JP2002528863A - Paste material having inorganic liquid conductor, and layer and electrochemical element obtained therefrom - Google Patents

Abstract

(57) Abstract: The present invention relates to a paste-like material that can be used for an electrochemical element, and (A) a matrix comprising or consisting of at least one organic polymer, a precursor thereof, or a prepolymer thereof, B) an electrochemically active inorganic or almost inorganic liquid that does not dissolve or essentially dissolves the matrix, and (C) optionally a powder that is inert to the electrochemically active liquid It consists of a hybrid mixture of solids. The present invention relates to (A) a matrix comprising or consisting of at least one organic polymer, a precursor thereof, or a prepolymer thereof; (B) an electrochemically active, insoluble or essentially insoluble matrix. A self-retaining layer consisting of a hybrid mixture of an inorganic or almost inorganic liquid, and (C) a powdered solid which is inert to the electrochemically active liquid, or a layer placed on a substrate And a composite layer having electrochemical properties comprising a plurality of such layers. These layers and composite layers can be advantageously used to manufacture batteries, low temperature fuel cells, solar cells, or electrochemical sensors.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a novel substance having electrochemical properties, in particular, a self-supporting or flexible paste-like material placed on a substrate and a layer made from the material. And a composite layer obtained from the layer and usable for a primary battery, a secondary battery, a low-temperature fuel cell, a solar cell, and the like.

[0002] Since the early 1970s, attempts have been made to manufacture electrochemical elements such as thin-layer secondary batteries. The purpose is to provide a composite film having particularly good charge / discharge characteristics because the contact area between individual electrochemical component members such as electrodes and electrolytes is extremely large compared to the volume of the electrochemically active component used. Is to get. In special cases, such composite films are required to have a high degree of flexibility, so that they can be rolled or conformed to another desired shape.

[0003] In the past, attempts to make such electrodes have begun with solid or viscous liquid Teflon. Carbon and the actual electrode material are added in a proportion to Teflon, then pressed or sprayed onto a suitable contact electrode. However, the resulting layer is not sufficiently flexible. Furthermore, it has been proposed to produce an electrode layer by making from PCV and tetrahydrofuran or another polymer soluble in a solvent, and then extracting the solvent therefrom. However, the conductivity of the product thus obtained is not preferred.

[0004] There are special problems in producing layers that can function as electrodes in suitable electrochemical composites. U.S. Pat. No. 5,456,000 describes a rechargeable battery cell obtained by laminating electrodes and electrolyte cells. A film or membrane made separately from a LiMn ₂ O ₄ powder in a matrix made from a polymer / copolymer and used as a positive electrode. The negative electrode consists of a dry coating of a dispersion of carbon powder in a polymer / copolymer matrix. The electrolyte / separation membrane is located between the electrode layers. To this end, polyvinylidene fluoride-hexafluoropropylene copolymers have been modified with organic plasticizers such as propylene carbonate or ethylene carbonate. A film is made from these components and then the plasticizer is extracted from the layer. The battery cells remain in this "inactive" state until used. In order to activate, a suitable electrolyte is immersed, whereby the cavity created by extracting the plasticizer is filled with a liquid electrolyte. The battery is now ready for use.

[0005] Such a configuration has the disadvantage that the battery must be activated immediately before use. This is unacceptable in most cases.

It is an object of the present invention to provide a ready-to-use electrochemical element that contains a suitable conductor (ionic or mixed conductor, especially an electrolyte, or at least one of a plurality of electrodes) in liquid form, An object of the present invention is to provide a paste-like material suitable for forming an electrochemically active layer including a body. These elements are suitable for a wide range of products, such as primary batteries, rechargeable batteries (rechargeable batteries), low-temperature fuel cells, solar cells, electrochemical sensors, etc., and have a layered shape, particularly a film laminated shape. However, it has very good conductivity, has high flexibility as required, and has no liquid leakage, and thus does not necessarily need to be placed in a container, especially a sealed container.

The above object has been achieved by the present invention, and the paste-like material of the present invention comprises (A) a matrix containing at least one organic polymer, a precursor or a prepolymer thereof,
(B) a mixture of an electrochemically active inorganic liquid which does not or essentially does not dissolve the matrix and, if necessary, (C) a solid powder which is inert to the electrochemically active liquid. Can be These pasty materials can be combined with a suitable self-supporting layer, or to produce an electrochemical element, or can be combined with other components that produce an electrochemical element (eg, a film, (A so-called tape).
Alternatively, in some cases, the material is produced by layering component (A) and (C) if necessary, and finally providing component (B).

The phrase “can be used in an electrochemical element” includes that the electrochemically active inorganic liquid can be an ionic or electronically conductive liquid suitable for electrode materials or liquid electrolytes. Electronically conductive liquids that alter stoichiometry (related to valence changes and charge transport numbers) are also included. Such a liquid can replace a solid intercalation electrode.

The material according to the invention obtains a pasty consistency, preferably using a suitable matrix (A) in combination with a solid powder (C). This solid powder functions as a filler and a support material. The term "pasty" means that the resulting material can be processed using current paste application means, such as a brush, spatula, lake or various pressing means on the base material. Means a state that can be applied. If desired, the material can be relatively thin to very viscous.

[0010] Several substances can be used for the matrix (A). Solvent or non-solvent systems can be used. Suitable non-solvent systems include, for example, crosslinkable liquids (
If necessary) or, inter alia, a paste-like resin system. Examples thereof include a resin made of a crosslinkable addition polymer or a condensation resin. For example, an initial condensate of phenoplast (novolak) or aminoplast can be used, the final polymerization is performed, and the paste-like material is formed into a layer of the electrochemical composite layer. Further examples are unsaturated polyesters, such as polyesters that can be cross-linked to styrene by graft polymerization, curable bifunctional epoxy resins that are partners of bifunctional reactions (eg, cold cured with polyamides). Bisphenol-A-epoxy resin), isocyanurates that can be cross-linked and polymerized with polyols, and binary polymethyl methacrylates that can be polymerized with styrene. The paste-like material is produced by using a more or less viscous precondensate or uncrosslinked polymer or its basic components together with component (B) as matrix (A).

Another option is to use the polymer or its precursor with a solvent or swelling agent for the organic polymer. In principle, there are no restrictions on the synthetic or natural polymers that can be used. Not only polymers having a carbon backbone, but also polymers having a heteroion in the main chain, such as polyamides, polyesters, proteins or polysaccharides, can be used. The polymer may be a homopolymer or a copolymer. The copolymer may be a random copolymer, a graft copolymer, a block copolymer or a polyblend, and is not limited. For polymers having a pure carbon backbone,
For example, natural or synthetic polymer rubber can be used. In particular, fluorinated hydrocarbon polymers such as Teflon, polyvinylidene fluoride (PVDF) or polyvinyl chloride are preferred. This is because good water repellency can be obtained particularly in a film or layer formed from a paste-like material. This gives good long-term stability to the electrochemical element thus obtained. Another example is polystyrene or polyurethane. Examples of copolymers include Teflon, an amorphous fluoropolymer, and a copolymer of vinylidene fluoride / 6 propylene hexafluoride (commercially available as Kynarflex). Examples of the polymer having a hetero atom in the main chain include diamine dicarboxylic acid or amino acid type polyamides, polycarbonates, polyacetals,
Polyethers and acrylics. Further, there are natural and synthetic polysaccharides (homoglycans and heteroglycans) and proteoglycans such as starch, cellulose, methylcellulose and the like. In addition, chondroitin sulfate, hyaluronic acid, chitin, natural or synthetic waxes, and many other substances can be used. Further, the above resin (precondensate) can be used in a solvent and a diluent.

[0012] Solvents and swelling agents for the above polymers are well known to those skilled in the art.

[0013] Plasticizers (as well as softeners) may be present in the polymer used, whether or not the matrix (A) contains a solvent or swelling agent. "Plasticizer" or "softener"
It should be understood to include substances that have a covalent bond to the plastic molecule or a molecule that binds to the plastic molecule by a secondary valence (Van der Waals force). Thus, these agents mitigate interactions between macromolecules and thus reduce the softening temperature, brittleness and hardness of the resin. This is different from swelling agents and solvents. Due to the higher volatility, they generally cannot be removed by evaporation from the resin. Rather, it can be extracted using a suitable solvent. The use of plasticizers results in high mechanical flexibility in layers that can be made from paste-like materials.

[0014] Suitable plasticizers for each of the resins are well known to those skilled in the art. They must be highly compatible with the resin to be treated. Common softeners are
High boiling esters of phthalic acid or phosphoric acid, such as dibutyl phthalate or dioctyl phthalate. Further, for example, ethylene carbonate, propylene carbonate, dimethoxyethane, dimethyl carbonate, diethyl carbonate, butyrolactone, ethyl methyl sulfone, polyethylene glycol, tetraglyme, 1,3-dioxolan, or S, S-dialkyldithiocarbonate is suitable.

One reason for adding the solids (C) is to improve the properties of the matrix (A) with respect to support or behavior, for example when making tapes. Solid (C)
Is preferably used in a form that can be finely distributed (for example, powder). All substances which are unaffected by the liquid (B), in particular unchanged by oxidation / reduction, are suitable.
Materials such as SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, and MgO are mainly used because they are often chemically aggressive. However, any other substance can be used if it is inert to the electrolyte or electrode material used.

Liquids used as electrodes, electrolytes and the like must be at least substantially inorganic. For example, it is possible to use vanadium oxychloride or oxybromide vanadium, wherein the vanadium increases VOX, the VOX _2, via the VO ₂ X + III valence from + V-valent oxide phase. A decomposition electrode can be obtained with such a substance. This has the advantage over the intercalation electrode that there is no volume expansion characteristic of the intercalation electrode. For this reason, the service life can be improved.

Basically, any liquid electrolyte can be used as a suitable electrolyte for the system, and several such systems and corresponding electrolytes are known.
For example, aqueous systems such as sulfuric acid or KOH can be used as proton conducting electrolytes in systems such as lead acid batteries or Ni-Pb batteries or nickel cadmium batteries or nickel hydride batteries, thereby providing an effective packing density. Can be obtained.

If necessary, in a water-repellent matrix, water-miscible alcohols or polar organic solvents can be added to the electrolyte to improve the transport number of the conductive liquid. In particular, straight-chain or branched monovalent having preferably 1 to 6 carbon atoms, such as methanol, ethanol, propanol, glycol, glycerin,
Dihydric or trihydric alcohols are suitable. In particular, the polymer matrix is used as a plasticizer (
When used together with (extracted from the polymer matrix), such an aqueous mixture wets (and optionally crosslinks) the matrix in the final layer, making transport easier. However, when referring to "substantially inorganic liquids", the exclusion of the possibility that the electrolyte consists or consists of a salt and a completely organic solvent such as ethyl carbonate, diethyl carbonate. Therefore, the amount of organic solvent present should be less than 70%, preferably less than 50% of the total amount of solvent. Depending on the nature of the matrix and / or the organic solvent, the highest values are for example 30% or 15%.
% Is sufficient.

In another approach, the matrix material can include a water-miscible softener or plasticizer. This increases the hydrophilicity of the matrix material, with the same result. The above applies to the maximum amount of organic additive. In another alternative, hygroscopic salts, for example, can be added MgCl _2, and the matrix material. Water is drawn into the matrix with the same consequence of facilitating the transport of the electrolyte within the matrix.

For the electrolyte, in addition to the aqueous system, there are also non-aqueous liquid inorganic electrolytes such as H ₂ SO ₄ or LiAlCl ₄ / SO ₂ (the latter is generated when sulfur dioxide gas reacts with lithium aluminum chloride). Can be added. Such systems have a high surface tension compared to a more hydrophobic polymer matrix. There are several means to enhance migration in the polymer matrix. Among them, the first two types of water-based electrolytes, namely, adding an alcohol or the like to the electrolyte and / or adding a plasticizer to the polymer matrix.

As mentioned above, the paste-like material of the present invention and the layers obtained therefrom are suitable for many electrochemical elements and are preferably embodied as a film / layer composite.
The person skilled in the art can select the same liquid (B) to be used for conventional electrochemical elements, ie a substance without added polymer.

The following components of the storage battery are examples that can be used arbitrarily in a lithium-based storage battery.

The lower contact electrode Al, Cu, Pt, Au, C cathode _{LiF, Li x NiVO 4, Li} x [Mn] 2 O 4, LiCoO 2, LiNiO 2, LiNi 0.5 Co 0 .5 O 2, LiNi 0.8 Co _0.2 O ₂ , V ₂ O ₅ , LixV ₆ O ₁₃ Electrolyte LiAlCl ₄ / SO ₂ (anhydrous) Negative electrode Li, Li _{4 + x} Ti ₅ O ₁₂ , Li _x MoO ₂ , Li _x WO ₂ , Li _x C ₁₂ , Li _x C ₆ , lithium alloy Top contact electrode Al, Cu, Mo, W, Ti, V, Cr, Ni The electrolyte layer of this storage battery can be made from the pasty material of the present invention, but other layers are required If so, a paste-like material containing a powdered electrode substance can be used instead of the liquid (B). Preferably, the electrode material does not dissolve in the polymer matrix. It is particularly preferred that the ratio of electrode material to polymer matrix is about 70 to 30% by weight. The polymer matrix can have the same components as the inventive material described above.

However, of course, the present invention is not limited to lithium-based storage batteries.
As mentioned above, there are many potential uses. For example, the material of the present invention can be a self-supporting film, or can be mounted on a substrate to provide a primary battery, a secondary battery, a decomposition battery, a low temperature fuel cell, a solar cell, or an electric battery. It can be used for chemical sensors and the like.

The above-mentioned components from which the paste-like material of the present invention can be prepared can be mixed by a conventional method, preferably by vigorous stirring or kneading. If necessary, the organic polymer or its precursor is pre-dissolved or swelled in a solvent or swelling agent before adding component (B) and (C), if any. If the component (C) is present, it is preferable that the component (C) is put into a paste-like material before it is hardened and then treated with the component (A). Component (B) can be added at this stage. Alternatives are described below.

The paste-like material of the present invention is suitable for manufacturing other electrochemical elements such as thin-film batteries and similar electrochemical sensors. This element is a so-called “thick film”
Preferred in the art. Each layer of this element is called a "tape".
Each electrochemically active or activatable layer is made of a thickness of about 10 μm to about 1-2 mm, placed on top of each other and adhered. A preferred range is from about 50 μm to 500 μm. A particularly preferred range is about 100 μm. However, according to the invention, the corresponding thin-film elements (this predicate is preferably from 100 nm to several μm
Means thickness). However, this application cannot be limited. This is because the corresponding elements often do not meet current requirements in terms of capacity. However, it can be inferred, for example, that it could be used as a backup.

Further, the paste-like material of the present invention can also have other forms. In this way, thicker layers (eg, in the range of about 1-10 mm) can be made, from which various shapes can be stamped or cut. For example, the latter are very small and are suitable for batteries and accumulators in medical technology, which must be very safe. One example of an application is a hearing aid battery. It has particularly stringent requirements for leakage, in addition to occupying or even implanting directly into or into the ear or inside, occupying a minimal amount of space.
The employed shape can of course be produced directly, for example by casting, injection molding or extrusion.

The invention therefore furthermore comprises a layer which can be made from the above-mentioned pasty material, preferably in the above-mentioned thickness, in a self-supporting form or on a substrate. This layer is preferably capable of flexing.

The preparation of both self-supporting layers (films, tapes) and layers that can be mounted on a substrate can be carried out using methods known in the art and includes the use of a suitable polymeric material in the matrix. Can be used. Depending on the substance, the pasty material is hardened by curing (eg, of a resin or precondensate) or crosslinking of a linear polymer, evaporation of a solvent (such as acetone, etc.), or similar means. When the polymer matrix contains a plasticizer, it is particularly advantageous that the solvent can be extracted and the viscosity of the paste-like material can be sufficiently maintained while keeping the distribution of the components homogeneous. When the present invention is used in a manner that does not imply that the plasticizer fulfills some other purpose (eg, to increase the hydrophilicity of the matrix material), the paste-like material becomes a self-supporting layer or a layer applicable to something. Once hardened, it can be removed. However, only when the polymer matrix is unlikely to be crystallized and therefore less brittle and flexible. An example of a polymer that is sufficiently flexible is the combination of polyvinylidene fluoride and propylene hexafluoride for the polymer / copolymer.

In a particular embodiment of the invention, component (B) is not added or only partially added during the production of the pasty mass. That is, as described above, the plasticizer is removed from the self-supporting layer or a layer formed after the material is placed on something and the material is hardened (for example, by adding and extracting a solvent such as hexane). If so, many cavities resembling a sponge are created in the consolidated matrix. Then, when immersed in the liquid (B), the liquid is sucked into the cavity of the hole where the liquid was generated by the capillary action, and the liquid remains stable therein.

In order to obtain a self-supporting film, for example, a paste-like material having an appropriate thickness can be obtained using a calender. For this, standard techniques can be used. The self-supporting layer can be obtained by applying the paste-like material to the substrate and removing the solidified product layer. The requirement is that the product has sufficient flexibility. The coating process can be performed using a conventional paste application method. For example, it can be performed by brush, rake, spray, spin coating, or the like. Pressing techniques can also be used. As described above, the liquid (B) is previously placed in the paste-like material, or at least the polymer matrix (A)
Or the paste-like material comprising the filler (C) may be solidified and filled in the cavities formed after the softener contained therein has been removed.

In a preferred embodiment of the present invention, a crosslinkable resin (initial condensate) is used as the paste-like material as described above, and after the layer is formed, it is cured by UV or electron beam. Of course, the curing may be thermal or chemical (eg, by immersing the formed layer in a suitable bath). If necessary, an appropriate initiator or accelerator for crosslinking may be added to the paste-like material.

Furthermore, the invention relates to composite layers having electrochemical properties, in particular to accumulators, other batteries or sensors made by or comprising such a series of corresponding layers.

FIG. 1 shows an example of an arrangement configuration. 1 contact electrode, 2 intermediate tape, 3 electrodes,
4 electrolyte, 5 electrodes, 6 intermediate tape, and 7 contact electrodes.

Hereinafter, a more detailed description will be given.

In order to form the composite layer, the respective paste-like materials can be applied to each other in a ply by a paste application method. Either each ply is cross-linked alone, or it is separated by a solvent or otherwise formed into a layer. However, the individual matrices can be hardened after all of the necessary layers have been applied, by crosslinking or evaporation of solvents or swelling agents. The latter is advantageous, for example, in that the electrochemically activated layer is applied using a pressing method similar to the multicolor painting method. An example of this is the Flexodruck technology, which allows multiple meters / seconds of a substrate to be printed continuously with the required electrochemically active layer.

[0037] Alternatively, all layers or films can be individually finally set. If self-retaining, the appropriate components of the element to be produced can be brought together by lamination. Conventional lamination techniques can be used. For example,
Extrusion coating, in which the second layer is bonded to the carrier layer by means of pressure rolls, calender coating, in which the substrate together with the pasty material enters two or three roll nips, or duplexing (preferably applying pressure and pressure to a heated roll) Bonding under opposite pressure). One skilled in the art would have no problem finding a suitable technique depending on the choice of the matrix of the pasty material.

[0038] Pressure treatment when joining (stacking) the individual layers is often desirable, for example, to improve bonding (and thus also improve conductivity) in the individual layers. For this purpose, current technology can be used. If the materials used permit, cold pressing (at a temperature below 60 ° C.) is advantageous. This leads to a particularly good contact between the individual layers.

In all applications, the advantage of using the pasty material of the invention, or a self-supporting foil layer made therefrom, or a layer made therefrom and mounted on a substrate, is cost-effective, compact Due to its simple structure, the practical energy density is high and the liquid electrolyte or liquid electrode is contained in a polymer matrix like a sponge, so that it has high reliability against liquid leakage.

The electrochemical member that can be made from the paste-like material of the present invention is not limited.
Therefore, the embodiments described below are merely examples and are preferred embodiments.

A rechargeable electrochemical cell is thus made by a thick film technique, ie, about 10
It can be made with an electrochemically active layer having a thickness of from μm to 1 to 2 mm, preferably 100 μm. If the electrochemical cell is based on lithium technology, the liquid of the electrolyte layer may be a material as evaluated above for this purpose. At least 3
One layer can be given. That is, those acting as a positive electrode, those acting as a solid electrolyte, and those acting as a negative electrode, that is, the layers 3, 4 in FIG.
And 5.

According to the present invention, a particularly advantageous current density can be obtained in a storage battery when viewed in a certain range. As is well known, the current density can be adjusted by the resistance of the electrolyte. If it is too high, polarization will occur and there will be electrode breakdown over an extended period. Conversely, if it is too low, the power of the storage battery obtained is not sufficient for only a few applications. The above limit is 1 mA / cm ² . If the electrolyte layer is about 100 μm, a current density of 1 mA / cm ² will reduce the voltage by negligible 0.1 V due to the resistance. For example, if the electrolyte has a conductivity of 10 ¹ S / cm, the fine area (micr) in the layer
o-geometry A) (filler and groove) is about 10 0 ^{S /} cm as a conductivity to the layer.
According to highly recommended criteria, the layer thickness d, conductivity σ _ion , ionic resistance (
Ω), the surface area A should be selected to satisfy the following equation: 200 Ω <d / (σ _ion · A) This criterion applies well when the tape according to the invention is used.

The three-layer battery (or other desired electrochemical element consisting of cathode / electrolyte / negative electrode) is further provided with contact electrodes (1 and 7 in FIG. 1). These contact electrodes are usefully comprised of a film of a suitable substance (a material for a contact electrode that can be used in lithium technology as described earlier herein).

In a particular embodiment of the invention, an additional thin polymer layer (“intermediate tape”, FIG. 1) between the lower contact electrode and the adjacent electrode and between the upper contact electrode and the adjacent electrode Layers 2 and 6). This can also be made using a paste-like material.
The thin polymer layer should include a conductive metallic element or alloy of such an element. It is suitable for transferring electrons from an electrode material to a contact electrode. Examples of this are gold, platinum, rhodium, and carbon, or alloys thereof, when a thin layer of polymer is placed between the positive electrode and the associated contact electrode. When placed between the negative electrode and the contact electrode, suitable elements are nickel, iron, chromium, titanium, molybdenum, tungsten, vanadium, manganese, niobium, tantalum, cobalt and carbon. The knowledge of the electrodes and electrolytes mentioned above, of course, also applies to the concentration and composition of the pasty material from which the layers are made. The embodiment for the contact electrode and the intermediate tape (see FIG. 1) has the charge / discharge curve of FIG. 3 when the electrolyte is made using Lithium technology as LiAlCl ₄ / SO ₂ .

In another embodiment of the present invention, an electrochemical cell is constructed from at least three layers and practiced according to the present invention with both electrodes as layers. The positive electrode side (electrode) is made protonic, while the negative electrode side (control electrode) is made aprotic. The "protonic", salts, for example, a system obtained by dissolving lithium salt such as lithium nitrate or lithium perchlorate "protonic", i.e., protons - are understood to separation system (H ₂ O). On the other hand, a solid electrolyte is selected as the intermediate layer. The cation (eg, lithium) is a conductive ion. In particular, in the present embodiment, the water repellency of the polymer matrix prevents water from moving to the negative electrode side and prevents decomposition there. The advantage is that the kinetic momentum at the positive electrode is increased due to the liquid electrolyte,
A wide choice of possible electrolytes (in this case the problem of corrosion due to the potential difference of the metal contact electrode of the positive electrode is avoided, so aluminum is preferred in terms of cost; for example, an electrolyte containing lithium perchlorate can The electrode is easily oxidized.) The material of the present invention is suitable for use in, for example, a primary battery, and is particularly suitable for forming an electrolyte layer. Suitable electrode systems include, for example, zinc-charcoal, alkali-
Manganese (Zn-MnO _2), zinc - mercury oxide (Zn-HgO), zinc - silver oxide (Zn-Ag ₂ O)
, Zinc - oxygen in the air (Zn-O _2), magnesium - oxygen in the air (Mg-O _2), aluminum - is in air oxygen (Al-O _2). Suitable electrolytes are alcoholic solutions of alkali bromide and chloride and ammonium or alkali hydroxides (particularly the alkali metals sodium and potassium).

The material of the present invention is further suitable for use in a secondary battery. The secondary battery is as described above, and is, for example, a lead storage battery or a nickel hydride battery. Other secondary batteries are nickel-cadmium, nickel-iron, zinc-silver oxide, and alkali-manganese batteries. Suitable electrolytes for these, for example, hydrous or anhydrous H ₂ SO ₄ (e.g., for a lead-acid battery) or potassium hydroxide.

The material of the present invention can be used for a new type of battery, a so-called decomposition type battery.
The positive electrode, for example, salt is decomposed in the MgBr _2, resulting bromine is stored in a carbon film (carbon tape). In this case, the electrolyte of the paste-like material or the film or layer made therefrom is MgCl ₂ and does not decompose because its decomposition voltage is higher than MgBr ₂ . Mg precipitates in situ as a negative electrode in a metal film or a carbon film and functions as a sponge. Alternatively, the magnesium precipitates on the material if the material is present in a closed form. However, the first form is preferred because of the preferred volume. Battery voltage is equal to the decomposition voltage of MgBr _2. In this case, in particular, in such a storage battery, the capacity increases with the valence, so that there is an advantage that ions having a higher valence can be used. In particular, light and low-cost Mg and Al are preferred. In these systems, mineral, aqueous, or at least liquid electrolytes should be used. Because, the mobility of higher valence ions in a solid electrolyte at room temperature is too low for battery and accumulator applications. The electrode can be present as a metal, as a carbon film, or even as a powder. In the case of powdered electrode materials, they are embedded in a polymer matrix film, as described above.

Another field of using the materials of the present invention is low temperature fuel cells. in this case,
Proton conducting polymer electrolytes (PEMs: proton exchange membranes), such as Nafion, have been used in the past. However, this polymer electrolyte is expensive and sensitive to drying. In particular, there is no simple way to recharge a fuel cell. In principle, hydrogen storage devices are small, expensive steel bottles that must be completely replaced. In the past, space requirements for such hydrogen storage devices made it impossible to design batteries such as thin-layer structures. According to the invention, an electrolyte layer is used with a polymer matrix loaded with a hygroscopic salt, which layer is kept in a humid environment. When the salt dissolves, this layer will contain the liquid electrolyte (the salt is in the supplied water) and the water can be decomposed electrochemically. The resulting hydrogen is stored in another stacked hydride storage device (Y, Pt, Pd or other hydrogen storage material in the form of a film, preferably in an organic polymer matrix). The water lost by the decomposition is replenished by the water drawn by the hygroscopic salt.

Also in this embodiment of the present invention, the electrolyte layer used is a polymer matrix (A), a polymer, a solvent and a softener, and a solid substance (C) mixed to form a paste-like material, This material is formed into the desired "tape", solidified, the solvent is removed if necessary, the softener is extracted, and the resulting cavity is filled with an alcoholic solution of a hygroscopic salt to evaporate the alcohol. On the other hand, the salt is dissolved in an alcohol as a temporary solvent in a solvent or a plasticizer, for example, and enters the paste-like material. In this case, the alcohol is preferably extracted together with the solvent. The filler (C) is preferably provided to improve the mechanical stability of the obtained film tape. If necessary, it can be omitted.

The paste-like material of the present invention and a film or layer made therefrom can also be used for a solar cell. Systems based on solar cells use the so-called Honda-Fujishima effect (1972) rather than silicon technology. When exposed to sunlight, oxides such as titanium dioxide or tungsten trioxide can degrade (electrolyze) water and even other substances such as formic acid. This is because electrons are excited in the conduction band and oxides are in the highest oxidation state known in chemistry,
This is because the residual gap has a high oxidation effect. Solar cells include three layers (tapes). One is for storing hydrogen and can be configured as described for low temperature fuel cells. Another is the electrolyte layer, which contains water that decomposes during use, which can also be implemented as described for fuel cells. Third, further
Tape containing TiO ₂ or WO ₃ , preferably metal powder or carbon (to ensure sufficient electronic conduction), otherwise configured similarly to the electrolyte layer. In contrast to fuel cells, solar cells are charged with light. During discharge, it acts like a fuel cell.

The paste-like material according to the invention and the films or layers made therefrom are also suitable for electrochemical sensors. For this use, a water-absorbing hygroscopic salt is added to the polymer matrix. The water content of the film made from the material depends on the salt concentration,
It can be finely adjusted using ambient humidity and temperature. Humidity can be measured because various voltages occur as a function of moisture content for the stacked tape reference electrodes.

The electrochemical element of the present invention can be sealed in, for example, a plastic container. There is an advantage that it is lighter than a metal container. It is also advantageous in terms of energy density.

The electrochemical composite layer (electrochemical element) can be embedded between two or more films on wax or paraffin coated plastic. This material acts as a seal and has the advantage of applying pressure to the composite layer by its nature and improving contact in the composite layer due to the pressure.

When the electrochemical element is sealed as described above or by another method, the inside is subjected to a predetermined hydrogen / oxygen partial pressure, so that high electrochemical stability can be obtained. For example, it can be performed by sealing the electrochemical element under an environment of appropriately selected and set parameters.

The successive layers of the invention of the electrochemical element can be arranged in any desired manner. For example, winding a flexible composite layer to achieve a particularly advantageous arrangement for compact storage batteries. This gives a very large active surface if the battery has a small volume. FIG. 2 shows such an embodiment, wherein reference numbers 1 to 7 are the same as in FIG. 1, and reference number 8 denotes an insulating layer.

The non-self-supporting composite layer can be applied to a solid base, such as the walls of an integrated energy storage (self-supporting composite films can, of course, be applied or fixed). In this case, the advantage that the surface area is large can be utilized. The storage battery itself has nothing to do with space requirements. A particular example of this type of embodiment is the integration of a battery composite layer into the solar cell substrate. In this way, an independent energy supply can be made. The composite layer of the battery can also be applied to solid or flexible substrates to function in the electronic structure of the integrated energy storage device.

The present invention is described in more detail in the following examples.

Example 1 Production of Primary Battery 1 g of PVDF-HFP, 1.51 g of dibutyl phthalate and 10 g of acetone, 7 g of zinc powder as an anode, 5 g of SiO ₂ as an electrolyte, and 7 g of Mn as a cathode
O ₂ to be mixed. The electrodes and electrolyte are pulled into a tape, the acetone is evaporated, and the plasticizer is extracted with hexane. The tape is filled with an aqueous-alcoholic KOH solution (solvent: 50% water, 50% alcohol). Press between two stainless steel electrodes. PVDF-HFP manufacturing 1g Example 2 secondary battery, dibutyl phthalate and 10g of acetone 1.51 g, 7g and Cd (OH) ₂ as an anode, and SiO ₂ of 5g as an electrolyte, of 7g as cathode N
Mix with i (OH) ₂ . The electrodes and electrolyte are pulled into a tape, the acetone is evaporated, and the plasticizer is extracted with hexane. Tape to aqueous-alcoholic KOH
Fill with solution (solvent: 70% water, 30% alcohol). Press between two stainless steel electrodes.

[Brief description of the drawings]

FIG. 1 shows an example of an arrangement configuration of the present invention.

FIG. 2 shows an example of the present invention in which a flexible layer is wound to form a compact storage battery.

FIG. 3 shows a charge / discharge curve of the electrochemical cell of the present invention having the arrangement shown in FIG.

[Explanation of symbols]

1 contact electrode, 2 intermediate tapes, 3 electrodes, 4 electrolytes, 5 electrodes, 6 intermediate tapes, 7 contact electrodes, 8 insulating layers.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] October 13, 2000 (2000.10.13)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

One reason for adding the solids (C) is to improve the properties of the matrix (A) with respect to support or behavior, for example when making tapes. Solid (C)
Is preferably used in a form that can be finely distributed (for example, powder). All substances which are unaffected by the liquid (B), in particular unchanged by oxidation / reduction, are suitable.
Since often chemically aggressive it _{is, SiO 2, Si 3 N 4} , Al 2 O 3, AlN, MgO, materials such as 及 beauty mixtures of these substances are mainly used. However, any other substance can be used if it is inert to the electrolyte or electrode material used.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

In a particular embodiment of the invention, an additional thin layer of polymer (between the lower contact electrode and the adjacent electrode and / or between the upper contact electrode and the adjacent electrode) Place the "intermediate tape", layers 2 and 6) of FIG. This can also be made using a paste-like material. The thin polymer layer should include a conductive metallic element or alloy of such an element. It is suitable for transferring electrons from an electrode material to a contact electrode. Examples of this are gold, platinum, rhodium, and carbon, or alloys thereof, when a thin layer of polymer is placed between the positive electrode and the associated contact electrode. When placed between the negative electrode and the contact electrode, suitable elements are nickel, iron, chromium, titanium, molybdenum, tungsten, vanadium, manganese, niobium, tantalum, cobalt and carbon. The knowledge of the electrodes and electrolytes mentioned above, of course, also applies to the concentration and composition of the pasty material from which the layers are made. The embodiment for the contact electrode and the intermediate tape (see FIG. 1) has the charge / discharge curve of FIG. 3 when the electrolyte is made using Lithium technology as LiAlCl ₄ / SO ₂ .

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] December 29, 2000 (2000.12.29)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

4. The matrix (A) comprises or consists of at least one organic polymer, which dissolves or swells in a solvent or a swelling agent, and comprises a synthetic resin and a natural resin. The paste-like material according to claim 1, wherein a mixture thereof is selected.

5., characterized in that to put the hygroscopic salt in the matrix (A), a paste-like material according to any one of the preceding claims.

6. The liquid (B) is an aqueous or non-aqueous, inorganic or almost inorganic liquid and is characterized by containing a solid electrolyte and / or a mixed conductor and / or an electrolyte material without being dissolved. The paste-like material according to any one of the preceding claims .

7. The inorganic liquid is characterized by containing magnesium chloride, pasty material according to any one of the previous SL claims.

8. A matrix comprising or consisting of (A) at least one organic polymer, its precursor, or its prepolymer, (B) an electrochemically insoluble or essentially insoluble matrix. An inorganic or almost inorganic liquid, or an electrolyte between two adjacent electrolytes / electrodes, or an ionic or electronic intermediate conductor, which can be arranged in an electrochemical element , provided that the electrolyte is the solvent used. Contains up to 70% of an organic solvent, based on the total weight of the solvent , which solvent is miscible with water, and (C) optionally, from a hybrid mixture of a powdered solid inert to the electrochemically active liquid. Or a self-supporting layer that can be applied to a substrate.

9. The layer according to claim 8, wherein (1) a flexible layer containing an organic polymer and a substance suitable for a positive electrode, (2) the layer according to claim 8 , wherein (B) is selected from the group of electrolytes , (3) A composite layer having electrochemical properties consisting of a flexible layer containing an organic polymer and a substance suitable for a negative electrode.

10. The method according to claim 8, wherein (1) (B) is selected from cathode or anode materials.
(2) a flexible layer comprising a solid electrolyte embedded in an organic polymer matrix; and (3) a liquid or solid electrode material embedded in an organic polymer matrix. A composite layer having electrochemical properties, comprising a flexible layer which can be a counter electrode of the electrode substance of the layer (1).

11. A said layer having positive electrode material, applying a layer acting as a bottom of the contact electrode, characterized by applying a layer acting as a top contact electrode said layer having a negative electrode material, according to claim 9 or A composite layer having the electrochemical properties according to 10 .

12. The cathode material is a salt, preferably a lithium salt, soluble in a proton separating solvent, preferably H ₂ O, and the anode material is an aprotic material. Item 12. The composite layer according to item 10 or 11 .

13. of the composite layer according to any one of claims 9 to 12, a primary battery,
Use in secondary or disassembled batteries.

14. Use of at least one layer according to claim 8 in a low-temperature fuel cell, a solar cell, an electrochemical sensor, in particular an electrochemical sensor for measuring moisture.

ClaimsFifteenThe initial polymerization that can be cross-linkedLiquid electrode material, electrolyte, or intermediate conduction body (B) and, if necessary, a mixture with the solid (C). 7 The method for producing a paste-like material according to any one of the above.

16. organic polymer, precursors thereof, or combinations thereof prepolymer, combined with if necessary a plasticizer and a solid (C), mixed well, this time, the solvent mainly plasticizer dissolves in addition, plasticizer dissolved in the solvent, washed out said workpiece, any solvent is removed from said workpiece, characterized in that added finally electrochemically active liquid (B), claim 1-7 The method for producing a paste-like material according to any one of the above.

17. A material in which the matrix (A) is composed of a crosslinkable polymer or an initial polymer is used as the paste-like material, and the layer obtained from the paste-like material is subjected to a crosslinking treatment of a polymer component. 9. The method according to claim 8 , wherein the method is carried out by electron irradiation, by heating or by immersion in a cross-linking chemical.

Claims18(A) at least one organic polymer, a precursor thereof, or
Initial polymer, Plasticizer and solvent, swelling agent, and (C) powdered solid if necessary.
Or make a paste-like material containing these components, then into the desired shape,
Evaporating the solvent or swelling agent and any additional material to solidify the shape,
The latter is then extracted from the solidified layer using a solvent or a plasticizer, and finally
Immersed in (B)MineralOr almost inorganic liquid
A liquid which is a body and which does not or essentially does not dissolve the matrixor Is between two adjacent electrolytes / electrodes so that they can be placed in an electrochemical element With an electrolyte, or an ionic or electronic intermediate conductor, provided that the electrolyte Contains 70% or less of an organic solvent based on the total amount of the solvent used, and the solvent is mixed with water. Wear Claims8Manufacture layers described in or above
how to.

19. The liquid (B) is a salt dissolved in the solvent at least partially organic, when the cavity has been filled, organic component of the solvent is extracted, mineral component, preferably H ₂ 19. The method according to claim 18, wherein the method is replaced by O.

20. The method according to claim 9 , wherein each paste-like material used for the layer is applied successively to the substrate by means of a paste application means, particularly preferably by a pressing method, and the layer is finally solidified. 13. The method according to any one of claims 12 to 12 .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01M 8/02 H01M 8/02 P 10/40 10/40 Z // H01M 8/10 8/10 (81 ) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW) ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR , C , CZ, DE, DK, DM, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, L K, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZWF terms (reference) 4J002 BG061 CC031 CC151 CD001 CF001 CG001 DD056 DD076 DE077 DE147 DE196 DF017 DG036 DJ007 DJ017 5H026 AA09 BB03 EE11 HH03 5H029 AJ14 AK01 AL01 CJ02 CJ03 CJ08 CJ12 CJ22 5H050 AA19 BA01 BA08 CA03 CA05 CB02 CB13 DA14 EA23 GA02 GA07 GA10 GA12 GA23 HA04

Claims (30)

[Claims] 1. A matrix comprising or consisting of (A) at least one organic polymer, a precursor thereof, or a prepolymer thereof, and (B) an electrochemically insoluble or essentially insoluble matrix. For use in an electrochemical element consisting of a hybrid mixture of an inorganic or almost inorganic liquid which is active at least and (C) a powdered solid which is inert with respect to said electrochemically active liquid. Paste material that can be made. 2. The paste-like material according to claim 1, wherein the matrix (A) contains a plasticizer and / or a solvent or a swelling agent. 3. The paste-like material according to claim 1, wherein the matrix (A) is a crosslinkable liquid or soft resin or contains it. 4. The resin according to claim 3, wherein said resin is selected from the group consisting of crosslinkable addition polymers and condensation resins, in particular aminoplasts, phenolplasts, epoxy resins, polyesters, polycarbonates and methyl methacrylate reaction resins.
Paste-like material described in 1. 5. The organic polymer of the matrix (A) comprises natural and synthetic polymers and mixtures thereof, especially natural and synthetic polysaccharides, proteins, resins, waxes and halogenated and non-halogenated polymers. The paste-like material according to claim 1 or 2, wherein the material is selected from rubber, thermoplast, and thermoelastomer. 6. The matrix (A) contains or consists of at least one organic polymer, which is soluble or swellable in a solvent or a swelling agent, and which comprises a synthetic resin and a natural resin and Characterized in that a mixture of
A paste-like material according to any one of the preceding claims. 7. A matrix (A) comprising a hygroscopic salt.
A paste-like material according to any one of the preceding claims. 8. The electrochemically active liquid (B) comprises a material suitable for a cathode material,
Or a material suitable for the negative electrode material, or a material suitable for the electrolyte, a material suitable as an intermediate conductor of ions or electrons between two such materials, a material which can be disposed adjacently in the electric science element. The paste-like material according to claim 1, wherein the paste-like material can be selected from the group consisting of: 9. The liquid (B) is an aqueous or non-aqueous, inorganic or almost inorganic liquid, and contains a solid electrolyte and / or a mixed conductor and / or an electrolyte material without being dissolved. The paste-like material according to claim 8. 10. The paste-like material according to claim 8, wherein the inorganic liquid contains magnesium chloride. 11. The paste according to claim 8, wherein the liquid is or substantially contains vanadium oxyhalide, aqueous or non-aqueous sulfuric acid, potassium hydroxide or LiAlCl ₄ / SO _2. Material. 12. A paste-like material according to claim 8, wherein said inorganic liquid contains a hydrophilic organic additive, preferably an alcohol. 13. The method according to claim 1, wherein the solid substance (C) is selected from SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, MgO or a mixture thereof. Paste-like material described in 1. 14. A matrix comprising or consisting of (A) at least one organic polymer, a precursor thereof, or a prepolymer thereof; (B) an electrochemically active, insoluble or essentially insoluble matrix. A layer which can be applied to a substrate consisting of a mixed mixture of an inorganic or almost inorganic liquid and (C) a powdered solid which is inert to the electrochemically active liquid, or Self-supporting layer. 15. The layer applicable to a substrate or the self-supporting layer according to claim 14, wherein the layer is a flexible layer. 16. A flexible layer containing an organic polymer and a substance suitable for a positive electrode, and (2) an electrochemically active liquid (B) is selected from substances having an electrolyte property. 16. A composite layer having electrochemical properties comprising a layer according to claim 14 or 15, and (3) a flexible layer containing an organic polymer and containing a substance suitable for a negative electrode. 17. The flexible layer according to claim 14, wherein (1) the inorganic liquid is a liquid substance suitable for a cathode or an anode, and (2) a solid electrolyte embedded in an organic polymer matrix. A flexible layer, and (3) a liquid or solid electrode material embedded in an organic polymer matrix, said electrode material being a counter electrode of said electrode material of said layer (1). Composite layer having electrochemical properties, comprising a layer with 18. The method according to claim 16, wherein a layer serving as a lower contact electrode is applied to the layer having a positive electrode material, and a layer serving as an upper contact electrode is applied to the layer having a negative electrode material. 18. A composite layer having the electrochemical properties according to 17. 19. Transferring electrons from said electrode material to said contact electrode between said layer serving as lower contact electrode and said layer having positive electrode material and / or between said upper contact electrode and said layer having negative electrode material. 9. The composite layer with electrochemical properties according to claim 8, characterized in that there is a thin plastic layer containing a conductive metal element or an alloy of these elements suitable for being applied. 20. The cathode material according to claim 1, wherein the cathode material is a salt, preferably a lithium salt, soluble in a proton-separating solvent, preferably H ₂ O, and the anode material is an aprotic material. Item 20. The composite layer according to any one of Items 17 to 19. 21. Use of the composite layer according to any one of claims 16 to 20 in a primary battery, a secondary battery, or a disassembled battery. 22. Use of a composite layer according to claim 21, characterized in that the composite layer has a thickness from about 10 μm to about 2 mm. 23. The at least one layer according to claim 14 or 15,
Use in low temperature fuel cells, solar cells, electrochemical sensors, especially electrochemical sensors for measuring moisture. 24. The polymerizable composition according to claim 1, wherein a crosslinkable prepolymer is mixed with the electrochemically active liquid (B) and, if necessary, the solid (C). The method for producing a paste-like material according to the above item. 25. The organic polymer, a precursor thereof, or a prepolymer thereof is combined, and if necessary, sufficiently mixed with a plasticizer and the solid (C). 14. The plasticizer according to claim 1, wherein the plasticizer dissolved in the solvent is washed out of the material, any solvent is removed from the material, and finally an electrochemically active liquid (B) is added. 2. The method for producing a paste-like material according to item 1. 26. A material in which the matrix (A) comprises a crosslinkable polymer or prepolymer is used as the paste-like material, and the layer obtained from the paste-like material is subjected to a crosslinking treatment of a polymer component. 16. The method for producing a layer according to claim 14 or 15, wherein the method is carried out by electron irradiation, by heating, or by immersion in a cross-linking chemical. 27. The method according to claim 26, wherein the matrix (A) is made of a resin, and the resulting layer is cured by using UV or electrons. How to make. 28. (A) At least one organic polymer, a precursor thereof, or a prepolymer thereof, a plasticizer, a solvent, a swelling agent, and (C) a powdered solid as required, or a component thereof. A paste-like material is prepared, which is then made into the desired shape, and the shape is solidified by evaporating the solvent or swelling agent and any additions, and then using a solvent or plasticizer to remove the latter from the solidified layer. And finally,
By immersing the resulting cavity in (B), the cavity is filled with a liquid which is an electrochemically active inorganic or almost inorganic liquid and which does not or does not substantially dissolve the matrix. The layer according to claim 14 or 15,
Or a method of manufacturing a layer to be placed on something. 29. The inorganic or almost inorganic liquid is a salt at least partially dissolved in an organic solvent, and when the cavity is filled, the organic component of the solvent is extracted and the inorganic component, preferably Characterized by being replaced by H ₂ O,
29. The method according to claim 28. 30. The method according to claim 17, wherein each paste-like material used for the layer is applied successively on the substrate by means of a paste application means, particularly preferably by a pressing method, and the layer is finally solidified. 20. The method according to