WO2005114755A2 - Tellurures presentant de nouvelles combinaisons de proprietes - Google Patents

Tellurures presentant de nouvelles combinaisons de proprietes Download PDF

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Publication number
WO2005114755A2
WO2005114755A2 PCT/EP2005/005345 EP2005005345W WO2005114755A2 WO 2005114755 A2 WO2005114755 A2 WO 2005114755A2 EP 2005005345 W EP2005005345 W EP 2005005345W WO 2005114755 A2 WO2005114755 A2 WO 2005114755A2
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WO
WIPO (PCT)
Prior art keywords
telluride
thermoelectric
peltier
thermoelectric generator
tellurides
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PCT/EP2005/005345
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German (de)
English (en)
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WO2005114755A3 (fr
Inventor
Hans-Josef Sterzel
Klaus KÜHLING
Original Assignee
Basf Aktiengesellschaft
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Publication of WO2005114755A2 publication Critical patent/WO2005114755A2/fr
Publication of WO2005114755A3 publication Critical patent/WO2005114755A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • 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
    • 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
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • the present invention relates to tellurides as semiconductor material, thermoelectric generators and Peltier arrangements containing them, processes for producing these semiconductor materials, their use in thermoelectric generators or Peltier arrangements and a method for increasing the Seebeck coefficient and / or the electrical conductivity of thermoelectrically active ones tellurides.
  • thermoelectric generators and Peltier arrangements as such have long been known, p- and n-doped semiconductors, which are heated on one side and cooled on the other side, transport electrical charges through an external circuit. These thermoelectric generators can be used to perform electrical work on a consumer in the circuit. Peltier arrangements reverse the previously described thermoelectric process.
  • thermoelectric effects and materials are given e.g. Cronin B. Vining, "ITS Short Course on Thermoelectricity", November 8, 1993, Yokohama, Japan, “1997 Proceedings, Sixteenth International Conference on Thermoelectrics (ICT),” CRC Handbook of Thermoelectrics “, CRC-Press 1995 and” Materials Research Society Symposium Proceedings Volume 545: Thermoelectric Materials 1998 - The next generation materials for small-scale refrigeration and power generation applications ".
  • thermoelectric generators are used in space probes and satellites to generate direct currents, to protect pipelines against cathodic corrosion, to supply lighting and radio buoys for energy, to operate radios and televisions, and as a cooling unit in cool bags.
  • the advantages of thermoelectric generators and Peltier arrangements are their high reliability: They work independently of atmospheric conditions such as air humidity; there is no mass transport susceptible to malfunction, only a charge transport; the fuel is burned continuously - even catalytically without a free flame - which only releases small amounts of carbon monoxide, nitrogen oxides and unburned fuel; any operating materials can be used, from hydrogen to natural gas, petrol, kerosene, diesel fuel to biologically produced fuels such as rapeseed oil methyl ester.
  • the thermoelectric energy conversion adapts extremely flexibly to future needs such as hydrogen economy or energy generation from renewable energies.
  • thermoelectrically active materials are essentially assessed on the basis of their efficiency.
  • Z factor (figure of merit) is characteristic of thermoelectric materials:
  • Thermoelectric materials are preferred which have the lowest possible thermal conductivity, the highest possible electrical conductivity and the highest possible Seebeck coefficient, so that the figure of merit assumes the highest possible value.
  • the dimensionless product Z • T is often given for comparison purposes.
  • Previously known thermoelectric materials have maximum values of Z • T of approximately 1 at an optimal temperature. Beyond this optimal temperature, the values of Z • T are often lower than 1.
  • Materials such as Bi 2 Te 3 or PbTe currently embody the best available technology.
  • thermoelectric materials that have a suitable band gap.
  • thermoelectric materials that have only a small band gap are undesirable because they degenerate or become intrinsic under the selected conditions, with a simultaneous increase in the electrical and thermal conductivity of the material. This increase has a negative impact on the figure of merit.
  • the bandgaps of thermoelectric materials should not be too large, since otherwise the energy required to lift an electron into a conduction band is too large.
  • Bi 2 Te 3 is mainly used at low temperatures in Peltier coolers because it has the most favorable values for Z • T in this temperature range.
  • PbTe is a typical material for generators.
  • thermoelectric generators or pellet arrangements with a telluride as the thermoelectrically active semiconductor material is then characterized in that a substituted semiconductor material is used in which the positively polarized atoms of the crystal lattice of the telluride are partially substituted by silicon and / or germanium.
  • a typical composition of a material in this sense is e.g. B. PbTe ⁇ (Si 2 Te 3 ) o, o ⁇ .
  • “partial” means a degree of substitution with preferably 0.002 to 0.05, particularly preferably 0.003 to 0.02, in particular 0.008 to 0.013, per mole of formula unit telluride.
  • thermoelectric materials with improved thermoelectric properties.
  • the unsubstituted tellurides are generally tellurides known per se.
  • the metal Me carries formally positive charges (positively polarized), which means that the tellurium is negatively polarized.
  • an electron density is transferred from the metal to the tellurium, corresponding to the form ⁇ + ⁇ - Me a Te b .
  • thermoelectric materials with a high degree of efficiency (figure of merit) are obtained.
  • the thermoelectrically active semiconductor material contains lead and / or bismuth atoms as positively polarized atoms which are partially substituted by silicon and / or germanium.
  • This preferably gives the empirical formula Bi 2 Te 3 and / or PbTe for the telluride in unsubstituted form.
  • lead and / or bismuth as positively polarized atoms of the unsubstituted telluride, it is surprising that it is possible to introduce silicon or germanium into the telluride host lattice as positively polarized atoms, since known phase diagrams teach that no binary compounds are formed Bismuth or lead with silicon or germanium exist.
  • the compounds Si 2 Te 3 , GeTe or mixtures are formed as a result of the partial substitution of the positively polarized metal atoms within the crystal lattice of the telluride.
  • the stoichiometry of these compounds does not have to be maintained as such in the thermoelectrically active semiconductor material. However, it turned out to be preferred.
  • effects can also be found if other stoichiometries, for example SiTe or SiTe 2 , are generated in the resulting telluride.
  • a substituted telluride of the general formula (I) results for the semiconductor material of the thermoelectric generator or the Peltier arrangement
  • Me Bi and / or Pb
  • the preferred concentration of the “misfits” produced in the telluride crystal lattice is through
  • Misfit compounds dissolve at least partially in the telluride guest grille.
  • This solubility depends on the composition of the guest grid and cannot be determined in advance. However, it has turned out to be particularly preferred if this
  • the electrical conductivity of the substituted telluride is significantly increased. It is preferably at least 50%, particularly preferably at least 100%, in particular at least 130%, especially at least 150%, of the electrical conductivity of the correspondingly unsubstituted telluride.
  • the present tellurides can be used without further doping. Alternatively, they can also be doped. If the tellurides are doped, the proportion of doping elements is preferably up to 0.1 atom% (10 18-10 19 atoms per cubic centimeter of semiconductor material), particularly preferably up to 0.05 atom%, in particular up to 0.01 Atom-%. Higher carrier concentrations cause disadvantageous recombinations and thus a reduced mobility of the carriers. It is doped with elements that cause an excess or deficit of electrons in the crystal lattice. Suitable doping metals for p-semiconductors are, for example, the following elements: lithium, Sodium, potassium, magnesium, calcium, strontium, barium and aluminum. Suitable doping metals for n-semiconductors are the elements chlorine, bromine and iodine.
  • the conduction type can be converted into the opposite by doping.
  • the present invention also relates to the semiconductor materials (tellurides) described above and to processes for their production.
  • the tellurides according to the invention are generally produced by reacting the individual elements at temperatures above the melting temperature of the resulting tellurides. If all the individual components have melted below the reaction temperature and the reaction temperature is above the melting temperature of the tellurides produced, generally short reaction times of 0.1 to 5 hours, in particular 0.5 to 3, especially 1 to 2, are required. If the reaction temperature is below the melting temperature of the components with the highest melting point, this must be solved by the melt already present, which generally requires increased reaction times of 5 to 120 hours, in particular 10 to 100, especially 60 to 90.
  • the melting is generally carried out under an inert gas atmosphere, preferably an inert gas such as argon.
  • an inert gas such as argon.
  • Si 2 Te 3 is used as a constituent, a preferred embodiment results from the fact that the compound Si 2 Te 3 is prepared in a separate, upstream process step and the reactant in the telluride formation is not separated from silicon and tellurium, but as a finished compound Si 2 Te 3 , which melts at 885 ° C, begins. In this way it can be avoided that the dissolution of the small portions of the silicon melting at 1410 ° C. takes a long time.
  • This procedure is suitable for all tellurides according to the invention in which an individual element has a higher melting point than the other individual elements and / or as the resulting telluride.
  • Another embodiment of the method according to the invention thus results from the implementation of binary telluride precursor compounds of the individual elements, optionally in combination with the remaining individual element.
  • Furnaces are preferably used to melt the individual components
  • Crucible material is inert at the reaction temperatures used. Quartz is preferably used; Graphite is preferably used if none of the components forms carbides at the specified reaction temperatures. For example, graphite is wise in the presence of silicon at temperatures below 1400 ° C as a crucible material, because under these conditions no silicon carbide forms yet.
  • thermodynamically less preferred or metastable phases and element distributions can be obtained.
  • tellurides according to the invention are produced by a sintering process, it is preferred to use a hydrogen-containing atmosphere or pure hydrogen during the sintering in order to remove oxide layers which can be reduced with hydrogen during the process. If a hydrogen-containing atmosphere is used, the hydrogen content should preferably be at least 1% by volume.
  • the finished contours are also produced in the sintering process, preferably avoiding sawing of the melted material, which could lead to breakage or cracking.
  • the final contours are produced by pressing before sintering and the “cuboids” produced in this way are sintered separately. A separation after sintering is not necessary.
  • the assembly of the individual semiconductor cuboids to form usable modules is carried out according to the prior art, for example according to US 5,817,188 AI. Care must, however, be taken to ensure that components of the contact materials do not diffuse into the semiconductors and vice versa that semiconductor components do not diffuse into the contact materials.
  • Suitable contact materials are inert contact materials such as nickel, chromium, titanium, titanium diboride or copper, which is coated with nickel, chromium, titanium or titanium diboride, or nickel-phosphorus alloys such as nickel-phosphide.
  • the present invention relates to a method for increasing the Seebeck coefficient and / or the electrical conductivity of thermoelectrically active tellurides of the formula PbTe and / or Bi 2 Te 3 by partial substitution of the lead or bismuth atoms by silicon and / or germanium.
  • the semiconductor materials described above are formed here.
  • Another object of the present invention is the use of the semiconductor material described above in thermoelectric generators and or Peltier arrangements.
  • the semiconductor material according to the invention is suitable for use in thermoelectric generators or Peltier arrangements in clothes dryers.
  • Another object of the present invention is accordingly a tumble dryer with at least one thermoelectric module, containing a thermoelectric generator according to the invention and / or a Peltier arrangement according to the invention, via which a laundry material to be dried is heated directly or indirectly and the water vapor produced during drying is directly cooled become.
  • a tube furnace was used to temper the samples, which was moved up and down around the transverse axis with a period of approx. 2 min for better mixing of the components or the melt.
  • the heating rate was 300 ° C / h to the final temperature.
  • the samples were left at 1,000 ° C for 4 hours and then allowed to cool uncontrollably at an initial cooling rate of 400 ° C / h.
  • n-conducting PbTe was taken from a commercially available high-performance module of a thermoelectric generator for comparison measurement.
  • the Seebeck coefficient S was determined as the average Seebeck coefficient in the temperature range from 30 ° C to 130 ° C.
  • the electrical conductivity was determined more realistically than in the literature, namely also in the Seebeck experiment, while the cold side was kept at 30 ° C and the hot side at 130 ° C.
  • the measure of the electrical conductivity results from the quotient of short-circuit current and open circuit voltage, the short-circuit current being measured with very low resistance using a measuring instrument with an internal resistance of 0.035 ⁇ .
  • the error in the measurement of the open circuit voltage was ⁇ 2%, that in the measurement of the short-circuit current was ⁇ 20%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Générateurs ou dispositifs Peltier thermoélectriques comportant un tellurure en tant que matière semi-conductrice à activité thermoélectrique. Les générateurs ou dispositifs Peltier thermoélectriques selon la présente invention sont caractérisés en ce que les atomes à polarisation positive du réseau cristallin du tellurure sont partiellement substitués par du silicium et / ou du germanium.
PCT/EP2005/005345 2004-05-18 2005-05-17 Tellurures presentant de nouvelles combinaisons de proprietes WO2005114755A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004025066A DE102004025066A1 (de) 2004-05-18 2004-05-18 Telluride mit neuen Eigenschaftskombinationen
DE102004025066.9 2004-05-18

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WO2005114755A2 true WO2005114755A2 (fr) 2005-12-01
WO2005114755A3 WO2005114755A3 (fr) 2006-05-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006089938A1 (fr) * 2005-02-24 2006-08-31 Basf Aktiengesellschaft Sulfures de bismuth semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique
WO2007104603A2 (fr) * 2006-03-16 2007-09-20 Basf Se Tellurides de plomb/germanium destinés à des applications thermoélectriques
WO2007104601A3 (fr) * 2006-03-16 2007-11-22 Basf Ag Tellurides de plomb dopés destinés à des applications thermoélectriques
CN115368136A (zh) * 2022-08-26 2022-11-22 武汉理工大学 一种适用于批量化制备多晶Bi2Te3基块体热电材料的方法

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EP1342828A2 (fr) * 2002-02-21 2003-09-10 Theodor Blum Sèche-linge
WO2004090998A2 (fr) * 2003-04-11 2004-10-21 Basf Aktiengesellschaft Composes pb-ge-te- pour generateurs thermoelectriques ou dispositifs a effet peltier

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US3224876A (en) * 1963-02-04 1965-12-21 Minnesota Mining & Mfg Thermoelectric alloy
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EP0115950A2 (fr) * 1983-01-31 1984-08-15 Energy Conversion Devices, Inc. Matériaux thermoélectriques du type N composés de particules de poudres comprimées et procédé pour les fabriquer
GB2259098A (en) * 1991-08-30 1993-03-03 Univ Cardiff Electrochemical preparation of single phase lead telluride
EP1342828A2 (fr) * 2002-02-21 2003-09-10 Theodor Blum Sèche-linge
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006089938A1 (fr) * 2005-02-24 2006-08-31 Basf Aktiengesellschaft Sulfures de bismuth semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique
WO2007104603A2 (fr) * 2006-03-16 2007-09-20 Basf Se Tellurides de plomb/germanium destinés à des applications thermoélectriques
WO2007104601A3 (fr) * 2006-03-16 2007-11-22 Basf Ag Tellurides de plomb dopés destinés à des applications thermoélectriques
WO2007104603A3 (fr) * 2006-03-16 2007-12-13 Basf Ag Tellurides de plomb/germanium destinés à des applications thermoélectriques
US8716589B2 (en) 2006-03-16 2014-05-06 Basf Aktiengesellschaft Doped lead tellurides for thermoelectric applications
CN115368136A (zh) * 2022-08-26 2022-11-22 武汉理工大学 一种适用于批量化制备多晶Bi2Te3基块体热电材料的方法
CN115368136B (zh) * 2022-08-26 2023-07-14 武汉理工大学 一种适用于批量化制备多晶Bi2Te3基块体热电材料的方法

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Publication number Publication date
DE102004025066A1 (de) 2005-12-08
TW200602259A (en) 2006-01-16
WO2005114755A3 (fr) 2006-05-11

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