KR100777506B1 - 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 paste-like material that can be used in an electrochemical device.

(A) a matrix containing at least one organic polymer, a precursor of this polymer, or a prepolymer of this polymer, and

(B) an electrochemically activatable inorganic liquid that does not dissolve the matrix

Heterogeneous mixtures thereof. In addition, the paste-like material

(C) a powder solid inert to said electrochemically activatable inorganic liquid

It may further include. The present invention also relates to a self-supporting layer comprising a heterogeneous mixture of (A) and (B), or a heterogeneous mixture containing even (C), or a substrate seating layer. And also related to composite layers comprising such layers. These layers and composite layers can be used to make cells, low temperature fuel cells, solar cells, or electrochemical sensors.

Description

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

The present invention relates to a new class of materials having electrochemical properties, and more particularly, to a paste-like material, a flexible layer made of the paste-like material (which may be freestanding or seated on a substrate), and The invention relates to a composite layer made of flexible layers. Such materials, flexible layers, or composite layers can be used in primary cells, accumulators, low temperature fuel cells, and solar cells.

Since the early '70s, research has been attempted to produce electrochemical devices such as batteries in the form of thin films. For this purpose, due to the very high area of contact between the individual electrochemical components, such as electrodes and electrolytes, relative to the volume of electrochemically active material used, composite films with particularly good charge and discharge properties can be produced. In certain special circumstances, such composite films have high flexibility and can be easily rolled or configured to meet other desired shapes.

In the past, attempts to make such electrode materials have begun using Teflon, a solid or viscous liquid. Teflon is mixed with a percentage of carbon and electrode material and pressed or sprayed onto the appropriate contact electrode. However, the flexibility of the layers thus formed was not sufficient. In addition, electrode layers made of PVC and tetrahydrofuran, or other polymers dissolved in a solvent, have been fabricated, suggesting ways to remove the solvent later. However, products manufactured in this manner have disadvantages of insufficient electrical conductivity.

The preparation of layers capable of functioning as suitable electrochemical complexes with electrolytes presents particular problems. US 5 456 000 discloses a rechargeable battery cell produced by laminating electrode and electrolyte cells. A thin film dried by dispersing the LiMn ₂ O ₄ -powder in the matrix of the polymer / copolymer is used as the anode. The negative electrode is made by dry coating powdered carbon on a polymer / copolymer matrix. An electrolyte / isolation film is arranged between the electrode layers. To this end, the poly (vinylidene fluoride) -hexafluoropropylene-copolymer is converted using an organic plasticizer such as propylene carbonate or ethylene carbonate. A film is formed from these components, and then the plasticizer is removed from this layer. This cell remains in an inactive state until used. To activate the cell, the cell is submerged in a suitable electrolytic solution, where the cavities formed by plasticizer extraction are filled with liquid electrolyte. At this point, the battery is ready for use.

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

Accordingly, it is an object of the present invention to provide a paste-like material having a suitable conductor (such as an ion or mixed conductor, in particular an electrolyte or an electrode) in liquid form, wherein the electrochemical device is provided with such a liquid conductor in an electrochemical It is to provide a paste-like material suitable for providing chemically active layers. These electrochemical devices can be used in a wide range of products such as primary cells, rechargeable cells (batteries), low temperature fuel cells, solar cells, electrochemical sensors. For the purpose herein, the paste-like material and the resulting products of this invention also have a good electrical conductivity while having a layer structure in the form of a film laminate, and also have high flexibility. In addition, there is no leakage and, therefore, does not need to be arranged in the housing.

The above object can be solved by providing a paste-like material which can be used in an electrochemical device according to the present invention, which paste-like material,
(A) a matrix containing at least one organic polymer, a precursor of this polymer, or a prepolymer of this polymer,
(B) an electrochemically activatable inorganic liquid that does not dissolve the matrix
It includes. In addition, the paste-like material
(C) a powder solid inert to said electrochemically activatable inorganic liquid
It may further include. Such a paste-like material may be processed into a self-supporting layer or into a layer that can be placed on a portion, such as a film or tape, to form an electrochemical device, or may be combined with other materials to form an electrochemical device. As an alternative to this, a paste-like material is made from the above-mentioned component (A), or from components (A) and (C), and they are pressed in a layer form and then provided with component (B) to form a paste-like material. May be

The expression “usable for electrochemical devices” means that the electrochemically activatable inorganic liquid may be an ion-conductive, or electron-conductive liquid suitable as a liquid electrode material or liquid electrolyte. Also included are electrically conductive liquids that may alter the chemical structure. These liquids can replace the solid insertion electrode.

The paste-like material is preferably used in combination with a suitable matrix (A), in combination with a solid powder (C) which functions as a filler. By "paste" material is meant that the material can be made and then processed and processed using current paste application techniques. For example, it can be applied to the base using a brush, spatula, rake, or other various pressing methods, or can be processed and formed into a film. This paste-like material can be made relatively thin and can be made highly viscous.

A plurality of materials can be used as the matrix A. Solvent-based or desolvent-based systems may be used. Suitable desolvent-based systems are crosslinkable liquid or paste-like resin systems. For example, there are resins made of crosslinked addition polymers or condensation resins. For example, pre-condensates of Novolake or AminoPlast may be used, after which the paste-like material is formed and finally polymerized to the electrochemical composite layer. Further examples are unsaturated polyesters, for example polyesters which can be crosslinked to styrene by graft copolymerizaiton, bifunctional epoxy resins which are curable bifunctional reaction objects (e.g., cold with polyamide). Polycarbonates that can be crosslinked with cured diphenol-A-epoxy resins), polyisocyanurates that can be crosslinked with polyols, and bicomponent polymethyl methacrylates that can be polymerized with styrene have. This paste-like material is formed by combining a viscous precondensate or a noncrosslinked polymer for matrix (A) with component (B).

Another option is to use a polymer or polymer precursor with a solvent for the organic polymer. In principle, there is no limit to the kind of synthetic or natural polymers that can be used. Not only polymers having a carbon main chain can be used, but also polymers having a main chain heteroion (eg, polyamide, polyester, protein, polysaccharide) can also be used. The polymer may be a homopolymer or a copolymer. The copolymer can be a static copolymer, a graft copolymer, a block copolymer or a poly blend. As the polymer having a pure carbon-chain, for example, natural or synthetic rubbers (eg halogenated and non-halogenated rubbers, thermoplastics, thermoelastics) can be used. In particular, fluorinated hydrocarbon polymers are preferred. For example, teflon, polyvinylidene fluoride (PVDF), or polyvinylchloride is preferred. This is because a thin plate or layer formed of such a paste-like material can have a very good water repellency. Accordingly, the stability of the electrochemical device to be manufactured can be maintained for a long time. Another example is polystyrene or polyurethane. Examples of copolymers are Teflon, amorphous fluoropolymers, and polyvinylidene fluoride / hexafluoropropylene (from Kynarflex). Examples of the polymer having hetero atoms in the main chain include dimine-dicarboxylic acid-type and amino acid-type polyamides, polycarbonates, polyacetals, polyethers, and acrylic resins. Other materials include natural and synthetic polysaccharides (both homologous and heterologous), proteoglycans such as starch, cellulose and methylcellulose. Materials such as chondroitin sulfate, hyaluronic acid, chitin, natural or synthetic waxes can be used. In addition, the above-mentioned resins (precondensates) may be used in the solvent and the diluent.

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

Regardless of whether the matrix (A) comprises a solvent, a plasticizer (or softener) may be present for the polymer used. Plasticizers or softeners include materials with molecules that are bound to plastic molecules by coordinating bonds or secondary valences (van der Waals forces). Thus, they reduce the interaction force between the molecules and thus lower the softening temperature of the plastic and lower the hardness and brittleness. This is different from the solvent. Due to the high velocity, it is generally impossible to remove plasticizers or softeners by evaporating from plastics. Instead, it should be extracted with a suitable solvent. Using a plasticizer increases the flexibility of the layer made of paste-like material.

One skilled in the art will know the appropriate softener for each of the plastic groups mentioned above. These softeners must have a high degree of compatibility with the plastic to be treated. Common emollients are esters of phthalic acid or sulfuric acid with high boiling points, for example dibutylphthalate or dioctylphthalate. 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 when drawing the tape. The solid material (C) may be used in finely divided form (eg, powder). This solid material (C) is not affected by the liquid (B) and in particular does not cause oxidation / reduction change. Since it is chemically very cohesive, materials such as SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, MgO, or mixtures thereof are mainly used. However, any other material that is inert for each electrolytic material or electrode material used may also be used.

Liquids intended to be used as electrodes or electrolytes must have inorganic properties. For example, vanadium oxychloride or vanadium bromide are used, wherein the oxidation step of vanadium can increase from + III to + V through VOX, VOX ₂ , VO ₂ X. By using such a material, volume expansion, which is a typical phenomenon of the insertion electrode, does not appear. This has the advantage of extending service life.

In principle, the liquid electrolyte which can be used in the present system can be used as the electrolyte material. Many such systems and corresponding electrolytes are well known in the art. For example, water-soluble systems such as sulfuric acid or KOH can be used for proton conducting electrolytic materials in systems such as lead-acid batteries or Ni-Pb-batteries or nickel-cadmium- or nickel metal-hybrid-batteries, which may lead to desired packing densities. Can be reached.

To deliver the conductive liquid to the water repellent matrix, alcohols or other polar organic solvents that can be mixed with water can be added to the electrolyte. Particularly suitable for this purpose are mono-, di-, tri-alcohols of straight-chain or branched-chain type with 1-6 carbon atoms such as methanol, ethanol, propanol, glycol, glycerin. In particular, when the polymer matrix is used with a plasticizer (which is later removed), this aqueous mixture easily wets the matrix in the final layer, facilitating the delivery of conductive liquids. The content of the organic solvent should be 70% or less by volume of the total solvent amount, and preferably 50% or less. Depending on the nature of the matrix or organic solvent, a volume ratio of up to 30% or 15% may also be sufficient.

In another embodiment, the matrix material may contain a plasticizer or softener that can be mixed with water. This improves the hydrophilicity of the matrix material. The foregoing applies to the maximum amount of organic additives. As another example, hygroscopic salts such as MgCl ₂ can be added to the matrix material. This allows water to be sucked into the matrix, making delivery of the electrolyte through the matrix much easier.

As the electrolyte, an anhydrous liquid inorganic electrolyte such as H ₂ SO ₄ or LiAlCl ₄ / SO ₂ can be used together with the aqueous system (in a system using LiAlCl ₄ / SO ₂ , the gaseous SO ₂ reacts with LiAlCl ₄ ). . In addition, these systems have a relatively high surface tension compared to hydrophobic polymer matrices. There are also a number of methods, in order to facilitate movement through the polymer matrix, of which two are mentioned with particular preference for aqueous electrolytes. In other words, the addition of alcohols or other hydrophilic organic solvents and the addition of plasticizers to the polymer matrix are preferred.

As mentioned above, the paste-like material of the present invention and the layers made from these materials are suitable for many electrochemical devices implemented with composite films / layers. One of ordinary skill in the art would be able to select the same liquid B (i.e., material without added plastic) as the liquid used for traditional electrochemical devices.

For example, options that can be used for lithium-based batteries include the following.

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 (Anhydrous)

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 alloy

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

While the electrolyte layer of the battery may be composed of the paste-like material according to the present invention, the remaining layers may be fabricated using a paste-type material including a powder electrode material instead of the liquid (B). At this time, this electrode material does not dissolve in the polymer matrix. In particular, it is preferable that the mass ratio of the electrode material to the polymer matrix is maintained at 70-30%. The polymer matrix may have the same components as the paste-like material according to the invention.

However, of course, the present invention is not limited to only lithium-based capacitors. As mentioned above, it can be used in various forms. Thus, the paste-like material according to the invention can be treated with a self-supporting thin plate or with a layer seated on a substrate, which can be used in primary cells, secondary cells, low temperature fuel cells, solar cells or electrochemical sensors. have.

The above-mentioned ingredients for preparing the paste-like material according to the present invention can be mixed according to the prior art and manner, mainly by vigorous stirring or kneading the ingredients. Prior to the addition of the components (B, C), the organic polymer or its precursors may already be dissolved in the solvent. Before consolidating the pasty material, component (C) may be treated with component (A) to form the pasty material. Component (B) may be added at this stage. Several alternatives to this are possible and are presented below.

The paste-like material according to the invention is useful for the manufacture of thin film cells, or in particular for the fabrication of other electrochemical devices such as electrochemical sensors. These are devices called "thick-film technology." The individual layers of these devices are called "tape". Individual layers that are electrochemically active or activatable are fabricated from 10 microns to 1 to 2 mm thick, placed on top of each other and in contact with each other. Those skilled in the art will be able to select a thickness suitable for this application. The preferred thickness range is 50 to 500 microns, with a particularly preferred value of 100 microns. However, according to the present invention, it is also possible to manufacture corresponding thin film elements. At this time, the thin film means a thickness range of 100 nm to 3 microns. However, this application may be limited because corresponding devices may not meet current requirements in terms of capacitance. However, this application can be used, for example, for backup chips.

In addition, the paste-like material according to the invention may be made in other forms. Therefore, after the thick film layers are produced, punching or cutting may be performed from the thick film layers depending on the shape. This is particularly suitable for batteries and accumulators for medical technology (which must be very small and safe). One example is a hearing aid battery. Hearing aid batteries are not only embedded in the ear or implanted at all, taking up minimal space, but also requiring very stringent requirements for leakage. Such forms may be fabricated directly using casting, injection molding, or extrusion.

Accordingly, the present invention includes layers that can be made from paste-like materials, either self-supporting or substrate seated, to the thicknesses indicated. It is preferred that these layers are flexible.

When making freestanding layers (film, tape) and substrate-seated layers, methods well known in the art that can be used as suitable polymeric materials of the matrix can be used. Then the consolidation of the paste-like material is carried out. Depending on the type of material, this may be by curing (curing of resins or other precondensates), by crosslinking of prepolyheadates or linear polymerates, by solvent vaporization (such as acetone), or else known in the art. Is done in a manner. When the polymer matrix comprises a plasticizer, the paste-like material is maintained at a sufficient viscosity when the solvent is extracted, and thus is preferable in that a uniform distribution of the components is maintained. In embodiments in which the plasticizer does not have to fulfill other additional purposes, the plasticizer may be removed if the paste-like material is compacted to a freestanding layer or to a substrate seated layer (the polymer matrix shows a strong tendency towards crystallization). No brittleness and lack of flexibility). One example of a polymer with sufficient flexibility is the combination of hexafluoropropylene and polyvinylidene fluoride for polymers / copolymers.

In certain embodiments of the present invention, component (B) is not yet added or only partly added during the preparation of the paste-like material. That is, as described above, when the plasticizer is removed from the freestanding layer or from the substrate seated layer, cavities are formed (similar to a sponge) in the compacted matrix. When immersed in the liquid B, with capillary force, the liquid can be drawn out of the empty space, and a stable state can be achieved therein.

In order to obtain freestanding films, a paste-like material can be formed on the calender at an appropriate thickness. Standard techniques can be used for this. Freestanding layers may be formed by applying a paste-like material to a substrate and then removing the resulting layer after consolidation. The requirement for this is that the product (ie paste-like material) must have sufficient flexibility. The coating process may be performed using a conventional paste coating method. For example, the application process can be performed by brushing, rakes, spraying, or spin coating. Pressurization techniques can also be used. As mentioned above, liquid (B) may already have been processed in the paste-like material and the cavity resulting from consolidation and removal of the softener of the paste-like material comprising the polymer matrix (A) and filler (C) may be removed from the liquid ( B) can be filled.

In a preferred embodiment of the present invention, a crosslinked resin (precondensate) is used as described above for the paste-like material, and when the layer is formed, the resin is cured by ultraviolet radiation or electron radiation. The curing may be high temperature curing or chemical curing. Appropriate initiators or promoters may be added to the resin for crosslinking.

In addition, the present invention relates to a composite layer having electrochemical properties, and more particularly, to a storage battery including the above-described layers and other batteries or sensors.

1 shows a possible sequence of such arrangements.

2 shows a compact structure of a battery provided with a very large battery active face.

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

1 shows a possible sequence of the arrangement of the invention, in which the conducting electrode 1, the intermediate tape 2, the electrode 3, the electrolytic material 4, the electrode 5, the intermediate tape 6, It consists of a conducting electrode 7.

To prepare the composite layer, individual paste-like materials can be applied in turn onto each other using a paste application method. Each layer may be crosslinked on its own or may be liberated by a solvent and embodied in a layer form in other ways. However, it is also possible to consolidate individual matrices by vaporizing or crosslinking the solvent after all the layers have been applied. This vaporization mode is particularly preferred when the electrochemically activatable individual layers are applied using the press method. One example of this is the Flexodruck technology, which allows substrates of different lengths to be printed continuously with electrochemically activatable layers.

Alternatively, each layer or film may be individually converted to a final consolidated state. If this layer or film is a freestanding film, the appropriate components of the device to be formed can be joined together by lamination. Conventional lamination techniques can be used for this. For example, injection coating (second layer bonded to the carrier layer by a pressure roller), or calender coating (using two or three roll nips) is an example of a lamination technique. One of ordinary skill in the art will have no difficulty finding the appropriate technology depending on the choice of matrix for the paste material.

The pressing process during bonding (lamination) of the individual layers is often desirable for improved bonding of the individual layers. Current commercial technologies can be used for this. If available for the material used, a low temperature pressurization process (up to 60 degrees Celsius) is preferred. This can provide good contact between the individual layers.

In all applications, using the paste-like material according to the invention, or freestanding foils or substrate-seated layers made from the paste-like material, is inexpensive, has a high energy density due to its compact structure, High reliability This is because the liquid electrolyte or the liquid electrode is bound to the polymer matrix like a sponge.

Electrochemical devices that can be manufactured using the paste-like material according to the present invention are not limited to the above disclosure. Therefore, the following contents are merely examples and should be understood as preferred embodiments.

Rechargeable electrochemical cells can be produced, for example, by thick-film technology, using individual layers that are electrochemically activatable at a thickness of 10 microns to 2 mm (particularly 100 microns thick is preferred). When the electrochemical battery is a lithium cell, the liquid for the electrolyte layer or the solid material for the electrode layer may be the materials described above for this purpose. At least three layers should be provided, such as layer 3 (FIG. 1) serving as an anode, layer 4 (FIG. 1) serving as a solid electrolyte, and layer 5 (FIG. 1) serving as a cathode.

According to the invention, particularly desirable current densities can be obtained in the capacitor when certain thresholds are observed. As is well known in the art, the current density can be adjusted by the resistance of the electrolyte. If the current density is too high, polarization can disturb the electrodes for a long time. If the current density is too low, the capacitor's power will only be available for a few purposes. The above threshold is 1 mA / cm ² . When the thickness of the electrolyte layer is 100 microns, a current density of 1 mA / cm < 2 > causes a voltage drop caused by the resistance, which is a negligible value of 0.1V. If the electrolyte had a conductivity of 10 ¹ S / cm, the microstructure of this layer would result in a conductivity of this layer of 10 ⁰ S / cm. The best recommendation is to set the relationship between thickness d, conductivity σ _ion , ion resistance, and surface area A to satisfy the following equation.
200 Hz <d / (σionA)

delete

These values appear in an excellent manner when the tapes according to the invention are used.

In addition, conducting electrodes (layers 1 and 7 in FIG. 1) may be further provided in the cell consisting of three layers (or other electrochemical components consisting of an anode / electrolyte layer / cathode). It is useful for these conducting electrodes to comprise films of suitable material. Materials for conducting electrodes that can be used in lithium-based batteries have been mentioned above.

In a particular embodiment of the invention, between the lower conducting electrode and the electrode adjacent to the lower conducting electrode and between the upper conducting electrode and the electrode adjacent to the upper conducting electrode, an additional thin plastic which can be produced using a paste-like material A layer (“intermediate tape”, layers 2 and 6 in FIG. 1) may be disposed, this thin plastic layer comprising a conductive metal or metal alloy suitable for transferring electrons from the electrode material to the conductive electrode. Is gold, platinum, rhodium, carbon, and an alloy of these elements (corresponds to the case where the plastic layer is arranged between the anode and the associated conducting electrode). , Iron, chromium, titanium, molybdenum, tungsten, vanadium, manganese, niobium, tantalum, cobalt, and carbon. The also it applies to the density and structure of the paste-like material for the production. Exemplary having a conductive electrode and the intermediate tape example (see Fig. 1) is made of a lithium-based technique described above using a LiAlCl ₄ / SO ₂ for the electrolyte When present, it has charge and discharge curves of the type shown in FIG.

delete

In another particular embodiment of the invention, an electrochemical cell consisting of three or more layers is provided, wherein two electrodes are formed of the layers according to the invention, the anode side (electrode) being a protonic system and the cathode side (counter- Electrode) is an aprotic system. A protic system is a system in which lithium salts such as lithium nitrate and lithium perchlorate are dissolved, and correspond to a proton-separating system (H ₂ O). Thus, the solid electrolyte is selected as the intermediate layer, and its cation (eg lithium ion) becomes the conductive ion. In particular due to the water repellency of the polymer matrix, in this embodiment, water cannot move to the cathode side and cannot decompose on the cathode side. Due to the liquid electrolyte, and due to the wide selection of possible electrolytes, it is an advantage that the mobility of the anode is improved. (In this case, the possibility of corrosion of the positive metal conducting electrode is eliminated. Aluminum is frequently used as a cost problem for the positive metal conducting electrode, and an electrolyte containing lithium perchlorate tends to easily oxidize the conducting electrode on the anode side. This oxidation can be prevented through the present invention)

The paste-like material according to the invention is suitable for use in, for example, primary cells. Therefore, this paste-like material is most suitable for producing an electrolyte layer. Examples of suitable electrode systems include 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 may be oxygen (Al-O ₂₎ - oxygen (Mg-O _2), aluminum. Examples of electrolytic materials are alcohol solutions of bromide and chlorides of alkali and ammonium series, or alkali hydroxides. Sodium and potassium are particularly preferred as alkali metals.

The paste-like material according to the present invention is also usefully used for the production of secondary batteries. Such systems, such as lead-acid batteries and nickel metal hybrid cells, have already been mentioned above. Other systems include nickel-cadmium, nickel-iron, zinc-silver oxide, and alkaline-manganese secondary batteries. Suitable electrolytes for this purpose include aqueous or anhydrous H ₂ SO ₄ (for lead batteries, for example) or potassium hydroxide.

The paste-like material according to the invention can also be used in a new kind of battery called a decomposition battery. Salt decomposes at the anode (eg MgBr ₂ ) and the resulting bromine is stored in a carbon film (carbon tape). In this case, the electrolyte of the paste-like material or the film made of this material is MgCl ₂ , and this electrolyte does not decompose. This is because the decomposition voltage is higher than the voltage of MgBr ₂ . However, the first example is preferred because it has a more preferred volume. The cell voltage is equal to the decomposition voltage of MgBr ₂ . It is a particular advantage of these batteries that their capacity increases with the valence electrons so that higher valence ions can be used. In particular, Mg and Al which are light and inexpensive elements can be used. In such systems, inorganic aqueous or liquid electrolytes must be used. This is because, in the solid electrolyte, the mobility of high valence electrons at room temperature is too low to be suitable for a battery and a storage battery. This electrode may be present as a metal or carbon film or as a powder electrode material embedded in a film-like polymer matrix.

Another field of use of the paste-like material according to the invention is low temperature fuel cells. Here, to date, positron-conducting polymer electrolytes (PEM: Proton Exchange Membrane), such as Nafion, have been used in the past. Used. However, this polymer electrolyte is expensive and sensitive to drying. In particular, it is difficult to simply recharge the fuel cell, and in general, the hydrogen tank provided in the form of a small and expensive steel container must be completely replaced. The space required for such hydrogen tanks makes it impossible to thin the cell. According to the present invention, an electrolyte layer is implemented using a polymer matrix in which hygroscopic salts are distributed. This layer is kept in an environment that retains moisture. Once the salt is dissolved, this layer will contain a liquid electrolyte (the salt in the absorbed water) and the water can be electrochemically decomposed. Hydrogen is then stored in another stacked hybrid tank (Y, Pt, Pd, or other hydrogen absorbing material in film form, especially in the form of an organic polymer matrix). Water lost by decomposition is continuously replenished with moisture absorbed by the hygroscopic salt.

In addition, in the embodiment of the present invention, using the electrolyte layer, a paste-like material is prepared by mixing a polymer, a solvent, and a softener for the polymer matrix (A) and the solid material (C), and the paste-like material is prepared as desired tape. "In the form, consolidating this tape form and, if necessary, removing the solvent, extracting the softener, and filling the cavity with an alcoholic solution of hygroscopic salts, thus evaporating the alcohol. Alternatively, salts dissolved with alcohol as a dissolution medium in solvents or plasticizers may be distributed in the pasty material. In this case, it is preferable that the alcohol is extracted with the solvent. Filler (C) is provided in this case, improving the mechanical stability to tape form. Of course, the filler may be omitted.

The paste-like material according to the invention and films made from these materials can also be used in solar cells. Systems used in solar cells are preferred to use the Honda-Fujishima effect (1972) instead of silicon technology. When irradiated with sunlight, oxides such as titanium dioxide and tungsten trioxide can decompose water and other substances such as formic acid.
This is because electrons are excited in the conduction band and the remaining energy gap has a high oxidation effect. Because the oxides are in the highest oxidation state known in the chemical arts. Solar cells contain three layers (tape). One layer stores hydrogen and may be configured as described above with respect to low temperature fuel cells. The branch layer also includes water that decomposes in operation as the electrolyte layer, and thus can be implemented as described for the fuel cell. Another layer is a tape containing TiO ₂ or WO ₃ , which preferably also contains metal powder or carbon (to ensure sufficient electronic conductivity). In contrast to fuel cells, solar cells are charged with sunlight. When discharged, it functions like a fuel cell.

Paste-like materials according to the invention and films made of these materials can also be used in electrochemical sensors. To this end, hygroscopic salts which absorb water are added to the polymer matrix. The water content of the film made of this paste-like material can be precisely controlled using salt concentration, atmospheric humidity, and temperature. Compared to a reference electrode implemented with a laminated tape, several different voltages occur as a function of moisture content and thus humidity can be measured.

The electrochemical elements of the invention can be sealed, for example in a plastic housing. Accordingly, it is lighter than the metal housing and has advantages in terms of energy density.

In addition, an electrochemical composite layer (ie, an electrochemical device) may be implemented between two or more films on plastic coated with wax or paraffin. These materials act as sealants and, due to their inherent properties, can exert mechanical pressure on the composite layer. This improves the contact of the composite layer due to the pressure.

As mentioned above, or when the electrochemical device is sealed in some other way, the interior thereof may be placed at a specified hydrogen / oxygen partial pressure that realizes high electrochemical stability. This can be achieved by sealing the electrochemical device in an appropriately set and selected environment.

The series of layers according to the invention for the electrochemical device can be arranged in any desired form. For example, the flexible composite layer can be rolled to achieve a structure suitable for compact capacitors. The small volume of the capacitor provides a very large active cell surface. FIG. 2 presents such an embodiment, in which reference numerals 1 to 7 show items as in FIG. 1, and 8 denotes an insulating layer.

A non-standalone composite layer may be applied to a solid base, such as a wall for an integrated energy tank (standalone composite films may of course be applied or fixed). In this case, a large surface area can be used. The capacitor itself is not related to space requirements. One embodiment of this kind is to integrate a composite layer for a capacitor into a substrate for a solar cell. Layer sequences for capacitors may be applied to a rigid substrate or a flexible substrate. Thus, the electrical structure of the integrated energy tank can be implemented.

Next, the present invention will be described in detail using examples.

Example 1                 

Primary battery manufacturing

1 g of PVDF-HFP, 1.5 g of dibutyl phthalate, and 10 g of acetone are mixed with 7 g of zinc powder as an anode, 5 g of SiO ₂ as an electrolyte, and 7 g of MnO ₂ as a cathode. These electrodes and electrolytes are drawn in the form of a tape, acetone is vaporized and the plasticizer is extracted with hexane. The tapes are filled with an aqueous-alcohol KOH solution (solvent (volume ratio): 50% water, 50% alcohol) and pressurized between two stainless steel electrodes.

Example 2

Secondary battery manufacturing

1 g of PVDF-HFP, 1.5 g of dibutylphthalate, and 10 g of acetone are mixed with 7 g of Cd (OH) ₂ as an anode, 5 g of SiO ₂ as an electrolyte, and 7 g of Ni (OH) ₂ as a cathode. These electrodes and electrolytes are drawn into a tape, acetone is vaporized and the plasticizer is extracted with hexane. These tapes are filled with aqueous-alcohol KOH solution (solvent (volume ratio): 70% water, 30% alcohol) and pressurized between two stainless steel electrodes.

Claims (30)

In the pasty material which can be used in an electrochemical device, the pasty material is A matrix containing an organic polymer, a precursor of this polymer, or a prepolymer of this polymer, Electrochemically activatable inorganic liquids, either liquid inorganic electrode materials which do not dissolve the matrix, or liquid inorganic electrolytes which do not dissolve the matrix, or ions between two adjacent electrolytes / electrodes which may be disposed in an electrochemical device The electrochemically activatable inorganic liquid comprising one of a liquid inorganic material which does not dissolve the matrix as a conductive or electron-conductive intermediate conductor Wherein the electrolyte may contain an organic solvent having a volume ratio of 70% or less relative to the total volume of the solvent used, and the solvent may be mixed with water. The paste-like material of claim 1, wherein the matrix further comprises a plasticizer and a solvent. The paste-like material of claim 1, wherein the matrix comprises a crosslinkable liquid or resin. The method according to any one of claims 1 to 3, Wherein the electrochemically activatable inorganic liquid is an ion-conducting or electron-conducting intermediate conductor between two materials that can be arranged adjacent to the material that can be used as an anode, a material that can be used as a cathode, or an electrochemical device. Paste-like material, characterized in that selected from the available materials. The paste-like material of claim 4, wherein the liquid is an aqueous or anhydrous inorganic liquid, and the liquid contains at least one of an insoluble solid electrolyte, a mixed conductor, and an electrolyte. 4. The resin of claim 3 wherein the resin is selected from crosslinkable additive polymers and condensation resins and may be selected from aminoplasts, phenoplasts, epoxy resins, polyesters, polycarbonates, and methylmethacrylate-reactive resins. Paste-like material, characterized in that. The method of claim 1, wherein the organic polymer of the matrix is selected from natural polymers and synthetic polymers, and mixtures thereof, and includes natural and synthetic polysaccharides, proteins, resins, waxes, halogenated and non-halogenated rubbers, thermoplastics ( thermoplast), and a paste-like material, characterized in that it can be selected from the thermoelastomer (thermoelastomer). The paste-like material of claim 1, wherein the matrix comprises at least one organic polymer dissolved in a solvent, wherein the organic polymer is selected from synthetic polymers, natural polymers, and mixtures thereof. The paste-like material of claim 1, further comprising a powder solid inert to the electrochemically activatable inorganic liquid. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

Images