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
  • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
  • H10N10/13—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 heat-exchanging means at the junction
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N5/00—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy
  • F01N5/02—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat
  • F01N5/025—Exhaust or silencing apparatus combined or associated with devices profiting by exhaust energy the devices using heat the device being thermoelectric generators
• • 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
  • H10N10/01—Manufacture or treatment
• • 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
  • H10N10/81—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
  • H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2510/00—Surface coverings
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2510/00—Surface coverings
  • F01N2510/02—Surface coverings for thermal insulation
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2510/00—Surface coverings
  • F01N2510/08—Surface coverings for corrosion prevention
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2530/00—Selection of materials for tubes, chambers or housings
  • F01N2530/02—Corrosion resistive metals
  • F01N2530/04—Steel alloys, e.g. stainless steel
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
  • F01N2530/00—Selection of materials for tubes, chambers or housings
  • F01N2530/06—Aluminium or alloys thereof
• • 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
  • H10N10/85—Thermoelectric active materials
  • H10N10/851—Thermoelectric active materials comprising inorganic compositions
  • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/10—Internal combustion engine [ICE] based vehicles
  • Y02T10/12—Improving ICE efficiencies

Definitions

• the invention relates to a thermoelectric module for thermoelectric power generation, in particular in an exhaust system of an internal combustion engine. Furthermore, the invention relates to a production method for such a thermoelectric module.
• thermoelectric modules for converting heat energy into electrical energy consist of a series connection of several thermocouples. Each of these thermocouples be available from at least one p-type device (leg), an n-type device (leg) and one of these two components electrically connecting, usually made of metal con tact bridge ( Figures 4A, 4b). Connected in series are a plurality of thermocouples by elec trically connecting the p-type device of a thermocouple with the n-type device of the next thermocouple, etc. Such an interconnection of thermocouples is referred to as a thermoelectric module. By generating a heat flow through the p-type and n-type device, from one contacting plane to the other contacting plane, an electrical voltage is generated by means of the Seebeck effect.
• Typical heat sources for such a process are e.g. Hot gas flows, as prevail in exhaust systems of internal combustion engines. But any other source of heat is conceivable.
• metallic heat exchanger systems are usually used. In order to avoid a short circuit between heat exchangers and contact bridges, an electrical insulation of the contact bridges towards the cherriestau shear is absolutely necessary.
• FIG. 1 shows a perspective view of a conventional thermoelectric module 1 for conversion of thermal into electrical energy by means of Seebeck effect, wherein the thermoelectrically sensitive module 1 according to the DCB connection technology (DCB: Direct Copper Bond) is made.
• DCB Direct Copper Bond
• the known thermoelectric module 1 on two parallel ceramic plates 2, which are arranged on the hot side or cold side.
• the lower ceramic plate 2 is cold angeord net and carries numerous contact surfaces 3 made of copper, the individual contact surfaces 3 each a p-type leg 4 and an n-type leg 5 electrically contact to the individual Ther moetti electrically in To switch row.
• the connection between the p-type legs 4 and the n-type legs 5 and the associated contact surfaces 3 takes place here by sintered, glued or soldered connections. 6
• thermoelectric module 1 is limited in terms of its size and the lateral extent.
• the invention is therefore an object of the invention to provide a correspondingly improved thermoelectric cal module.
• thermoelectric module initially has a base plate in accordance with the prior art. It should be mentioned that the base plate and then also the other layers of the thermoelectric module are preferably flat. However, theoretically, it is also possible that the base plate and the other layers are bent.
• thermoelectric module according to the invention in accordance with the prior art includes a plurality of thermocouples each having two legs, wherein the Thermocouples are electrically connected in series and mounted on the base plate.
• thermocouples each having two legs, wherein the Thermocouples are electrically connected in series and mounted on the base plate.
• the thermocouples are each connected in series in groups, wherein the groups are then connected in parallel.
• the base plate in the thermoelectric module according to the invention is not made of a ceramic material but of a metallic material (eg copper, aluminum, stainless steel).
• thermoelectric module can be produced more cheaply.
• thermoelectric module of the invention is also mechanically much less sensitive than a base plate made of ceramic.
• the metallic base plate is disposed on the cold side of the thermoelectric module, i. H. on the side of the thermoelectric module, which is exposed to a lower temperature during operation than the opposite hot side.
• thermoelectric module has a cold-side insulating layer, which is disposed between the metallic base plate on the one hand and the thermocouples on the other hand and serves to electrically isolie the metallic base plate relative to the thermocouples ren and to fix the thermocouples on the base plate.
• This insulating layer consists of an organic adhesive layer.
• the insulating layer may be at least partially filled with ceramic material.
• thermoelectric module according to the invention preferably comprises a plurality of electrically conductive contact surfaces on the contact-side insulating layer.
• the individual contact surfaces are each used for contacting two legs of different thermocouples elements for an electrical series connection of the thermocouples in the Ther moelekthariator module according to the invention.
• thermoelectric module according to the invention preferably has a cold-side corro sion protective layer, which covers the contact surfaces on the insulating layer and protects against corrosion.
• this corrosion protection layer may consist of a nickel-gold layer, as is known per se from the prior art.
• an electrical insulating layer (eg ceramic layer) is provided on the warm side in order to insulate the thermocouples from the electrically conductive heat conductor plate.
• a further intermediate layer eg graphite foil
• graphite foil can be arranged to compensate for surface irregularities.
• thermocouples a plurality of electrically conductive contact surfaces is provided on the hot side to contact two legs of different thermocouples for an electrical series connection of the thermocouples.
• the hot-side contact surfaces can hereby also - as on the cold side - by a Kor rosionsschutz für (eg., Nickel-gold layer) are covered in order to avoid corrosion on the justifyflä chen.
• Kor rosionsschutz für eg., Nickel-gold layer
• this second aspect of the invention provides that the contacting of the thermocouples takes place on the hot side on the one hand and on the cold side on the other hand at different joining temperatures.
• the connection between the contact surfaces on the one hand and the legs of the thermocouples on the other hand preferably on the hot side by a higher Fügetem temperature than on the cold side, for example by a Flartlötharm at a temperature of for example 900 ° C.
• thermoelectric module On the cold side, the connection between the contact surfaces and the legs of the thermocouples, however, at a lower temperature, for example by soldering at a temperature of, for example, 300 ° C.
• the Flartlöttheticen on the hot side of the thermoelectric module are useful when the thermoelectric module at a temperature in an exhaust line of an internal combustion engine on its warm side temperatures of up to 600 ° C must withstand. This requires a braze (eg, a silver-based braze), whereas a braze joint will not stand up to these relatively high temperatures would.
• braze eg, a silver-based braze
• thermocouples are therefore preferably first preassembled, wherein in the framework of the pre-assembly a braze joint is produced. Subsequently, the premonten, brazed thermocouples are then mounted on the base plate and contacted by a soft solder connection. In this Weichlötthetic the entire thermoelectric module must be heated to only about 300 ° C, which is much less than a braze joint. This reduces the mechanical stresses in the thermoelectric module. In addition, these temperature reductions during the manufac turing process, the manufacturing costs are reduced. Furthermore, much larger modules are possible, please include. Finally, the leg pairs can also be used for different types of modules, which allows standardization.
• the invention also includes a third inven tion aspect, which is described below.
• thermocouples consist of different thermoelectric materials, which are set in the various thermocouples to different operating temperatures out.
• thermoelectric module in operation on the hot side is exposed to a temperature gradient parallel to the hot side so that the temperature on the hot side of the thermoelectric module decreases from a high temperature region to a low temperature region.
• the thermocouples in the high temperature range are then preferably designed for a higher operating temperature than in the low temperature range.
• thermocouples in the high temperature region may be at least partially high-temperature stable semi-Heusler alloys, skutterudite, silicide or lead telluride, while the thermocouples in the low-temperature range consist at least partially of bismuth telluride.
• thermoelectric module allows a very large number of thermocouples in the thermoelectric module, wherein the number of thermocouples may be greater than 100, 200, 400 or even greater than 600, for example.
• the individual contact surfaces for the thermocouples may for example have a length of 2 mm - 10 mm, a width of 0.5 mm - 4 mm and a thickness of 0.1 mm - 1 mm.
• the individual legs of the thermocouples may each have a thickness of 0.3 mm - 3 mm and a length of 0.3 mm - 3 mm.
• the base plate of the thermoelectric module may, for example, have an edge length of at least 2 cm, 4 cm or even 15 cm.
• the insulating layer on the metallic base plate may have a layer thickness of, for example, 5 ⁇ m-100 ⁇ m.
• the metallic material of the metallic base plate may be, for example, copper, a copper alloy, aluminum, an aluminum alloy or stainless steel, to name just a few examples. However, the invention is not limited to these examples in terms of the metallic material of the metallic base plate.
• thermoelectric module not only claims protection for the above-described thermoelectric module as a single component. Rather, the invention also claims protection for a complete exhaust system of an internal combustion engine with such a thermoelectric module for generating electricity from the waste heat of the hot gas stream.
• thermoelectric module according to the invention is arranged.
• thermoelectric module thermoelectric module
• Figure 1 is a perspective view of a conventional thermoelectric module for
• FIG. 2 shows a perspective view of a section of a thermoelectric module according to the invention
• thermocouple 3 shows a sectional view through a thermocouple of the thermoelectric module according to the invention to illustrate the layer structure
• FIG. 4A shows a side view of a single thermocouple of the ther moelectric module according to the invention
• FIG. 4B shows a plan view of the thermocouple according to FIG. 4A
• FIG. 5 shows a plan view of a metallic base plate of the thermoelectric module according to the invention
• FIG. 6 shows a flow chart for explaining the production method according to the invention, as well as FIG
• Figure 7 is a schematic representation of a thermocouple for powering an electrical load.
• thermoelectric rule rule module 7 according to the invention, which can be used for example for thermoelectric power generation by the thermoelectric module 7 is exposed to a hot exhaust gas stream of an internal combustion engine (eg gasoline engine, diesel engine).
• the thermoelectric module 7 according to the invention initially has a cold-side base plate 8 made of metal (eg copper, aluminum, stainless steel).
• the metallic base plate 8 carries an electrically insulating insulating layer 9 of an organic's adhesive, so that the contact surfaces 10 can be easily adhered to the base plate 8.
• electrically conductive contact surfaces 10 are applied, which in turn are covered by a corrosion protection layer 11 (eg nickel-gold layer) in order to prevent corrosion at the contact surfaces 10.
• a corrosion protection layer 11 eg nickel-gold layer
• the insulating layer 9 prevents a short circuit between the contact surfaces 10 via the electrically conductive base plate 8.
• thermoelectric module 7 the legs 13 of the thermocouples 22 are connected by a solder joint 12 with the cold side contact surfaces 11.
• thermoelectric module 7 Adjacent to the hot side of the thermoelectric module 7 is first a heat meleiterplatte 15, which may for example consist of stainless steel and for thermal coupling to the heat source to be exploited (eg., Hot gas stream) is used.
• This heat conductor plate does not belong to the actual thermoelectric module itself and is only illustrative Darge presents.
• an intermediate layer 16 which may consist of a graphite foil, for example, and has the task of compensating surface irregularities.
• thermoelectric module 7 This is then followed by an insulating layer 17, which consists of ceramic, so that they can withstand the high temperatures occurring on the hot side of the thermoelectric module 7.
• This layer may for example consist of graphite, boron nitride or a metallic solder.
• the insulating layer 17 prevents a short circuit between the contact surfaces 19 via the electrically conductive heat conductor plate 15th
• connection between the legs 13 of the individual thermocouples on the one hand and the hot-side contact surfaces 19 on the other hand takes place here, for example by Hartlötverbindun conditions 21, which can hold the occurring on the hot side of the thermoelectric module 7 high Tempe temperatures.
• FIG. 3 shows a sectional view through a single thermocouple 22.
• the base plate 8 carries a multiplicity of contact surfaces 10, so that the thermoelectric module 7 can correspondingly contain a large number of the thermocouples 22 which are electrically connected in Series are switched.
• thermoelectric module 7 is set from a hot gas flow, which runs in the drawing in the vertical direction from top to bottom. On the cold side of the thermoelectric module 7, however, a cooling water flow in the drawing runs in a horizontal direction from left to right. As a result, the temperature at the hot side of the thermoelectric module 7 is not uniform. Rather, the temperature in a high temperature region 23 is greater than in a subsequent low temperature region 24 on the hot side of the thermoelectric module 7.
• the individual thermocouples 22 are therefore adapted to the locally fluctuating operating temperatures.
• the thermocouples 22 in the high temperature region 23 of semi-Heusler alloys which are extremely high temperature stable.
• the thermocouples 22 in the low temperature region 24 exist against there from Bismuttelluriden, which are optimized for lower temperature ranges.
• thermoelectric rule rule module 7 first the individual thermoelements 22 are produced by connecting the legs 13 to the hot side contact surfaces 19, for example by means of a brazed connection.
• any other joining technology such as sintering, which meets the requirements of electrical conductivity and temperature stability.
• the brazing on the hot side of the thermoelectric rule rule module 7 is advantageous because the thermoelectric module 7 can then be exposed to the hot side very high operating temperatures.
• a step S2 the contact surfaces 10 are glued by the insulating layer 9 on the base plate 8.
• the corrosion protection layer 11 is then applied to the contact surfaces 10.
• thermocouples 22 are then connected to the electrical con tact surfaces 10 on the cold side.
• This connection occurs e.g. by a soft soldering at about 300 ° C. It is important that the joining temperature in this process is lower than the temperature that would be necessary to resist the pre-assembly of the thermocouples.
• soldering significantly lower temperatures occur than in a brazing process on the hot side of the thermoelectric module 7. This has the advantage that the thermoelectric module 7 only needs to be heated to about 300 ° C. As a result, the mechanical stresses occurring in the thermoelectric module 7 during the soldering process are also reduced. Another advantage is the reduction of the manufacturing costs and it is possible grö ßere thermoelectric modules 7.
• the individual pairs of legs can also be used for different types of modules, which enables standardization.
• the intermediate layer 18 is then optionally applied in a step S5 in order to compensate for surface irregularities.
• a step S6 the hot-side insulating layer 17 made of ceramic is then applied.
• the use of ceramic as a material for the insulating layer 17 is important since the warm side very high temperature occur, so that the insulating layer 17 must be correspondingly temperature resistant.
• the intermediate layer 16 is then applied in a step S7 in order to compensate for surface irregularities.
• the interspaces may also be provided with a highly heat-insulating solid, such as e.g. egg nem fiber cement to be filled.
• thermocouple cold and warm side each touching a metallic contact.
• the heat flow dQ / dt from the hot side heat conductor plate 15 to the cold side base plate 8 is in this case the result of a corresponding temperature difference, which generates a corresponding thermal voltage.
• thermocouple materials depending on the local variation of the operating temperature.
• thermoelectric module according to the prior art
• thermocouples 4 p-type legs of the thermocouples
• thermocouples 5 n-type legs of the thermocouples
• thermoelectric module according to the invention

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Measuring Temperature Or Quantity Of Heat (AREA)

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• 2018
  • 2018-03-01 DE DE102018104716.9A patent/DE102018104716B3/de active Active
• 2019
  • 2019-02-26 EP EP19709387.5A patent/EP3729529A1/de not_active Withdrawn
  • 2019-02-26 CN CN201980011134.4A patent/CN111670505A/zh active Pending
  • 2019-02-26 US US16/976,271 patent/US20210057629A1/en not_active Abandoned
  • 2019-02-26 DE DE202019005451.0U patent/DE202019005451U1/de active Active
  • 2019-02-26 WO PCT/EP2019/054652 patent/WO2019166390A1/de unknown
  • 2019-02-26 KR KR1020207027769A patent/KR20200125672A/ko not_active Application Discontinuation
  • 2019-02-26 JP JP2020545671A patent/JP2021515403A/ja active Pending

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