EP1502320A2

EP1502320A2 - Chemoelectric transformer, chemoelectric transformer system, method for the production of electrical power, and method for operating a chemoelectric transformer system

Info

Publication number: EP1502320A2
Application number: EP03747083A
Authority: EP
Inventors: Reinhart Radebold; Irmgard Radebold; Walter Radebold; Helmut Radebold
Original assignee: Individual
Current assignee: Individual
Priority date: 2002-04-26
Filing date: 2003-04-25
Publication date: 2005-02-02
Also published as: WO2003092086A2; WO2003092086A3

Abstract

The invention relates to a chemoelectric transformer comprising electrodes, which is able to tap electrical power from a liquid hydrogen carrier, particularly an aqueous glucose solution, and oxygen as starting materials via reaction centers and secondary donors or via reaction centers and secondary acceptors. The electrodes are embodied as two porous solid bodies (7, 8) conducting electrons and protons. The volume of the first solid body (7) contains the reaction centers (RZA1, RZA2) and secondary acceptors (A) while the volume of the second solid body (8) contains the reaction centers (RZD1, RZD2) and secondary donors (D) as solid compounds (24). The first and the second solid body (7, 8) are in contact with each other by means of a proton-conducting membrane (6).

Description

Chemoelectric converter, che oelectric converter system,

Process for generating electrical energy and process for

Operation of a che oelectric converter system.

Description:

The present invention relates to chemoelectric converters according to the preamble of claim 1, chemoelectric converter systems according to the preamble of claims 29 and 55, a method for generating electrical energy according to the preamble of claim 60 and methods for operating a chemoelectric converter system according to the preamble of the claims 63 and 64.

The terms that are important for the following are first explained in a brief outline.

As is known, all air-breathing chemoelectric converters based on hydrogen basically work according to a scheme that is simple at first glance, which is shown in FIG. 1 to explain the state of the art: hydrogen atoms 2H are located at the interface 1 between an electronic (mostly metallic ) Conductor 2 and a protonic (usually consisting of an electrolyte) conductor 3 each divided into two electrons 2e ^" and protons 2H ⁺ ; hydrogen, in whatever form it was transported to the interface, has the function of a donor for e ^" and H ⁺ . The arrangement consisting of interface 1 and conductors 2, 3 forms an electrode. If the two electrons e ^" succeed in a quantum mechanical (tunnel) process on the electronic see conductor 2 to arrive, this is negatively charged. At the interface 1 an electrical double layer has built up, consisting of the negative electrons and the protons remaining in the protonic conductor 3 (electrolytes) because they are much larger. The distance between the charges of different signs is fractions of nanometers (nm = 10 ^"9 m), a microscopic electric field of very high field strength due to the extremely small distance between the charges has built up with a corresponding potential. Such a double layer can be very high as a charged capacitor Capacity to be understood.

A chemoelectric converter consists of two electrodes, with oxygen (mostly) in the form of 0 _{2 being} transported to the second electrode. 0 ₂ is used here as an acceptor for two e ^" and two H ⁺ , provided that two electrons succeed in leaving the electronic (here mostly made of graphite) conductor 2 of this electrode and again using a quantum mechanical tunneling process to the 0 ₂ Here too, an electrical double layer with an electrical field and corresponding potential has formed, consisting of the two remaining positive electron holes 2h ⁺ and the chemically reduced oxygen as negative ion (0 ₂ ) ^{2 "} .

It can be seen that protons and oxygen ions are located in the same protonic conductor 3, but separated from one another by a membrane 4. The membrane 4 prevents the hydrogen that has been transported from accidentally reacting chemically with the oxygen that is being transported in a parasitic reaction with the uncontrolled release of considerable energy. The task of the chemoelectric converter is to control the chemical reaction between hydrogen and oxygen in such a way that the energy released can largely be used in the form of electrical energy. That happens in 1 at the moment when the two electronic conductors are connected to one another via an electrical consumer, which is shown in FIG. 1 as a resistor, in such a way that the electrons 2e ^"of the (negative) hydrogen Electrode can fall into the electron holes 2h ⁺ the (positive) electrode that has been exposed to oxygen, but an electronic current can only flow and do electrical work via the chemical energy released, if at the same time an equally large protonic current flows over the Proton conductor and flows through the membrane to the (0 ₂ ) ^{2 "} - ion to form the reaction product H ₂ 0 ₂ according to the gross reaction 2H + 0 ₂ - H ₂ 0 ₂ .

From the point of view of electrodynamics, the two double layers have now dissolved as a result of the chemical reaction, and with them the two electrical fields have disappeared, not without having previously performed electrical work on the intermediate consumer. The sum of the two individual potentials corresponds to the voltage at the consumer between the two electrodes. The resulting short current pulses can be joined together to form a quasi-continuous (direct) current if the two starting materials hydrogen and oxygen are continuously transported accordingly.

Chemoelectric converters that work close to the ambient temperature have different technical structures and different properties, depending on the chemical form (and therefore also the physical state) in which the hydrogen is supplied. Air-breathing alkaline and PEM (Proton Exchange Membrane) fuel cells are known which are operated with gaseous, molecular hydrogen H ₂ as a hydrogen transfer agent and with gaseous, molecular oxygen 0 ₂ . There are three problems to be solved: First, to ensure the transport of the gaseous H ₂ and 0 ₂ to the chemoelectrically active respective interface (1) between the electronic conductor (2) and the protonic conductor (3), without the build-up of the electrical double layer by the addition of gas molecules block or prevent the transport of the gas molecules by flooding the transport routes.

Second, to convert the hydrogen carrier H ₂ into the active form of 2H.

Thirdly, to separate the two electrodes in a gas-tight but proton-conducting manner.

As is known, the first problem is solved by hydrophobizing the gas-permeable electronic conductors. The activation of H ₂ as a second problem is optimally achieved by attachment to an electrode provided with Pt, which serves as a catalyst. In the third case, in the case of alkaline converters, a porous membrane predominantly separates the two electrolyte spaces 3 serving as proton conductors, or a combination of proton conductors 3 and membrane 4 in the form of a polymeric membrane is omitted into the quasi-microscopic, acidic, water-containing channels, without alkaline electrolyte spaces are installed for proton conduction.

The potential difference occurring under load at the output of a chemoelectric converter operated with H ₂ and 0 ₂ is approximately 0.5 V. Almost all electrical consumers require AC or three-phase current at voltages of 220V or 380V. Voltages that can be usefully used for an inverter with a downstream transformer can be achieved if a plurality of the described arrangement is electrically connected in series to form stacks using bipolar electrodes. The individual potentials add up while the same current flows through the stack. Less known are chemoelectric converters that work with a liquid hydrogen transfer agent, such as, for example, aqueous solutions of hydrazine N ₂ H ₄ , methanol CH ₃ OH or glucose C ₆ H ₂ 0 ₆ , and which take their oxygen requirement from the atmosphere. In principle, these converters directly use hydrogen in the form of 2H, which is logistically packed with N ₂ or C0 ₂ . Here, too, the electrodes have three layers and, according to FIG. 1, consist of an electronic conductor 2, a protonic conductor 3 and an interface 1 for building up the double layer; both electrodes are separated by a membrane 4. In their case, however, the negative electrode is constructed much more simply and without the use of noble metal, since on the one hand a gaseous phase with the problems associated therewith does not occur, and on the other hand activation of the hydrogen via a catalyst is not necessary. The costly and operationally complex PEM is no longer necessary and is replaced by a membrane that is compatible with the aqueous solutions. As a new task, the degradation of the fluid hydrogen carriers up to the stage of 2H with removal of N ₂ or C0 _{2 has} to be solved. The problems of the positive electrode with gaseous oxygen are the same as in the previously known fuel cells for gaseous hydrogen. This no longer applies if hydrogen peroxide H ₂ 0 _{2 is used} as the liquid oxygen transmitter, unless this is decomposed into 0 ₂ and H ₂ 0 at the positive electrode.

DE 195 19 123 C2 describes a method for generating electrical energy from renewable biomass. Glucose as a C6 sugar is obtained from renewable biomass using known methods and is used in aqueous solution as a liquid hydrogen carrier together with 0 ₂ from the air for chemoelectric conversion. A reaction center is built according to FIG. 2 for further explanation of the prior art RZDl reduces the glucose via two C3 sugars practically to the level of 2H, while an analogous reaction center RZAl binds the gaseous 0 ₂ and reduces it to the liquid H ₂ 0 ₂ . However, the known method does not work with the 2H from the glucose and the 0 from the H ₂ 0 ₂ as donor and acceptor on the negative and the positive electrode, but rather the actual secondary donor D and the two additional reaction centers RZD2 and RZA2 actual secondary acceptor A formed in the electrolyte. The secondary donors and secondary acceptors are two fluid redox systems that, after having released or taken up their electrons and protons upon contact with one of the electrodes, can be regenerated chemically via 2H or O at RZD2 and RZA2. The electrodes on which the double layers are built up are graphite particles, which are suspended in the electrolyte and are components of a fluidized bed reactor, each with two fixed collecting electrodes. Theoretically, this method can achieve potential differences well above 1.2 V.

The method according to DE 195 19 123 C2 is based on biochemical principles of energy conversion in living cells. The aim is to utilize the great potential of the radiation from the sun stored in the renewable raw materials through photosynthesis in a novel chemoelectric converter into electrical energy. From DE 196 48 691 AI an improvement of the above-mentioned method is known, in particular through a qualitative and quantitative thermodynamic analysis of photosynthesis and breathing. (A block diagram with an exergy-anergy flow diagram of photosynthesis and respiration was published in VDI Report No. 1594 (2001), pages 345 to 354 as Fig. 1 by the applicant). The reaction sequences of breathing in a living cell serve as a model for a process for converting the free reaction enthalpy stored in hydrogen-containing substances and oxygen into the energy of an electrodynamic field for / application in macroscopic and microscopic technical systems. In this process, electrical energy from chemoelectric conversion is stored microscopically on molecules, macroscopically stored in synthetically produced structures with the function of a rechargeable battery. For example, alternating and three-phase currents of higher voltage can be obtained if the battery molecules discharge at a multiplicity of mutually insulated parallel electrodes, and the electrodes are then connected in series.

DE 198 21 980 AI describes a partial aspect of chemoelectric conversion in the form of a further method for decoupling electrical energy. Among other things, it is proposed to use a structure with a large inner surface between the two fixed electrodes of a transducer, which conducts electrons and protons and at the same time separates the donor and acceptor sides of the electrolyte. This structure has the function of a central electrode, which is connected to the other two electrodes via a transformer and a switch. Since the center electrode has a capacitance that cannot be neglected, it forms, together with the transformer, a resonant circuit which can be excited by alternating, opposite current pulses from the negative electrode to the center electrode or from the center electrode to the positive electrode.

The state-of-the-art chemoelectric converters with liquid hydrogen transfer and gaseous or liquid oxygen transfer are constructed as macro systems. Macro systems, regardless of whether they are loaded with gaseous or fluid products, must be sealed against their surroundings. They are therefore always equipped with pressure-resistant seals to the environment between the membrane, metallic conductors and electrical rolyte with the dissolved redox partners contained therein, as well as with pipes and pumps for conveying the fluid products and products, with devices for the elimination of the C0 ₂ or N ₂ as gaseous products as well as for the removal of the inevitable electrical and chemical Losses as heat with a relatively small temperature difference to the environment.

The construction of a chemoelectric converter to be used in a decentralized manner using structures and with elements from macroscopic process engineering therefore has considerable weak points. The weak points can hardly be mastered reliably even with the use of additional stabilizing structures such as pressure plates, which are clamped with bolts in order to apply large forces, since the forces easily cause deformations of seals and flanges, for example, of deformation of channels and electrodes with the risk of Cause blockages and leaks.

Macro systems are cumbersome to use; in the event of malfunctions, they have to be completely emptied and largely dismantled in order to reach defective areas. Relatively high pressures are required internally in order to generate turbulent flows in the channels, necessary to obtain very thin boundary layers on the electrodes. Compared to the dimensions of the double layers, the fluid dynamic boundary layers, in which the speed drops practically to zero and the liquid adheres, are, however, many orders of magnitude thicker: The exchange of starting materials and products with the electrodes essentially only comes about through diffusion, hardly through convection conditions .

As far as is known, there are no publications on experimental investigations of chemoelectric converters with liquid hydrogen transfer. Applicant's experience show, however, that the construction of such a converter as a macro system in principle poses the same problems as are known from fuel cells with gaseous starting materials and, for example, in the VDI Progress Report Series 6, No. 454 (2001) on current density distribution and performance of the polymer electrolyte fuel cell to be discribed. The main advantages of air-breathing chemoelectric converters with glucose as hydrogen carriers, working with secondary donors and secondary acceptors in the liquid phase, as described for FIG. 2, without the occurrence of a gaseous phase with the problems described in the construction of the potential-determining microscopic double layers occur because of the macroscopic problems in the background.

It is therefore an object of the present invention to provide a chemoelectric converter and a chemoelectric converter system which can be embodied as a microsystem and which enables efficient energy conversion. It is also an object to specify a method for generating electrical energy using chemoelectric converters and a method for operating a chemoelectric converter.

The object is achieved by a chemoelectric converter with the features of patent claim 1.

Accordingly, a chemoelectric converter with electrodes from a liquid hydrogen transmitter, in particular aqueous solution of glucose, and oxygen as starting materials can couple electrical energy either via reaction centers and secondary donors or via reaction centers and secondary acceptors. According to the invention, two porous, electron and proton-conducting solid bodies are provided as electrodes, the reaction centers and the secondary acceptors in the volume of the first solid body and the volume of the second solid body the reaction centers and the secondary donors are in the form of solid compounds and the first and second solids are in contact, separated by a proton-conducting membrane.

It is advantageous to design the pores of the solid so that they have a capillary action for liquid educts. Microscopic capillarity can be achieved through disordered, but also through ordered structures. In this way, it is possible to easily transport starting materials and products as well as reaction heat without the use of seals or the need to build up high pressures.

The control of the water content in the porous solids of the electrodes is essential. In addition to microcapillarity, macroscopic, capillary-active separate conduction paths with the function of wicks are therefore provided, both for the distribution of liquid starting materials and for the targeted removal of excess liquid.

It is particularly advantageous if the electrodes are also used to store electrical energy. In this way, energy can be stored by the secondary acceptors and secondary donors, since, like a battery, they can initially take up or release electrons without the need for an external supply of starting materials.

In an advantageous embodiment, metal-oxide compounds, for example MnO ₂ , in particular alkaline Fe (VI) oxide, serve as the secondary acceptor. It is advantageous to use organic compounds, in particular C-hinone or flavine, as reaction centers for the secondary acceptor. It is also advantageous to use inorganic cerium compounds as reaction centers for the secondary acceptor. It is advantageous as a secondary donor metal-organic compounds, organic Compounds or metals, especially bismuth, lead or iron, but also metal oxides such as Fe (II). By using these materials, the energy can be extracted efficiently.

From a chemical point of view, the electrodes of different signs designed as solid bodies do not have to work at the same pH values. For example, the positive electrode with its acceptors can work in the neutral or weakly acidic range, the negative electrode with its donors in the strongly basic range. This does not change the fact that protons ultimately have to flow from the boundary layer of the negative to the boundary layer of the positive electrode. Depending on the selected conditions, a protonic hole line can also be involved.

In an advantageous embodiment of the invention, the secondary donors and / or the secondary acceptors can be regenerated chemically after their use via the reaction centers and / or by feeding in electrical energy. This makes it possible to electrically charge the chemoelectric converter, which can also serve as a memory.

It is advantageous to integrate the reaction centers and / or the secondary donors and / or the secondary acceptors in a gel-like matrix. Different materials and substances can be integrated flexibly. A binder which is elastic in the hardened state can also advantageously be used.

It is also advantageous to design the solid bodies of the chemoelectric converter serving as electrodes and memory in a cuboid shape. In an advantageous development, at least one of the solid bodies is electrically conductive Contact contacted. It is advantageous to design the electrically conductive contact as a metallic grid that advantageously contacts the solid body on exactly one of its side surfaces. In a further advantageous embodiment of the invention, nickel, carbon and / or another organic compound is applied to the metallic grid. It is advantageous to use a chemically inert graphite foil, which is used, for example, perforated or punched as a grid for contacting.

It is advantageous to integrate the electrically conductive contact into a solid. A structure of the solid bodies serving as electrodes and storage can be achieved in this way, which structure can be arranged in such a simple manner in a technically advantageous form, for example next to one another. Furthermore, reliable contacting is possible, which enables the electrical energy to be derived efficiently from the electrodes.

In an advantageous development of the invention, a spray device is provided with which educts and / or water can be sprayed onto the solid body. It is advantageous to use an aqueous solution of hydrazine N ₂ H _{4 /} methanol CH ₃ 0H or glucose C ₆ H ₂ 0 ₆ as the product, in particular as a hydrogen transfer agent. This ensures efficient transport of hydrogen carriers. Because macroscopic, capillary-active conduction paths are provided in the electrodes for the further transport and distribution of the liquid educts, the liquid educts can also be directly injected at a few excellent points on these conduction paths.

The object is further achieved by a chemoelectric converter system with the features of patent claim 29. Accordingly, a chemoelectric converter system can couple electrical energy out of a liquid hydrogen transmitter, in particular an aqueous solution of glucose, and oxygen as starting materials via reaction centers and secondary donors and / or reaction centers and secondary acceptors. According to the invention, at least one of the chemoelectric converters described above is provided, the electrodes of which are designed as porous, electrons and proton-conducting solids being in contact with one another via a proton-conducting layer and the proton-conducting membrane is arranged between the proton-conducting layer and the solids.

It is advantageous to contact the electrodes on their side facing away from the proton-conducting layer via electrically conductive contacts. In a preferred variant, the proton-conducting layer is flat, the at least two electrodes, which can also serve as a memory, being in contact with the same side of the surface of the proton-conducting layer. It is advantageous to arrange the electrodes next to one another on the proton-conducting layer in such a way that they do not touch. The proton-conducting membrane can advantageously also be arranged between the electrodes. The electrodes are preferably arranged on the proton-conducting layer in such a way that two electrodes with different doping are always adjacent to one another. In this way, a scalable system can be produced from positive and negative electrodes, with the protons being transported via the proton-conducting layer.

It is advantageous to provide a spraying device with which products and / or water can be sprayed onto the electrodes designed as porous solid bodies. The spray device is advantageously movable, in particular also rotatable. orderly. In a further advantageous embodiment, the spraying device is designed as a solid matrix which can spray educts onto the electrodes at the desired locations. A constant transport of starting materials and thus constant energy decoupling can be ensured via the spray device. Water can serve as a phase transition agent for the removal of heat of reaction. As already mentioned, the control of the water content in the electrodes is essential, for which purpose separate capillary-active conduction paths are provided. This applies regardless of whether the liquid educts are supplied via a spray device or a direct injection.

In an advantageous development of the invention, the proton-conducting layer additionally has either reaction centers and secondary acceptors or reaction centers and secondary donors which serve for the intermediate storage of electrical energy. It is advantageous to contact the proton-conducting layer on its side facing away from the electrodes via electrically conductive contacts. The proton-conducting layer can thus be operated as an energy store, in principle a battery that can be regenerated from the outside by the chemoelectric converter and / or by feeding in energy.

In an advantageous development of the invention, the proton-conducting layer and the electrodes in contact with it are arranged on a flat or curved circuit board. Means for controlling the electrochemical conversion and / or means for decoupling the electrical power and / or means for feeding in electrical energy are advantageously provided on the circuit board. In a preferred variant, a push-pull flux converter for decoupling electrical power, in particular for transforming a low voltage, is included on the circuit board arranged. It is advantageous not to perform the parallel connection of the electrodes galvanically but inductively. For this purpose, a transformer operating at high frequency contains one primary winding per pair of electrodes, with the associated switching transistors in the circuit thus formed.

It is advantageous to design the circuit board from several layers, the means for controlling the electrochemical conversion and / or means for decoupling the electrical power and / or means for feeding in electrical energy, in particular also a push-pull flux converter, at least partially between the layers the board are arranged. In a preferred development of the invention, proton-conducting layers and electrodes are attached on both sides of the circuit board, so that the additional means for controlling the electrochemical conversion and / or means for decoupling the electrical power and / or means for feeding in electrical energy are located between them , In this way, modules can be produced which have both a converter area and the means necessary for controlling this converter area, in particular control electronics and means for decoupling electrical power. A space-saving "sandwich" module is created by equipping the board with electrodes on both sides.

From a "sandwich" module, economically advantageous and production-technically simpler and less expensive "economy versions" of a module of the chemoelectric converter according to the invention can be derived. In this case, the additional means for controlling the electrochemical conversion and / or means for decoupling the electrical power and / or means for feeding electrical energy from the "sandwich" and moved to one end of the module, the proton-conducting layers are combined or else on reduced a single proton-conducting membrane. In this case, the individual electrodes of the same sign are combined on one side of the module. If the proton-conducting layers are omitted, their existing redox systems must be integrated into the positive electrode; the oxygen-breathing electrodes are covered with a layer of the known hydrophobic carbon mats.

Several boards are advantageously arranged in a circle and / or in a spiral. It is also advantageous if several boards can be sprayed with starting materials and / or water with a single spraying device. The chemoelectric converter system can be scaled modularly by using several boards, whereby all the necessary means for controlling and coupling and decoupling energy are already on the boards. The modules can be interconnected in different arrangements. It is advantageous to connect the chemoelectric converters, in particular the circuit boards, to one another via a plurality of electrical leads. In this way, a scaled system can be produced that is suitable for high performance.

In an advantageous embodiment of the invention, an ultrasound source is provided with which at least parts of the chemoelectric converter system can be set into high-frequency mechanical vibrations. It is also advantageous to provide a container with which at least a part of the chemoelectric converter system, in particular the porous solids and / or circuit boards with chemoelectric converters, can be closed in a pressure-tight manner with respect to the environment. It is advantageous if an atmosphere of oxygen, nitrogen, water vapor and CO ₂ can be maintained in the container in a steady state. The pressure in the container is advantageously periodic and / or too fixed. times can be changed, the container is advantageously coolable. Through these advantageous configurations, the throughput of starting materials, products and water through the porous solid body can be increased, as a result of which the coupling output can be increased.

The object is further achieved by a method having the features of patent claim 60.

Accordingly, with a method for generating electrical energy with chemoelectric converters, with which electrical energy can be coupled out from a liquid hydrogen carrier, in particular aqueous solution of glucose, and oxygen as starting materials via reaction centers and secondary donors and / or reaction centers and secondary acceptors. The starting materials according to the invention are applied to at least one electrode which is designed as a porous, electron and proton-conducting solid and in the volume of which the reaction centers and the secondary acceptors or the reaction centers and the secondary donors are present as solid compounds.

In an advantageous embodiment of the invention, the products are transported capillary into the porous solid. The starting materials are thus transported without additional technical aids.

Furthermore, a chemo-electrical converter system described above is advantageously operated in one of the following four operating states:

a) Operation at standard power in a state in steady state, in which the delivery of electrical energy via secondary donors D and secondary acceptors A of supplying the starting materials and thus their chemical regeneration is proportional, b) operation with a greatly increased short-term output of electrical power as a permissible overload compared to the standard power, in which (compared to the requirements of the operating state a) excess donors D and secondary acceptors A are consumed without immediate chemical regeneration, c ) Operation with a greatly increased short-term absorption of electrical energy from an external source for the direct electrical regeneration of used secondary donors and secondary acceptors, equivalent to the electrical charging of the internal storage, in particular also in parallel with chemical regeneration, d) Operation at low load for the used secondary donors and secondary acceptors of the chemoelectric conversion system are electrically regenerated internally, the spent secondary donors and secondary acceptors of some electrodes being replaced by the secondary donors and secondary acceptors of others, electrodes are regenerated in steady state according to the operating state a).

It is also advantageous to operate a chemoelectric converter system described above in such a way that the low voltage generated by the chemoelectric converter system is transformed up with a push-pull flux converter to technically usual voltages, in particular 110V, 220V or 380V. The voltage is preferably converted into two-phase or multi-phase alternating currents of adjustable frequency. In this way, technically usable voltages and currents can be achieved from the low voltage supplied by the chemoelectric converters.

The present invention is based on the idea that the previous coupling of microscopic processes with macroscopic Pick up technology as much as possible. It goes without saying that today's modern technologies (nanotechnology) only begin to penetrate into the nm range, their range of action should begin above 100 nm. The present invention builds on this technology, for example on disordered microporous, capillary-active structures, on microdrops and their conveying systems, on condensation and evaporation on microroughness, on macroscopic wick-like conductor tracks for liquids. It is more advantageous to use the disordered, ordered microporous structures, for example in that electronically and protonically conductive, permeable microscopic capsules, for example in the range of 10 μm, enclose the redox systems and reaction centers and in that the capsules are lined up to form quasi-crystalline structures.

The present invention thus integrates the components, redox systems and conductors for protons required for the chemoelectric conversion, storage and coupling-out of the electrical energy, and, as far as possible, dispenses with macroscopic hydrodynamic and hydraulic structures.

The present invention thus leaves methods and arrangements for chemoelectric conversion as described in the prior art, in which reaction centers and donors and acceptors are dissolved in the aqueous electrolyte, with excess water being present. The invention is based on the use of reaction centers RZD1, RZD2, RZAl and RZA2 as well as of secondary donors D and acceptors A as shown in FIG. 2, but in contrast to the patent specification mentioned, it describes methods and arrangements,

who work with chemoelectrically active, non-fluid three-dimensional structures in which reaction centers, donors and acceptors are fluid connections, and in which water occurs only to the extent that it is required as a starting material and / or as a means for heat transport, and as it is found as a product.

The invention provides new degrees of freedom for chemo-electrical conversion. Only now that seals, hydrodynamic and also stabilizing structures and devices with their pressures and forces are no longer necessary, does a modular structure of the converter system, as in microelectronics, appear possible with its great advantages in production, operation and also accidents. In the case of a modular chemoelectric converter system, in principle any output power required by the customer can be achieved simply by adding modules that are plugged onto a common busbar and thus electrically connected in parallel.

According to the invention, only those substances or compounds capable of redox reactions are used as (secondary) donors D and acceptors A which

are introduced as solid substances in microporous structures or in gel-like matrices, and which after use can be regenerated both chemically via the reaction centers RZD2 and RZA2, but also directly electrically.

In the simplest case, a metal such as bismuth or lead can advantageously be used as the donor, since, for example, its oxides can be reduced by glucose via reaction centers RZD1 and RZD2, but also metal oxides, for example based on Fe (II), which change in value, for example Fe (III) function can also be reduced by glucose via the reaction centers RZD1 and RZD2. Even organic and metal-organic compounds come into consideration.

As a secondary acceptor A compounds may, for example, such as Mn0 ₂ are used on the basis of metal oxides, then alkaline Fe can (III) oxide on H ₂ 0 ₂ to Fe0 ^{2 ",} an Fe (VI) oxide, as oxidize very effective acceptor.

Organic compounds such as quinones have already been mentioned as the RZAl reaction center; here, for example, in addition to flavins and other organic compounds, inorganic cerium compounds which bind molecular oxygen as a complex and reduce it to H ₂ 0 _{2 are also} suitable.

Under the second condition, it is in principle possible to feed electrical energy from an external source - such as braking energy in a vehicle drive (which generally accounts for around 15% of the drive energy) - into the converter system and thus recover it to a large extent.

The invention is further explained below with reference to the figures in the drawings. Show it:

FIG. 1 shows a schematic representation of a chemoelectric converter according to the prior art,

FIG. 2 shows a schematic representation of a method for generating electrical energy from renewable biomass according to the prior art,

FIG. 3 shows a schematic exploded view of a chemoelectric converter system according to the invention,

Figure 4a schematic, not to scale sectional view by a microporous, disordered solid of a chemoelectric converter according to the invention,

FIG. 4b shows a schematic, not to scale, sectional view through a microporous, ordered solid of a chemoelectric converter according to the invention,

FIG. 5 shows a schematic exploded view of a chemoelectric converter system according to the invention in a second embodiment,

FIG. 6 shows a schematic exploded view of a chemoelectric converter system according to the invention in a third embodiment,

FIG. 7 shows a schematic circuit diagram of a push-pull flux converter,

FIG. 8 shows a schematic sectional illustration of a further, cost-effective “economy version” of a module of the chemoelectric converter system according to the invention, and

FIG. 9 shows a schematic illustration of an inductive coupling of a plurality of electrode pairs via a high-frequency transformer.

3 shows a schematic exploded drawing of the invention which is not to scale, based on the chemoelectric part of a chemoelectric converter system.

The individual electrodes of the chemoelectric converter system are designed as strip-like, porous and capillary-acting solid bodies 7, 8. The electrodes also act as storage for electrical energy. The solids 7, 8 are on the one hand, by integrating reaction centers and secondary donors present as solid connections into the porous structure as a negative electrode storage structure 7 and, on the other hand, by integrating reaction centers and secondary acceptors in the porous structure as a positive electrode storage structure 8. On a flat layer 5 made of proton-conducting material there is also a proton-conducting membrane 6 as a separating layer for an arrangement of strip-shaped negative and positive electrode storage structures 7, 8 which are electronically separated from one another by a separating joint and which are protected by protective, supporting and current collectors. Grid 9 alternately connected to negative and positive electron-conducting power lines 10 of a two-strand power bus 11, that is to say connected in parallel overall.

A further development is not shown here, in which each pair of the electrode storage structures 7 and 8 is inductively coupled to one another via a secondary winding via switching transistors and a separate, separate primary winding of the high-frequency transformer. Such a coupling is shown for example in FIG. 9.

In an embodiment not shown here, the proton-conducting membrane 6 can also be arranged in the joint between the two electrode storage structures 7, 8 or contain the material of the proton-conducting membrane 6. The parting line can also be filled with an isolator. The proton-conducting layer 5 and the membrane 6 are assigned to all of the electrode storage structures 7, 8 together.

The formation of the electrode storage structures 7, 8 as strips, as shown here, is expedient but not mandatory. In principle, any geometrical shapes and arrangements can gene, such as circles or in the form of a chessboard.

The electrode storage structures 7, 8 are formed by porous, capillary-active, electronically and protonically conductive solid bodies, in which the protective, supporting and current collecting grid 9, advantageously with a prepared surface, is integrated or placed. The respective solid 7, 8 contains either reaction centers RZD1 and RZD2 or RZAl and RZA2 according to FIG. 2 and the description of the prior art therein, including the redox system of the secondary donors D or secondary acceptors A, but not now in dissolved, fluid the form, but as fixed connections.

Similar to activated carbon, the inner interfaces to build up the potential-determining double layers are very large. Since the porous solid-state structure, for example by adding graphite or carbon black, is also electron-conductive because an electron-conducting matrix is formed, the secondary donors D integrated into the porous solid-state structure can accept electrons via the protection, support and current collecting grid 9 give off the power bus 11 and the secondary acceptors A receive electrons via the power bus 11. In the embodiment shown in FIG. 9, the galvanic coupling is replaced by an inductive coupling.

A heat transfer takes place between the electrodes 7, 8 with one another and with the proton-conducting layer 5, in which the resulting thermal energies can be exchanged with one another. The structure internally transfers heat at the temperature of the structure (anergy). During the chemoelectric oxidation of 24H from glucose, anergy is released, roughly the same level as the removal of 24H from glucose. This ensures a constant flow of heat between see the electrodes instead.

FIG. 4a is a schematic sectional view, not to scale, of one of the microporous, disordered, capillary-active solid bodies which form the electrode storage structures. It shows the electron-conducting matrix formed from the particles 22 and the particles 23 of the corresponding proton-conducting matrix arranged offset therefrom. Furthermore, the complexes 24, to which the reaction centers RZD1, RZD2 and donors D are combined in the case of a negative electrode storage structure and the reaction centers RZAl, RZA2 and acceptors A in the case of a positive electrode storage structure. The complexes 24 are present as solid connections in the porous solid. The complexes 24 can also be present in a gel-like matrix.

The interfaces 21 required to build up the double layers arise between the particles 22 of the electron-conducting matrix and the complexes 24. The spaces between the different particles 22, 23 and the complexes 24 form the microscopic capillary system. In this illustration, the capillary-active macroscopic conductor tracks are omitted.

FIG. 4b is a schematic sectional illustration, not to scale, of a microporous, ordered, capillary-active solid in a further embodiment, which are used as electrode storage structures. It shows electronically and protonically conductive, permeable microscopic capsules in which the reaction centers RZD1, RZD2 and donors D in the case of a negative storage structure 7 or reaction centers RZAl, RZA2 and acceptors A in the case of a positive electrode storage structure 8 are enclosed. The complexes 24 are present as fixed connections. The capsules are more or less made of electron-conducting, much smaller ones too spherical particles 22, for example formed from carbon, which surround the more or less spherical complex 24 in a thin, crystalline layer. The proton conductor 23 is located in the cavities between these particles. These capsules can be arranged in ordered layers and are in electronic contact. The gussets between the capsules form the microscopic capillary system. As in FIG. 4a, the macroscopic, capillary-active conductor tracks are not shown.

If the proton-conducting layer 5 is understood as a common "protonic mass", the corresponding protons migrate through this layer from the negative electrode storage structure 7 to the two adjacent positive electrode storage structures 8. The narrower the electrode storage structures, the shorter their path 7, 8 are designed. In contrast to conventional fuel cells, the common proton-conducting layer 5 makes it possible to supply the positive and negative chemoelectric converters 7, 8 together with starting materials from one side (and not, as previously, from two sides).

To regenerate the spent donors and acceptors on the reaction centers chemically, must diffuse memory structures electrodes 8 in the oxygen 0 ₂ in the positive, while dissolved glucose or other liquid hydrogen transfer agent to the negative electrode storage structures 7 to be supplied from above. In the embodiment shown here, the liquid hydrogen carrier is sprayed onto the negative electrode storage structures 7 via a spray device in the form of a printer system with a printer head 13, nozzles and delivery systems, as is known in terms of the dimensions and function of inkjet printers. The oxygen from the surrounding atmosphere has access to the positive electrical the memory structure 8.

Instead of the printhead 13 to be guided biaxially over the entirety of the electrode memory structures 7, 8, a printhead bar, not shown here, to be moved or a permanently installed printhead matrix can be used as the spraying device.

In a variant of the invention, not shown here, each printer head 13 has at least one second nozzle and conveying system, with which it can spray water as a reaction partner and means for heat transport onto the electrode storage structures 7, 8. This second nozzle and delivery system is programmed in such a way that aqueous solutions of glucose or hydrazine and the additional water, if necessary, spray onto the corresponding electrode storage structure 7, 8 or parts thereof, leaving out the joints between the solids 7, 8.

The microdroplets 12 are picked up by the capillary-active electrode storage structures 7, 8 and distributed within them by the acting capillary forces. The reservoirs, from which the printer head 13 is supplied via flexible supply lines, as well as its mechanics and its control bus, are not shown in the drawing.

The removal of the reaction products C0 ₂ or N ₂ takes place through the channels of the capillary system as well as the removal of the H ₂ 0 including the (additional) H ₂ 0 components used in the gaseous phase to dissolve the glucose or to dilute the hydrazine: this water, which is initially in liquid form within the porous, capillary-active electrode storage structures 7, 8, is evaporated by the sum of the losses of the chemoelectric conversion in the form of heat at the temperature of the electrode storage structure 7, 8. preferably on quasi-crystalline areas or microroughness, which act as a seed for evaporation. If there is an excess of liquid that cannot escape through evaporation, the macroscopic, capillary-active conductor tracks come into operation for removal. An almost isothermal removal of the heat loss from the microporous electrode storage structure 7, 8 into the atmosphere surrounding it is possible, the heat loss from the surrounding atmosphere being subsequently removed again by condensation of the water vapor on appropriately cooled surfaces.

In order to accelerate the throughput of starting materials and products through the porous, capillary-active electrode storage structures 7, 8, in order to accelerate the assembly and disassembly of the double layers, the electrode storage structures 7, 8 are converted into high-frequency by an ultrasound transmitter (not shown here) mechanical vibrations offset.

The concept of the printer head 13 is fully used when a liquid oxygen carrier such as H ₂ O ₂ , diluted with water, is sprayed on via a third nozzle and conveyor system in the printer head 13. Oxygen diffusion is eliminated, current density and voltage increase dramatically. If the entire system is still to be air-breathing, it is necessary to outsource the reduction of 0 ₂ via the RZAl to a type of lung, i.e. to decouple the functions of RZAl and RZA2 spatially and temporally. High power density is achieved with increased effort. The electrode storage structure 8 changes only insignificantly, if at all.

The electrical regeneration of the used donors D and acceptors A can be achieved as an alternative to the chemical regeneration described so far in the variants of the invention described here directly via externally supplied electrical energy. consequences. The electrical energy is coupled into the electronically conductive matrix of the electrode storage structures 7, 8 via the power bus 11 with its power lines 10, via the protective, support and current collecting grids 9. From an electrical point of view, the electrical regeneration of the redox systems means charging the internal storage. Here, too, a protonic current of equal size must flow internally.

The chemoelectric conversion system according to the present invention has the property of being able to charge its memory not only externally via electrical energy but also internally by supplying chemical energy. The converter system therefore knows four operating states:

1. The state in steady-state equilibrium, in which the release of electrical energy via secondary donors D and secondary acceptors A is proportional to the supply of 0 ₂ or H ₂ 0 ₂ and the liquid hydrogen transfer agent such as glucose together with additional water and thus its chemical regeneration, in which the converter system can achieve its maximum output depending on the load,

2. the greatly increased short-term output of electrical power as a permissible overload in comparison to the standard power in operating state 1 via (in comparison to the requirements of operating state 1) excess secondary donors D and secondary acceptors A without immediate chemical regeneration,

3. The greatly increased short-term absorption of electrical energy from an external source for the direct electrical regeneration of used secondary donors and secondary acceptors, synonymous with the electrical charging of the internal storage, possibly parallel to the chemical see regeneration,

and as a combination of operating states 3 and 1

4. the internal electrical regeneration of used secondary donors and secondary acceptors at low load of the chemoelectric conversion system, the used secondary donors and secondary acceptors of some electrode storage structures being regenerated by the secondary donors and secondary acceptors of other electrode storage structures operated in a steady state according to FIG. 1.

The great technical advantage of the internal regeneration of the redox systems of the secondary donors D and the secondary acceptors A, which are built in as storage, is that the charging of the storage is no longer dependent solely on electrical energy from external sources, but at low load or zero load can be done.

5 shows a further variant of the invention, based on the chemoelectric part of the converter system, with direct air breathing, expanded oxygen diffusion and with a greatly enlarged memory. The air-breathing, positive electrode storage structure 8 in FIG. 3 is traced back to an exclusively air-breathing electrode structure 14, which has now been increased in volume and thus correspondingly in surface area. The formerly associated storage structure with its secondary acceptors A is shifted into the common proton-conducting layer 5 according to FIG 3, so that a new proton line electrode storage structure 15 has arisen. Correspondingly enlarged and equipped with its own protection, support and current collecting grid 9, this third structure is connected via power lines to the now three-strand power bus 16. tet. The entire chemoelectric converter system is modular.

In operating state 1 (steady state), the electrical energy is released by electrode structures 7 and 14, while in operating states 2 and 3 the electrode structures 7 and 15 are activated via the power bus 16. During internal charging of a part of the memory structures integrated in the converter system in operating state 4, the regenerating electrode memory structures operate via the electrode structures 7 and 14, while other electrode memory structures to be regenerated are connected to the power bus 16 via their electrode memory structures 7 and 15, so that electrical energy is transferred internally.

Several modules can be operated simultaneously, which can be coupled in parallel or in series via an electrical busbar, depending on the requirements. In the event that a module in operating state 4 emits electrical energy in order to regenerate the redox systems of a second module, this requires the transfer of electrical energy via a busbar common to all modules, at the level of the power bus 16 each Module adjusting chemoelectric potential difference.

One of the great advantages of the chemoelectric converter system according to the invention, however, is, as will be shown in the following example, that each chemoelectric module can deliver electrical energy to a common busbar as a two-, three- or multi-phase current with adjustable frequency and with technically usual voltage , A cross-module internal regeneration of the redox systems requires the use of two common rails, a direct current rail with low voltage and high currents and an alternating or rotary Busbar with voltages of, for example, 380 V require, which means a considerable technical effort. The preference is given to a non-cross-module operating state 4 for which a low-voltage direct current rail is unnecessary.

FIG. 6 shows an example of a complete, internally regenerable module of a chemoelectric conversion system, consisting of the chemoelectric part, here in the form of the variant according to FIG. 5, together with its periphery, constructed as a multilayer board and from its printer system.

The exploded view shows the different layers and layers of the module. The upper layers are used for chemoelectric conversion, here sprayed by a single printer head 13, as shown in a simplified manner by way of example. The lower layers contain the periphery, consisting of power electronics 18 and a microelectronic control system 19 together with data and energy bus 20. The multilayer circuit board 17 forms the support structure of the module in terms of construction.

As shown here by way of example, the circuit board is composed of non-conductive foreign layers 17.1 to 17.4, the individual strands of the power bus 16 being located in the three intermediate layers. These are, insulated from one another and lying close to one another, in the form of electron-conducting plates 16.1 to 16.3 with very low internal resistance, each connected to the chemoelectrically active structures via the leads 10. The bus 20 also reaches the sensors via intermediate layers.

The connection of the module to a busbar common to all modules of the converter system for the electrical performance and to a common data bus.

The microelectronic control system with 19 with its bus 20 for data transfer and for supplying actuators and sensors with energy has the task of detecting the state of the individual components of the module with regard to the reactions and processes taking place, and the printer system in its various embodiments as an actuator to control depending on the chemoelectric conversion and its operating states.

Since different heat losses occur in the module depending on the load on the chemoelectric converter, the supply of water as a means of transport must be adjusted in addition to the metering of the educt (s). The high heat of vaporization of the H ₂ 0, however, requires only a small supply of additional water via the spray head 13 ^' and therefore a very careful control of the moisture and the temperature within the structures and the surrounding atmosphere, because any excess of water in the chemoelectric structures causes the chemoelectric Change adversely affected. This control, expanded by measurements of the current density, enables microsensors, not shown here, distributed in particular in the structures. Together with reference electrodes, which are also integrated, the potential difference between the respective electrode and proton conductor can also be recorded (the measurement of the voltage between the electrodes only provides indirect information about the situation of the individual electrode). The microelectronic control system 19 of each module is connected via plug connectors and via a bus, not shown here, to a higher-level computer, not shown here, which is responsible for the control of the entire chemoelectric converter system.

The function of the power electronics 18 is based on the four led operating conditions coordinated. In principle, the power electronics consist of a known push-pull flux converter, the diagram of which is shown in FIG. 7, i.e. of semiconductor switches such as transistors, of a transformer with two windings on each side and of a capacitance and of diodes on the output side. This arrangement is operated at frequencies from approximately 50 kHz, which reduces the dimensions of the transformer to such an extent that it can be inserted into the module. According to the invention, the transformer is connected directly to the plates 16.1 to 16.3 of the power bus 16, for example via vias and partially integrated, not only to save space, especially to reduce the leakage inductances. According to the invention, only the double-layer capacitance of the chemoelectric structures is used as the capacitance of the push-pull flux converter on the low-voltage side.

In operating states 1 and 2, the current coming from the collecting plates, broken down into high-frequency pulses via the semiconductor switches and brought to technically customary voltages via the transformer is then, according to the invention, adjustable in two-phase or multi-phase alternating currents from approximately 400 Hz to below implemented a few Hz, for example to operate three-phase motors for vehicle drives via the chemoelectric converter system or to supply a fixed network with 50 Hz, 60 Hz or 400 Hz. Each module of the converter system has corresponding plug connections for connection to busbars, not shown here.

According to the invention, the push-pull flux converter, extended by appropriate circuits and components and thereby modified, is used in operating state 3 in the opposite direction, namely for feeding braking energy in the form of frequency-variable three-phase currents when using the modular chemoelectric Converter system, for example in vehicles.

In operating state 4, the storage of the chemoelectric converter system is charged by internal regeneration of the redox systems, advantageously in each module of the variant according to FIG. 6 independently of the other modules, the push-pull flux converter blocking the module. In this case, the regeneration within the module is controlled via the control of the printer head, in that it supplies only part of the chemoelectric structures and the structures that are not supplied are charged accumulatively.

8 shows a schematic illustration of a further, cost-effective “economy version” of a module of the chemoelectric converter system according to the invention in a schematic sectional view. This module basically consists of two parts, a first part of the chemoelectric conversion shown in the drawing in the upper area and a second part, which is arranged in the lower area in the drawing and which comprises the entire microelectronic components and the power electronics 18, 19. The chemoelectric part of the module is enclosed by two printed circuit boards 29 which are rigidly connected to one another via spacers 28. The structure is as shown in FIG The electrode storage structures 7 and 8 face each other and are only electronically isolated from one another by the proton-conducting membrane 6. The positive electrode 8 is covered with one of the known hydrophobized carbon mats 25. The contacting 9 takes place through a graphite foil or another derivative into which channels 27 for conducting air or air with an enriched 0 ₂ component are stamped or molded.

The negative electrode storage structure 7 is also provided with a graphite foil 9 or another derivative. In the drainage channels 26 are introduced, which continue through the board 29, necessary to spray or inject the liquid hydrogen carrier.

Because air or air with an enriched 0 ₂ content can be introduced under pressure onto the positive electrode, the electrode storage structures can be pressed against the leads 9 and the membrane 6 and against one another, so that the contacts are secured. Incidentally, it is achieved that oxygen does not come into contact with the donors. The pressure build-up required for enriching the air with 0 ₂ in an external, known pressure change machine for N ₂ removal via special coal preparations is used to advantage in the modules described.

In order to achieve a converter system with a higher standard output, as already indicated, depending on the requirements of the system, several of the modules described above are connected in parallel via plug connections both to a common two-, three- or multi-phase busbar and to a common data bus for control purposes switched by the superior intelligent center of the chemoelectric converter system. Depending on the number of parallel modules, it is not necessary for each board to have its own printer system and reservoir; Arrangements are conceivable in which a printer system alternates between several flat boards as modules or circulates in the space between spirally arranged, slightly curved boards. In the latter case, the area of each independent board as a module can be increased in length with the same height in order to increase the specific power per board with the same periphery.

The entirety of the modules is represented by a enclosed container, so that the aforementioned, controlled atmosphere can build up inside. Nitrogen, water vapor and C0 ₂ are in a steady state, whereby oxygen can be added depending on the arrangement. In order to force in particular the supply and diffusion of oxygen into the microporous structures and of C0 ₂ from the structures, a periodic or temporary change in the pressure of the inner atmosphere (as with lung breathing) is advisable. According to the invention, the mean value of the pressure of the internal atmosphere differs only slightly from the pressure of the surrounding atmosphere.

The container contains the bushings required for the operation of the modular chemoelectric converter system for the transfer of liquids and gases, electrical energy and data as well as surfaces cooled from outside for heat transfer to the outside through internal condensation.

Figure 9 shows schematically the principle of inductive power coupling. A pair of electrodes 7, 8 are short-circuited via an inductor 30 and the circuit thus created is switched at high frequency by a transistor 31, in particular a MOSFET. The high frequency can be in the range of 50-70 kHz, for example. The intermediate inductor 30 simultaneously forms a primary winding of a high-frequency transformer, the inductors 30 of a plurality of electrode pairs 7, 8 thus forming the entire primary winding of the high-frequency transformer. The coupling of the individual electrode pairs 7, 8 takes place via the magnetic flux of the transformer core, which is transformed into high-voltage pulses in the secondary winding 32 of the high-frequency transformer.

The invention is not limited to the above performed exemplary embodiments. It is essential for the invention that a chemoelectric converter, which can couple electrical energy from a liquid hydrogen carrier, in particular an aqueous solution of glucose, and oxygen as starting materials either via reaction centers and secondary donors or via reaction centers and secondary acceptors, at least one porous, electron and proton conductive solid is provided, in the volume of which either the reaction centers and the secondary acceptors or the reaction centers and the secondary donors are present as solid compounds.

* * * * *

Claims

claims:

1. Che oelectric converter with electrodes, which can couple electrical energy from a liquid hydrogen carrier and oxygen as starting materials via reaction centers and secondary donors and via reaction centers and secondary acceptors,

characterized,

that two porous, electron and proton-conducting solid bodies (7, 8) are provided as electrodes, the reaction centers in the volume of the first solid body (7)

(RZAl, RZA2) and the secondary acceptors (A) and in the volume of the second solid (8) the reaction centers

(RZDl, RZD2) and the secondary donors (D) are present as solid connections (24) and the first and second solids (7, 8) are in contact with each other through a proton-conducting membrane (6).

Chemoelectric converter according to claim 1, characterized in that the pores of at least one solid (7, 8) act capillary for liquid educts.

3. Chemoelectric converter according to claim 1 or 2, characterized in that the electrodes can additionally store electrical energy.

Chemoelectric converter according to one of the preceding claims, characterized in that as a secondary ac zeptor (A) metal-oxide compounds, especially alkaline Fe (VI) oxide or Mn (IV) oxide, are used.

5. Chemoelectric converter according to one of the preceding claims, characterized in that organic compounds, in particular quinones or flavins, serve as the reaction center (RZA2) for the secondary acceptor (A).

Chemoelectric converter according to one of Claims 1 to 4, characterized in that inorganic cerium compounds serve as the reaction center (RZA2) for the secondary acceptor (A).

7. Chemoelectric converter according to one of the preceding claims, characterized in that the secondary donor (D) are metal-organic compounds, organic compounds or metals, in particular bismuth, lead or iron, or metal oxides, in particular Fe (II) oxides.

Chemoelectric converter according to one of the preceding claims, characterized in that the secondary donors (D) and / or the secondary acceptors (A) can be regenerated chemically via the reaction centers (RZA2, RZD2) and / or by feeding in electrical energy after their use.

9. Chemoelectric converter according to one of the preceding claims, characterized in that at least one solid (7, 8) is formed from particles (22) electro- NEN-conducting matrix and a proton-conducting matrix formed from particles (23), offset to the electron-conducting matrix, and having the reaction centers (RZAl, RZA2) and the secondary acceptors (A) or the reaction centers (RZD1, RZD2) and the secondary donors (D ) are arranged as complexes (24) in the matrices.

10. Chemoelectric converter according to claim 9, characterized in that the particles (22, 23) and the complexes (24) are disordered in the at least one solid (7, 8), with spaces between the particles (22, 23) and the Complex (24) form a microscopic capillary system.

11. Chemoelectric converter according to claim 9, characterized in that the particles (22, 23) and the complexes (24) are arranged in the at least one solid (7, 8), the complexes (24) being capsule-shaped, in particular spherical and are surrounded by a permeable layer of particles (22, 23) and the spaces between the capsule-shaped complexes (24) coated with particles (22, 23) form a microscopic capillary system.

12. Chemoelectric converter according to claim 11, characterized in that the particles (22, 23) are also capsule-shaped, in particular spherical, the volume of the capsule-shaped particles (22, 23) being substantially less than that of the capsule-shaped complexes (24). ,

13. Chemoelectric converter according to claim 12, characterized in that the capsule-shaped complexes (24) surrounded by particles (22, 23) are arranged essentially in a grid.

14. Chemoelectric converter according to one of claims 9 to 13, characterized in that the particles (22, 23) and / or the complexes (24) are integrated into the matrix via an elastic binder such that the at least one solid (7, 8) is essentially elastic.

15. Chemoelectric converter according to one of the preceding claims, characterized in that the reaction centers (RZDl, RZD2, RZAl, RZA2) and / or the secondary donors (D) and / or the secondary acceptors (A) are integrated in a gel-like matrix.

16. Chemoelectric converter according to one of the preceding claims, characterized in that at least one of the solid bodies (7, 8) is cuboid.

17. Chemoelectric converter according to one of the preceding claims, characterized in that at least one of the solid bodies (7, 8) is contacted via at least one electrically conductive contact (9).

18. Chemoelectric converter according to claim 17, thereby indicates that the at least one electrically conductive contact is designed as a metallic grid (9).

19. Chemoelectric converter according to claim 18, characterized in that the metallic grid (9) contacts a solid (7, 8) on exactly one of its side surfaces.

20. Chemoelectric converter according to claim 18 or 19, characterized in that nickel, carbon and / or another organic compound is applied to the metallic grid (9).

21. Chemoelectric converter according to claim 17, characterized in that the electrically conductive contact (9) is designed as a graphite contact, graphite grid and / or as a graphite foil.

22. Chemoelectric converter according to one of claims 17 to 21, characterized in that the at least one electrically conductive contact (9) is integrated in the solid body (7, 8).

23. Chemoelectric converter according to one of claims 17 to 22, characterized in that the at least one electrically conductive contact directly contacts the proton-conducting membrane (6).

24. Chemoelectric converter according to one of the preceding claims, characterized in that a spray device (13) is provided, with which the starting materials and / or water can be sprayed onto at least one of the solid bodies (7, 8).

25. Chemoelectric converter according to one of the preceding claims, characterized in that at least one macroscopic, capillary-active conductor track is provided in and / or on at least one solid body (7, 8) for supplying and / or discharging liquid.

26. Chemoelectric converter according to claim 24 and claim 25, characterized in that educts and / or water can be applied to defined points on the conductor track with an injection device.

27. Chemoelectric converter according to one of the preceding claims, characterized in that an aqueous solution of hydrazine N ₂ H ₄ , methanol CH ₃ OH or glucose C ₆ H ₂ 0 ₆ serves as the starting material.

28. Chemoelectric converter according to one of the preceding claims, characterized in that the first and the second solid (7, 8) have different pH values.

29. Chemoelectric converter system, which consists of a liquid hydrogen carrier and oxygen as starting materials via action centers and secondary donors and can couple electrical energy via reaction centers and secondary acceptors,

characterized,

that at least one chemoelectric converter is provided according to one of the preceding claims, its electrodes designed as porous, electron and proton-conducting solid bodies (7, 8) being in contact with one another via a proton-conducting layer (5, 15) and the proton-conducting membrane (6) is arranged between the proton-conducting layer (5, 15) and the solid bodies (7, 8).

30. Chemoelectric converter system according to claim 29, characterized in that the electrodes (7, 8) on their side facing away from the proton-conducting layer (5, 15) are contacted via electrically conductive contacts (9).

31. Chemoelectric converter system according to claim 29 or 30, characterized in that the proton-conducting layer

(5, 15) is flat and the at least two

Electrodes (7, 8) are in contact with the same side of the surface of the proton-conducting layer (5, 15).

32. Chemoelectric converter system according to claim 31, characterized in that the at least two electrodes (7, 8) are arranged next to one another on the proton-conducting layer (5, 15), the electrodes (7, 8) not touching directly.

33. Chemoelectric converter system according to claim 32, characterized in that the proton-conducting membrane (6) is additionally arranged between the electrodes (7, 8).

34. Chemoelectric converter according to one of claims 29 to 33, characterized in that the electrodes (7, 8) of the chemoelectric converter are applied to the proton-conducting layer (5, 15) such that always two electrodes (7, 8) different Doping are arranged side by side.

35. Chemoelectric converter system according to one of claims 29 to 34, characterized in that the proton-conducting layer (15) additionally has either reaction centers (RZA2) and secondary acceptors (A) or reaction centers (RZD2) and secondary donors (D), which act as solid Compounds (24) are present.

36. Chemoelectric converter system according to claim 35, characterized in that the proton-conducting layer (15) is contacted on its side facing away from the electrodes (7, 8) via electrically conductive contacts (9).

37. Chemoelectric converter system according to one of claims 29 to 36, characterized in that a spray device (13) is provided with which educts and / or water can be sprayed onto the electrodes designed as porous solid bodies (7, 8).

38. Chemoelectric converter system according to claim 37, characterized in that the spray device (13) is movable, in particular rotatable.

39. Chemoelectric converter system according to claim 38, characterized in that the spray device (13) is designed as a solid matrix.

40. Chemoelectric converter system according to one of claims 29 to 39, characterized in that at least two electrodes (7, 8) are coupled to one another via an inductance (30).

41. Chemoelectric converter system according to claim 40, characterized in that the coupling of several electrode pairs takes place via a high-frequency transformer, each electrode (7, 8) having its own primary winding (30).

42. Chemoelectric converter system according to one of claims 29 to 41, characterized in that the proton-conducting layer (5, 15) and the electrodes (7, 8) in contact therewith are arranged on a flat or in one plane curved circuit board (17) are.

43. Chemoelectric converter system according to claim 42, characterized in that in addition means for controlling the electrochemical conversion (19) and / or means for switching off Coupling of the electrical power (18) and / or means for feeding electrical energy on the circuit board (17) are provided.

44. Chemoelectric converter according to claim 42 or 43, characterized in that a push-pull flux converter for decoupling electrical energy, in particular for transforming a low voltage, is arranged on the circuit board (18).

45. Chemoelectric converter system according to one of claims 42 to 44, characterized in that the circuit board (17) consists of several layers (17.1 to 17.4) and the additional means (18, 19) at least partially between the layers (17.1 to 17.4) Circuit board (17) are arranged.

46. Chemoelectric converter system according to one of claims 42 to 45, characterized in that electrodes (7, 8) are arranged on both sides of the circuit board (17), and the additional means (18, 19) are located in between.

47. Chemoelectric converter system according to one of claims 42 to 46, characterized in that a plurality of circuit boards (17) are arranged in a circle and / or in a spiral.

48. Chemoelectric converter system according to one of claims 42 to 47, characterized in that a plurality of circuit boards (17) can be sprayed with starting materials and / or water with a single spraying device (13).

49. Chemoelectric converter system according to one of claims 29 to 48, characterized in that an ultrasound source is provided with which at least parts of the chemoelectric converter system (7, 8, 15) can be set in high-frequency mechanical vibrations.

50. Chemoelectric converter system according to one of claims 29 to 49, characterized in that a container is provided with which at least part of the chemoelectric converter system, in particular the porous solids (7, 8, 15) and / or circuit boards (17) with chemoelectric Transducers, can be locked pressure-tight against the environment.

51. Chemoelectric converter system according to claim 50, characterized in that an atmosphere in the flow equilibrium of nitrogen, water vapor and C0 ₂ can be maintained in the container, wherein oxygen can be added.

52. Chemoelectric converter system according to claim 50 or 51, characterized in that the pressure in the container can be changed periodically and / or at fixed times.

53. Chemoelectric converter system according to one of claims 50 to 52, characterized in that the container can be cooled.

5. Chemoelectric converter according to one of claims 42 to

53, characterized in that at least two boards

(17) with chemoelectric converters via at least one electrical derivative, in particular via three electrical ones

Derivatives to be connected.

55. Chemoelectric converter system which can couple electrical energy from a liquid hydrogen carrier and oxygen as starting materials via reaction centers and secondary donors and via reaction centers and secondary acceptors,

characterized,

that at least one chemoelectric converter is provided according to one of claims 1 to 27, wherein its proton-conducting membrane (6) is arranged between the electrodes designed as porous, electron and proton-conducting solid bodies (7, 8) and the electrodes are advantageously each on their outer sides Contacts (9) are contacted.

56. Chemoelectric converter system according to claim 55, characterized in that the electrodes (7, 8) contacted with the contacts (9) are arranged between two boards (29) and the boards can be arranged vertically.

57. Chemoelectric converter system according to claim 56, characterized in that the circuit board (29) arranged on the negative electrode (7) has openings (26) for the injection of Has educts.

58. Chemoelectric converter system according to claim 56 or 57, characterized in that between the on the positive electrode (8) arranged board (29) and the positive electrode (8) channels (27) for conducting gases, in particular air, are provided ,

59. Chemoelectric converter system according to one of claims 55 to 58, characterized in that a hydrophobic carbon mat (25) is arranged between the positive electrode (8) and the contacts (9).

60. Process for generating electrical energy using chemoelectric converters which have electrodes and with which electrical energy is coupled out from a liquid hydrogen carrier and oxygen as starting materials via reaction centers and secondary donors and via reaction centers and secondary acceptors,

characterized,

that the starting materials are applied to at least one electrode which is designed as a porous, electron and proton-conducting solid (7, 8), in the volume of which the reaction centers (RZAl, RZA2) and the secondary acceptors (A) or the reaction centers (RZD1, RZD2) and the secondary donors (D) are present as solid compounds.

61. The method according to claim 60, characterized in that the starting materials are sprayed onto the solids (7, 8, 14) using a spray device (13), in particular a movable spray head.

62. The method according to claim 60 or 61, characterized in that the educts are transported capillary in the porous solid (7, 8, 14).

63. Method for operating a chemoelectric converter system according to one of claims 29 to 59, characterized in that the chemoelectric converter system is operated in one of the following four operating states:

a. Operation at standard power in a state in steady state, in which the delivery of electrical energy via secondary donors D and secondary acceptors A is proportional to the supply of the starting materials and thus their chemical regeneration, b. Operation with a greatly increased, short-term output of electrical power as a permissible overload compared to the standard power, in which (compared to the requirements of the operating state a) excess donors D and secondary acceptors A are consumed without immediate chemical regeneration, c. Operation with greatly increased short-term absorption of electrical energy from an external source for the direct electrical regeneration of used secondary donors and secondary acceptors, equivalent to the electrical charging of the internal storage in parallel with the chemical regeneration, ie. Operation at low load with the secondary used Donors and secondary acceptors of the chemoelectric converter system are regenerated electrically internally, the used secondary donors and secondary acceptors of some electrodes being regenerated by the secondary donors and secondary acceptors of other electrodes which are operated in a steady state according to operating state a).

64. Method for operating a chemoelectric converter system according to one of claims 29 to 59, characterized in that the low voltage generated by the chemoelectric converter system is transformed up with a push-pull flux converter to technically usual voltages, in particular 110V, 220V or 380V.

65. The method according to claim 64, characterized in that the voltage is converted into two-phase or multi-phase alternating currents of adjustable frequency.

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