WO2006027232A2 - Composes pb-ge-te pour generateurs thermoelectriques et dispositifs a effet peltier - Google Patents

Composes pb-ge-te pour generateurs thermoelectriques et dispositifs a effet peltier Download PDF

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Publication number
WO2006027232A2
WO2006027232A2 PCT/EP2005/009614 EP2005009614W WO2006027232A2 WO 2006027232 A2 WO2006027232 A2 WO 2006027232A2 EP 2005009614 W EP2005009614 W EP 2005009614W WO 2006027232 A2 WO2006027232 A2 WO 2006027232A2
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WIPO (PCT)
Prior art keywords
semiconductor material
dryer
thermoelectric generator
ternary compound
thermoelectric
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PCT/EP2005/009614
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German (de)
English (en)
Inventor
Klaus KÜHLING
Original Assignee
Basf Aktiengesellschaft
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Publication of WO2006027232A2 publication Critical patent/WO2006027232A2/fr

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    • 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

Definitions

  • the present invention relates to semiconductor materials containing germanium, lead and tellurium (Ge-Pb-tellurides) as well as thermoelectric generators and deposition arrangements containing them.
  • 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, carry electrical charges through an external circuit, to a consumer electrical work can be done in the electric circuit.
  • 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 the generation of direct currents, for the cathodic corrosion protection of pipelines, for the energy supply of light and radio buoys, for the operation of radios and television sets.
  • 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 incinerated continuously, also catalytically without a free flame, whereby only small amounts of CO, NO x and unburned fuel are released; Any fuels can be used, from hydrogen through natural gas, gasoline, kerosene, diesel fuel to biologically produced fuels such as rapeseed oil methyl ester. As a result, the thermoelectric energy conversion adapts very flexibly to future requirements, such as hydrogen economy or energy generation from regenerative energies.
  • a particularly attractive application would be the use for conversion into electrical energy in electrically powered vehicles. There was no need to change the existing filling station network. However, efficiencies greater than 30% are required for such an application.
  • Concentrators such as parabolic troughs, with efficiencies of 95 to 97%, can concentrate the solar energy into thermoelectric generators, thereby generating electrical energy.
  • thermoelectrically active materials are evaluated essentially on the basis of their efficiency. Characteristic of thermoelectric materials in this regard is the so-called Z factor (figure of merit):
  • thermoelectric materials that have the lowest possible thermal conductivity, the highest possible electrical conductivity and the largest possible Seebeck coefficient, so that the figure of merit assumes the highest possible value.
  • thermoelectrically active material which has the highest possible value for Z and a high temperature difference that can be achieved. From the point of view of solid-state physics many problems have to be overcome:
  • a high ⁇ requires a high electron mobility in the material, ie electrons (or holes in p-type materials) should not be strongly bound to the atomic hulls.
  • Materials with high electrical conductivity ⁇ usually have at the same time a high heat conductivity (Wiedemann - Franz's Law), whereby Z can not be favorably influenced.
  • Currently used materials such as Bi 2 Te 3 are already compromises. Thus, the electrical conductivity through alloying is less reduced than the thermal conductivity. Therefore, it is preferable to use alloys such as (Bi 2 Te 3 ) 90 (Sb 2 Te 3 ) 5 (Sb 2 Se 3 ) 5 or Bi 12 Sb 23 Te 65 , as described in US Pat. No. 5,448,109.
  • thermoelectric materials with high efficiency preferably further marginal conditions are to be fulfilled. Above all, they must be temperature-stable in order to be able to work at working temperatures of up to 1,500 K for years without significant loss of efficiency. This requires a high-temperature-stable phase per se, a stable phase composition and a negligible diffusion of alloy constituents into the adjacent contact materials.
  • thermoelectric materials can be found in the more recent patent literature, for example in US Pat. No. 6,225,550 and EP-A-1 102 334. - A -
  • the US 6,225,550 relates to materials substantially consisting of Mg x Sb z, with a further element, preferably a transition metal, are doped.
  • EP-A-1 102 334 discloses p- or n-doped semiconductor materials containing an at least ternary material from the classes of suicides, borides, germanides, tellurides, sulfides, selenides, antimonides, plumbides and semiconducting oxides.
  • the (Pb I- x Ge x) Te-blocks are then in a melting zone furnace at 1000 0 C with a Wachs ⁇ tums civil of 1 mm / min produced.
  • the blocks are then ground to a powder having a size of 90 to 250 microns.
  • Reduktions ⁇ includes treatment b 400 ° C. for 24 hours in an H 2 / Ar atmosphere.
  • the powders are cold and then hot pressed in a vacuum at 650 0 C and 750 0 C.
  • thermoelectric materials with the GeTe component x in the semiconductor material increase, while the thermal conductivity decreases with the increase in the GeTe component x in the semiconductor material .
  • the best Seebeck coefficient obtained is approximately - 150 ⁇ V / K, the electrical resistance being 1 m ⁇ » cm.
  • the thermal conductivity is in the minimum 2 W / (m ⁇ K).
  • the object of the present invention is to provide semiconductor materials (thermoelectrically active materials) which have a high degree of efficiency and exhibit a suitable property profile for different fields of application.
  • Pb or Te is replaced by Ge or - Ge is added to PbTe or
  • Ge parts of the Pb or Te positions takes over, in each case the ratio of Pb: Te - starting from 1: 1 - changes.
  • the Seebeck coefficients of these materials are generally in the range of -250 to -380 ⁇ V / K for series (Ib) and (Ic).
  • the Seebeck coefficients for the compounds of the series (Ia) are generally up to 500 ⁇ V / K at a temperature of 300 ° C.
  • from 0 to 10% by weight, preferably from 0 to 5% by weight, particularly preferably from 0 to 1% by weight, of the ternary compound may be obtained by other metals or metal compounds which are also in the form of p or n -Dot michsstoff can be substituted.
  • suitable metals or metal compounds are Tl, Sn, Sb, Bi, Se, Si, Mg and mixtures thereof, Mn, Na, K, antimony, lead and Bismutha- logenide and silicon, antimony and Bismuttelluride.
  • Preferred dopants are BiI, SbI, BiTe, SbTe, Sb 2 Te 3 , Si 2 Te 3 , preferably in an amount of 0.1 to 0.5 wt .-%. Further suitable dopants are familiar to the person skilled in the art. The dopants and the other metals and metal compounds are preferably selected so that the Seebeck coefficient of the materials is not adversely affected.
  • the materials may also contain other compounds or dopants, as far as the aforementioned Seebeck coefficients are retained.
  • the materials of the present invention are generally made by fusing together mixtures of the respective constituent elements or their alloys. In general, a reaction time of melting together of at least one hour has proven to be advantageous.
  • the melting together is preferably carried out for a period of at least 1 hour, more preferably at least 5 hours, in particular at least 10 hours.
  • the melting process can be carried out with or without mixing the starting mixture. If the starting mixture is mixed, then in particular a rotary kiln is suitable for ensuring the homogeneity of the mixture. If no mixture is made, generally longer melting times are required in order to obtain a homo geneous material. If a mixture is made, the homogeneity in the mixture is obtained earlier.
  • the melting time is generally 2 to 50 hours, in particular 30 to 50 hours.
  • the melting temperature is at least 800 ° C., preferably at least 950 ° C.
  • the melting temperature is in a temperature range from 800 to 1100 ° C., preferably 950 to 1100 ° C.
  • the material is annealed at a temperature of generally at least 100 ° C., preferably at least 200 ° C., lower than the melting point of the resulting semiconductor material.
  • the annealing temperature is 450 to 750 0 C, preferably 600 to 700 0 C.
  • the annealing is carried out for a period of preferably at least 0.5 hours, more preferably at least 1 hour, in particular at least 2 hours. Usually, the annealing time is 0.5 to 5 hours, preferably 1 to 3 hours. In ei ⁇ ner embodiment of the present invention, the annealing is carried out at a temperature which is 100 to 500 0 C lower than the melting temperature of the resultie ⁇ in power semiconductor material. A preferred temperature range is 150 to 350 ° C. lower than the melting point of the resulting semiconductor material.
  • thermoelectric materials according to the invention is generally carried out in a heatable quartz tube.
  • a mixing of the components involved can be ensured by using a rotatable and / or tiltable furnace. After completion of the reaction, the furnace is cooled.
  • the quartz tube is subsequently removed from the oven and the semiconductor material in the form of blocks is cut into slices. These disks are now cut into pieces of about 1 to 5 mm in length, from which thermoelectric modules can be produced.
  • quartz tube and pipes made of other materials can be used instead of a quartz tube and pipes made of other materials, such as tantalum. This is preferred because the thermal conductivity of this material is higher than that of quartz.
  • tubes instead of tubes, other containers of suitable shape can be used. Other materials, such as graphite, can be used as container material.
  • the cooled material can be ground at a suitable temperature, so that the semiconductor material according to the invention in conventional particle sizes smaller than 10 microns is obtained.
  • the ground erfindungsge ⁇ Permitted material is then preferably pressed into moldings, which have the desired shape.
  • the bulk density of the moldings pressed in this way should preferably be greater than 50%, particularly preferably greater than 80%, than the bulk density of the raw material in the uncompressed state.
  • Compounds which the compression of the inventive Materials can be added in amounts of preferably 0.1 to 5 vol .-%, particularly preferably 0.2 to 2 vol .-%, in each case based on the powdered material according to the invention added.
  • Additives which are added to the materials according to the invention should preferably be inert to the semiconductor material and preferably dissolve out of the material according to the invention during heating to temperatures below the sintering temperature of the materials according to the invention, if appropriate under inert conditions and / or vacuum , After pressing, the pressed parts are preferably placed in a sintering furnace in which they are heated to a temperature of preferably at most 20 0 C below the melting point
  • the pressed parts are sintered at a temperature of generally at least 100 0 C, preferably at least 200 0 C lower than the melting point of the resulting Halb ⁇ conductor material.
  • the sintering temperature is 350 to 750 0 C., preferably 600 to 700 0 C.
  • the sintering is carried out for a period of preferably at least 0.5 hours, more preferably at least 1 hour, in particular at least 2 hours. Normally, the annealing time is 0.5 to 5 hours, preferably 1 to 3 hours. In one embodiment of the present invention, the sintering is carried out at a temperature which is 100 to 600 0 C lower than the melting temperature of the resulting semiconductor material. A preferred temperature range is 150 to 350 ° C. lower than the melting point of the resulting semiconductor material.
  • the sintering is preferably carried out under hydrogen or a protective gas atmosphere, for example of argon.
  • the pressed parts are preferably sintered to 95 to 100% of their theoretical bulk density.
  • the present invention also relates to a p-type or n-type semiconductor material comprising a ternary compound of the general formula (I)
  • Another object of the present invention is the use of the previously described semiconducting material and the semiconductor material obtainable by the method described above as a thermoelectric generator or Peltier arrangement.
  • thermoelectric generators or Peltier arrangements which contain the semiconductor material described above and / or the semiconductor material obtainable by the method described above.
  • Another object of the present invention is a method for producing thermo ⁇ electrical generators or Peltier arrangements, in which series-connected thermo-electrically active blocks (“legs") are used with thin layers of the previously described thermoelectric materials.
  • thermoelectric generators or Peltier arrangements In a first embodiment of this method, the production of the thermoelectric generators or Peltier arrangements takes place as follows:
  • the semiconductors according to the invention according to a first conductivity type are applied to a substrate by means of conventional semiconductor fabrication techniques, in particular CVD, sputtering technique or molecular beam epitaxy.
  • the semiconductors according to the invention are likewise applied to a further substrate by means of sputtering technique or molecular beam epitaxy, whereby, however, the conductor tion type of this semiconductor material is inverse to the first semiconductor material used (n- or p-doped).
  • thermoelectrically active building blocks each of a different charge type are arranged alternately.
  • thermoelectrically active building blocks have a diameter of preferably less than 100 .mu.m, more preferably less than 50 .mu.m, in particular less than 20 microns and a thickness of preferably 5 to 100 .mu.m, more preferably 10 to 50 .mu.m, in particular 15 to
  • the area occupied by a thermoelectrically active building stone is preferably less than 1 mm, particularly preferably less than 0.5 mm, in particular less than 0.4 mm 2 .
  • thermoelectric generators or Peltier arrangements are produced in such a way that layers of inventive semiconductor materials of different charge types (p- and n-doped) are alternately produced on a substrate by suitable deposition methods, for example molecular beam epitaxy ,
  • the layer thickness is in each case preferably 5 to 100 nm, more preferably 5 to 50 nm, in particular 5 to 20 nm.
  • thermoelectric generators or Peltier arrangements which are known per se to those 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 are.
  • thermoelectric generators or Peltier arrangements according to the invention generally extend the available range of thermoelectric generators and Peltier arrangements. By varying the chemical composition of the thermoelectric generators or Peltier arrangements, it is possible to provide different systems which meet different requirements in a multiplicity of application possibilities. Thus, the thermoelectric generators or Peltier arrangements according to the invention expand the range of application of these systems.
  • the present invention also relates to the use of a thermoelectric generator according to the invention or a Peltier arrangement according to the invention in a laundry dryer.
  • the present invention relates to a dryer comprising at least ei ⁇ NEN thermoelectric generator according to the invention or a Peltier arrangement according to the invention via the or a material to be dried directly or indirectly heated and over the or the resulting in the drying water or solvent vapor is cooled directly or indirectly.
  • the dryer is a clothes dryer and the material to be dried is laundry.
  • the thermal energy is determined by the fact that the material to be examined between a hot and a cold contact, which are each electrically heated, is placed, wherein the hot contact has a temperature of 200 to 300 0 C.
  • the cold side is kept at room temperature so that a .DELTA.T of typically 150 to 280 0 C resul ⁇ advantage.
  • the measured voltage at the respective temperature difference between hot and cold contact provides the respectively specified Seebeck coefficient.
  • the total amount of material is 17 g.
  • the quartz tube is evacuated, sealed and then for 20 hours under Bewe ⁇ supply heated in a rotary furnace for mixing at 1,050 0 C. Subsequently, the quartz tube is cooled in an upright position.
  • any other inert material can be used in this melting process.
  • the resulting material shows no phase transition.
  • the melting point is 928 0 C.
  • the Seebeck coefficient is -320 to -342 uV / K at 300 0 C and -330 to -355 uV / K at 200 0 C on the hot side.
  • thermoelectric material obtained has a Seebeck coefficient of -350 to - 360 uV / K at 300 0 C.
  • the melting point is 920 0 C.
  • Example 2 The procedure described in Example 1 is repeated, wherein now as a sample Pb 0 ⁇ 7 GeO 1 O 3 Te 11 O 2 is used and the total amount of material is 16.8 g.
  • thermoelectric material has a Seebeck coefficient of 330 to 350 ⁇ V / K at 300 ° C.
  • the melting point is 925 0 C.
  • Example 2 The procedure described in Example 1 is repeated, using now as sample Pb 0197 Ge 01O3 TeI O3 and the total amount of material is 16.7 g.
  • thermoelectric material has a Seebeck coefficient of 335 to 342 ⁇ V / K at 300 ° C. and 257 to 352 ⁇ V / K at 200 ° C.
  • the melting point is 924 0 C.
  • Example 2 The procedure described in Example 1 is repeated, using now as a sample PbGeo, o 3 Te and the total amount of material is 10.8 g.
  • the resulting thermoelectric material is ground and pressed into 7 or 13 mm diameter pressings.
  • the pellets are sintered in an evacuated quartz glass tube or under protective gas (argon) at 700 ° C. for 2 h. Only a small shrinkage ( ⁇ 0.2%) is observed.
  • Example 5 The procedure described in Example 5 is repeated, using now as a sample PbGeo, oiTeo, 99 (total 11.6 g).
  • thermoelectric material is ground and pressed to a 7 mm diameter crimp.
  • the pressing is sintered in an evacuated quartz glass tube or under protective gas (argon) for 2 h at 700 0 C. Only a small shrinkage ( ⁇ 0.2%) is observed.
  • thermoelectric material ground and pressed to a 13 mm diameter crimp.
  • the pressing is sintered in an evacuated quartz glass tube or under protective gas (argon) for 2 h at 700 0 C. Only a small shrinkage ( ⁇ 0.2%) is observed. Measurement:

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un matériau semi-conducteur de type p ou de type n, constitué d'un composé ternaire de formule générale Pb<SUB>x</SUB>Ge<SUB>y</SUB>Te<SUB>z</SUB> (I), les indices x, y et z satisfaisant à l'une des relations suivantes : (a) x = 1 - y; z = 1; 0,50 < y < 1; (b) z = 1 - y; x = 1; 0 < y < 1 ; (c) x = z = 1; 0 < y = 0,5; (d) 0,8 = x = 1,2; 0 < y = 0,5; 0,8 = z =1,2.
PCT/EP2005/009614 2004-09-08 2005-09-07 Composes pb-ge-te pour generateurs thermoelectriques et dispositifs a effet peltier WO2006027232A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004043787.4 2004-09-08
DE102004043787 2004-09-08

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WO2006027232A2 true WO2006027232A2 (fr) 2006-03-16

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