Application of the compatibility factor to the design of segmented and cascaded

thermoelectric generators
G. Jeffrey Snyder

Citation: Applied Physics Letters 84, 2436 (2004); doi: 10.1063/1.1689396
View online: http://dx.doi.org/10.1063/1.1689396
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/84/13?ver=pdfcov
Published by the AIP Publishing

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The relevant materials properties are the Seebeck demonstrate how the materials selection can be made ratio- coefficient ␣. The thermoelectric material gov. defined by z dimensional heat flow problem. A refractory metal with high p-type thermopower 共⬎100 ␮V/K兲 is required for development.gov tric generators. tance ( ␳ ␬ ⫽0) solution. 1. while filled skutterudite increases the efficiency from 10. while incompatible SiGe alloys actually reduce the efficiency. ment to another. California Institute of Technology 4800 Oak Grove Drive. Ideally.aip. the goal is to select high figure of merit materials that have similar compatibility factors. Jeffrey Snydera) Jet Propulsion Laboratory. ␳. To calculate the with temperature.or p-type兲 efficiencies were differences and a high figure of merit materials are desired. For compu- efficiency at low temperature. bility. Compatibility is most im- FIG. ⌬T. which all vary with temperature. large temperature d 共 1/u 兲 1 du d␣ drop. different materials can be segmented together ⫽⫺ 2 ⫽⫺T ⫺u ␳ ␬ .42. and similar p-type material.1689396兴 The efficiency of a thermoelectric generator is governed portant for segmented generators because the thermoelectric by the thermoelectric properties of the generator materials material properties may change dramatically from one seg- and the temperature drop across the generator.28. 09 Apr 2014 11:18:29 . Thus. The following examples ⫽ ␣ 2 / ␬ ␳ .2 The overall efficiency is close to the average of Since the material thermoelectric properties 共␣.nasa. we erns how close. Pasadena California 91109 共Received 25 November 2003. 1兲. the differential equation the same material throughout an entire. the thermal conductivity ␬. Reuse of AIP content is subject to the terms at: http://scitation.5% to 13. 共1兲 共Fig. nal by considering both z and s. These include thermal and chemical sta- side (T c ) sets the upper limit of efficiency through the Car. accepted 27 January 2004兲 Using thermoelectric compatibility. With examples. the efficiency can be to Carnot primarily consider only the thermoelectric properties in the one- through the thermoelectric figure of merit. the thermoelectric compatibility must also be considered. Schematic diagram comparing segmented and cascaded thermoelec- a兲 Electronic mail: jsnyder@jpl. High efficiency generators are designed with compatible n-type La2 Te3 . NUMBER 13 29 MARCH 2004 Application of the compatibility factor to the design of segmented and cascaded thermoelectric generators G.1063/1.and p-type single element efficiencies. The compatibility factor explains why segmentation of (AgSbTe2 ) 0. in that a material with high efficiency at high tem.15(GeTe) 0. Other factors 共not considered here兲 may also ture difference. If the compatibility factors differ by a factor of 2 or more. 关DOI: 10.85 共TAGS兲 with SnTe or PbTe produces little extra power. calculated. z. Thus. efficient thermoelectric generators are rationally designed. process- not efficiency ␩ c ⫽⌬T/T h . This article is copyrighted as indicated in the article. ing requirements. coefficient of thermal expansion.00 2436 © 2004 American Institute of Physics On: Wed. This way. to achieve high efficiency. The maximum efficiency 共determined by z兲 is only achieved1 when the relative current density u 共ratio of the electrical current density to the heat flux by conduction: u⫽J/ ␬ ⵜT兲 is equal to the compatibility factor s⫽( 冑1⫹zT ⫺1)/ ␣ T. To provide quantitative results that are easy to compare. Cascaded generators avoid the compatibility problem. The thermoelectric potential provides a simple derivation of the cascading ratio. availability and cost. For this analysis. electric efficiency. must be solved. tivity ␳. and electrical resis. heat losses. between the hot side (T h ) and the cold affect the selection. this can be approximated by combining the zero operating only in their most efficient temperature range. it is not desirable or even possible to use variation of u(T) with temperature.org/termsconditions. Downloaded to IP: 158.33 0003-6951/2004/84(13)/2436/3/$22. The tempera. APPLIED PHYSICS LETTERS VOLUME 84. © 2004 American Institute of Physics. In an efficient generator the relative current density is roughly a constant throughout a segmented element 共typi- cally u changes by less than 20%兲. ␬兲 vary the n. Thomson effect (d ␣ /dT⫽0) solution with the zero resis- We have shown1 that for the exact calculation of thermo. a given u cannot be suitable for both materials and segmentation will not be efficient. dT u dT dT perature is segmented with a different material with high derived from the heat equation. compatible and incompatible systems are explained and materials proposed for targeted development. both large temperature the single element 共n.6%. both materials are tation.

Vol. the efficiency of a single thermo- terudite (CeFe4 Sb12 and CoSb3 ) and increasing the hot side electric element 共n or p type兲 can be calculated from temperature 共e. lower than that of TAGS. the change in u at the interface between segmented materials Further increases in efficiency of PbTe/TAGS generators where ␣ is discontinuous (⌬T⫽0.00 n-pbTe/CoSb3 11.3 factors 共SiGe. 2–5兲. Maximum single element efficiencies for thermoelectric genera- ⬇0.30 100 600 700 ⫺1. or skutterudite it must have s⬎1.and n-type skut- Once u(T) is known. Efficiency Tc T interface Th u(T c ) Material 共%兲 共°C兲 共°C兲 共°C兲 共V⫺1兲 p-TAGS 10. Phys.org/termsconditions.33 p-TAGS/SnTe 11.aip. ␣ h ⫽ ␣ (T h )]. 2兲. Downloaded to IP: 158. On: Wed. Lett. 1000 is ⫺1.23 525 1000 0. Since s⬇z/2␣ . it appears that p-type PbTe would be a PbTe and skutterudite thermoelectric materials.6%.56 100 600 1000 ⫺1. FIG. p-type SiGe is so incompatible.88 p-SiGe 4. decrease in efficiency would actually occur 共Table I兲. By alloying PbTe and SnTe.56 100 525 700 2. Even if the material has low zT⬇0. the zT TABLE I. 09 Apr 2014 11:18:29 .09 100 525 600 2.5.85Fe3. ␣ c T c ⫹1/u c For the highest efficiency. polaron semiconductor. hot or cold side 关 T h ⫽hot side temperature. ideally s⬇3 V⫺1 . u(T c ) is the relative current density that gives the maximum efficiency. a high zT ma- in a decrease in efficiency 共Table I兲. Jeffrey Snyder 2437 FIG. Compatibility factor 共s兲 for p-type materials.97 p-TAGS/PbTe 10. TAGS.87 100 525 600 2.85兴 must be duce their suitability for segmentation with PbTe.87 100 600 ⫺2. Appl. SnTe has a closer com- terial that is also compatible with PbTe.4 particularly La2 Te3 . and therefore low compatibility been used successfully on several NASA space missions.85 p-TAGS/SiGe 9.g. can be achieved by segmenting with both p. power.46 n-PbTe/La2 Te3 15.42. only have high zT..76 100 600 1000 ⫺1. the lower zT. Filled where ⌬ ␣ ⫽ ␣ (T 2 )⫺ ␣ (T 1 ) and ␳ ␬ denotes the average of skutterudite produces over twice the increase in efficiency ␳␬ between T 1 and T 2 . a segment of another p-type Rare earth chalcogenides. or maintained below 525 °C 共or lower for long term applica. To utilize La2 Te3 in the n ele- produces a higher efficiency segmented generator. 3兲 for p-PbTe drops much 9. To achieve a 600 °C system.97 n-PbTe/SiGe 13. 3. 1 1 ⫽ 冑1⫺2u 21 ␳ ␬ ⌬T⫺T̄⌬ ␣ .89 100 525 1000 1. A compatible and high efficiency material to segment 共2兲 u2 u1 with TAGS is p-type filled skutterudite such as Ce0.5Co0. it is necessary to use the high- ␩ ⫽1⫺ .4 have low electrical conductivity with a mented p-type thermoelectric generator element that has high Seebeck coefficient. 共3兲 ␣ h T h ⫹1/u h est temperature difference possible because of the Carnot factor. the compatibility factor 共Fig. 5 not material is added to the TAGS p leg between 525 and 600 °C. Equation 共2兲 is also valid to calculate 共Table I兲 compared to SnTe. How- PbTe with La2 Te3 results in an increase in efficiency from ever. Many of the refractory materials with high zT. and thus dite has not been identified. For a material with a low and this is used in actual TAGS generators.12 n-PbTe 9. Figure of merit 共zT兲 for p-type materials. 84. No.44 600 the article. to 700 °C in Table I兲. it will produce some a more compatible material is produced with acceptable zT. or boron carbide. 13. zT to be compatible with PbTe. as long as it is compatible. 29 March 2004 G. consider the TAGS-SnTe seg.5 V⫺1 . that a tions兲.29 Reuse of AIP content subject to the terms at: http://scitation.28.⌬ ␣ ⫽0).45 100 525 2. The thermoelectric hot side in a thermoelectric gen- The subscripts h and c denote the value at the thermoelectric erator used for space applications can achieve 1000 °C. while the PbTe n-type element can operate to 600 °C.33 FIG. compared to PbTe. and segmentation actually results For the high temperature p-type element. or skutteru- patibility factor to TAGS 共higher is also beneficial兲.84 p-TAGS/CeFe4 Sb12 11.80 n-SiGe This article is copyrighted as indicated in5. 2. TAGS.5Sb12 (CeFe4 Sb12 in Figs.. The low compatibility factors re- The TAGS material 关 (AgSbTe2 ) 0. but also have higher s compatible with From zT 共Fig. Figure of merit 共zT兲 for n-type materials. despite ment. 4. 2 and 3兲. Segmenting better choice than SnTe for the 525– 600 °C segment.9% to 15. skutterudite materials. TAGS.5 material cannot be a high Seebeck coefficient band or tors.33 100 525 600 2. some high temperature p-type material must be used. such as SiGe As the first example.94 p-TAGS/CeFe4 Sb12 13. Figs.15(GeTe) 0.

stages directly to the load. This can be expressed suc. Long Beach. Jeffrey Snyder cinctly by using the thermoelectric potential ⌽⫽ ␣ T⫹1/u 共Ref. Lett. Compatibility factor 共s兲 for n-type materials 共negative兲.6 For SiGe cascaded with TAGS/PbTe. With this cas- and ␳ increasing linearly with T. under contract with NASA. and Fig. 531. 1471 共1958兲. Phys. 7兲.n T⫺ s 2. gives: ties typical of high ␣ metals. Ursell and G.冊 共4兲 which includes the Peltier and conduction heat terms 共the Peltier contribution is missing in Ref. operating with the same electrical current I. Thus.39%⫹4.n ⫽ ⬇ . CA 共IEEE. 7 T.28. because if they have low electrical resistance they will Thierry Caillat for skutterudite data. In practice. there will Technology. PA. New temperature stage 共Fig. Skrabek and D. Phys. heat out of the hot stage to the heat input to the cold stage. J. J.p s 1. 1. much like a p-type version of La2 Te3 . M. 2 G. California Institute of Franz law兲. Appl. ture between the two stages. the material that is most necessary for the devel- ␬兲 are constant with respect to temperature is given by opment of high efficiency thermoelectric generators is a re- Harman. 13. 91. Ben Heshmatpour for TAGS. T in the following formulas is the interface tempera.33 On: Wed. FL. Energy for the here called the cascading ratio. 5. C. Equating the heat from N 1 stage 1 couples with N 2 stage 2 couples. and C. Tristan Ursell for preliminary work. 3 The differing values of u are provided by having a dif. 1兲. Snyder and T. Raag. u will be approximately equal FIG. to s. This article is copyrighted as indicated in the article. number of couples (N 2 /N 1 ) in the cooler stage 共Stage 2. 2002兲. 1985兲.4 N2 ⌽1 s 1. La Grande Motte. in principle. Materials with high z and s have thermoelectric proper. 84. 459 共1988兲. Such connectors would be ineffi. J. Snyder. In this way. E. and SnTe data. 6 T. out by the Jet Propulsion Laboratory. S. 09 Apr 2014 11:18:29 . Downloaded to IP: 158. 1兲. In a cas- mum efficiency of a stage is approximately the average of caded system 共Fig. Warrendale. in Thermoelectric Handbook. be additional Joule losses. S. 412. optimal values of u can be The author thanks Katherine Whitehead for program- used for each stage. so that there should be about twice as ficient.org/termsconditions. Vol. For maximum efficiency. This work was carried conduct heat away from the hot side 共due to Wiedemann. N 2 5 L.p s 2. and cient. Wood.p T⫹ ⫺ ␣ 2. York.39%⫽14. 共5兲 ⫻10⫺8 V2 /K2 . where L⬇2. France 共IEEE. edited by ferent number of couples in each stage. Rev. p. 3. To avoid such losses. Vol. 2003兲. which has ␣ many TAGS/PbTe couples as SiGe couples. the optimum fractory p-type metal with a reasonably high Seebeck coef- cascading ratio is 2. it is best not to connect the high temperature useful discussions. New York. 51. 4 C. A. Wood. Reuse of AIP content is subject to the terms at: http://scitation. in Proceedings of ICT’03: The Twenty-second International load by going through the thermoelectric elements of the low Conference on Thermoelectrics. The rate of heat entering or existing a thermoelec- tric couple is simply the current I times the sum of the ther- moelectric potential for the n and p elements: 冉 Q couple⫽I⌽ couple⫽I ␣ p T⫹ 1 up ⫺ ␣ n T⫺ 1 un . The approximation where the thermoelectric properties 共␣.p T⫹ ⫺ ␣ 1. V. 267. the thermal conduc- 1 1 tivity is dominated by the electronic contribution given by ␣ 1.and p-type element兲. cading ratio.aip. 29. Phys.6 is derived by equating the Twenty-First Century 共SAE. independent the n. 148301 共2003兲. The ratio of the D. p. 2438 Appl. In a metal. in Proceedings of the 20th Inter- couples兲 to that of the hotter stage 共Stage 1.. PbTe. Rowe 共CRC. International Conference on Thermoelectrics. if they have high electrical resistance. No. Rep. Jean-Pierre Fleurial for SiGe data. the electrical current should pass from the high temperature stage to the 1 G.42. Snyder. Danielson.n 100 ␮V/K at 1000 K. p. 1995兲. Ursell. in Proceedings of ICT’02: The Twenty-first Thus. N 1 couples兲. allowing for independent values of u. Lett.2 electrical circuits for each stage. ming the calculations.78% 共the maxi- stead of segmenting兲 a thermoelectric generator. Harman. society Energy Conversion Engineering Conference. the efficiency of the generator can achieve the The compatibility issue can be avoided by cascading 共in- sum of the two stages.21. Prog. Phys.n T⫺ the Wiedemann-Franz law ␬ e ⫽LT/ ␳ . The compatibility factor s⬇ ␣ /(2 ␬ ␳ ) N1 ⌽2 1 1 ⬇ ␣ /(2LT) would then be appropriate if ␣ is greater than ␣ 2. different. 10. Boca Raton. J. Trimmer. R. 29 March 2004 G. 1兲 there are. ␳.