DE19624887A1 - Electrochemical cell including solid electrolyte system formed by thin film technologies - Google Patents

Abstract

An electrochemical solid electrolyte cell system is based on a flat, gas- permeable, non-conductive flexible polymer substrate (1). The cell regions (3,4,5) consist of a porous, electrically-conductive, flexible electrode layer (7); a proton conducting, flexible membrane layer (8, 9, 10); and a second porous, flexible, electron-conducting electrode layer (11) laid one over the other, using coating technologies. Also claimed is a procedure to make the electrochemical cell system by successive deposition of layers on a substrate, as described. Further claimed are the use of the cell as an electrolysis system, splitting water into hydrogen and oxygen, and its use as a fuel cell converting hydrogen or methanol into electricity.

Description

The invention relates to an electrochemical festival electrolyte cell system, in which by means of layer technology on a surface of a gas permeable support body pers a first porous electrically conductive electro layer, a proton-conducting membrane layer and a second porous electronically conductive electro layer is applied.

For example, electrochemical cells are in shape the fuel cell or the electrolysis cell knows. Fuel cells e.g. B. convert chemical energy directly into electrical energy with high efficiency grade (50-60%). They simply consist of two electrodes and an intermediate elec trolyten. The chemi introduced and electrochemical implemented. As a typical example  Called hydrogen-oxygen fuel cell, where one electrode with hydrogen and the other Electrode is supplied with oxygen. To the kataly table electrodes then run voluntarily following electrochemical reactions.

Hydrogen electrode (anode): H₂ → 2 H⁺ + 2 e⁻
Oxygen electrode (cathode): 0.5 O₂ + 2 H⁺ + 2 e⁻ → H₂O.

There is a between the two electrodes proton-conducting electrolyte, which is in the case le of a PEN fuel cell (polymer electrolyte mem bran fuel cell) around a proton conductive Po lymer membrane. Can on the two electrodes then a tension can be tapped that ever after electrical load typically in the area moved between 0.5 and 1 V.

For higher output voltage for practical applications to be realized in the so-called bipolar Stack construction of a large number of cells by means of elec tronically conductive bipolar plates in a row connected in series. The cells have in macroscopic extents in all directions and who made from a variety of components, which are then pressed together in the cell stack by means of pressure will. Such a stack is e.g. B. in the patent US 4,175,165 "Fuel Cell System utilizing ion exchange membranes and bipolar plates ", Inventor: Otto S. Adlehart.

The heart of such a cell stack is the Membra nen, which is typically on both sides with elek coated trochemically active catalyst material  are. The membrane surfaces usually move between 1 and 1500 cm², the membrane thickness between 30 and 200 µm. On the two catalyst coatings th surfaces of the membrane press gas permeable and electronically conductive power distributors that are used for a good electronic cross conductivity and a homogeneous Ensure gas supply to the membrane. The power distribution ler are separate structures with a thickness of z. B. 200-500 µm. They close on both sides electronically conductive bipolar plates where the tension can be tapped and the internal channels for the gas supply of the respective elec trode included. They have thicknesses in the range of some Millimeters to centimeters. To secure the gas tight activity of the cell stack is between the membrane side and bipolar plate each provided a seal. This whole arrangement is, for example, by means of Ver compress the screw connection, on the one hand, to electri cal contacting of the membrane and the other Achieve gas tightness.

In the course of the smallest possible volume of the cell stack and the lowest possible electrical losses tries the arrangement described above so run small and thin as possible. Principle is such a miniaturization with a Kon according to the above state of the art only very limits possible: The entire arrangement must be together be pressed so that the individual components (Membrane, plates etc.) strong mechanical and front withstand all stresses that did not appear homogeneous have to hold. A drastic reduction in thickness of the components involved is therefore ruled out because very thin components inevitably break or  would tear. Miniaturization of the cells area in the square millimeter range, for example assign high voltages with only low currents with this concept reaches the limits of Feasibility. A mechanical assembly of hundreds smallest individual parts and their screw connection not feasible from a practical point of view.

In addition, a fuel cell arrangement is in the DE 39 07 485 A1 described. It refers to a so-called SOFC (Solid Oxide Fuel Cell) order. This type of fuel cell is in one Operating temperature range between 800 and 1000 ° C. and for this reason must be temperature accordingly resistant inorganic materials used the. The electrolytes are ion-conducting oxide ceramics miken and the guiding mechanism is almost done finally about oxygen ions. In addition to the electro lyten is also used according to DE 39 07 485 Carrier material is a porous ceramic material, such as e.g. B. magnesium aluminum spinel (MgAl₂O₄) or zirco nium oxide. Next to the high demands the materials used disadvantageously that the before known fuel cell arrangement also accordingly must have large dimensions, so that the use not in any shape and in any place can be carried out.

Ceramic materials are beyond doubt beyond those existing advantages also with the disadvantage that they are very brittle, afflicted. Once specified Shape can no longer be changed and it is therefore only rigid structures can be maintained. One after sluggish change of shape or geometry or  an adaptation to different site modifications NEN is no longer available.

DE 43 29 819 A1 is a so-called Strip membrane described as being electrochemical Form a cell with at least one core area the strip membrane, on which poly mere solid electrolyte as an electrode layer are brought and in which several single cells in series are switched, is formed. Such a fight fenmembran can then be used in fuel cells will. Here, however, the low strength must be be taken into account and a corresponding housing recording. It is further with the disadvantageous solution that for achieving high Tensions a correspondingly large number of individual cells must be connected in series, which ent require large space requirements. There an insert cannot be variably sent to the ver can be adapted to different locations.

Another arrangement is known from DE 40 33 284 A1 of fuel cells based on a high temperature Tur solid electrolytes known. This just belongs if to the previously mentioned group of SOFC burners fabric cells with which already in the description of the Fuel cell arrangement according to DE 39 07 485 Disadvantages.

The object of the present invention was therefore a new electrochemical solid electrolyte cell system to propose a miniaturization of a Cell stack in the area and / or in the thickness of the Components should be possible.  

The task is carried out in relation to the cell system the characterizing features of claim 1 according to the characteristics of the An Proverb 21 and according to use by the mark nenden features of claims 24 and 25 solved. The Subclaims show advantageous configurations on.

According to the invention, it is therefore proposed that a flat, gas-permeable, non-conductive supporting body using a fuel cell system in layer technology bring to. This makes the cell analogous to the elec and integrated circuits as a chip applicable.

Is essential to the invention in the subject of the application, that a flat, gas-permeable, non-conductive flexible support body is used, on the The cell surface is then layered on is brought. The applied by means of layer technology Cell is only one-sided, i.e. H. only on one Surface arranged so that it thereby in verbin possible with the gas-permeable support body will, a first, in the fireplace reaction partners on which the cell area is opposite opposite side through the gas-permeable support body the cell and the second reaction partner lead directly to the surface of the cell.

Particularly noteworthy in the cell according to the invention system is that this structure makes it possible to arrange several cell areas on a supporting body and electrically interconnect. This makes an on order realizable, that of the state of the art  Technology known stack design corresponds.

Basically, this can be done analogously to the integrated circuits at least up to 1,000,000 Arrange cell ranges.

According to the invention, this is under a cell area an isolated structure of a cell understood, each consisting of a first porous, flexible, elec trically conductive electrode layer, a proton conductive membrane layer and a second porous, flexible, electronically conductive electrodes layer. These individual cell areas can each through appropriate layer technology (e.g. masks technology) applied, and by means of suitable, elec trical contacts. Through which he Open layering technology used according to the invention there are thus numerous possibilities for one behind the other switching of the individual cell areas. So can on the one hand several of the cells described above areas, preferably 2-10,000, in a row in a row can be connected so that a one-dimensional cell l arrangement arises. With the cell according to the invention system is also any arrangement of consecutive cells possible. Such Two-dimensional arrangements can be designed in this way be that several rows of cells in a row bigen forms are arranged on the support body, or also that several individual cell rows are preferred 2-10 000, which are then par with each other are all interconnected (redundant arrangement).

The basis of the cell system according to the invention is thus with the gas-permeable, flat, non-conductive,  flexible supporting body. This support body serves as me chan basic structure for all following, to bring up layers. The burning takes place at the same time Material supply for the one electrode also through this support body. Since according to the invention also several Cells applied next to each other on the supporting body the support body need not be conductive, because otherwise the individual cells over the supporting body would be short-circuited. The turned according to the invention set support body has a thickness of 10 µm to 10 mm and an area of 1 mm² to 1 m². The dimension tion of the support body depends on the type use case, d. H. whether one or more cells are applied to the surface. It is preferred the support body is a non-conductive, gas permeable ge, flat membrane. The materials for the support Bodies are typically polymeric supports made of e.g. B. Polysulfone. Such porous membranes can symmetrical, d. H. same membrane structure over the entire membrane cross-section, or asymmetrical, d. H. Changes in membrane structure across the membrane cross cut, have. Composite membranes are also possible Lich. An overview of usable according to the invention Materials for the support body are e.g. B. from "Membra nen ", Prof. Dr. Eberhard Staude, from Ullmann's Enzy Klopedia of technical chemistry, 4th edition, 1978, 16, pages 515 to 535.

In contrast to the SOFC fuel cells, it acts around the trained according to the invention PEMFC fuel cells (polymer electrolyte membrane fuel cell), typically in a temperature range work between 80 and 100 ° C and the ion conduction not about the oxygen ions, but about proto  Conductive membranes, which are usually made of protons conductive polymer material exist. Since that solid electrolyte cell system designed according to the invention stem consists of polymer materials, they are for the Suitable for use in PEMFC fuel cells and ins special very light and flexible what this enables appropriate flexible structures. With the polymer materials, porous, gas permeable films are produced, the known phase inversion ver in membrane technology driving can be applied. A poly solution immersed in a cell bath and a Ent mixing the solution into a polymer-rich and into a low polymer phase takes place. After the membrane ge has been dried, a gas-permeable, porö structure can be obtained. All other layers of the cell system according to the invention (ion-conducting Plastic film or conductive structures) then on the porous polymer support thus obtained, the is also flexible to be applied. Here is a completely flexible layer structure enough. The cell system thus produced then has the Shape one flexible film that continues in various forms can be used. For example Winding modules are made, the be in advance Written film structure of the cell according to the invention systems with a second non-functional, not conductive, thin flexible plastic film other is laid and wound up accordingly. There at should between the latter plastic foil and the "fuel cell foil" gas spaces are formed so that the fuel cell film on the one hand with hydrogen and on the other hand with  Oxygen or air can be brought into contact so that a functional fuel cell with through the possibility of daisy chaining achievable ho forth output voltage is formed. For example as the cell system is designed as a winding module, so can by using the plastic starting mat rialien the sealing of the edges on the two End faces of the winding module by simple gluing ben or welding the plastics with a ge suitable closure (lid) can be achieved. The Ver conclusions are made from a stable, non-conductive gas impermeable material.

With the cell system designed according to the invention Besides the use as a winding module, the ver various structures and forms the so that it becomes possible in a relatively small space To provide fuel cells, the ge desirably deliver a high output voltage can.

The surface of the support body usually has an area of 1 cm² to 1000 cm².

An overview of this is e.g. B. from "membranes", Prof. Dr. Eberhard Staude, from Ullmann's encyclopedia of technical chemistry, 4th edition, 1978, vol. 16, Page 515-535.

The on the support body described above electrodes deposited using layer technology layers typically have a thickness of 10 nm to 100 µm. Everyone arrives as materials for this and already be from the state of the art  knew electrode materials in question.

The prerequisite for the electrode layers is that the electronically conductive and catalytically active are. They are usually used to run the electro suitable chemical reactions necessary to avoid high transition voltages. So is for a hydrogen-oxygen fuel cell typically platinum as electrodes material catalyst used. Other examples of electronics The materials are platinum-coated coal or iridium. Furthermore, additives such. B. Hydrophobia agents are included.

In the membrane layer, which is also deposited by means of layer technology on the most electrode layer, it is important that this is proton-conductive in order to ensure the ionic charge transport between the two electrodes. Typically, polymers containing sulfonic acid, carboxylic acid or phosphonic acid groups have the property of proton conductivity in the presence of water. Examples are sulfonated polysulfones or sulfonated polyether sulfones. Another possibility is the organic-inorganic polymer class of the Ormolytes (ORganicaly MOdified ceramics elektroLYTES), such as for example aminosile, poly (benzylsulfonic acid) siloxane or sulfonamidosile, all of which are produced via sol-gel processes. Aminosils are obtained from a solution of aminated organotrisiloxane, an acid HX and water. Materials of the general formula SiO _3/2 , R- (HX) _x , 0 x 0.5 are obtained via a sol-gel process. An example of an aminosil is

SiO _3/2 (CH₂) ₃NH (CH₂) ₂NH₂- (HCF₃SO₃) _0.2 .

Inorganic compounds can also be protons have conductivity, especially at higher ones Temperatures, examples are modified alkaline earths cerates or zirconates such as

SrCe _0.95 Yb _0.05 O _{3- α} or CaZr _0.95 In _0.05 O _{3- a} .

According to the invention, according to a preferred embodiment tion form proposed several of the above be to arrange the written cell areas on the supporting body and electronically interconnect. This execution form is particularly preferred since ana log the stack known from the prior art very high output voltages due to rear implement interconnection of the individual cells to let. According to the invention, this is achieved by that the electrical connection via one, the pro tone-conducting membrane layers from neighboring Separating cell areas, not proton-conducting, electrical contact is made. It is important that the Proton conduction between the individual membranes and is broken. At the same time, an electro African conductivity of z. B. the membrane underside of the first cell area to the membrane top of the second cell area can be guaranteed. this will now achieved in that an electrical contact the two membrane layers, the face to face borders, separates from each other and each with the bottom electrode layer and with the top Electrode layer of the neighboring cell area in Contact is there. The contact can be designed in this way be that an electrode surface between the two  Membranes is passed through and with the first electrode surface opposite electric the next cell area in contact stands. This contact is preferably made so forms that he in the area of the proton-conducting membrane bran is not porous and is not catalytically active. Examples of such materials are titanium or conductive polymers. The invention continues to see before that in addition to electrical contact an insulating layer, d. H. non conductive Be rich, which also by means of layering technology can be brought between the contact and the mem are arranged. This non-conductive area che, d. H. insulating layers, may neither io be electronically conductive. As materia For this reason, metal oxides such as Alumina or non-conductive polymers such as for example polysulfones are used.

In addition to the cell structure described above it is also possible to use narrow stripes or git ter of electronically conductive material on the Apply electrode surfaces. On the one hand, this leads to improve the transverse conductivity of the elec tread layers and on the other hand to an improvement the stabilization of the mechanical properties. This embodiment is advantageous if it excessive mechanical stress on the electrical system the surface comes what z. B. is the case if with ion-conducting electrolyte is used since it this leads to volume changes in operation by What reception and delivery can come.

The substances are applied by typical  Methods of layering technology, such as sputtering, CVD-Pro processes, plasma-assisted CVD processes, plasma polymers risation, sol-gel technology, galvanic or coating from solution or from suspensions with powders. So metal layers can be sputtered Apply metal oxides are also reactive Sputtering accessible. CVD processes, e.g. B. the Zer settlement of organometallic starting compounds, enable metal oxide layers, whereby plasmaun supported CVD coatings with temperature sensitivity offer substrates. For example by the decomposition of πcyclopentadienyltrimethyl platinum in the plasma thin platinum layers accessible. Organic layers are also through, for example Plasma polymerization of ethylene or other organi not accessible. The incorporation of carboxylate groups in plasma polymerization enables production of proton-conducting plasma polymers. Ormolytes as Proton conductors are used, for example Sol-gel process manufactured, other sulfonated polymers can be applied as a solution. This is how sul formulated polysulfones usually well in dimethyl sulfoxide and can be applied in a viscous form will.

Suitable masks during the deposition process or Covering with photoresists enables application of geometrically defined areas as they are for the integrated fuel cell system is necessary are.

Because the integrated fuel cell is self-supporting is a simple encapsulation in plastic housing possible. After applying all layers  the layered fuel cell is placed on the supporting body system in the corresponding plastic housing welded or cast.

As described above, it is thus possible to Fuel cells in an appropriate plastic container weld or cast housing. This installation wise it also allows cooling the cell this is necessary by applying cooling fins to enable.

The inventive concept described above for electrochemical solid electrolyte cell systems on the one hand, suitable for. B. hydrogen or Me to energize ethanol, also for water electrolysis cells.

Other features, details and advantages of the Erfin dung result from the following description three embodiments, and based on the drawing Here show:

Fig. 1 is a cross sectional view of the schematic structure of a cellular system according to the invention with an additional insulating layer;

FIG. 2 shows the structure analogous to FIG. 1, but with an insulating layer that only partially projects into the membrane in cross section;

FIG. 3 shows a construction according to the invention analogous to Fig 1, but here with only egg nem electrical contact.

Fig. 4 shows the one-dimensional arrangement of four single cells one behind the other in plan view;

Figure 5 shows the two-dimensional arrangement of several rows of cells one behind the other in the top view.

Fig. 6a in side view and cross section the installation of a cell system according to the invention in a housing, and

Fig. 6b in the front view;

Fig. 7a shows another embodiment regarding the installation of the cell system in a housing, but here with an integrated gas supply;

Fig. 7b this arrangement in the front view.

Fig. 8a installing several cell systems in housing a Ge, again in cross section,

Fig. 9 shows the integration of a water cooling system in a housing,

Fig. 10 shows a structure according to the invention in the form ei nes wound module in cross section,

Fig. 11 shows another embodiment using additional gas-impermeable, non-conductive foils and

Fig. 12 shows an arrangement in which the embodiment shown in Fig. 11 is wound on a Kör by.

Fig. 1 shows in cross section schematically showing the structure of a cell system according to the invention using the example of a fuel cell.

In the embodiment of Fig. 1, four individual cells (cell 1-4) are connected in series ver. The cell 1 is formed by the cell region 3 and a part of the supporting body which is assigned to this region 3. The basis of the cell system according to the invention is the gas-permeable, flexible supporting body 1 . The gas-permeable support body 1 is shown in Fig. 1 as in the following figures only for better clarity in the form of a perforated support body. However, the invention includes all variants of a support body, provided that they are gas permeable. The support body can therefore itself be made of porous material or be made of non-porous material and have corresponding openings for the gas inflow. A support body which is otherwise made of a closed material, but has corresponding openings for the gas flow, can be used. The dimensioning of the supporting body, ie the thickness and the surface, is selected depending on the conditions of use and the desired output voltages. The thickness is in the range from 10 µm to 10 mm, the surface in the range from 1 mm² to 1 m². To produce the cell system according to the Invention, a likewise flexible insulating layer 15 made of non-conductive material is now placed on the gas-permeable, flexible support body 1 in a first step on its surface 2 at certain intervals using layering technology. This non-conductive material serves to isolate the cell regions 3 that then arise. The thickness of the insulation 15 is in the range from 10 nm to 1 mm. In the embodiment of FIG. 1 exi stieren thus three applied to the supporting body 1, insulating layers 15. The height of the layer is chosen so that the upper edge runs almost flush with the membrane layer 8 to be produced. In the next step, the gas-permeable support body 1 is coated with an electronically conductive, flexible material for producing the electrode layer 7 . At this electrode layer 7 , the electronic partial reactions z. B. hydrogen oxidation. This layer (first electrode) must not be tight, but, like the supporting body 1 , must have a certain porosity. In the following step, small, electronically conductive areas, which represent the electrical contact 12 , are then applied directly next to the insulating layer 15 and on the first electrode layer 7 . In the resulting deepenings between the insulating layer 15 and the conductive contact 12 , a flexible proto-conductive layer is applied. This proton-conducting layer then forms the membrane layer 8 . The membrane layer 8 is in contact with the conductive material of the electrode layer 7 on the underside. A coating is then again carried out with an electronically conductive flexible material for producing the second electrode layer 11 , on which the other partial electrochemical reaction then takes place (second electrode).

In the case of the example of a hydrogen-oxygen fuel cell described above, the oxygen reduction then takes place here. This layer must be such that a three-phase contact between the supplied gas, second electrode 11 and membrane layer 8 is possible, ie it must not be a dense layer. Furthermore, the layer 11 must be applied so that an electro nically conductive connection between the lower electrode 7 of a cell and the upper electrode 11 of the following cell with the help of the electrical contact 12 comes about. An internal electrical series connection of the individual cells 1 to 4 is thus realized and the sum of all cell voltages can be tapped at the first upper electrode with the connection 20 and the last lower electrode with the connection 21 .

, FIG. 2 shows another embodiment of a cell system according to the invention. The structure corresponds essentially to the structure according to FIG. 1, however, according to FIG. 2, the connection is realized differently by means of the electrical contact. The connection according to Fig. 2 takes place here by an electrical contact 13, which is embodied so that it directly connects the upper electrode layer 7 layer to the lower electrode 7. The electrical contact 13 is consistently made of a dense material. In the embodiment according to FIG. 1, the material was only arranged in the area of the proton-conducting membrane layer. Such an arrangement comes z. B. to wear when the electrical contacts ( 13 ) are only inserted in the last manufacturing step by z. B. appropriate conductive structures are inserted from above into the cell system with pressure. In a modification of Ausführungsbei game of FIG. 1 here, the insulating layer 16 is not formed so that it leads 9 over the entire thickness of the membrane layer, but only partially. With this embodiment too, a series connection of the cell region 4 according to the invention can be realized. Fig. 3 shows an embodiment in which it is completely dispense with the insulating layers. In this embodiment, the membrane layer 10 is formed so that it is guided up to the support body 1 in the region of the electrical contact 14 . This also allows a series connection of the cell area 5 to be realized.

It is essential in all the embodiments according to FIGS. 1 to 3 that the individual cells 3, 4, 5 are connected in series one after the other, the electrical contact 12 , 13 , 14 having to separate the two adjacent membrane layers.

FIG. 4 now shows the cell structure according to the invention according to FIG. 1 in a top view. The cells 1 to 4 arranged one behind the other can be seen, the individual voltages of which, according to the series connection according to FIG. 4, add up to form a total voltage which can be tapped off at the connections 20 and 21 . This arrangement of the individual cells is an arrangement in one direction.

Fig. 5 shows an embodiment in which the individual cells are arranged so that they expand in two directions, which is easily possible with the help of the layering technique. Fig. 5 shows the example of the 16 individual cells, whereby in each axis Rich each tung 4 cells (cell range 1-4) are arranged. All cells are brought up on the support body 1 and connected in series according to the principle described in Fig. 1, so that the 16-fold output voltage compared to a single cell is available. The voltage can then be tapped at the connections 20 and 21 . In the embodiment according to FIG. 5, the support body regions which are not covered by the cell arrangement are coated with a non-conductive substance 40 in such a way that no gas penetration takes place from the bottom to the top. The sequence and type of electrical connection in a cell arrangement in two directions is shown in FIG. 5 as an example. Other arrangements and interconnections are also possible. So mixed series / parallel connections can be used. For example, 4 cells are then connected in series and these arrangements are then connected in parallel by applying conductive layers, so that redundant power supplies are available which continue to work even at full voltage even after failure of a single cell.

FIGS. 6 to 9 now show an example of how the fuel cell according to the invention simply by Ver encapsulation in a plastic housing 17, 18, 19, carrying in bar is. Fig. 6a shows an example in the Be tenansicht, Fig. 6b in the front view. The inte grated fuel cell 22 is welded or cast in a gas-tight manner in a non-conductive plastic housing 17 , openings 23 , 24 for the fuel supply being provided on both sides of the cell. The electrical connections 25 , 26 of the cell are also encapsulated and are led to the outside as a metal contact.

Fig. 7a and 7b show a further variant of an advantageous gas supply multiple integrated fuel cell systems. Here, too, the integrated fuel cell 22 is welded / sealed in a gas-tight manner into a non-conductive plastic housing 18 , but channels 27-30 running through the entire cell for fuel supply and removal are present. Using the example of a hydrogen-oxygen cell, there would be a hydrogen supply channel 27 , which is connected to one side of the integrated fuel cell 22 , and an oxygen supply channel 30 , which is connected to the other side of the integrated fuel cell. Any inert gases can be discharged through the discharge channels 28 and 29 for each side of the integrated fuel cell. The electrical connections of the cell 25 , 26 are just cast if and are led to the outside as metal contacts. In this arrangement, a large number of these encapsulated cells can be arranged one behind the other via seals, the channels meaning a central fuel supply for all cells.

The encapsulation technology also allows the installation of several integrated fuel cell systems in a plastic housing 19 as shown in Fig. 8 Darge.

Should it be necessary to cool the cells this z. B. possible by applying heat sinks.  

Metallic heat sinks, for example made of aluminum, can be glued onto the cell. Water cooling is also possible ( FIG. 9), in which case a channel for the water supply 31 and a channel for the water discharge 32 are integrated into the housing 33 in addition to the fuel supply channels 27-30 . The front and back of the housing contain corresponding large-area depressions 34 , and then when assembling several modules z. B. by gluing, welding or using seals and pressure, the actual cooling structures arise.

If only a single module is to be cooled, the depressions 34 described above are to be integrated as cavities in the housing.

It is possible in a further variant, the gas-permeable support body through which the fuel gas flows, serves as a heat exchanger, which means that the coolant channels through this support body fen.

The plastic housing 17 , 18 , 19 and 33 are before formed from a flexible material. The housing walls and the fuel cells 22 are kept at a distance, so that the gas supply to the fuel cell 22 can take place without interference. Since can be used in the examples of FIGS. 6a, 7a, 7b, 8 and 9 spacer not shown there ter made of non-conductive material.

Fig. 10 shows the construction diagram of a fuel cell winding module, which is based on the described, flexi ble fuel cell film, in cross section, which is particularly advantageous and can be used in a small space.

The structure initially consists of the fuel cell film, which in turn in the variant shown here consists of the porous support body 40 , the electrodes 41 on both sides, the polymeric solid electrolyte 42 , the electronically conductive regions 43 and the insulation regions 44 . This fuel cell film is wound together with a non-conductive and gas-permeable film 45 , so that two separate gas spaces - 46 and 47 - are formed. In these gas spaces, the chemical energies are supplied for the fuel cell foil, in the case of H₂ / O₂ or H₂ / air fuel cells, these are hydrogen in gas space 46 and air in gas space 47, for example.

Thus, the electrodes 41 applied on both sides to the polymer electrolyte regions receive the energy carriers required for the oxidation and reduction processes of the fuel cell. So that this fuel supply is possible, there must be spaces between the fuel cell film and the non-conductive separating film 45 , which are generated, for example, by spacers 48 . Such spacers can be produced practically by polymer networks, which are coiled in the module and generate free volume for a glass flow. Another possibility is that no spacers are used, but that there are small channels in the separating film 45 on both sides through which the gas can flow to the electrodes.

The spacers 48 can also be used for the cooling and coolant can be passed through a tubular or tubular design ge. The end faces not recognizable in the illustration, of the particularly advantageous winding module, are closed gas-tight with lid-shaped closures which consist of a non-directing material.

FIG. 11 shows a further, universal and affordable way to embodiment of the invention. First 3 foils are needed and placed one on top of the other. A gas-impermeable, non-conductive film 50 , a fuel cell film according to the invention and a further gas-impermeable, non-conductive film 52 . Such a combination has a gas-impermeable film on both the top and bottom and is therefore gas-tight on both sides. So it does not have to be completely wound in itself as in Fig. 10, but can be wound on any curves or body.

The two required gas spaces are located between foils 50 and 51 and between foils 51 and 52 and, as already described, can be produced by inserting porous foils or meshes between foils 50 and 51 on the one hand and foils 51 and 52 on the other hand.

The arrangement shown in Fig. 11 is then wound up, for example on a body 53 , as shown in Fig. 12. The gas supply can be done in different ways:
On the one hand, the sides A and D ( FIG. 11) can each be sealed gas-tight between the foils 50 , 51 and 52 by gluing, welding or by inserting strips of sealing material between the foil ends. In addition, the space between film 50 and 51 is sealed on side B and the space between film 51 and 52 on side C. After winding, the gas is supplied on each side of the roll, for example hydrogen being fed on one side (wound side B) and oxygen on the other side of the roll (wound side C).

On the other hand, sides B, C and D ( FIG. 11) can each be sealed gas-tight between foils 50 , 51 and 52 by gluing, welding or by inserting strips of sealing material. The gas is then supplied and removed, for example, for hydrogen on side A between foils 50 and 51 and for oxygen between foils 51 and 52 .

In both cases, gas guiding structures can ensure an optimal supply of the gases to the electrodes. The gas guiding structures can be channels, for example, which are integrated in the impermeable foils 50 and 52 .

Mate are preferred as materials for the foils rialien into consideration, which manufactures as a flexible film bar and the conditions in the fuel cell can withstand d. H. oxygen resistant, water are resistant to substances and resistant to hydrolysis. Example Foils are made of polysulfones or perfluorinated materials can be used.

Claims (25)

1. Electrochemical solid electrolyte cell system, consisting of a flat gas-permeable non-conductive and flexible support body ( 1 ) made of polymer material, in which on a surface ( 2 ) at least one cell area ( 3 , 4 , 5 ), consisting of a first porous, electrically conductive Capable flexible electrode layer ( 7 ), a proton-conducting, flexible membrane layer ( 8 , 9 , 10 ) and a second porous, flexible, electronically conductive electrode layer ( 11 ) one above the other, by means of layering technology, is brought up. 2. Electrochemical solid electrolyte cell system according to claim 1, characterized in that 2-1 000 000 cell areas ( 3 , 4 , 5 ) are arranged on the support body and electrically connected. 3. Electrochemical solid electrolyte cell system according to claim 1 or 2, characterized in that 2-10 000 cell areas ( 3 , 4 , 5 ) are connected in series in a row. 4. Electrochemical solid electrolyte cell system according to claim 3, characterized in that 2-10 000 rows are connected in parallel.   5. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 4, characterized in that the electrical circuit via a Ver, the proton-conducting membrane layers ( 8 , 9 , 10 ) of adjacent cell areas ( 3 , 4 , 5 ) separating, Non-proton-conducting electrical contact ( 12 , 13 , 14 ) takes place, which connects an electrode surface ( 7 ) of a first cell area ( 3 , 4 , 5 ) with the opposite electrode surface ( 11 ) of the next cell area. 6. Electrochemical solid electrolyte cell system according to claim 5, characterized in that the electrical contact ( 12 , 13 , 14 ) in the region of the proton-conducting membrane layers is not porous and not catalytically active. 7. Electrochemical solid electrolyte cell system according to claim 5 or 6, characterized in that between the elec trical contact ( 12 , 13 , 14 ) and the neighboring th, proton-conducting membrane layer ( 8 , 9 , 10 ) additionally one, brought up by means of layering technology, insulating layer ( 15 , 16 ) is arranged. 8. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 7, characterized in that on the electrically conductive electrode layer ( 7 , 11 ) electro nically conductive material, for. B. is applied in the form of strips or grids. 9. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 8, characterized in that the support body ( 1 ) is a non-conductive, gas-permeable, flat membrane which can be constructed symmetrically, asymmetrically or as a composite membrane. 10. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 9, characterized in that the material of the support body ( 1 ) consists of polymeric materials such as polysulfones, or of such carrier-supported materials. 11. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 10, characterized in that the material for the electrode layers ( 7 , 11 ) is selected from elements of subgroup VIII, and their alloys, oxides, mixed oxides, or mixtures thereof or from mixtures or composites of the named materials with carbon. 12. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 11, characterized in that the material for the proton-conducting membrane layer ( 8 , 9 , 10 ) is selected from organic polymeric ionic conductors or flexible organic-inorganic polyme. 13. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 12, characterized in that the material for the electrical contact to connect the cells areas in the area of the membrane layer, metals such as titanium or conductive carbon or are electronically conductive polymers. 14. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 13, characterized in that the insulating layer ( 15 , 16 ) is an organically non-conductive polymer such as polysulfones or plasma polymerized te polymer layers. 15. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 14, characterized in that 1-10,000,000 cell systems are poured or welded into a non-conductive plastic housing ( 17 , 18 , 19 ), the connections of the cell being cast around and are led as a contact to the outside. 16. Electrochemical solid electrolyte cell system according to claim 15, characterized in that 1-2000 encapsulated Cell systems using seals one behind the other arranged and central material supply or -ab own driving channels. 17. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 16, characterized in that a flexible film consisting of support body ( 40 ), the electrodes ( 41 ), solid electrolyte ( 42 ) together with a non-conductive, gas-impermeable flexible film ( 45 ) forming a gas space ( 46 ), arranged and wound at a distance, so that a second gas space ( 47 ) is formed and the end faces of the winding module-shaped system are closed. 18. Electrochemical solid electrolyte cell system according to claim 17, characterized in that in the two gas spaces ( 46 ) and ( 47 ) spacers ( 48 ) are arranged. 19. Electrochemical solid electrolyte cell system according to at least one of claims 1 to 16, characterized in that the cell system is designed as a flexible film ( 51 ) which is surrounded on both sides by non-conductive separating films ( 50 ) and ( 52 ) and the sides (A), (B), (C) and (D) are connected to one another in such a way that two gas spaces on both sides of the flexible film ( 51 ) are formed with a separate gas supply. 20. Electrochemical solid electrolyte cell system according to claim 19, characterized in that the foils ( 50 , 51 , 52 ) are wound around a body ( 53 ). 21. Process for producing an electrochemical the solid electrolyte cell system after at least one of claims 1 to 20, characterized in that on the support body one after the other a first electrically conductive  Electrode layer, a proton conductive Membrane layer and a second, porous, electro nically conductive membrane layer, by means of and known methods of film technology be deposited. 22. The method according to claim 21, characterized in that the layers with PVD, CVD, thermal or plasma support decomposition of organometallic compound, galvanic methods or pressing processes be put. 23. The method according to claim 21 or 22, characterized in that the generation defi geometrical structures to be applied layers using masks on the Substrate are placed, or by means of suitable The photoresist takes place. 24. Use of the electrochemical solid electrolyte cell system according to at least one of claims 1 to 20
as an electrolysis system that splits water into hydrogen and oxygen. 25. Use of the electrochemical festival Electrolyte cell system according to at least one of the claims 1 to 20, as a fuel cell, which is hydrogen or Me ethanol turned into electricity.