US2896005A - Thermoelectric heat pump - Google Patents

Thermoelectric heat pump Download PDF

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US2896005A
US2896005A US512436A US51243655A US2896005A US 2896005 A US2896005 A US 2896005A US 512436 A US512436 A US 512436A US 51243655 A US51243655 A US 51243655A US 2896005 A US2896005 A US 2896005A
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lead
compositions
tellurium
selenium
weight
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Robert W Fritts
Karrer Sebastian
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to BE543676D priority Critical patent/BE543676A/xx
Priority to BE543675D priority patent/BE543675A/xx
Priority to NL202808D priority patent/NL202808A/xx
Priority to US394074A priority patent/US2790021A/en
Priority to US475488A priority patent/US2811571A/en
Priority to US512436A priority patent/US2896005A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to GB20101/55A priority patent/GB814594A/en
Priority to DEM27647A priority patent/DE1106968B/de
Priority to GB35169/55A priority patent/GB827724A/en
Priority to FR1143255D priority patent/FR1143255A/fr
Priority to DEM29059A priority patent/DE1278111B/de
Priority to CH2778655A priority patent/CH389701A/de
Priority to CH2778555A priority patent/CH386504A/de
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • F25B21/02—Machines, plants or systems, using electric or magnetic effects using Peltier effect; using Nernst-Ettinghausen effect
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/02—Details of machines, plants or systems, using electric or magnetic effects using Peltier effects; using Nernst-Ettinghausen effects
    • F25B2321/021—Control thereof
    • F25B2321/0212—Control thereof of electric power, current or voltage

Definitions

  • thermoelectricl heat pumps having at least one improved thermoelectric element which when connected in circuit with a source of direct current liabilitiesds heat transfer through the thermoelectric element with resultant cooling of one portion and heating of another portion of the element in sudicient amount for practical use.
  • Another object is to provide heat pumps of the character aforedescribed comprising thermoelectric elements 2,896,05 Patented July 21, 1959 through the junction.
  • the proportionality factor between heat absorption or evolution rate and electric current is called the Peltier coeicient and is equal to the heat transferred when unit quantity of electricity traverses the junction.
  • the Peltier coeflicient may be directly determined as the product of absolute temperature and the derivative with respect to temperature of the Seebeck Accompanying such eiect under the circumstance stated is a transformation between thermal energy and electrical energy which takes place within each individual conductor, called the Thomson effect, which is delined as the heat absorbed or emitted per unit volume by a unit current passing through a unit temperature gradient. Such effects are reversible.
  • Metallic conductors when joined to form a thermoelectric junction as aforedescribed, exhibit low Peltier coefficients and low thermoelectric power. Moreover, such metallic conductors exhibit high thermal and electrical conductivity.
  • thermoelectric circuit When an external voltage is introduced into the ther- 1 moelectric circuit, as aforementioned, the electric charges mo've according to the laws of conduction and as they pass the junctions of dissimilar conductors absorb or emit heat, thereby suiering a change in their electrostatic potential. This is called Peltier heat pumping, the Thomson elect being neglected since the temperature gradients within the thermoelectric elements are quite low in pumping.
  • thermoelectric eiects there are two other more common eiects which must be considered in understanding the'behavior of semimetallic compositions and more particularly certain binary and ternary compositions having semiconductor-like conductivity or conductance.
  • FIG. 1 is a somewhat schematic illustration of a single thermoelectric element heat pump embodying, the invention
  • FIG. 2 is a ⁇ somewhat schematic illustration of a compound or double thermoelectric element heat pump comprising thermoelectric elements of opposite polarity embodying the invention
  • FIG. 3 is a graphic illustration of certain leadselenium-tellurium compositions comprising thermoelecltric heat pump elements of the invention
  • FIG. 4 is a graphic illustration of certain leadselenium-sulphur compositions comprising thermoelectric heat pump elements of the invention
  • FIG. 5 is a graphic illustration of certain electrical characteristics of negative thermoelectric heat pump elements embodying the invention.
  • Figure 5A is a graphic illustration of certain electrical characteristics of certain positive thermoelectric heat pump elements embodying the invention.
  • FIG. 6 is a graphic illustration of the performance factors of heat pumps embodying the invention.
  • FIG. 7 is a graphic illustration of certain electrical characteristics of additional positive thermoelectric heat pump elements embodying the invention.
  • thermoelectric heat pump When a direct current is passed through a junction between two dissimilar conductors the junction is heated or cooled depending not only upon the direction of current flow but also upon the nature of the conductors. This heating or cooling of the junctionsis called the Peltier eiect and is linearly dependent upon the current of a thermoelectric heat pump. These are the conventional Joule heating, or 12R dissipation (wherein I denotes current and R denotes resistance), and normal heat conductivity. In most applications of the Peltier heat pump these effects, which are irreversible, should be minimized for they are detrimental. Therefore, the resistivity and thermal conductivity of thermoelectric elements used in ⁇ heat pumps should be as low as possible.
  • thermoelectric element 10 conductively joined as at A and B to ordinary metallic conductors 11 and 12 completing a circuit to a source of direct current.
  • the conductivity type of the thermoelectric element 16 is s uch that as unit current ows across junctions A and B, Pa units of heat are absorbed at junction A and Pb units of heat are emitted at B.
  • the magnitudes of Pa and Pb depend upon the value of Peltier coeicient between the therrnoelectric element 10 and the conductors 11 and 12 and upon Vthe temperatures of the respective junctions. Where the junction temperatures are identical the heat absorbed at A equals the heat emitted at B.
  • Ta and Tb dier from Tn depends upon the magnitudes of the irreversible effects aforementioned as well as upon the magnitude of Peltier
  • the electrical energy input to the pumping element in the form of 12R dissipation within the volume of the thermoelectric element raises the temperature of the thermoelectric element slightly. This irreversible input alters the temperature distribution within the thermoelectric element until it is balanced by an equal flow of heat out through the junctions.
  • the other irreversible effect, heat conduction causes a ow of heat from the high temperature region' to the cooler portions; this is denominated as Qc.
  • Qb specifies the rate at which heat can be delivered (exhausted) to an external source in contact with the heating junction B.
  • T b-Ta is the temperature difference through which the thermal energy is transferred.
  • thermoelectric element of Figure l The direction of heat transfer of the thermoelectric element of Figure l is characteristic of elements having positive polarity of thermoelectric power and conductivity and with the current flowing in the direction indicated.
  • thermoelectric elements of negative polarity the heating and cooling of the junctions are just reversed.
  • Figure 2 wherein is shown a thermoelectric element 13 of positive polarity and a thermoelectric element 14 of negative polarity arranged in series circuit with respect to each other and a source of direct current.
  • the arrow indicates the direction of electric current in the conventional sense-the electron ow is, of course, in the opposite direction.
  • thermoelectric elements 14 and 13 heating occurs at the junctions indicated as C and D between the thermoelectric elements 14 and 13 and electrical conductors 15 and 16, respectively, while cooling occurs at junctions designated E and F between thermoelectric elements 14 and 13 and a metallic conductor 17, respectively.
  • the heat transfer and consequent heating of junctions C and D and cooling of junctions E and F are additive, as will be apparent, thereby affording a heat pump of greater efficiency than one comprising a single thermoelectric element as shown in Figure l.
  • the heat pump of Figure 2 is, of course, possible only by virtue of utilization of thermoelectric elements 13 and 14 exhibiting Peltier and conductivity opposite in sign.
  • the conductors, 15, 16 and 17 are metallic incomposition and hence exhibit electrical and thermalproperties characteristic of metals as aforedescribed.
  • thermoelectric elements having at one and the same time high values of Peltier (1r) and low values of thermal conduction (K) and of resistivity (p), or high conductivity.
  • thermoelectric heat pumps ernbodying this invention may also be stated in terms of the heating and cooling afforded at the junctions in relation to the amount of electrical energy required for such heating or cooling.
  • An expression of this factor is denominated herein the Performance Coefficient.
  • the performance coeicient of a heat pump (with respect to the cooling junction) is definedA as the ratio of heat absorbed at the cooling junction to the electrical energy dissipation within the pump and can be set forth as follows:
  • the performance coefficient of heating is equal to the performance coeflicient fof cooling plus one.
  • thermoelectric elements of Vnew-compositions exhibiting electrical characteristics as aforementionedfsuperior forheat pumping purposes ⁇ than.. known metallic alloys ⁇ and therrnoelectric elements of known semiconductive compositions.
  • Performance factors for semiconductors are low because of their high resistivities.
  • Our invention i is Vbasedon the fact that we havefound a way to alter the electrical properties of certain intermetallic compounds (which in a pure state exhibit high Peltier coefficient and resistivity and low values of thermal conductivity) to reduce their resistivity without a proportionate reduction in Peltier coefficient or a significant increase in thermal conductivity.
  • These ⁇ intermetallic compounds, which in a pure state are semiconductors, 4are altered by adding small concentration ofl beneficial impurity which render the semiconductors somewhat more metallic in nature, thereby vastly improving the performance factor.
  • the resulting compositions exhibit high values of Peltier coeiiicient andlow values of resistivity and thermal conductivity in a relationship which 3cannot be achieved in eitherpure ⁇ metals or pure semiconductors.
  • compositions we ⁇ have ⁇ denominated semi-metallic alloys o r compositions (to distinguish them yfrom metallic alloys on the one hand and semiconductor alloys on the other-hand).
  • VSuch semi-metallic alloys or compositions for ⁇ 7the rst time afford Peltier heatpumping with induced ternperaturedifferences and ⁇ pumping rates of suicient magnitude Lfor ⁇ utilization in practical applications.
  • the semi-metallic alloys or compositions aforemenizionedv may, we have found, be characterized as binary metallic compounds'of slightly imperfect composition, i.e. containing beneficial impurities constituting departures from perfect stoichiometry by reason of an excess of one of the metals over the other, .and/or containing added beneficial kimpurity substancesl denominated hereinafter promoters
  • Such semi-metallic compositions have semiconductor-like conductance (both electrical and thermal, as aforementioned).
  • Semi-metallic alloys or compositions also include mixtures of such binary metallic compounds, which' may be denominated ternary metallic alloys or compositions.
  • thermoelectric elements comprising lead and at least one member of the group tellurium, selenium and sulphur in proportions hereinafter described and to which may be added beneficial impurity substances in the form of promoters, as Will also hereinafter be described.
  • beneficial impurity substances in the form of promoters, as Will also hereinafter be described.
  • certain of these alloys or compositions exhibit. negative and certain exhibit positive electrical characteristics thereby affording, if desired, a compound or double. heat pump unit as shown in Figure 2.
  • the left-hand vertical scale (in terms of percent by weight) gives the amount .of lead which can be alloyed with the tellurium, selenium or tellurium-selenium constituent for any proportions, of the latter While the right-hand vertical scale conversely gives the percent by weight of the tellurium, selenium or selenium-tellurium constituent for any proportions of the latter in the final composition, the remainder, of course, being lead.
  • Figure 3 ygraphically illustrates compositions or alloys comprising lead and either tellurium or selenium or both since, we have discovered, selenium and tellurium when alloyed with leadwithin the proportions indicated are mutually soluble throughout the range of compositions illustrated and that tellurium and selenium are interchangeable for purposes of providing suitable thermoelectric heat pump elements falling within the class of binary metallic compounds aforementioned, and due to such mutual solubility, such binary compounds of the constituents indicated may bermixed, as is also graphically illustrated, toprovide'the ternary alloys or compositions .also hereinbeforeV mentioned.
  • thermoelectric elements of the character aforeindicated inpthat it eliminates the .necessity for separating selenium' from tellurium and "vice versa (these two constituents being invariably found togetheras contaminants one to the other), a dificult :and expensive procedure, and indeed impossible of com- Accordingly, even the end extremes of the compositions illustratedin Figure 3, i.e.
  • thermoelectric element of lead, selenium and tellurium aiording the desired characteristics could consist, as aforedescribed, of a selenium'- tellurium constituent in which the selenium is but a trace.
  • such constituent should'constitute from 35.0% to 38.05% by weight of the composition, the balance (65.0% to 61.95% by weight) being lead.
  • the selenium and tellurium are equal (in atomic percent) in the ,selenium-tellurium constituent, the latter should constitute from 30.0% to 32.8% by weight ofthe composition, the remainder (70.0% to 67.2% by weight) being lead.
  • FIG. 4 there -are graphically illustrated therein a further multiplicity of examples of semi-metallic compositions or alloys for thermoelectric heat pump elements comprising lead and selenium or sulphur.
  • the horizontal coordinate of the graph of Figure 4 represents the various proportions of selenium and sulphur given in atomic percent and ranging linearly from selenium containing but a trace, as above'deiined, of sulphur on the left to sulphur containing but a trace of selenium on the right.
  • the left-hand vertical scale (in terms of percent by weight) gives the amount of lead which can be alloyed withV the selenium, sulphur of selenium-sulphur constituent for any proportions of the latter, while the righthand vertical scale conversely gives the percent by weight of the sulphur, selenium, or selenium-sulphur constituent for any proportions of the latter in the final composition, the remainder, of course, being lead.
  • Figure 4 further graphically illustrates compositions or alloys comprising lead and either selenium ⁇ or sulphur or both since, we have discovered, selenium and sulphur when alloyed lwith lead
  • selenium ⁇ and sulphurY are interchangeable for purposes of providing suitable thermoelectric heat pump elements falling within the class of binary metallic compounds aforementioned, and due to such mutual solubility such binary compounds of the constituents indicated may -be mixed as is also illustrated to provide the ternary alloys or compositions also hereinbefore mentioned.
  • thermoelectric elements of the character aforeindicated in that-it eliminates the necessity'for separating selenium from sulphur and vice versa (these two constituents being invariablyV found together as contaminants one to the other), a difficult and expensive procedure and indeed impossible of achievement. Accordingly, even the end extremes of the compositions illustrated in Figure 4, i.e.
  • sfeleniumand sulphur affording the desired characteristics could consist, as gaforedescrihed, of' a selenium-sulphur i constituent inwhich the sulphur is rbut a trace. 'In this case, such constituent 'should constitute from 25.0% to 27.55% Vby 'Weight'of the composition, the balance almosty entirely yof sulphur with but a trace of selenium,
  • copper is one example of such an impurityrhavy the desiredfelectrical .propertiesk aforementioned may be yAs ya yfurther example, Where'the selenium and sulphur arey equal (in atomic percent) in yther s'elenium-sulphury y constituent, the latter should constitute from 18.90% toy 20.46%y 'by' weight of.
  • kthe terminal ⁇ composi- 'tionsy aforedescrib'ed consisting substantially yentirely of 'lead and tellurium may yto a limited extent contain somer sulphur (ic.y to the extent thatk sulphur is yfound yasy a contaminant incommercially available tellurium) as well as selenium.
  • theterminal compositions afnrey described consisting substantially' of lead and selenium may contain to' a limitedy extent ytellurium and sulphur
  • the terminali compositions rafore-y n described consisting substantially yof lead and sulphur may contain telluriurn to aflimited extent as yaforeindicated as well as selenium.y yLikewisey anyfof' the intermediatek or ternary alloys or compositions consisting of lead and at least two members of the group tellurium, selenium, sulphur, may contain such limited amounts of the other element of the group.
  • the proportions and ranges aforedescribed considered to be critical, but so also is the purity. More 'speciiically, the limit of tolerable metallic impurity in the final composition has been found to be on the order of 0.01% and the composition must be substantially oxygen free if the mechanical and electrical properties desired are to be obtained and be reproducible. Such purity may be achieved by utilization of lead, tellurium, selenium and Isulphur which d0 not contain metallic impurities exceeding the order of 0.01%. Alternatively, starting constituents of lesser purity maybe utilized to ⁇ be of the 1.
  • any given ,composition illustratedr 'in Figures 3 andl 4 depends upon the meltf i f ing point of thatcompositionfwhich ycan, readily substitutedy by those skilled inthe artffrom that of yrninal compositions given by Way of example. yDuring such heating the molten mass is ypreferably insure good mixing and then cooled. y ,y Aftery 'the composition has been formed as aforementioned, the 'solidified ingot can beremoved from the tube agitated to y ⁇ ,and east in molds of graphite or the like under an, at y mosphe're of inert gas.
  • kduring casting we have found it preferable to cover the mold with an inert gas such as, for example, argon or carbon dioxide under positive pressure.
  • an inert gas such as, for example, argon or carbon dioxide under positive pressure.
  • crucibles which do not react with or contaminate the composition since, as aforeindicated, minor amounts of undesired impurities may very deleteriously aect the electrical and/or physical properties of the element.
  • Suitable crucibles are, we have found, those made of carbon, Alundum, pre-fired lavite and Vycor or quartz. e
  • the ingots After casting the ingots ⁇ may be machined if necessary.
  • the shaped ingots are then preferably annealed in a reducing atmosphere at from 540 C. to 815 C. for from 20 ⁇ to 10 hours. rIhis ⁇ annealing treatment insures homogeneity of 4the ingots ,and ⁇ enhances its electrial and physical properties. e
  • An alternate method of forming the composition comprises melting the constituents aforementioned in an open crucible under an atmosphere of argon or any inert and/reducing gas. Since the vapor pressure of selenium and sulphur are relatively high, some loss of selenium or sulphur may be encountered and adjustments in the initial amount of this constituent, Where used, must be made to account for this loss. In all other respects this method is ⁇ similar to that previously described.
  • Thermoelectric heat pump elements comprising alloys or compositions of the invention can be achieved as aforementioned through utilization of starting constituents o f such purity that the compositions and resultant alloy containsno more impurity than that aforeindicated.
  • an alloy of such purity may be afforded by forming the composition as to be hereinafter described from less pure starting constituents and reducing the impurity content by recrystallization from the melt.
  • the aforementionedfalloys of lead and atleast oney of the group tellurium, selenium, sulphur, may be best described metallographically as two-phase-alloys. It has been observed that these two-phase alloys, when sectioned and examined microscopically, comprise a major phase comprising crystal grains varying usually'from 1 to millimeters in size and between such grains there exist thin, relatively darker regions of a second'phase.
  • the grains of the primary phase are crystals of the intermetallic compounds lead-telluride, lead-selenide and leadsulphide (or mixed crystals thereof), which contain approximately 61.89%, 72.41% and 86.60% lead by weight, respectively.
  • the function of the second phase in such alloys is thought to be three fold.
  • the thermal equilibrium between the two phases which is established by the heattreatment aforementioned, induces negative Peltier and conductivity in the primary lead-telluride, lead-selenide or lead-sulphide phase which, because of its high concentration in the alloy, controls the electrical properties of the two-phase alloy.
  • the thin layers act as a cementing agent for the grains of the primary phase, thereby improving the mechanical strength of the alloy when compared with that of the pure intermetallic compound.
  • this cementing action of the second phase alfords good electrical conductivity in the polycrystalline .alloy by rendering the intergrannular component of electrical resistivity negligible.
  • concentration of second phase is not critical so long as the composition is maintained within the aforementioned specified ranges.
  • the first terminal composition consisting substantially of lead and tellurium contains from 61.95% to 65.0% by weight lead, or from .16% to 8.9% lead by Weight of the total'composition over-and above the,61.89% lead stoichiometrically necessary to" combine with the tellurium.
  • the terminal composition consisting substantially of lead and selenium contains from .15% to 10.4% lead by Weight of the total composition over and above the 72.41% by weight lead stoichiometrically necessary for combination with the selenium.
  • the terminal composition consisting substantially of lead and sulphur wherein the amount of Vlead specified forcomposition of the present invention is from .23% to 4.7% lead by Weight of the total composition more than that necessary to stoichiometrically combine with the sulphur present, i.e. 86.60% by weight lead.
  • the amount of Vlead specified forcomposition of the present invention is from .23% to 4.7% lead by Weight of the total composition more than that necessary to stoichiometrically combine with the sulphur present, i.e. 86.60% by weight lead.
  • beneficial impurities that affords the compositions of this invention their desired electrical characteristics and distinguishes the semi-metallic alloys or compositions of this invention from the primary phase intermetallic compounds leadtelluride, lead-selenide and lead-sulphide. More speciiically, such beneficial impurities afford such intermetallic compounds, whether the binary compounds of the terminal compositions or the ternary alloys of the intermediate compositions, a lower resistivity without proportional sacrice of Peltier E.M.F. or low thermal conductivity and which results in a composition having what may be termed semiconductor-like electrical conductance or conductivity.
  • thermoelectric elements for heat pump Yapplications of the aforedescribed lead-tellurium, lead-selenium, lead-tellurium-selenium, lead-sulphur and lead-selenium-sulphur compositions of the aforementioned range and purity can be markedly and advantageously altered in a reproducible manner by the addition thereto of controlled amounts of matter other than the constituents of the base composition.
  • Such additions may also be denominated beneficial impurities as distinguished from undesired impurities as aforementioned.
  • the lead content of the base composition should be slightly less; e.g. a maximum of 63.0%, 73.5% and 87.10% by weight, respectively, for the various terminal compositions.
  • Negative compositions or alloys are to be understood throughout this specification and appended claims as meaning an alloy or composition which exhibits negative conductivity as evidenced by Hall etect measurements or thermoelectric effect measurements, both taken at room temperature.
  • positive ⁇ compositions or alloys are to be understood as meaning an alloy or composition which exhibits positive conductivity as evidenced by I -Iall effect measurements or thermoelectric etect measurements,both taken at room temperature.
  • Negative promoters are ⁇ those which when addedoto the base alloys aforedescribed alter the electrical conductivity thereof without changing the polarity of the conductivity or Peltier E.M.F. of the base alloys (it being negative according to the preceding definition).
  • Positive promoters are those Which when added in amounts hereinafter disclosed to the base alloys aforedescribed and certain base alloys hereinafter disclosed are effective in enhancing the electrical conductivity in a positive sense as above defined with only slight descrease in the thermoelectric power of the promoted base alloy.
  • promoters which we have found effective for the purposes of the present invention when added in minor amounts to the base compositions aforementioned will for convenience be discussed in terms of the ⁇ terminal compositions modied as to purity and lead content as aforedescribed, it being understood that such promoters may also be added to any of the intermediate compositions with beneficial results. In this case the promoters added should be proportioned both in kind and in amountV according to the relative concentrations of the terminal compositions in the intermediate composition comprising a mixture of such terminal compositions.
  • Table I below., first column thereof, lists the additions which we have found effective as negative promoters when added to the aforementioned lead-tellurium base alloys or compositions.
  • the second column of Table. I lists the order of the maximum concentration limits by weight percent of such promoters to the ybase alloys effective for achieving the objects of the invention. It is to be understood that these concentration limits are the maximum which effectively alter the electrical properties of the base alloy. Concentrations in excess of the stated amounts of such additives have no ⁇ appreciable effect in beneficially altering theielectrical properties with which this invention is concerned, and in this sense the limits indicated are to be considered critical.
  • the third and fourth columns of Table I set forth the electrical properties at room temperature of lead-tellurium alloys promoted with the maximum useful concentrations of the negative promoters after high temperature annealing as hereinbefore described.
  • Uranium .1 The range set forth is discussed below.
  • certain positive promoters may also be alloyed with the aforementioned lead-tellurium base alloys and such promoters are listed in column l of Table II.
  • the second column of Table ll like the corresponding column of Table I sets forth the order of the maximum concentration limits by weight percent of such promoters to the base alloys effective for achieving the objects of the invention.
  • concentrations of the positive promoters to the lead-tellurium base alloys in amounts in excess of that contained in column 2 of Table Il have no appreciable effect in beneficially altering the electrical properties with which this invention is concerned, and in this sense the limits indicated are to be considered critical.
  • the lead-tellurium base alloy previously described is a two-phase alloy.
  • promoter additions are incorporated in the base alloy, such promoter additions become distributed; be-
  • the maximum effective concentration is dependent upon the lead content of the lead-tellurium base alloy within the range stated therefor.
  • 1.00% by weight thallium to be the maximum effective concentration for lead-tellu-rium base alloys containing 63.0% lead; for base alloys containing less lead the maximum effective thallium concentration is somewhat less, that is ranges down to 0.25% by Weight when the lead content ranges down to 61.95
  • the maximum eiective concentration is dependent upon the lead content of the lead-tellurium base alloy within the range stated therefor and rangesfrom 0.25% for base alloys containing 63.0% lead down to 0.07% for base alloys containing 61.95% lead.
  • thallium promoted base alloys ranges from 0.01% to 0.04% as the lead constituent of the lead-tellun'um base composition 'varies from 61.95% to 63.0%.
  • the minimum effective concentration weight percent-ranges from 0.002% to 0.006% as the lead content of the base alloy varies from 61.95% to 63.0%.
  • Gal Table III 15 Gal Table III below, first column thereof, lists the additions whichwe have found effective as negative promoters when added tothe aforementioned lead-'selenium base alloys Vor compositions.
  • the second column of Table III lists the order yof the maximumconcentration limits by weight percent of such promoters to the base alloys effective forachievin-g the objects of the invention. .It is y to Vb'e understood that theseconcentration limits are the maximum ,which Aeifectively'allter the electrical properties of the base alloy. Concentrations in excess of the stated amounts of such additives-have no appreciable effect in beneiiciallyaltering the electrical properties with which this inventionis concerned, 'and in this sense the limits indicated are to be considered critical.
  • Columns 4 and 5 set forth the Peltier and resisi tivity characteristics at room temperature of the alloy or composition resulting from the addition of the aforedescribed positive promoters in the amount shown in column 2 after high temperature annealing as aforedescribed.
  • the lead-selenium base alloypreviously described is a two-phase alloy.
  • promoter additions areY incorporated in theY base alloy, such promoter additions become distributed between the vtwo phases.
  • Wel have discovered. thatl the nature of such distribution hasrnegligible effect onl the electrical properties of the composition in allY cases exl lead content ofv theV lead-selenium basealloy WithinA the range stated therefor.
  • antimony we have found 1.5% by weight antimony to be the maximum effective concentration for lead-selenium base alloys containing 73.5% lead; for base alloys containing less lead ⁇ the maximum effective antimony concentration is somewhat less, that is ranges dow-n to 0.20% by weight when the lead content ranges down to 72.45%.
  • Table V below lists the additions which we have found effective as negative promoters when added to the aforementioned lead-sulphurV base alloys or compositions.
  • the second column of Table V lists the order of the maximum concentration limits by weight percent of such promoters to the base alloys effective for achieving the objects of the invention. It is to be understood that these concentration limits are the maximum which effectively alter the electrical properties of the base alloy. Concentrations in excess of the stated amounts of such additives have no appreciable effect in beneficially altering the electrical properties with which this invention is concerned, and in this sense the limits indicated are to be considered critical.
  • the third and fourth columns of Table V set forth the electrical properties at roomtemperature of lead-sulphur alloys promoted with the maximum useful concentrations of the negative promoters after high temperature annealing as hereinbefore described.
  • certain positive promoters may also be alloyed with the aforementioned lead-sulphur base alloys and such promoters are listed in column 1 of ⁇ T able VI.
  • tion limit tion limit volts by weight by weight percent percent Silver 2.0 0.70 0.081 0.020
  • the lead-sulphur base alloy previously described is a two-phase alloy.
  • promoter additions When the aforedescribed promoter additions are incorporated in the base alloy, such promoter additions become distributed between the two phases.
  • the nature of such distribution has negligible effect on the electrical properties of the ⁇ composition in all cases except that of bismuth and antimony. Accordingly, in the case of bismuth and ⁇ antimony the maximum effective concentration is dependent upon the lead content of the ⁇ lead-sulphur base alloy within the ranges stated therefor as shown in Figure 3.
  • the maximum amount of benelcial impurity for any promoted composition is 6.9% by weight.
  • the maximum amount of beneficial impurity for any unpromoted composition is 10.4% by weight. Accordingly, it can bei said that the maximum amount of Vbenecialimpurity for any composition aforede'scrbed is, in round numbers, about 10% by Weight.
  • Typical data ofthe aforedescribedv compositions are, by way of example, shown in Figures and 5a wherein the Peltier E.M.'F. in volts (left-hand scale) and p in watts per centimeter (righthand scale) are plotted against the log of the resistivity inclini-centimeter.
  • curves G, H and I represent compositions consisting essentially of leadand tellurium, lead'and selenium, and lead -and sulphur, respectively, within the ranges aforeindicated, and which curves graphically illustrate variation in the relationship between Peltier coel ⁇ n ⁇ cient (1r) and resistivity (p) with additions of negative promoters to the respective base compositions (the right-hand ends of such curves representing the base compositions).
  • curves I, K and L represent compositions consisting essentially of lead and tellurium, lead and selenium, and lead and sulphur, re spectively, within the ranges afor'eindicated, and which curves graphically illustratevvariations in the value of the quotient Y k P with additions of negative promoters to the base composition (the right-hand ends of such curves representing the base compositions).
  • Curves M, N and O represent compositions consisting essentially of lead and tellurium, lead and selenium, and lead and sulphur, respectively, within the ranges aforeindicated, and which curves graphically illustrate variation in the relationshipV between Peltier coeiicient (1r) and resistivity (p) with additions of positive promoters to the respective base compositions v(the right-hand ends of such curves representing the minimum effective concentration of positivenprornoters aforedescribed).
  • Acurves P, Q and R l represent compositions consisting essentially of lead and tellurium, lead and selenium, and lead and sulphur, respectively, within the ranges aforeindicated, and which curves 'graphically illustrate variation in the value of the quotient P Y with additions of positive"l promoters to theY baseconiposition (the right-hand ends of such curves represent ing the minimum effective concentration of positive promoters aforedescribed).
  • l Y V AIn Figures ⁇ 5 and 5u curves I, K, L and P exhibit maximum values of the quotient
  • the curves Q and R exhibit extremal valuesfor the maximum concentration of positive promoter.
  • the resistivity of the right-hand coordinate of Figures 5 and 5a (0.1 ⁇ ohm-cm.) is characteristic of semi-conductor vmaterials.
  • the resis'itivity of the left-hand coordinate of Fig ure's 5' and 5d (0;0001 ohmlcm.) is characteristio of a metal.
  • the maximum and e'xtremal values aforementioned occur at values o'f Peltier coeicient and resistivity intermediate to those of'me'tals'and semi-conductors.
  • semi-metallic lements embodying the present invention exhibit low thermal conductivity approaching that of a semi-conductor, High values of the quotient i l and simultaneously the low values of thermal conductivity (K) afford the high performance factors desired for heat pump elements.
  • curve yS isla representative performance coein'cient curve for' compost tions consisting essentially of lead and tellurium while curve T isa representative curve ofthe vpumping lrate (Qa) for the sarne compositions:
  • curve Ui is a representative performance coeicieiit curve for compositions consis'ting'essentially of leadY and sulphur
  • curveV is a representative' pumping rate curve (Qa) for the same compositions.
  • thermoelectric heat pump elements comprising binary metallic compounds and ternary comp'ositioiisr or alloys thereof having semiconductor-'like conductivity afford heat.
  • pump characteristics of sullicent magnitude for practical application.
  • Table VII illustrating siich improved heat pumping characteristics.
  • the irst column in terms of composition and percent by weight lists various examples of compositions of the class described; theseond cluinn indricates the Peltier' E.M.F.in volts derivable fromfch of such compositions; theV third column lists foreach' of such compositions the thermal co'ridctivity in lwatts" per centimeter degrees Centigrade; the fourth column lists for each of such compositions their resistivityrinmohmf cm.; and the fifth 'colii indicates for each of such compositions the performance factor thereof. It will be noted ⁇ that ⁇ tli'e ex'ar'iplesl f compositions" given include examples of Ieach of the Base alloys and at least one example ofeach of the base alloys to which a promoter has been added.
  • thermoelectric heat pump elements of positive as well as negative polarity gives typical data for all of the aforedescribed compositions applicable Vequally to thermoelectric heat pump elements of positive as well as negative polarity. ly way of example Table IX following gives heat pumping data for a specific thermoelectric heat pump element of positive polarity.
  • suitable additional positive thermoelectric elements exhibiting positive electrical characteristics as previously defined, and useful for heat pumping may comprise lead and tellurium in which there is an excess of tellurium over and above the amount thereof necessary for satisfying the stoichiometric proportions of the compound ⁇ lead-telluride.
  • Such additional alloys or compositions may contain added beneficial impurity substances, and such substances, as before, are also denominated hereinafter as positive promoters.
  • These additional alloys or, compositions may also be characterized as binary metallic compounds of slightly imperfect composition by reason of the excess of tellurium over lead and/or containing added beneficial impurity substances.
  • Such additional alloys or compositions, as previously related may be termed semi-metallic alloys or compositions, and have semiconductor-like conductance, (both electrical and thermal), similarly to the binary and ternary alloys already discussed.
  • thermoelectric elements exhibiting positive electrical characteristics, base alloys .or compositions consisting essentially of lead and tellurium in which lead is present inthe range of from 58.0% to 61.8% by weight and the balance in the range of from 42.0% to 38.2% by weight tellurium.
  • the portions of the lead and tellurium constituents as last set forth must be considered critical if the compositions are to have the electrical properties desired in heat pumps.
  • the tellurium rich base lead-tellurium alloys may also be described metallographically as a two-phase alloy.
  • the excessv of tellurium in the tellurium rich compositions behaves much as the excess of ⁇ lead in the first discussed alloys in that it controls the polarity of ⁇ the conductivity and thermoelectric power inthe primaryjlead-telluride phase, and it also forms a detectable second phase at the grain boundaries as already above discussed.
  • the compositions are further adequately stable for temperature applications ranging up to 400 C.
  • tellurium rich base lead-tellurium compositions contain from 38.20% to 42.0% by ⁇ weight tellurium, or from 0.14% to 6.7% by weight tellurium of the total composition over and abovethe tellurium stoichiometrically necessary to combine with the lead.
  • thermoelectric elementsffor heat pumps of the last v'mentioned range of excess tellurium impurity can be markedly 'and advantageously altered in a reproducible manner by the addition thereto of controlled amounts of matter other than the constituentsl of such base compositions.
  • Such additions are also here denominated beneficial impurities as distinguished from undesired impurities as previously discussed.
  • such additions are denominated promoters since, as will hereinafter appear, they tend to enhance the electrical characteristics desired in thermoelectricl heat pump elements of the last mentioned base composition.
  • the amounts of such promoters in tenns of percent by weight of the base composition are very small, and for such promoters to be most effective and afford reproducibility of electrical properties the base composition to which they are added should be of even greater purity, i.e. containing even less of undesired and uncontrolled impurities.
  • the tellurium rich base leadtellurium compositions should be of such purity in this regard as to contain not in excess of 0.001% by weight undesired impurity.
  • the lead content of the instant vbase composition should be in the range of from 59.0% to 61.8%*lead by weight as against the range of lead of from 58.0% to 61.8% by weight above disclosed for the unpromoted compositions.
  • the aforementioned base compositions of tellurium rich lead-tellurium compositions exhibit positive Peltier and positive conductivity.
  • the promoters to be hereinafter described such positive electrical properties may be enhanced by the addition of certainV promoters and such positive promoters in connection withA the last mentioned basealloy effect an increase in the conductivity of the alloy andslight decrease inthe Peltier Table X 22 properties atA room temperature of theaforementioned tellurium rich lead-tellurium base'compositions ⁇ promoted withA the usefulconcentrations of the' positive promotersfafter annealing.
  • the' maximum concentrations of lbeneficial* impurity for the last disclosed promoted tellurium rich lead-tellurium compositions varies from aminimum of'0.28% by weight (i.e., 0.14% by weight excess tellurium plus 02I4% by weight sodium) to 5.5% by weight (iie. 4.9%Y by' weight Y excess tellurium plus 0.60%V by weight thallium'), which fall Well withinY the aforementionedv maximum amount of beneficial impurity of about 10% by weight.
  • curve X represents compositions of tellurim rich leadLtelluriuIn Within the range afore-indicated and which curve graphically ⁇ illustrates variations in the' relationship between Peltier coefiicient (1r) and resistivityv with addition ofA positive promoters tothe last noted base compositions (the right-hand end of such curve representing the effective concentration of positive promoters last described),
  • curve W represents the; last aforementioned tellurium richtle'adtellurium compositions Within4 the range .afore-indicated and Whichl curve graphically illustrates variations in the value of the quotient p
  • the resistivity of the right-hand coordinate of Figure 7 (0;1 ohmcmr.) is characteristic ofsemic'onductor materials.
  • the resistivity of the left-hand coordinate of Fig urev7 (0.00041l ohm-cm.) is characteristic of a metal.
  • the maximum-.and extrenial values aforementioned occur at values of Pelti'er'co'eflicient' and resistivity intermediate to those ofmetals and' semiconductors;- Moreover, aspre'- viously' mentioned, semi-'metallic elements Vembodying thel present invention exhibit'low tl'i'ernial'V conductivity approaching that' offa semiconductor.
  • High' values of the quotientA i Y and: simintan'eosly the low values of'thennal' conductivity (K) afford the high performance effect desired for heat pump elements.
  • the examples of compositions given include tellurium rich lead-tellurium base alloys and including each of the positive promoters last discussed.
  • thermoelectric heat pump comprising, at least a pair of thermoelectrically dissimilar electrical conductors joined in circuit to provide at least a pair ofthermoelectric junctions, at least one of said conductors being a semimetallic element selected from the class of binary and ternary alloys of slightly imperfect stoichiometric composition and having semiconductor-like conductivity, said l semi-metallic element affording transfer of heat therethrough when said circuit is energized, thereby effecting cooling at one of said junctions and heating at the other of said junctions.
  • thermoelectric heat pump according to claim 1 in which the imperfection of composition of said semi-metallic element comprises a departure from stoichiometry of said alloy by an amount not in excess of 10.4 ⁇ percent y by weight of said alloy.
  • thermoelectric heat pump according to claim 1 in which the imperfection of composition of said semi-metallc element comprises a stoichiometric excess of one of the constituents.
  • thermoelement comprising two circuit members of diierent respective materials, a heat absorbing element having good heat conductivity and slight thermoelectric power conductively joined intermediate said members to form together therewith a thermoelectric junction, at least one of said two members consisting of a binary compound of two metals of a slightly imperfect composition departing from perfect stoichiometry by an amount of at most 2 percent by weight of the total material of said member, and having semiconductorlike electric conductance.
  • thermoelement consisting of an excess of one of the two metals over the other.
  • thermoelement comprising two circuit members of different metallic materials, heat absorbing element having good heat conductivity andrslight .thermoelectric power of large diierential thermoelectric power, and an intermediate part of larger conductance and of negligible differential thermoelectric power as compared with said two members, said members and said part being joined together to form a thermoelectricjunction, at least one of said members consisting of a binary compound of two metals of a slightly imperfect composition departing from perfect stoichiometry by an amount of at most 2 percent by weight of the total material ofsaid member and having semiconductor-like electric conductance.
  • a cold producing thermoelement comprising two circuit members of different metallic materials, and an intermediate part of larger conductance and of negligible differential thermoelectric power as compared with said two members, said members and said part being joined together to form a thermoelectric junction, at least one of said members consisting of a binary compound of two metals of a slightly imperfect composition departing from perfect stoichiometry by an amount of at most 2 percent by weight of the total material of said member and having semiconductor-like electrical conductance.
  • thermoelectric heat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members consisting of abinary compound of two metals in which there is a departure from perfect stoichiometry by an amount not in excess of 10.4% by weight of said one member and having semiconductor-like electric conductance.
  • thermoelectric heat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members consisting of a binary compound of two metals in which there is a departure from perfect stoichiometry consisting of an excess of one of the two metals over the other by an amount not in excess of 10.4% by weight of said one member and having semiconductor-like conductance.
  • thermoelectric heat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members consisting of a binary compound of two elements in which there is a departure from perfect stoichiometry consisting of a stoichiometric excess of one of ysaid elements over the other of said elements and a beneficial impurity substance not in excess of 6.9% by weight of said one y member and having semiconductor-like conductance.
  • thermoelectricheat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members being a semi-metallic element from the class of binary and ternary alloys of metals in which there is a departure from perfect stoichiometry by an amount not in excess of 10.4% by weight of said one member and having semiconductor-like conductance.
  • thermoelectric heat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members being a semi-metallic element from the class of binary and ternary alloys of metals of imperfect composition in which there is a departure from perfect stoichiometry consisting of an excess of one of the metals of an amount not in excess of 10.4% by weight of said one member and having semiconductor-like conductance.
  • thermoelectric heat pump comprising a pair of circuit members joined in circuit to provide a thermoelectric junction, at least one of said two members being a semi-metallic composition from the class of binary and ternary alloys of elements of imperfect composition in which there is a departure from perfect stoichiometry consisting of a stoichiometric excess of at least one of said elements and a beneficial impurity substance not in excess of 6.9% by weight of said one member and having semiconductor-like conductance.

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BE543676D BE543676A (cs) 1954-12-15
BE543675D BE543675A (cs) 1954-12-15
NL202808D NL202808A (cs) 1954-12-15
US394074A US2790021A (en) 1953-11-24 1953-11-24 Thermoelectric generator
US475488A US2811571A (en) 1954-12-15 1954-12-15 Thermoelectric generators
US512436A US2896005A (en) 1954-12-15 1955-06-01 Thermoelectric heat pump
GB20101/55A GB814594A (en) 1954-12-15 1955-07-12 Improvements in thermoelectric generators
DEM27647A DE1106968B (de) 1954-12-15 1955-07-12 Als Schenkel von Thermoelementen geeignete tellur- und selen- bzw. selen- und schwefelhaltige Bleigrundlegierung
GB35169/55A GB827724A (en) 1954-12-15 1955-12-07 Improvements in or relating to thermoelectric heat pumps
FR1143255D FR1143255A (fr) 1954-12-15 1955-12-14 Pompe thermo-électrique
DEM29059A DE1278111B (de) 1954-12-15 1955-12-14 Als Schenkel fuer Thermoelemente geeignetes Halbleitermaterial aus p-leitendem Bleitellurid
CH2778655A CH389701A (de) 1954-12-15 1955-12-15 Thermoelektrische Wärmepumpe
CH2778555A CH386504A (de) 1954-12-15 1955-12-15 Thermoelektrischer Generator

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157801A (en) * 1960-03-07 1964-11-17 Itt Cooling means for thermostats
US3460008A (en) * 1965-12-08 1969-08-05 Telefunken Patent Controllable tunnel diode
US3460996A (en) * 1968-04-02 1969-08-12 Rca Corp Thermoelectric lead telluride base compositions and devices utilizing them
US3527622A (en) * 1966-10-13 1970-09-08 Minnesota Mining & Mfg Thermoelectric composition and leg formed of lead,sulfur,and tellurium
US4019113A (en) * 1974-11-20 1977-04-19 James Keith Hartman Energy conversion device
US20050056799A1 (en) * 2003-09-11 2005-03-17 Malone Steven J. Valves having a thermostatic actuator controlled by a peltier device
KR20120019701A (ko) * 2010-08-26 2012-03-07 삼성전자주식회사 열전재료, 이를 포함하는 열전모듈과 열전장치
CN111799360A (zh) * 2020-07-03 2020-10-20 中国科学院合肥物质科学研究院 一种n型PbTe基热电材料及其制备方法
CN114538544A (zh) * 2022-03-21 2022-05-27 中国科学院沈阳应用生态研究所 一种以废铁屑为铁源硫诱导稳定化处理含硒废水的方法

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GB1043530A (en) * 1961-12-26 1966-09-21 Minnesota Mining & Mfg Improvements in or relating to thermoelectric devices

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US2811440A (en) * 1954-12-15 1957-10-29 Baso Inc Electrically conductive compositions and method of manufacture thereof
US2811571A (en) * 1954-12-15 1957-10-29 Baso Inc Thermoelectric generators

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DE822397C (de) * 1949-02-19 1951-11-26 Siemens Schuckertwerke A G Anordnung zur elektrothermischen Kaelteerzeugung mittels Peltier-Effekt
DE823299C (de) * 1949-02-19 1951-12-03 Siemens Schuckertwerke A G Verfahren zur Herstellung von Thermoelementen zur elektrothermischen Kaelteerzeugung
DE872210C (de) * 1949-03-25 1953-03-30 Siemens Ag Anordnung zur Waermefoerderung mittels Thermoelementen, insbesondere zur elektrothermischen Kaelteerzeugung
US2602095A (en) * 1950-06-03 1952-07-01 Gen Electric Thermoelectric device
DE829171C (de) * 1950-06-15 1952-01-24 Siemens Schuckertwerke A G Elektrothermische Kaelteerzeugung
DE829170C (de) * 1950-08-17 1952-01-24 Siemens Schuckertwerke A G Einrichtung zur elektrothermischen Kaelteerzeugung
DE906813C (de) * 1951-11-03 1954-03-18 Siemens Ag Thermoelement, insbesondere zur elektrothermischen Kaelteerzeugung

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US2811440A (en) * 1954-12-15 1957-10-29 Baso Inc Electrically conductive compositions and method of manufacture thereof
US2811571A (en) * 1954-12-15 1957-10-29 Baso Inc Thermoelectric generators

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157801A (en) * 1960-03-07 1964-11-17 Itt Cooling means for thermostats
US3460008A (en) * 1965-12-08 1969-08-05 Telefunken Patent Controllable tunnel diode
US3527622A (en) * 1966-10-13 1970-09-08 Minnesota Mining & Mfg Thermoelectric composition and leg formed of lead,sulfur,and tellurium
US3460996A (en) * 1968-04-02 1969-08-12 Rca Corp Thermoelectric lead telluride base compositions and devices utilizing them
US4019113A (en) * 1974-11-20 1977-04-19 James Keith Hartman Energy conversion device
US20050056799A1 (en) * 2003-09-11 2005-03-17 Malone Steven J. Valves having a thermostatic actuator controlled by a peltier device
KR20120019701A (ko) * 2010-08-26 2012-03-07 삼성전자주식회사 열전재료, 이를 포함하는 열전모듈과 열전장치
US20120055526A1 (en) * 2010-08-26 2012-03-08 Samsung Electronics Co., Ltd. Thermoelectric material, and thermoelectric module and thermoelectric device comprising the thermoelectric material
US9093597B2 (en) * 2010-08-26 2015-07-28 Samsung Electronics Co., Ltd. Thermoelectric material, and thermoelectric module and thermoelectric device comprising the thermoelectric material
CN111799360A (zh) * 2020-07-03 2020-10-20 中国科学院合肥物质科学研究院 一种n型PbTe基热电材料及其制备方法
CN111799360B (zh) * 2020-07-03 2022-08-05 中国科学院合肥物质科学研究院 一种n型PbTe基热电材料及其制备方法
CN114538544A (zh) * 2022-03-21 2022-05-27 中国科学院沈阳应用生态研究所 一种以废铁屑为铁源硫诱导稳定化处理含硒废水的方法
CN114538544B (zh) * 2022-03-21 2023-08-18 中国科学院沈阳应用生态研究所 一种以废铁屑为铁源硫诱导稳定化处理含硒废水的方法

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DE1278111B (de) 1968-09-19
NL202808A (cs)
CH389701A (de) 1965-03-31
BE543675A (cs)
CH386504A (de) 1965-01-15
FR1143255A (fr) 1957-09-27

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