Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/80—Constructional details
  • H10N10/81—Structural details of the junction
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/80—Constructional details
  • H10N10/81—Structural details of the junction
  • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
  • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
  • H10N10/80—Constructional details
  • H10N10/82—Connection of interconnections
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
  • D06F58/00—Domestic laundry dryers
  • D06F58/20—General details of domestic laundry dryers 
  • D06F58/206—Heat pump arrangements
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49117—Conductor or circuit manufacturing
  • Y10T29/49204—Contact or terminal manufacturing
  • Y10T29/49206—Contact or terminal manufacturing by powder metallurgy
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49117—Conductor or circuit manufacturing
  • Y10T29/49204—Contact or terminal manufacturing
  • Y10T29/49208—Contact or terminal manufacturing by assembling plural parts
  • Y10T29/4921—Contact or terminal manufacturing by assembling plural parts with bonding
  • Y10T29/49211—Contact or terminal manufacturing by assembling plural parts with bonding of fused material
  • Y10T29/49213—Metal
  • Y10T29/49215—Metal by impregnating a porous mass

Definitions

• thermoelectric modules Use of porous metal materials as contacting in thermoelectric modules
• thermoelectric modules which are suitable for application to non-planar, solid heat transfer surfaces.
• Thermoelectric generators and Peltier devices as such have long been known, p-type and n-type doped semiconductors, heated on one side and cooled on the other, carry electrical charges through an external circuit, electrical work being done to a load in the circuit can be performed.
• the achieved conversion efficiency of heat into electrical energy is thermodynamically limited by the Carnot efficiency.
• an efficiency of (1000 - 400): 1000 60% is possible.
• efficiencies up to 10% are achieved.
• Such a Peltier arrangement operates as a heat pump and is therefore suitable for cooling equipment parts, vehicles or buildings.
• the heating via the Peltier principle is cheaper than a conventional heating, because more and more heat is transported than the supplied energy equivalent corresponds.
• thermoelectric generators are used in space probes for generating direct currents, for cathodic corrosion protection of pipelines, for powering light and radio buoys, for operating radios and televisions.
• the advantages of the thermoelectric generators lie in their extreme reliability. So they work regardless of atmospheric conditions such as humidity; there is no fault-susceptible mass transfer, but only a charge transport; The fuel is burned continuously - even without catalytic free flame -, whereby only small amounts of CO, NO x and unburned fuel are released; It can be used any fuel from hydrogen to natural gas, gasoline, kerosene, diesel fuel to biologically produced fuels such as rapeseed oil methyl ester.
• thermoelectric energy conversion fits extremely flexibly into future needs such as hydrogen economy or energy production from renewable energies.
• a thermoelectric module consists of p- and n-legs that are electrically connected in series and thermally in parallel.
• FIG. 1 shows such a module.
• the classic structure consists of two ceramic plates, between which the individual legs are applied alternately. In each case two legs are contacted electrically conductive over the end faces.
• thermoelectric components An essential element of thermoelectric components is the contacting.
• the contacting establishes the physical connection between the material in the "heart" of the component (which is responsible for the desired thermoelectric effect of the component) and the "outside world".
• the structure of such a contact in detail is shown schematically in Fig. 2.
• thermoelectric material 1 within the component provides the actual effect of the component. This is a thermoelectric leg.
• the material 1 is flowed through by an electric current and a heat flow in order to fulfill its purpose in the overall structure.
• the material 1 is connected on at least two sides via the contacts 4 and 5 to the Zulei- lines 6 and 7 respectively.
• the layers 2 and 3 are intended to symbolize one or more intermediate layers which may be necessary (barrier material, solder, adhesion promoter or the like) between the material 1 and the contacts 4 and 5.
• the layers 2/3, 4/5 may or may not always be present. Their use depends on the used TE material and the respective application.
• a ceramic for example, oxides or nitrides such as Al 2 0 3 , Si0 2 or AIN.
• This typical construction has a number of disadvantages.
• the ceramic and the contacts have only limited mechanical load. Mechanical and / or thermal stresses can easily lead to cracks or breakage of the contact making the entire module unusable.
• thermoelectric module the classical structure is also limited in terms of an application since only planar surfaces can always be connected to the thermoelectric module. A close connection between the module surface and the heat source / heat sink is essential to ensure sufficient heat flow.
• Non-planar surfaces such as a round waste heat pipe, are inaccessible to direct contact with the classical module, or require a corresponding straightened heat exchanger structure to provide a transition from the non-planar surface to the planar module.
• the contacting in the thermoelectric modules is usually rigid.
• Mat. Res. Soc. Symp. Proc. Vol. 234, 1991, pages 167 to 177 Bleitellurid application concepts are described.
• thermoelectric converter which contains in various compartments n- and p-type thermoelectric materials. each Material in each compartment is thermally bonded to a substrate with a thermally conductive metal fiber pad.
• the object of the present invention is the provision of thermoelectric modules that can be flexibly adapted to non-planar heat transfer surfaces and react flexibly to a thermal and mechanical load.
• the contacting should ensure a good thermal connection of the thermoelectric material to the electrically insulated substrate.
• the object is achieved by a thermoelectric module of p-type and n-type thermoelectric material legs, which are mutually connected by electrically conductive contacts, wherein at least a portion of the electrically conductive contacts on the cold and / or the warm side of the thermoelectric module between or embedded in the thermoelectric material limbs is constructed of porous metal materials.
• thermoelectric material limbs have points of flexibility which permit bending and slight displacement of the thermoelectric material limbs against one another and compression and relaxation.
• the term "flexibility location” describes a location in the course of the electrical contact that permits bending or displacement of the contact associated with the p-leg and the n-leg, and that the two material legs should be slightly displaceable and compressible. describes a displacement or compression by a maximum of 20%, more preferably not more than 10% of the distance between the respective p- and n-type, thermoelectric material legs or the leg height. The possibility of bending ensures that the contacting does not break off any of the material legs when the thermoelectric module is adapted to a non-planar surface or is stressed by thermal expansion and / or mechanical stress.
• the porous metal materials may have any suitable shape, the porosity ensuring sufficient mechanical flexibility of the metal materials.
• porous metal materials it is possible according to the invention to use, for example, metal foams, metal nonwovens, metal mesh or metal knitted fabrics.
• metal foam describes electrically conductive contacts made of metal, wherein the metal has a certain porosity, ie contains cavities which are delimited by webs from one another a liquid metal and solidification of the foam restricted.
• the metal foam can be removed by Any suitable method can be produced which lead to the formation of a porous structure.
• the metal foam is designed so that a certain flexibility, displaceability and compressibility of the contacts is given.
• the porosity can also increase the contact surface.
• Metal nonwovens, metal mesh or metal knitted fabric can be produced, for example, from nanowires or nanotubes by electrospinning. Suitable electrospinning methods for producing very thin metal wires are described, for example, in EP-B-1 969 166 or WO 2007/077065.
• the wires used for the production preferably have a diameter of less than 1 mm, more preferably less than 0.5 mm, in particular less than 0.1 mm. Electrospinning may, under suitable conditions, result in crosslinking of the spun fibers or in the formation of porous fiber structures. It is also possible to subsequently obtain from the produced fibers metal fleeces, metal mesh or knitted metal by appropriate post-treatment and processing. In particular, there are interwoven, forbidden or crosslinked fibers.
• the preparation of the metal nonwovens, metal mesh or Metallgewirke can also be done by foaming, rolling or pressing or twisting of the fibers. Typically, electrospinning is accomplished by spinning metal salt solutions and subsequent reduction.
• porous metal materials used according to the invention are preferably metal foams, metal nonwovens, metal mesh or metal knitted fabrics.
• the bending should preferably be possible at an angle of at most 45 °, particularly preferably at most 20 °, without the contacting of the thermoelectric material legs breaking off.
• the invention also relates to the use of porous metal materials for electrically conductive contacting of thermoelectric material legs or for thermal contacting of thermoelectric material legs with non-electrically conductive substrates.
• the porous metal material preferably metal foam, according to the invention preferably 99 to 20%, particularly preferably 99 to 50%, of the macroscopic volume is formed by metal.
• the remaining volume fraction is attributable to the pores.
• the porosity in the metal material is preferably 1 to 80%, more preferably 1 to 50%.
• the metal foam may be closed or open pores. There may also be a mixture of closed and open pores. Open pores are interconnected.
• the porosity can be determined, for example, by mercury porosimetry, in particular for open-cell metal materials such as metal foams. Otherwise, the determination of the porosity can also be made by means of a density measurement, in which the density of the metal material is compared with the density of the compact metal.
• the porosity, the pore size distribution and the proportion of through channels can be adjusted according to the practical requirements.
• the porosity should be sufficiently high, so that a good mechanical flexibility of the metal (foam) contact is given. However, the porosity should not be too high to ensure good electrical or thermal conductivity through the metal material.
• the suitable porosity can be determined by simple experiments.
• the pore diameter can z. B. be adjusted by the production of the metal foam.
• the metal foam can be produced starting from a granulate, powder or compact of a metal powder.
• the mean pore diameter here is smaller by a factor of 15 to 40, in particular 20 to 30, than the average particle diameter.
• the granules, powder or Kompaktat is sintered to the metal foam.
• a method for producing the metal foam is characterized by subjecting a metal powder to a shape in which the particles of the powder are bonded so as to form the porous structure.
• the powder can be processed for example by compression, optionally in conjunction with a heat treatment, or by a sintering process or by a foam-forming process.
• the powder When processed by compression, the powder is in a specific particle size distribution which ensures the desired porosity. Preferably, the average particle diameter for this application is 20 to 30 times the desired mean pore diameter.
• the powder is pressed into a mold suitable for the contact or produced in any desired geometry, which can then be cut into the desired shape.
• the pressing can be carried out, for example, as cold pressing or as hot pressing.
• the pressing process can be followed by a sintering process.
• the metal powders are first made into the desired shape of the molded article and then bonded together by sintering, whereby the desired molded article is obtained.
• a foaming process can be carried out in any suitable manner, for example, an inert gas is blown into a melt of the metal so as to result in a porous structure. The use of other propellants is possible. Foaming can also be done by vigorously beating, shaking, splashing or stirring the melt of the metal.
• the metal powder into a polymeric binder, to subject the resulting thermoplastic molding composition to a shaping, to remove the binder and to sinter the resulting green body. It is also possible to coat the metal powder with a polymeric binder and subjected to molding by compression, optionally with heat treatment. Further suitable methods for the formation of metal foams are known to the person skilled in the art.
• the surface finish of the metal foams is not limited according to the invention.
• a rough foam surface leads to a dense toothing and increased contact surface between TE material and bonding material in the thermoelectric module.
• the flexibility point is from the porous metal material, for. B. metal foam and may also have any suitable shape, provided that the function described above is fulfilled.
• the point of flexibility is in the form of at least one metal material strand, which may also be present in a U-shaped, V-shaped or rectangular bulge of the respective contact to increase the flexibility.
• the flexibility point may preferably be in the form of a wave, spiral or in sawtooth shape of the respective contact, provided that, in comparison with a metal material strand z. B. in cuboid shape, again increased flexibility or flexibility of the contact is necessary.
• thermoelectric module according to the invention is particularly advantageous if the thermoelectric material legs are not arranged planar or if the application makes an increased contact pressure on the thermoelectric module necessary for optimal function.
• inventive design of the thermoelectric material leg allows the spiral winding of the thermoelectric module on a pipe of any cross section. These can be rectangular, round, oval or other cross sections.
• thermoelectric module adaptation of the thermoelectric module to any three-dimensional surfaces of the heat exchange material is possible.
• Non-planar heat sources or heat sinks are thus accessible to a close connection with the thermoelectric module.
• thermoelectric modules for the conversion of car waste heat or exhaust waste heat requires flexible and vibration-resistant thermoelectric modules.
• thermoelectric modules Due to the windability of the thermoelectric modules, you can wrap a strand of alternating p- and n-legs without breaking the contacts around a round or oval tube. This allows a cost-effective, quick and easy integration of thermoelectric components, for example in the exhaust system of an automobile, in a motor vehicle catalytic converter, in a heating device, etc.
• thermoelectric module made of p- and n-conducting thermoelectric material legs which are interconnected via electrically conductive contacts and thermally contacted with electrically insulated substrates, wherein at least a portion of the thermally conductive contacts on the cold and / or or the warm side of the thermoelectric module between the electrically contacted thermoelectric material legs and an electrically insulated substrate made of porous metal materials.
• thermoelectric materials and the electrically nonconductive substrates can thus also be achieved according to the invention.
• the porous metal material for.
• the heat conduction between the substrate and thermoelectric material is thus made possible, see also the illustration in Figure 1, which shows the substrate layers above and below, between which the thermoelectric materials are embedded with their contact.
• the thermal connection to the substrates can be produced according to the invention via the porous metal material.
• the metal material allows compensation of thermal stresses in the material, as they are obtained by heating or cooling of the thermoelectric element.
• the porous metal material for.
• the metal foam preferably such a structural design that a certain compressibility, z.
• the foam results, wherein after the elimination of an external pressure z. B. the foam decompressed again and thus ensures a continuous good thermal contact of the thermoelectric leg with the substrate.
• metal foam leads in comparison to, for example, the use of copper fleece to a significantly improved electrical conductivity and thermal conductivity.
• a foam there is a continuous metal compound, but not in a nonwoven.
• the application properties of the metal foam are again clearly superior to the application properties of a metal fleece.
• the porous metal material for.
• the metal foam can be made according to the invention of all thermally and electrically conductive metals.
• the porous metal material contains copper, silver, aluminum, iron, nickel, molybdenum, titanium, chromium, cobalt or mixtures thereof.
• the porous metal material gives the electrically conductive contacts, it may also be constructed of the materials listed below.
• the electrically conductive contacts may be constructed of any suitable materials. Typically, they are constructed of metals or metal alloys, such as iron, nickel, aluminum, platinum or other metals. It is important to ensure a sufficient temperature resistance of the electrical contacts, especially when the thermoelectric modules are often exposed to high temperatures above 500 ° C.
• thermoelectric material legs are embedded in a solid, non-electrically conductive matrix material.
• thermoelectric module In order to stably hold the thermoelectric material in a wrapped form, it is advisable to use a matrix or a grid to stabilize the thermoelectric module.
• materials with low thermal conductivity and lack of electrical conductivity are used.
• suitable materials are aerogels, ceramics, particularly foamed ceramics, glass wool, Glasses, glass ceramic mixtures, electrically insulated metal mesh, mica organic polymers (polyimide, polystyrene, polyester, polyether, etc.) or a combination of these materials.
• suitable materials are aerogels, ceramics, particularly foamed ceramics, glass wool, Glasses, glass ceramic mixtures, electrically insulated metal mesh, mica organic polymers (polyimide, polystyrene, polyester, polyether, etc.) or a combination of these materials.
• mica organic polymers polyimide, polystyrene, polyester, polyether, etc.
• synthetic carbon-based polymers such as polyurethanes, polystyrene, polycarbonate, polypropylene
• the matrix materials can be used as a powder, as a shaped body, as a suspension, as a paste, as a foam or as a glass.
• the matrix By tempering or (UV) irradiation, the matrix can be cured, as well as by evaporation of the solvents or by crosslinking of the materials used.
• the matrix or the grid can be adapted to the appropriate application prior to use by molding or poured, sprayed, sprayed or applied in the application.
• the electrical contacts can be connected in any way with the thermoelectric material legs. They can, for example, be applied in advance to the thermoelectric legs, for example by laying on, pressing on, pressing, sintering, hot pressing, soldering on, welding on before installation in a thermoelectric module, and they can also be applied to the electrically insulating substrate. In addition, it is possible to press, solder or weld together in a one-step process together with the electrically insulated substrates and the thermoelectric legs.
• a stable connection with an increased contact surface can be produced as follows: First of all, the electrical contact is made in a mold which can be constructed, for example, from graphite, vitrified graphite, high temperature stable metal alloys, quartz, boron nitride, ceramic or mica. Then, a separator wall is inserted perpendicular to the contact, and p-type and n-type thermoelectric materials are inserted into the two resulting chambers.
• the thermoelectric material can be inserted directly as a finished leg or can be cast as powder or melt. When using powder, the thermoelectric material should be brought to melting temperature together with the electrical contact in the mold for a short time, preferably 1 minute to 1 hour.
• thermoelectric legs are completed by a sintering step.
• a sintering step in the mold is also advantageous. Preference is given to working at sintering temperatures of 100 to 500 ° C below the melting point of the thermoelectric material and with sintering times of 0.5 to 72 hours, more preferably 3 to 24 hours.
• the separator wall between the p and n legs can either be an organic compound, for example based on polymer, which is burned out during sintering, or a temperature-stable material which is electrically insulating and is retained in the module. high-temperature temperature-stable materials such as oxidic materials, nitrides, borides and mica are known in the art.
• the production also makes it possible for the legs to be contacted on both sides when the electrical / thermal contact is inserted into the lower part of the mold and contacted offset via the thermoelectric leg, so that an electrical series connection is obtained.
• one or more protective layers are first applied to the thermoelectric materials, and then the contacts are made of porous metal materials.
• the metal foam contacts can either serve as flexible electrical contacts or only as flexible heat conductor bridges.
• the metal foam contacts can be applied as a foam or as a metal bridge, which is foamed in situ. In situ production of the foam can simplify the application of the contacts to the thermocouples, since no further connection steps are necessary for direct foaming.
• the electrically conductive contacts made of porous metal materials, for. As metal foam, be constructed. This means that not all contacts must be constructed of metal foam. If, for example, a band-shaped thermoelectric generator is to be applied to a tube with a cuboidal cross-section by wrapping, flexible contacts are necessary only at the corners of the cuboid.
• at least half, more preferably at least 85%, of the electrically conductive contacts are made of porous metal materials, e.g. B. metal foam, constructed.
• all electrically conductive contacts are constructed of metal foam.
• thermoelectric module it is possible to distinguish between a contacting of the cold and the warm side of the thermoelectric module.
• a contacting of the cold and the warm side of the thermoelectric module For example, only the contacts on the cold side or on the warm side of the thermoelectric module of porous metal materials, for. As metal foam, be constructed. Different materials can also be used for the module cold side and module hot side. For use on the module cold side z. As any metal foam with a good thermal conductivity and, if desired, also a good electrical conductivity can be used. For use on the module hot side, a good temperature resistance of the contact material is necessary.
• thermoelectrically contacted legs can be contacted in any suitable manner with the heat transfer medium.
• a winding of the thermoelectric module can for example be done externally, ie around an electrically insulated tube, as well as internally, ie on an inner carrier mounted in the tube.
• the inner support may be an electrically insulating coating.
• the thermoelectric module (thermoelectric leg, electrically contacted in series) can be encapsulated in an electrically insulated metal, ceramic, glass or mixtures thereof and then introduced directly into a heat or cold medium.
• thermoelectric modules for waste heat recovery on the non-mirrored side of the parabolic troughs in the photovoltaic.
• the invention also relates to the use of the thermoelectric modules for application to non-planar, solid heat transfer surfaces and exhaust pipes with thermoelectric modules wound on them in a spiral manner, as described above.
• the invention also relates to a method for producing thermoelectric modules, as described above, by applying the thermally or electrically conductive contacts of porous metal materials to the thermoelectric material limbs by pressing, soldering, welding or foaming.
• the invention also relates to a method for producing thermoelectric modules as described above, by pressing a powder of the thermoelectric material on the contacts of porous metal materials and subsequent sintering.
• the advantages for the use of metal foam or metal fleece are: a flexible contact is made possible; the thermal stress due to thermal expansion is reduced; through the porous surface at the contacting boundary a higher contact area is obtained; a better contact or connection between electrical contact and thermoelectric leg is achieved by crosslinking or penetration of the thermoelectric powder or the thermoelectric melt with the surface / in the surface of the metal fleece or metal foam; Due to the porous structure of the contacts, mechanical stresses in the contacting boundary are reduced.
• thermoelectric generators or Peltier arrangements, which are known per se to the person skilled in the art and are described, for example, in WO 98/44562, US Pat. No. 5,448,109, EP-A-1 102 334 or US Pat. No. 5,439,528.
• the present invention also relates to the use of a thermoelectric generator according to the invention or a Peltier arrangement according to the invention.
• the present invention relates to a heat pump, a refrigerator, a (laundry) dryer or a generator for using heat sources, comprising at least one thermoelectric generator according to the invention or a Peltier arrangement according to the invention, over the one or more in the (laundry) dryer to be dried Material is heated directly or indirectly and is cooled directly or indirectly over the or the resulting during drying water or solvent vapor.
• the dryer is a clothes dryer and the material to be dried is laundry.

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