2 to 6% by weight, of the discharge catalyst (E). The electrode of the present invention comprises Ag particles covered with carbon as a discharge catalyst (E). In a preferred embodiment, the electrode of the present invention comprises a discharge catalyst (E) in the range of from 1 Torr to 8% by weight of 'conductive to % by weight based on the total of conductive carbon (8), polymer (6) and &amp; (D). In the present invention, the electrode of the present invention may have other components. Suitable other components are, for example, a solvent, which is understood to mean an organic solvent: especially isopropanol, N-methyl. Specific phase, n, n_: methyl acetamide, 'n-propanol or hexanone. More suitable solvent ring Or acyclic organic carbonated vinegar 'for example, carbonic acid diethylation, carbonic acid extension g |, carbonic acid propylene vinegar, carbonic acid dimethyl vinegar and ethylene carbonate @ 甲甲3; and cyclic or acyclic organic 156873. Doc 201228081 and cyclic or non-vinegar 'for example 'methyl formate, ethyl acetate or γ-butane vine cyclic ether, for example, hydrazine, 3 -dioxolane. Furthermore, the electrode of the invention may comprise water. Second, the bright electrode can be constructed in various forms. For example, in the case where the carrier (4) is selected from a metal mesh, the form of the electrode of the present invention can be substantially defined by the form of a metal grid. Further, the carrier (4) is selected from activated carbon. In the case of finely dispersed activated carbon (eg, having an average particle size within the range of H1), the electrode is applied to the metal mesh as a formulation (eg, as a paste or paste). a gas diffusion medium composed of carbon or a gas diffusion medium composed of a carbon-coated metal mesh. The present invention further provides an electrode of the invention to an electrochemical cell, for example, a non-rechargeable electrochemical cell (also referred to as Primary battery pack) or rechargeable Use in a chemical battery (also referred to as a secondary battery pack). The invention further provides a method of making an electrochemical cell using at least one electrode of the invention. The invention further provides an electrochemical cell comprising at least one electrode of the invention. In a preferred embodiment of the invention, the electrochemical cell of the invention comprises

Cd-air battery pack, Fe_air battery pack, A1 air battery pack or zinc/air battery pack. The electrochemical cell of the present invention may have other components, for example, an outer shape, particularly a cylindrical, disc or rectangular parallelepiped casing, and at least one counter electrode. The opposite electrode contains as an essential component a metal in the form of an element 'for example, Fe, A, Cd or especially zinc. 156873.doc • 17- 201228081 The metal in elemental form may be a solid slab, a sintered porous electrode or a metal powder or The form of the pellets, which are sintered as needed. In one embodiment, the metal (especially zinc) is in the form of an element having a powder having an average particle diameter (average number of values) in the range of, for example, 2 μm to 500 μm, preferably 30 to 100 μm. In one embodiment, the metal in powder form is mixed with an organic binder to improve dimensional stability. Suitable organic binders are polysulfones, polyethersulfones and especially fluorinated (co)polymers such as polytetrafluoroethylene (pTFE) and polyvinylidene fluoride (PVDF). In a preferred embodiment, the metal in powder form, especially zinc in powder form, is used in combination with a paste or paste of an organic binder. The electrochemical cell of the present invention may further comprise at least one spacer that mechanically separates the electrically charged electrodes from one another, thereby preventing short circuits. Suitable spacer polymer films&apos; are in particular porous polymer films which are not reactive towards metals in elemental state and media which are generally strongly alkaline in the electrochemical cells of the invention. Particularly suitable materials for the spacer are polyolefins, especially porous polyethylene films and porous polypropylene films. Polycarbonate spacers, especially polyethylene or polypropylene spacers, may have from 35 to 45. Porosity in the range of /. A suitable pore size is, for example, in the range of 3 Å to 5 Å nm. In another embodiment of the invention, the spacer may be selected from PET nonwovens filled with alkali stabilized inorganic particles. These spacers may have a porosity in the range of 4 〇 to 55 〇 / 。. A suitable aperture system is, for example, in the range of 8 〇 to 75 〇 nm. 156873.doc 18·201228081 To fabricate an electrochemical cell of the present invention, the procedure can be, for example, combining the electrodes, spacers, and opposing electrodes of the present invention with one another and introducing them into a housing having any other components. The electrochemical cell of the present invention may further comprise at least one electrolyte which is a combination of at least one solvent and at least one type of salt compound or salt. Examples of suitable electrolytes are, in particular, aqueous alkaline solutions, for example sodium hydroxide solutions or hydroxide decompression solutions. In one embodiment of the invention, the electrochemical cell of the present invention may comprise another electrode, for example, as a reference electrode. Another suitable electrode is, for example, a zinc wire. The invention further provides a method of making the electrode of the invention, hereinafter also referred to as the method of manufacture of the invention. To practice the manufacturing method of the present invention, the procedure may be to (B) at least one electrically conductive carbonaceous material, (C) at least one organic polymer, and (D) at least one in particulate form and having from 1 to 3 〇〇m2/g The compound of formula (I) having a BET surface area in the range is applied in one or more steps to (A) a solid medium through which the gas can diffuse. The procedure may specifically be as follows: (B) at least one electrically conductive carbonaceous material (C) at least one organic polymer and (D) at least one in particulate form and having a BET surface area in the range of from 1 to 3 〇〇 m 2 /g The compound of the formula (I) 156873.doc • 19·201228081 is applied in the form of an aqueous or solvent-based ink or a preferred aqueous paste or preferably an aqueous paste to (A) a solid medium through which the gas can diffuse. The compound of formula (I) is as described above. The remaining variables are also as described above. Compound (D) (e.g., coating) may also be treated first with conductive carbon (B), and then mixed with polymer (C) and applied to carrier (a). For example, the coating can be applied by spraying (e.g., spraying or misting) and knife coating, printing, or by pressing. In the context of the present invention, the spray also includes application by squirting. This method is often also referred to as "air brushing" or simply "airbrushing". The manufacturing process of the present invention is, for example, from one or more compounds (d). For example, compound (D) can be prepared by mixing suitable compounds of (4) and/or m4 as needed, for example, in dry form or as a solution or suspension. Preferably, according to the stoichiometry of Μ1, Μ, Μ and Μ# in the compound (D), the ratio of the compound to the desired compound is selected. The mixture obtained in this way is then passed through a heat; for example, the pot can be calcined, for example, at a temperature of from 250 to, preferably in the range of just t: the calcination can be carried out in an inert gas or in an oxidizing atmosphere, for example Air (or another mixture of inert gas and oxygen) is carried out. The calcination time can range from a few minutes to a few hours. Suitable starting materials which can be used to make the compound (9) include oxides, gas oxides or base oxides of μ1, yttrium, W and MW. Other such compounds which may be used, M, M2, M3 and/or M4, are present in the presence of oxygen or in the presence of 156873.doc 201228081 due to the heating reaction to produce oxides, hydroxides or base oxides. Compound (D) can be prepared by mixing the starting materials in a dry or wet form. If it is to be carried out in a dry form, the starting material for the preparation of the compound (D) can be used in the form of a fine powder, and after calcination and, if necessary, calcination. However, it is preferred to carry out intimate mixing in a wet form. In general, this involves mixing the starting materials f used to prepare the compound (D) with each other in the form of an aqueous solution and/or a suspension. The starting of the preparation of the compound (D) can be obtained by starting from the compound of M丨, M2, M3 and/or Μ# in a dissolved form and precipitating a compound of ruthenium, osmium, M3 and/or μ4. A very good mixture of substances. The aqueous material obtainable therefrom is then dried in an excellent drying manner at a temperature in the range of preferably from 1 (10) to 15 (rc), and is spray dried, especially at an outlet temperature in the range of (10) to thief. The step of establishing the desired particle size of the compound (9) may be carried out before, during or after the heat treatment, for example, screening, grinding or grading. In the optional step, the ruthenium is treated with conductive carbon (8) (9), for example, coated. () To carry out this treatment, for example, the compound (D) can be sufficiently blended with the conductive carbon (B), for example, if it is ground. For example, a grinder, especially a ball mill, is suitable for grinding. In another variation in which the compound (D) is treated by conductive carbon (8) as needed, carbon may be deposited on the compound (D), for example, by decomposing an organic compound. This is then mixed with polymer (C) which can be added, for example, in the form of an aqueous dispersion or pellet. 156873.doc -21- 201228081 In another embodiment, compound (D), conductive carbon (B) may be mixed in one step, for example, by stirring the corresponding solid with one or more organic solvents or with water as needed. And polymer (C) wherein polymer (c) can be added, for example, in the form of an aqueous dispersion or pellet. As the mixing, for example, a stirring device such as a stirring tank or a grinder (for example, a ball mill and especially an agitating ball mill) can be used. In other embodiments, ultrasonic waves are used, for example, by means of a sonotrode. This results in a preferred aqueous formulation. Subsequently, the desired properties of the preferred aqueous formulation to be applied, such as viscosity or solids content, are determined. In the present invention, these preferred aqueous formulations having a solids content in the range of 0.5 to 25% are referred to as inks. These preferred aqueous formulations having a solids content greater than 25% are referred to as pastes. In one embodiment of the invention, the preferred aqueous formulation comprises at least one surfactant. In the context of the present invention, the surfactant is a surface active substance. The surfactant may be selected from the group consisting of cationic, anionic and preferably nonionic surfactants. Subsequent length 1 supply; quality (A) or carrier (A), and preferably aqueous formulation or comprising conductive carbon (B), polymer (c), compound (D) and any discharge catalyst (E) Preferred aqueous formulations are applied to the medium (a) or carrier (4) in one or more steps. This application can be carried out, for example, by dusting, spraying (especially by spraying), and by knife coating or preferably printing. In another embodiment of the present invention, the solvent-free conductive carbon (B) poly-sigma (C) can be, for example, at a pressure in the range of 3 Torr to 3 Torr and a temperature in the range of 150 to 320 C. , compound (D) and optionally discharge catalyst (E) component 156873.doc -22- 201228081 The mixture is compressed with each other. For this purpose, it can be self-paste, preferably starting from an aqueous paste, the layer height of which can be adjusted to the desired size by means of rolling and cutting, and applied to the medium of interest (A) . After application, it can be followed, for example, by heat treatment, especially at 15 to 35 Torr. (: is fixed at a temperature within the range, especially at a temperature close to the glass transition temperature of the polymer (c). In this case, for example, when a vinylidene fluoride-hexafluoropropylene copolymer is selected as the polymer ( In the case of c), it is preferred to select the temperature, for example, in the range of from 125 to 175 C, preferably about i5 Torr. In another variation, the temperature selected is from 175 to 225^, preferably about 2 〇. (rc, and the selected polymer (C) is polyvinylidene fluoride. In another variation, the temperature selected is 300 to 350 C', preferably 320 to 325 ° C, and the selected polymer (C) Polytetrafluoroethylene. In a variant, it can be fixed mechanically, for example by calendering. This is an electrode of the invention which can be combined with other components to form the electrochemical cell of the invention. This has excellent overall properties. An electrochemical cell of the present invention. Another aspect of the invention is a formulation, also referred to as a formulation of the invention, comprising at least one organic solvent or water and (B) at least one electrically conductive carbonaceous material; (C) at least one Organic polymer and (D) at least one comprising molybdenum or tungsten A mixed oxide of at least one element selected from the group consisting of Fe, Ag, a lanthanide metal, and V. An aqueous formulation is preferred. Conductive carbon (ruthenium), polymer (C), and compound (D) have been defined above. .doc • 23-201228081 In a preferred embodiment of the present invention, the preferred aqueous formulation of the present invention comprises at least one other component selected from the group consisting of surfactants, thickeners, and antifoaming agents. The preferred aqueous formulation of the present invention may have a solids content in the range of from 0.5 to 60%. The invention is illustrated by the working examples. Basic Remarks: In the context of the present invention, the numbers are expressed as percentages unless otherwise explicitly stated. Refers to the weight percentage. I. Manufacture of aqueous formulation 1.1 Manufacture of aqueous ink, WF1.1 In a stirred vessel, mix 2 g of ethoxylated trimethyldecyl alcohol and 66.5 g of water using a magnetic stirrer. 4 g Nis, 〇4 gw〇^ig FeAgM〇2〇8 (D.1) (BET surface area 1 5 m2/g) and 3 g Ag activated carbon (9% Ag coating (Β·υ, while stirring. Use ultrasonic waves to be dispersed by the following procedure: 14 mm US sonic pole, loop owing, vibration 45% ' 8. Cooling, magnetic stirrer 75 〇 /. 'Enlarged energy input of 0.025 kWh. Then add 3.8 g of aqueous dispersion of polytetrafluoroethylene (ci) with 60% solids content, and: no further The mixture was stirred for 15 minutes under ultrasound. The ink of the invention was obtained by filtering the mixture through a 19 pm mesh screen, which is also referred to below as WF 1.1. 1.2 Manufacture of aqueous ink, WF 1.2 in a stirred vessel, using a magnetic force Agitator was used to mix 2 g of ethoxylated dimethyl decyl alcohol and 66.5 g of water. Subsequently, 〇4 g Nis, 〇4 g WC and 0.4 g Fe2(W04)3(D.2) (BET surface area 3 m2/g) and 3 g^active stone anaesthesia (9〇/〇Ag coating C) were added (B 1), while mixing. Subsequent use of ultrasonic waves by 156873.doc -24· 201228081 under the program: 14 mm US sound pole, cycle 1 time, amplitude 45% ' 8 ° C cooling 'magnetic stirrer 75%, up to 0.025 kWh energy input . Subsequently, 3.8 g of an aqueous dispersion of polytetrafluoroethylene (C1) having a solid content of 60% was added, and the mixture was stirred for 15 minutes without further ultrasonication. The ink of the present invention was obtained by filtering the mixture through a 19 Å μηι sieve, which is also referred to as WF1.2 hereinafter. II. Application of the aqueous formulation WF1" or WF1.2 of the present invention and the carrier (A.1) used for the manufacture of the electrode of the invention are coated on one side by a mixture of (B.1)/(C·) Metal mesh. The coated metal mesh is 400 μηι thick with the coating and has a gas permeability of 90 Gilliseconds/1 Torr. Subsequently, the aqueous formulation WF. 1 of the present invention was sprayed on a vacuum table having a temperature of 75 C by means of spray blasting, and spraying was carried out using nitrogen gas. This yields a loading of 25 mg/cm2 based on the sum of (Bl), (cl) and (D.1). Then the calendering is carried out using a calender with the following calender settings: 2 N/mm2 pressure 0.5 The roll temperature of 100 ° C before the m/min is then heat treated in an oven at a temperature of 32 CTC. At this temperature, the polytetrafluoroethylene becomes soft. This obtains the electrode electr l of the present invention.制造. The electrochemical cell of the present invention was fabricated and tested. The electrode of the present invention exhibited an open circuit potential of 1.35 to 1.5 volts. During the discharge period 156873.doc •25- 201228081' battery voltage is reduced to 1.2 to 1.25 volts at a discharge current of 20 mA/cm2. During the charging operation, the battery voltage is ramped up to a value between 1.95 and 2.00 V at a current density of 2 mA/cm2. At higher current densities (e.g., 50 mA/cm2), the voltage during discharge is i丨 to 丨15 volts. For the charging operation, a voltage between 2 〇〇 and 2·〇 5 V was observed at a current density of 50 mA/cm 2 . The electrode of the present invention achieves more than 100 commission rings in an electrochemical test cell (semi-battery). 156873.doc -26 -

Claims (1)

201228081 VII. Patent application scope: 1. An electrode comprising: (A) a solid medium through which a gas can diffuse, (B) at least one conductive carbonaceous material, '(C) at least one organic polymer, (D) At least one compound of the formula (1) M1aM1bM2cM3dHeOf (I) in the form of particles, wherein the variables are defined as follows: selected from the group consisting of Mo, W, V, Nb and Sb, and the lanthanum 1 is selected from the group consisting of Fe, Ag, Cu, Ni, Μ and Lanthanide metal, M is selected from the group consisting of B, C, N ' A1, Si, P and Sn, and M is selected from the group consisting of Li, Na, K, Rb, Cs, NH4, Mg, Ca and Sr, a is from 1 to 3 Within the range, b is in the range of 〇·1 to 10, c is in the range of 〇1, d is in the range of 0 to 1, 6 is in the range of 〇5, and f is in the range 1. Within the range of 28, and the compound of the formula (1) has a BET surface area in the range of 1 to 300 m1/g. An electrode according to claim 1, wherein the compound (D) is selected from the group consisting of mixed oxides and isopolyacids and salts thereof. 2 The electrode of claim 1 or 2 wherein the compound (D) is selected from the group consisting of 卩6_八经_父_〇, Fe-VX·0, Ag-XV-0, Ce-XO and Fe-XO, Wherein X system 3 156873.doc 201228081 is selected from the group consisting of molybdenum and gamma β 4. The electrode of claim 1 or 2, wherein the organic polymer (c) is selected from a halogenated (co)polymer. 5. The electrode of claim 1 or 2, wherein the solid medium (A) is selected from the group consisting of a metal mesh and a gas diffusion medium composed of carbon. 6. The electrode of claim 1 or 2, wherein the electrically conductive carbonaceous material (B) has a BET surface area in the range of from 20 to 1500 m2/g. 7. The electrode of claim 1 or 2, wherein the compound (D) has an average primary particle size in the range of 1 〇 to 5 〇 nm. 8. For example. The electrode of the first or second item, wherein the compound (9) is a coalesced particle, has a mean diameter of from 20 nm to 50 μm. 9. The electrode of claim 1 or 2, further comprising a discharge catalyst. 10. The use of an electrode according to any one of items 1 to 9 of March in an electrochemical cell. 11. The use of claim 10, wherein the electrochemical cells comprise a cadmium/air battery, an aluminum-air battery, an iron-air battery, or a speech-air battery. 12. An electrochemical cell comprising at least one electrode as claimed in any one of claims 1 to 9. 13. A method of operating an apparatus using an electrochemical cell as claimed in claim 12. 14. A manufacturing as requested! The method of any of the electrodes of any one of the preceding claims, comprising: (B) at least one electrically conductive carbonaceous material, (C) at least one organic polymer, and 156873.doc 201228081 (D) at least one in particulate form and having The compound of formula (I) having a BET surface area in the range of from 1 to 3 〇〇 m 2 / gi is applied in one or more steps to (A) a solid medium through which the gas can diffuse. 15. The method of claim 14, wherein (B) at least one electrically conductive carbonaceous material, (C) at least one organic polymer, and (D) at least one in particulate form and having a range of from 1 to 3 〇〇 m2/gs The compound of the formula (1) having a BET surface area is applied in the form of an ink or a paste or a paste to (A) a solid medium through which a gas can diffuse. 16. The method of any of claims 14 and 15, wherein the applying is followed by heat treatment. a formulation comprising at least one organic solvent or water and (B) at least one electrically conductive carbonaceous material, (C) at least one organic polymer, and (D) at least one compound of the formula (1) in particulate form M1aM2bM3cM4dHeOf (I) wherein the S-equivalent variables are defined as follows: M1 is selected from the group consisting of Mo, W, V, Nb and Sb, and Μ2 is selected from the group consisting of pe, Ag, Cu, Ni, Μ and lanthanide metals, and M is selected from Β. , C, Ν, A1, Si, Ρ and Sn ' Μ are selected from the group consisting of Li, Na, K, Rb, Cs, NH4, Mg, Ca and Sr, 156873.doc 201228081 a is in the range of 1 to 3, b In the range of 0.1 to 10, c is in the range of 0 to 1, d is in the range of 0 to 1, e is in the range of 0 to 5, f is in the range of 1 to 28, and Wherein the compound of the formula (I) has a BET surface area in the range from 1 to 300 m2/g. 156873.doc 201228081 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 156873.doc