KR20010080177A - Pasty materials comprising inorganic, fluid conductors and layers produced therefrom, and electrochemical components made from these layers - Google Patents

Abstract

The present invention relates to a pasty material which can be used in electrochemical components and comprises a heterogeneous mixture, the heterogeneous mixture comprising or consisting of at least one organic polymer, a precursor of this polymer or a precursor polymer of the matrix (A); Inorganic or essentially inorganic fluids (B) which are electrochemically active and which do not dissolve or essentially dissolve the matrix; In some cases, it is made of a powdered solid (C) which is essentially inert, taking into account the fluid which can be electrochemically activated. The present invention also relates to a layer that is free standing or seated on a substrate and comprising a heterogeneous mixture, wherein the heterogeneous mixture contains or consists of at least one organic polymer. A matrix (A) as defined in any of the claims; An inorganic fluid (B) which is electrochemically active and which dissolves or hardly dissolves the matrix; In some cases, it is made of a powdered solid (C) which is essentially inert, taking into account the fluid which can be electrochemically activated. In addition, the present invention relates to a layer combination having electrochemical properties and comprising a layer of the type described above, wherein said layers or layer combinations are preferably used in the field of battery, low temperature fuel cell, solar cell or electrochemical sensor manufacturing. Can be.

Description

Paste materials comprising inorganic, fluid conductors and layers produced therefrom, and electrochemical components made from these layers}

Since the early 1970s, research has been attempted to develop electrochemical components such as accumulators in the form of thin layers. In addition, among the objectives of the study, foil bonds having particularly advantageous charging and discharging characteristics are formed by forming very large contact surfaces between the respective electrochemical constituents such as electrodes or electrolytes with respect to the capacity of the electrochemically active material. assembly). Moreover, in certain cases the binder may be rounded or adjusted to other desired forms because of its high flexibility.

To produce such an electrode material, a solid or viscous teflon has been used so far, where a certain percentage of carbon and the intrinsic electrode material are mixed and then pressed or ejected onto a suitable lead electrode. However, the layers composed of Teflon did not have sufficient flexibility. Also proposed is an electrode layer made of PVC and tetrahydrofuran or other polymer dissolved in a solvent and subsequently passing through the solvent. Of course, the product in this case is disadvantageous in conductivity.

In particular, particular problems are also involved in the preparation of layers which can serve as electrolytic layers in the corresponding electrochemical binders. US Pat. No. 5,456,000 describes a rechargeable battery produced by laminating an electrode cell and an electrolytic cell. As the positive electrode in this cell, a film or membrane prepared by separating the LiMn ₂ O ₄ -powder in matrix form from the polymer-copolymer is used. Here, the negative electrode is prepared by coating the powdered carbon-dispersion in a dry state in the matrix of the polymer-copolymer. An electrolyte / separation membrane is disposed between the electrode layers. To this end, the poly (vinylidenefloor) -hexafluoropropylene-copolymer is converted into an organic plastic mass such as propylene carbonate or ethylene carbonate. A film is formed from this component, after which the plastic mass is removed from the layer. The cell remains in an "inactive" state until it is used. To activate the cell, the cell is immersed in a suitable electrolytic solution, after which the cell is ready for use after the fluid electrolyte is filled with the cavitation formed by exiting the plastic mass medium.

The disadvantage of this structure is that the cell must be activated just before it is used. However, this has not been done in most cases.

FIELD OF THE INVENTION The present invention relates to a new class of materials having electrochemical properties, more specifically, self-supporting or seating on a substrate, and in some cases primary batteries, accumulators, low temperatures The present invention relates to a flexible layer that can be used as a low temperature fuel cell, a solar cell, and the like, and to a special paste-like material constituting a layers assembly made of these layers.

1 shows a possible sequence of such arrangements.

2 shows a compact structure of the accumulator provided with a very large cell active face.

3 is a graph showing the change in voltage over time in accordance with an aspect of the present invention.

Accordingly, it is an object of the present invention to comprise a corresponding conductor (ion or mixed conductor, in particular an electrolyte or at least one electrode) in fluid form, using which fluidic conductor to prepare an electrochemically active layer and to use it immediately. It is an object to provide paste-like materials suitable for the possible electrochemical components. The pasty material may be used over a wide range, such as primary cells, rechargeable batteries (accumulators), low temperature fuel cells, solar cells, electrochemical sensor products and the like, and the pasty material may also be in the form of layers, in particular of laminated thin sheets. It does not need to be provided in the housing, in particular in a sealed housing, because it not only takes the form but also has very good conducting properties and in some cases high flexibility and can also be discharged.

The above object can be solved by providing a paste-like material which can be used in an electronic component according to the present invention, which paste-containing material contains at least one organic polymer or contains a prepolymer or a prepolymer of the polymer or A matrix A composed of these; An inorganic fluid (B) which is electrochemically active and which dissolves or hardly dissolves the matrix; In some cases, it consists of a mixture of powdered solids (C) which are almost inert, taking into account the fluids which can be electrochemically activated. This paste-like material is treated with a corresponding freestanding or seated layer (eg foil, so-called "tape"), which layer can be applied to an electrochemical component or can be combined with other components to produce the component. have. In many cases, the pasty material is optionally composed of component A and optionally C and then solidified in the layer, after which component B is provided.

By "availability of the electrochemical component" is meant that the electrochemically active inorganic fluid can be an ionically conductive or electronically conductive fluid suitable as a flowable electrode material or fluid electrolyte. Also belonging to the inorganic fluid may be an electrically conductive fluid, which may vary in stoichiometry, which relates to a change in load as well as a change in valence. The fluid may replace the solid insertion electrode.

The material is stable in paste state, mainly by using an appropriate matrix (A) which is combined with the powder solid (C), which powder solid is used as the filling and supporting material. In addition, "paste phase" means that after the material has been produced it can be processed by a general paste lamination process, for example it can be installed at the bottom or plated by a coating, decomposition, lacquer or reverse printing process. do. Depending on each request, the material can be kept relatively thin until it is very sticky.

As the matrix A, a plurality of materials may be used. At this time, for example, it can be combined as a desolvent type, and in particular, it can be combined with a fluidized paste resin. For this purpose, for example, a resin composed of a bondable copolymer or a condensation resin can be mentioned. Thus, for example, a series capacitor consisting of phenolic resin (Novolake) or amino paste may be used, which is finally bonded after forming the pasty material into an electrochemical bonding layer. As another example, unsaturated polyesters that are combined with styrol via prop-polymerization, epoxy resins that can be cured into dual-functional reaction objects (e.g., phenol-A-epoxy resins cold cured with polyamide), And bondable polycarbonates such as polyisocyanate linkable with polyyl, or double polymethylmethacrylic salt, which may optionally be polymerized by styrol. The pasty material is generally formed of a mucoscopic series capacitor, or a polymer bound as matrix (A) with component or component (B) being substantially used.

Another possibility is that polymers or polymer-pre-steps can be used with solvents for organic polymers. In principle, no consideration is given here to synthetic or natural polymers. As well as polymers with carbon-main chains, polymers with hetero ions in the form of main chains such as polyamides, polyesters, proteins, or polysaccharides are possible. The polymer may be a homopolymer or a copolymer, which may be, but is not limited to, a static copolymer, a prop copolymer, a block copolymer or a poly blend. As the polymer having a purified carbon-main chain, for example, natural or synthetic rubber can be used. In particular, fluoro hydrocarbon-polymers such as teflon, polyvinylidene fluoride (PVDF) or polyvinyl chloride are preferable because the thin plates or layers formed of the paste-like material can have a very good waterproof property. These are especially electrochemical substances that can last for a long time. As another example, polystyrene and polyurethane are mentioned. Examples of copolymers include Teflon polymers and amorphous fluoropolymers or polyvinylidene fluoro / hexafluoro propylene (commercially available as Kynarflex). Examples of the polymer having hetero atoms in the form of main chain include diamine-dicarbonate-type and amino-type tandem polyamides, polycarbonates, polyacetols, polyethers and acrylic resins. Other materials include natural and synthetic polysaccharides (heterogeneous and homologous glycogen), proteoglykens such as cellulose mill methylcellulose. Substances such as chondroisulfate, hyaluronic acid, chitin, natural or synthetic beeswax and numerous other materials may be used. In addition, the above-mentioned resin (precatalytic) can be used in a solvent or a diluent.

Solvents for such polymers are well known to those skilled in the art.

Depending on whether the matrix (A) contains a solvent or not, a plastic mass (also a plasticizer) for the polymer used can be provided. Here, materials should be provided under "plastic mass" or "plasticizer", whose molecules are bonded to the synthetic resin valence via ancillary valence (Fan der Waals forces). As a result, the material can reduce the interaction force between the macro atoms, thereby lowering the softening temperature and roughness, and the hardness of the synthetic resin. This is distinguished from the solvent. Based on the fluidity of the material, the material should be dissolved by the corresponding solvent, not primarily in the form of evaporation from the resin. By treating the plastic mass, the high mechanical flexibility of the layer made from the pasty material is affected.

Those skilled in the art will know the appropriate plasticizer for each group of resins. This plasticizer can be favorably affinity using the synthetic resin to be treated. Typical plasticizers are phthalic acid and sulfuric acid esters having a high boiling point, for example, dibutyl phthalate and dioctyl phthalate. Further, for example, ethylene carbonate, propylene carbonate, dimethoxyethane, dimethyl carbonate, diethyl carbonate, butyloactone, ethyl methyl sulfone, polyethylene glycol, tetraglyme, 1,3-dioxolane or S, S-dialkyl Dithiocarbonate is suitable.

In particular, by adding the solid material (C), it is possible to improve the properties of the matrix (A), for example with regard to support or retention in the drawing of the tape. The solid material (C) may be used in finely divided form (eg powder). This material is not corroded by liquid (B) and is particularly suitable for all materials which do not change to the oxidation / reduction form. This is often due to chemically very high cohesion, which makes it possible to use materials such as SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, MgO and the like. However, any other material that is incompatible with each electrolytic material or electrode material used may also be used.

The liquid to be used as the electrode, the electrolytic material, etc. should have at least some inorganic properties. As the electrode material, for example, vanadium octacyclo or vanadium oxybromide can be used, wherein the oxidation process of vanadium can be improved to VOX, VOX ₂ , VO ₂ X or more of + III to + V. By using such a material, a decomposition electrode is maintained, which has the advantage that the typical volumetric expansion of the mutual electrode does not occur compared to the insertion electrode.

In principle, as the electrolytic material, a suitable flowable electrolytic material can be used for each system, and many electrolytic materials corresponding to the above systems are known. Thus, water-soluble systems such as sulfuric acid or KOH can be used as proton conducting electrolytic materials in systems such as lead accumulators or Ni-Pb-accumulators or nickel-cadmium- or nickel metal-hybrid accumulators, thereby reaching the desired packing density. can do.

In order to facilitate delivery of the conducting liquid to the water-soluble matrix in a possible manner, the electrolytic material is optionally added with an alcohol or other ionic organic solvent which can be mixed with water. Here, mono-, di- or trialcohols of straight chains or branched chains with 1-6 carbon atoms, particularly preferably methanol, ethanol, propanol, glycol, glycerin and the like, are suitable. In particular, when the polymer matrix is used as a plastic mass which dissolves again from this polymer matrix, the water soluble mixture can easily wet the optionally bound matrix in the production layer, thereby consequently facilitating delivery. However, " substantially inorganic liquid " excludes forms in which the electrolytic material consists substantially or substantially of salts and purified organic solvents such as ethylcarbonate, diethoxyethane and the like. Therefore, the content provided in the inorganic solvent is about 70 Vol .-% of the total amount of solvent, preferably 50 Vol .-%. Furthermore, depending on the nature of the matrix and the organic solvent, for example up to 30 or 15 Vol .-% is sufficient.

In another embodiment, the matrix material may contain plasticizers or plastic masses that can be mixed with water. This improves the hydrophilicity of the matrix material. The predetermined amount is treated here as the maximum amount of the organic additive. As another variant, the matrix material may be mixed with a moist salt, for example MgCl ₂ . This generates moisture in the matrix and consequently passes the matrix to facilitate delivery of the electrolytic material.

As the electrolytic material, a dehydrated inorganic fluid electrolyte material such as H ₂ SO ₄ or LiAlCl ₄ / SO ₂ may be used together with the water-soluble system (the water-soluble system is composed of lithium aluminum claroid when sulfuric acid in gaseous form occurs). The system also has a relatively high surface voltage for strong hydrophobic polymer matrices. In addition, in order to facilitate movement through the polymer matrix, a series of measures are again provided, in particular by modification of the water soluble electrolytic material, ie by adding alcohol or the like to the electrolytic material or by adding a plastic mass to the polymer matrix.

The paste-like material according to the invention and the layers made from these materials are suitable for a plurality of electrochemical components, as described above, which predominantly take the form of thin layer bonds. One skilled in the art can select the above-mentioned liquid (B) to be used without adding an electrochemical component, that is, a synthetic resin.

For example, the possible components of the accumulator are referred to below as lithium technology:

Lower conducting electrodes Al, Cu, Pt, Au, C

Anode LiF, Li _X NiVO ₄ , Li _X [Mn] ₂ O ₄ , LiCoO ₂ , LiNiO ₂ ,

LiNi _0.5 O ₂ , LiNi _0.8 Co _0.2 O ₂ , V ₂ O ₅ , Li _X V ₆ O ₁₃

Electrolytic Material LiAlCl ₄ / SO ₂ (dewater soluble)

Cathode 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 stack

Upper conducting electrodes Al, Cu, Mo, W, Ti, V, Cr, Ni

While the electrolytic layer of the accumulator may be composed of the paste-like material according to the invention, in some cases another layer may be formed by the paste-like material, which is an electrode in powder form instead of liquid (B). It can be treated with material. At this time, the electrode material does not dissolve in the polymer matrix. Particularly preferably, the magnification of the electrode material with respect to the polymer matrix is maintained at approximately 70 to 30 Gew .-%. The polymer matrix may have the same components as the material according to the invention.

However, of course, the present invention is not limited to accumulators using lithium technology. As mentioned above, it can be used in various forms. Thus, the material according to the invention can be treated with a layer seated on a freestanding sheet or substrate, which can be used in primary cells, secondary cells, decomposition cells, low temperature fuel cells, solar cells or electrochemical sensors. .

The above-described components made of the paste-like material according to the present invention can be mixed according to the prior art and the manner, which can mainly be mixed by vigorously stirring or kneading the components. In contrast, the organic polymer or the preceding step of this polymer is dissolved or called in a solvent prior to the addition of component (B) and optionally component (C). Mainly, component (A) is provided to component (C) before treating the matrix with a so-called paste-like material. Component (B) may also be added in advance in this step. Other cases will be described further below.

The paste-like material according to the invention is particularly suitable for the manufacture of thin film cells and for other corresponding electrochemical components such as, for example, electrochemical sensors. Preferably, for the preparation of the components, so-called "thick layer techniques" can be used. Each layer of the parts is also called a "tape." To this end, each electrochemically active and activatable layers have a thickness of about 10 μm to about 1 or 2 mm, stacked side by side and installed in intimate contact. One skilled in the art can select the method of use depending on the thickness. Preferably, it has a width of 50 μm to 500 μm, particularly preferably about 100 μm. Of course, it can be produced according to the invention in a corresponding thick layer structure (which has a thickness of mainly from 100 nm to several μm). However, the method of use is not limited so long as the corresponding components are sufficient for the usual dosage values in various cases. Of course, the method of use may, for example, consider a backup chip.

In addition, the pasty material according to the present invention may be installed in other forms. Therefore, the thicker layer (for example, an area of about 1 to 10 mm) is formed in the form of perforation or cutting. In the case of cutting, it is suitable in pharmaceutical technology, for example, which must be very small and very stable for batteries and accumulators. Examples of the use include a deep battery. These cells stick or are implanted outside or inside the ear, thus eliminating the possibility of small, especially breakaway. Of course, this form is possible, for example, in a mold, injection molding or extrusion process.

Accordingly, the present invention comprises an electrochemically active and activatable layer that is free standing or seated on a substrate and preferably has a predetermined thickness that can be prepared from the pasty materials described above. The layer is mostly flexible.

In order to produce freestanding layers (thin plates, tapes) as well as layers seated on a substrate, processes generally known in the art can be followed, which can be used for the corresponding matrix of polymeric material. At this time, the stabilization of the paste-like material is possible by curing (of a resin or other series capacitor), combining prepolymerization or linear polymerization, removing a solvent (for example, acetone, etc.), or by similar techniques and methods. . If the polymer matrix comprises a plastic mass, the pasty material maintains sufficient viscosity during the outflow of the solvent, allowing for homogeneous distribution of the components. In one embodiment in which the plastic mass of the present invention can meet other purposes (e.g. improve the hydrophilicity of the matrix material), the polymer matrix is strongly strong in some cases after the paste-like material solidifies on the freestanding or seated layer. By not crystallizing it can be removed again so as not to have broken and defective solubility. For example, a polymer with sufficient plasticity is a combination of polyvinylidene fluoro and hexafluoro propylene as polymer / copolymer.

In a particular embodiment of the invention, the combination (B) is only partly added to the preparation of the pasty material. That is, as described above, the plastic mass can be compared with a sponge when the material is removed after solidifying on a free standing or seated layer (e.g., when a diffusion process is performed after addition of a solvent such as hexane). Form a solidified matrix cavitation. By precipitating in liquid B, the plastic mass can be assisted by capillary forces, which are sucked into the corresponding hollow chamber and remain in a stable state there.

In order to keep the thin plate freestanding, for example, a suitable paste-like material can be molded to a suitable thickness on a calender. Here, it can be obtained according to a standard technique. The freestanding layer can be formed by laminating a paste-like material on a substrate and peeling off the layer after it has solidified. At this time, it is assumed that the product has sufficient plasticity. Coating is carried out by a general paste lamination process. Examples include coatings, lacquers, jets, spin coatings, and the like. Printing techniques are also possible. At this time, the liquid (B) is added to the pasty material as described above, or at least after the pasty material composed of the polymer matrix (A) and the filler (C) is solidified and then filled after the plasticizer contained in the cavitation is removed.

In a preferred embodiment of the present invention, a resin material (serial capacitor) bonded as described for the pasty material is used, which is cured by ultraviolet rays or electron beams after forming the layer. The curing can be done naturally, as well as heat or chemically (for example by immersing the generated layer in a corresponding bed). In some cases, the material may be bonded at an appropriate strength, speed, or the like.

The present invention also specifically deals with layer assemblies having electrochemical properties, such as accumulators and other cells or sensors, which cells or sensors are formed or include according to the corresponding order of the layers described above.

1 shows a possible sequence of the arrangement, in which reference is made to a conductive electrode 1, an intermediate tape 2, an electrode 3, an electrolytic material 4, an electrode 5, an intermediate tape 6. , The conducting electrode 7, and will be described in more detail below.

In order to produce the layered binder, each pasty material may be arranged layer by layer in parallel with each other by a paste lamination process. The individual layers can then be staggered from one another or can be released by a solvent or installed in the form of layers in this manner, but this is achieved by evaporation or staggering of the solvent or source material after stacking all the necessary layers. Condensation may occur in the matrix. In the case of evaporation, it is advantageous, for example, to carry out after laminating each electrochemically viable layer by a printing process similar to the printing of a plurality of fibers. To this end, for example, in the case where a flexo printing technique is chosen, the substrate can be continuously printed in several meters / seconds with the electrochemically active layer required by this printing technique.

Alternatively, each layer or sheet can be converted individually in the final condensation state. As the layer or thin plate, a freestanding thin plate can be handled and the corresponding components of the component to be prepared can be joined to each other by lamination. To this end, conventional lamination techniques are used. Here, so-called, for example, compression coating is used, in which the second layer is combined with the carrier layer via a pressing roller and the calender coating is combined with two or three roller gaps in which the carrier passage together with the pasty material contracts or Overlapping (preferably a combination of the pressure of the heated roller and the opposing pressure). Those skilled in the art can freely use the corresponding technology obtained through the roller of the matrix for each pasty material.

Often, the press process that takes place during the bonding (lamination) of each of the layers must, for example, improve the bonding of the respective layers (thus obtaining improved conductivity). To this end, conventional techniques can be used. Preferably, if the material used is capable of cold extrusion, a cold extrusion (at temperatures below 60 ^° C.) process is used. This allows very good contact between the layers.

The advantage obtained by using the paste-like material according to the present invention, or the self-supporting thin plates made from these materials, or the layers seated on the substrate, means that in any field of application, the flowable electrolyte or flowable electrode is bound like a sponge in the polymer matrix. This is advantageous in terms of cost, high practical energy density through compact structure, and high stability against leakage.

The electrochemical component is not only able to be prepared from the paste-like material according to the invention. Therefore, the embodiments described below should be understood as only examples or as particularly preferred embodiments.

Therefore, rechargeable electrochemical cells can be made with thick-layer-technology, each of which is electrochemically active, through which the electrochemical cells can be made from about 1 to 2 mm from a thickness of about 10 μm. To thickness, it preferably has a thickness of about 100 μm. If the electrochemical cell is based on lithium technology, the liquid described above is provided as the electrolytic material and the solid described above is provided as the electrode layer. At this time, at least three layers are provided, specifically, one layer 3 serving as an anode in FIG. 1, a layer 4 serving as a solid electrolytic material, and a layer 4 serving as a cathode. Is provided.

In accordance with the present invention, a particularly preferred current density is provided to the accumulator within certain constraints. The current density is controlled by the resistance of the electrolytic material, as is known. If a high current density is selected, the electrode can be destroyed for a long time by polarization, and if the current density is low, the conductivity of the manufactured accumulator is utilized only in a narrow area of use. Usually, the limiting condition is 1 mA / cm ² . When the electrolytic layer is formed to a thickness of about 100 mu m, the current density of 1 mA / cm ² is negligible as the voltage drop limited by the resistance as 0.1V. For example, if the electrolytic material has a conductivity of 10 ¹ S / cm, the conductivity associated with this layer in the layer (insertion material and channel) via micro-geometry represents about 10 ^o S / cm. As the most recommended reference value, the thickness d of the layer is chosen so as to satisfy the following equation 1 in relation to the conductance σ _ion and the ion resistance, and with respect to plane A.

200 Ω <d / (σ _ionA )

The reference value is important when using the "tape" according to the present invention.

In addition, the cell consisting of three layers (or any other electrochemical component consisting of an anode / electrolyte layer / cathode) is provided with conducting electrodes (layers 1 and 7 in FIG. 1). These are preferably composed of a suitable thin plate material (conducting electrode material which can be used in the lithium technology mentioned above at the outset).

In a particular embodiment of the invention, a further thin between the lower conducting electrode and the electrode adjacent to the lower conducting electrode, or between the upper conducting electrode and the electrode adjacent to the upper conducting electrode may optionally be prepared as a paste-like material. A resin layer (“intermediate tape”, layers 2 and 6 in FIG. 1) is disposed. The resin layer of this thin plate contains a conductive and metal component or a laminate of these components, where appropriate electrons of each electrode material are carried to each conductive electrode. For this purpose, when the resin layer is to be disposed between the anode and the corresponding conductive electrode, for example, gold, platinum, radium and carbon or a laminate thereof can be mentioned.

If they are disposed between the cathode and the conducting electrode, nickel, iron, chromium, titanium, molybdenum, tungsten, vanadium, manganese, niobium, tantalum, cobalt or carbon are used as constituents. For the concentration and composition of the layered paste-like material, of course, electrodes and electrolytic materials are used. In the lithium technology described above, in order to configure the conducting electrode and the intermediate tape (see FIG. 1) when made of LiAlCl ₄ / SO ₂ as an electrolytic material, charge and discharge curves as shown in FIG. 3 are constructed.

In another particular embodiment of the invention, an electrochemical cell consisting of three or more layers is provided, wherein both electrodes are formed as layers according to the invention and the positive layer (anode) represents a pro clock and the negative layer (opposite) Electrode) represents an approach clock. By "professional" it is to be understood that salts, for example lithium salts such as lithium acetate or lithium perchlorate, are dissolved in "professional" or proton separation system (H ₂ O). Correspondingly, a solid electrolytic material is selected for the intermediate layer, and the cation (for example lithium) of this electrolytic material is a conductive ion. In particular, due to the waterproofness of the polymer matrix, in this embodiment, the cathode decomposes without water seeping. Preferably, the mobility is improved by the flowable electrolytic material at the anode and the electrode material selected here is selected in view of the cost of the corrosion potential of the positive metallic conductive electrode, for example, electrolytic containing lithium perchlorate. A variety of choices are possible), including the problem that the conducting electrode is easily oxidized at the anode of the material.

The material according to the invention is suitable for use in primary cells, in particular for the preparation of an electrolytic layer. Here, as a suitable electrode system, for example, zinc-carbon, alkali-manganese (Zn-MnO ₂ ), zinc-mercury oxide (Zn-HgO), zinc-silver oxide (Zn-Ag ₂ O), zinc-oxygen (Zn- O ₂ ), magnesium-oxygen (Mg-O ₂ ), and aluminum-oxygen (Al-O ₂ ). As electrolytic materials there are provided alcohol solutions such as alkali and ammonium bromide or chlorides or alkali hydroxides (in particular sodium and potassium of alkali metal groups).

The material according to the invention is also suitable for use in secondary batteries. Some systems are already known, such as lead accumulators and nickel metal hydroxide cells, with the addition of nickel-cadmium, nickel-iron, zinc-silver oxide and alkaline manganese secondary cells. Suitable electrolytic materials for this purpose include, for example, water soluble or anhydrous H ₂ SO ₄ (eg in lead accumulators) or potassium solutions.

The material according to the invention can also be used in new types of cells, that is to say so-called decomposition cells. Here, the salt is decomposed at the anode composed of MgBr ₂ , for example, and the corresponding bromine is stored in a carbon thin film (carbon tape). The electrolytic material of the pasty material or the thin plate or layer prepared from the electrolytic material is MgCl ₂ , which is not decomposed because the decomposition voltage of the battery is higher than MgBr ₂ . The cathode is coated with Mg, which acts as a sponge in the metal sheet or carbon sheet. Alternatively, the surface of the material is coated with magnesium when present in a closed form, with the first variant being preferred due to the advantageous volume ratio. The voltage of the battery is equal to the decomposition voltage of MgBr ₂ . In particular, Mg and Al, which are light and inexpensive elements, are advantageous. In this system, inorganic water soluble or at least flowable electrolytic material should be used because the mobility of the solid electrolytic material at room temperature is of paramount importance for battery and accumulator use. The electrodes may be provided in the form of metal or carbon foil or as an electrode material in powder form, which are embedded in the polymer matrix in the form of a foil as described above.

Another field of use of the paste-like material according to the invention is low temperature fuel cells. Heretofore, a potential conductive polymer electrode (PEM: Proton Exchange Membrane) such as nafion is used. However, this polymeric electrolytic material is expensive and sensitive to drying. In particular, the simple recharging of fuel cells is difficult, in general the hydrogen tank provided with a small and expensive steel flange has to be completely replaced. The condition for the installation space of the hydrogen tank is that at present the battery must be formed in a thin layer. According to the present invention an electrolytic layer is installed by using a polymer matrix added to the absorbent salt and the electrolytic layer is maintained in a humid environment. By decomposing the salt, the layer contains a flowable electrolytic material (so-called salt in an aqueous solution), and the water can be electrochemically decomposed. The corresponding hydrogen is then stored in a stacked other hybrid (Y, Pt, Pd, or other water soluble material) tank in the form of a thin plate, preferably in the form of an organic polymer matrix. The water loss obtained by decomposing water can always be rebalanced by adding liquid through the wet salt.

In addition, embodiments of the present invention provide a mixture of polymers, solvents and plasticizers for polymer matrices (A) and solids (C) for pasty materials, " tape " -form conversion of the materials, form coagulation, solvent removal, An electrolytic layer may be used in which the plasticizer is removed and the alcohol is evaporated after "filling" the cavitation with the alcohol solution of the wettable salt. In contrast, the salts are dissolved in a solvent or plastic mass with, for example, an alcohol as solvent intermediate and then treated in a pasty material. In this case, the alcohol is preferably separated with the solvent. Here, the solid material (C) is provided mainly for mechanically stabilizing the tape in the form of a membrane. This solid material is omitted in some cases.

The pasty material according to the present invention is also used for solar cells, and thin plates or layers can be produced from the pasty material. The solar cell-based system preferably utilizes the so-called Honda Fujishima effect (1972) rather than silicon technology. Oxides such as titanium dioxide and wolframtrioxide decay (electrolyte) in the sun's rays into other materials such as water and formic acid. This is because the electrons are active in the conduction band and the remaining pores oxidize to a high degree, which causes the oxide to be in the best oxidation state known in chemistry. The solar cell comprises three layers (tape), more specifically a hydrogen storage layer as already described in the low temperature fuel cell, an electrolyte layer containing water and, if necessary, operation as already described in the fuel cell. Decay upon time, containing additional TiO ₂ or WO ₃ and a tape layer containing predominantly metal powder or carbon (to ensure sufficient electronic conductivity) and installed similarly to so-called electrolyte tapes. In contrast to fuel cells, solar cells are "charged" with light. During discharge, the solar cell is like a fuel cell.

In addition, the paste-like material according to the invention and the thin plates or layers produced therefrom are suitable for electrochemical sensors. Polymer matrices are used instead of absorbent salts such as water. At salt concentrations, ambient humidity and temperature, the moisture content is very finely controlled in the thin plates made of the material. Compared to the standard electrode formed as a corresponding laminated tape, humidity measurement is possible because different voltages are generated to control the amount of moisture.

The electrochemical component according to the invention can be sealed in a synthetic resin housing, for example. Thus, the weight can be reduced compared to the metal housing, which also has an additional advantage for energy density.

In addition, an electrochemical layer binder (electrochemical component) can be inserted between two or more thin plates made of synthetic resin coated with beeswax or paraffin. This metal serves as a seal and can be improved in contact with the pressing action in the layer binder in a preferred manner since mechanical pressure can be exerted on the layer binder based on the inherent properties.

The electrochemical component is sealed by conventional or other means, and the interior may have a predetermined water / oxygen-partial pressure that enables high electrochemical stability. This affects the correspondingly selected variable in the environment, for example through the sealing of electrochemical parts.

The layer structure of the electrochemical component according to the invention can be arranged in any form. For example, since the flexible layer binder can be wound, a compact accumulator can be obtained as a particularly preferred form. In the compact structure of the accumulator, a very large battery active side is provided. FIG. 2 shows such a structure, wherein reference numerals 1 to 7 are the same as the components described in FIG. 1 and reference numeral 8 denotes an insulating layer.

Also, for energy storage, non-standing layer bonds may be stacked on a solid bottom, such as a wall (free-standing sheet bonds may be naturally installed or attached). Here, a large plane can be used, which does not show a suitable installation space for the accumulator. As a special example of such a structure, a layer assembly for forming an accumulator in a solar cell substrate is shown. Due to this structure, a freestanding energy supply unit can be provided. The layer sequence for the accumulator may also be installed on a solid or soluble substrate to serve as an electrochemical structure for energy storage.

Hereinafter, the present invention will be described in detail with reference to embodiments.

Example 1

Primary battery manufacturing

7 g of MnO ₂ mixed with 7 g of zinc powder as an anode, 5 g of SiO ₂ as an electrolyte, 1 g of PVDF-HFP as a cathode, 1.5 g of dibutylphthalate, and 10 g of acetone were used. The electrode and electrolyte are formed into a tape, acetone is vaporized and the plastic mass is dissolved in hexane. The tape is filled with a water soluble alcohol KOH solution (solvent: 50% water and 50% alcohol) and stamped between two special steel electrodes.

Example 2

Secondary battery manufacturing

7 g of Ni (OH) ₂ mixed with 7 g of Cd (OH) ₂ as an anode, 5 g of SiO ₂ as an electrolyte, 1 g of PVDF-HFP as a cathode, 1.5 g of dibutylphthalate, and 10 g of acetone, respectively do. The electrode and electrolyte are formed into a tape, acetone is vaporized and the plastic mass is dissolved in hexane. The tape is filled with a water soluble alcohol KOH solution (solvent: 70% water and 30% alcohol) and stamped between two special steel electrodes.

Claims (30)

For paste-like materials which can be used in electrochemical components and comprise heterogeneous mixtures, The heterogeneous mixture is, (A) a matrix containing or consisting of at least one organic polymer, a precursor of the polymer or a precursor polymer of the polymer; (B) an inorganic fluid or an almost inorganic fluid that is electrochemically active and that dissolves or hardly dissolves the matrix; (C) Paste-like material consisting of a powdered solid, which is optionally in an inert state in consideration of a fluid which can be electrochemically activated. The paste-like material according to claim 1, wherein the matrix (A) further contains a plastic mass and a solvent or spring water. The paste-like material according to claim 1 or 2, wherein the matrix (A) is or contains a bondable fluid or other resin. 4. The method of claim 3 wherein the resin is selected from bondable copolymers and condensation resins, in particular from aminoplasticizers, phenol plasticizers, epoxy resins, polyesters, polycarbamates and methylmethacrylate-reactive resins. Paste material. The organic polymer according to claim 1 or 2, wherein the organic polymer of matrix (A) is a natural polymer and a synthetic polymer or a mixture thereof, in particular natural and synthetic polysaccharides, proteins, resins, beeswax, halogenated and dehalogenated rubbers, thermoplastics And a thermoelastomer. The matrix (A) according to any one of claims 1 to 6, wherein the matrix (A) contains or consists of organic polymers that are at least partially dissolved or ejected in one or more solvents or spring waters. The organic polymer is a pasty material, characterized in that selected from synthetic polymers and natural polymers and mixtures thereof. The pasty material according to any one of claims 1 to 6, wherein an absorbent salt is added to the matrix material (A). 8. The electrochemically active fluid (B) according to any one of claims 1 to 7, wherein the electrochemically active fluid (B) is composed of a material suitable as an anode material, a material suitable as an anode material, a material suitable as an electrolyte, and an ionic or electron intermediate conductor. Paste material, characterized in that the material selected from among the materials or materials that can be disposed adjacent to the two electrochemical components. 9. The fluid (B) according to claim 8, wherein the fluid (B) is a functional or dehydrated inorganic fluid or an almost inorganic fluid as functional or dehydrated, and comprises a dissolved solid electrolyte and mixed conductor and electrolyte material. Paste material. 10. The pasty material according to claim 8 or 9, wherein the inorganic fluid contains magnesium chloride. 9. The pasty material of claim 8, wherein the fluid is or substantially contains vanadium-oxyhalogen, water soluble or dehydrated sulfuric acid, caustic potassium liquor, or LiAlCl ₄ / SO ₂ . 12. Paste material according to any of claims 8 to 11, characterized in that the inorganic fluid contains a hydrophilic organic additive, preferably an alcohol. The paste-like material according to any one of claims 1 to 12, wherein the solid (C) is selected from SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, MgO, or mixtures thereof. . In a layer that is self-supporting or seated on a substrate comprising a heterogeneous mixture, The heterogeneous mixture is, (A) a matrix according to any one of claims 1 to 7 containing or consisting of at least one organic polymer; (B) an inorganic fluid or a substantially inorganic fluid that is electrochemically active and that dissolves or hardly dissolves the matrix; (C) In some cases, a layer that is self-supporting or seated on a substrate, consisting of a powdered solid that is in an almost inert state in view of a fluid that can be electrochemically activated. 15. The layer of claim 14, wherein the layer is a flexible layer. For layer binders having electrochemical properties, (1.) a flexible layer containing an organic polymer and comprising a material suitable for the anode; (2.) a layer according to claim 14 or 15, wherein a fluid (B) which is electrochemically active in a material having electrolyte properties is selected; (3.) A layer combination having electrochemical properties, containing a flexible layer containing an organic polymer and comprising a material suitable for the cathode. For layer binders having electrochemical properties, (1) a layer according to claim 14 or 15 having an inorganic fluid which is a fluid material suitable for the cathode or anode; (2) a flexible layer comprising a solid electrolyte immersed in an organic polymer matrix; (3) A layer combination having electrochemical properties, consisting of a flexible layer comprising a fluid or solid electrode material that can represent the opposite electrode of the electrode material of the layer (1) in an organic polymer matrix. 18. The layer having the anode material is provided with a layer serving as a lower conducting electrode, and the layer having the cathode material is provided with a layer serving as an upper conducting electrode. Layer binders with electrochemical properties. 19. A thinner synthetic resin layer according to claim 18, wherein an additional thin resin layer is provided between the layer serving as the lower conducting electrode and the layer having the anode material and between the layer serving as the upper conducting electrode and the layer having the cathode material, The synthetic resin layer comprises a metallic conductive component or a laminate of the components, And the laminate is an electrode delivered from each electrode material to each conducting electrode. 20. The cathode material according to any of claims 17 to 19, wherein the cathode material is a salt dissolved in a proton splitting solvent, preferably H ₂ O, preferably a lithium salt, And the anode material is an approach material. A method of using the layer combination according to any one of claims 16 to 20 in a primary cell, a secondary cell or a decomposition cell. The method of claim 21, wherein the layer has a thickness of about 10 μm to about 2 mm. Process according to claim 14 or 15, for use in low temperature fuel cells, solar cells or electrochemical sensors, in particular electrochemical sensors for humidity measurement. A manufacturing method for producing a paste-like material according to any one of claims 1 to 13, A process for producing a bondable prepolymer salt, characterized in that an electrochemically active fluid (B) and optionally a solid (C) are added so that they are intimately mixed. A manufacturing method for producing a paste-like material according to any one of claims 1 to 13, In the organic polymer, the previous stage of the polymer or the prepolymer layer of the polymer, a plastic mass and, optionally, a solid (C) are added and mixed intimately, Thereafter, in particular, a solvent capable of dissolving the plastic mass is added, The plastic mass dissolved in the solvent is converted back into a material and optionally the material is separated from the solvent, Finally, the electrochemically active fluid (B) is added. In the method for producing a free standing or seated layer according to claim 14 or 15, As the pasty material, a matrix (A) composed of a polymer or a prepolymer that can be bonded is used. And wherein said layer of paste-like material interacts with a polymer component and photochemically acts in a chemical interaction agent through immersion of an electron beam, heat, or layer. The manufacturing method according to claim 26, wherein the matrix (A) is made of a resin, and the formed layer is cured by ultraviolet rays or electron beams. The method of claim 14 or 15, wherein the pasty material comprises a heterogeneous mixture (A) consisting of one or more organic polymers, a preceding step of the polymer, or a prepolymer of the polymer, a plastic mass, a solvent or a spring or Thus consist of or contain powdered solids (C), The pasty material is then converted into the form of the desired layer, which in this form can be dissolved from the solidified layer by a solvent for dissolving the plastic mass later through evaporation of the solvent or spring, and optionally other measures. To solidify, Finally, the cavitation formed in the dissolved site is filled with an inorganic fluid or an almost inorganic fluid (B) which is electrochemically active and which dissolves or hardly dissolves the matrix. 29. The method of claim 28, wherein the inorganic fluid or substantially inorganic fluid is a salt at least partially dissolved in an inorganic solvent, The organic component of the solvent is ejected in connection with the filling of the cavitation and is replaced by an inorganic component, mainly H ₂ O. 21. The method according to any one of claims 17 to 20, wherein each paste-like material provided in the layer is installed side by side on the substrate by a paste lamination process, particularly preferably by a printing process, after which the layer is finally The manufacturing method characterized by being installed in a condensed state.