The U.S. military uses large amounts of fuel during deployments and battlefield operations. Consequently, the U.S. military has a strong need to develop technologies that increase fuel efficiency and minimize fuel requirements all along the logistics trail and in all battlefield operations. There are additional requirements to reduce and minimize the environmental footprint of various military equipment and operations and reduce the need for batteries (non-rechargeable) in battlefield operations. The tri-agency SERDP (Strategic Environmental Research and Development Program) office is sponsoring a challenging, high-payoff project to develop a lightweight, small form-factor, soldier-portable advanced thermoelectric generator (TEG) system prototype to recover and convert waste heat from a variety of deployed equipment with the ultimate purpose of obtaining additional power for soldier battery charging, advanced capacitor charging, and other battlefield power applications. The project seeks to achieve power conversion efficiencies of 10% (double current commercial TE conversion efficiencies) in a system with ˜1.6-kW power output for a spectrum of battlefield power applications. In order to meet this objective, the project is taking on the multi-faceted challenges of tailoring LAST/LASTT-based thermoelectric (TE) materials for the proper temperature ranges (300 K – 700 K), fabricating these materials with cost-effective hot-pressed and sintered processes while maintaining their TE properties, measuring and characterizing their thermal fatigue and structural properties, developing the proper manufacturing processes for the TE materials and modules, designing and fabricating the necessary microtechnology heat exchangers, and fabricating and testing the final TEG system. The ultimate goal is to provide an opportunity to deploy these TEG systems in a wide variety of current military equipment. This would help the Army in achieving one of the Office of Secretary of Defense’s major strategic objectives to maintain and enhance operational effectiveness while reducing total force energy demands. The presentation will review the progress made on 1) the performance of LAST / LASTT TE materials and tailoring their temperature dependency; 2) evaluating the structural (Elastic modulus, Poisson’s ratio and mechanical strength) properties of these materials, 3) development of the necessary LAST/LASTT-based TE modules, 4) development of the required hot- and cold-side microtechnology heat exchangers, and 5) the overall system designs for 30 kW and 60 kW TQG applications and potential performance pathways/differences for these two TQG cases. This work leverages critical fundamental research performed by the Office of Naval Research in developing LAST/LASTT materials.

Thermoelectric modules are of great interest for power generation applications where temperature gradients of approximately 500K exist, and hot side temperatures near 800K. The fabrication of such modules requires optimization of the material compositions, low contact resistivities, and low thermal loss.

AgPbmSbTe2+m (LAST) and Ag(Pb1-xSnx)m SbTe2+m (LASTT) compounds are among the best known materials appropriate for this temperature range. Various measurement systems have been developed and used to characterize bulk samples in the LAST and LASTT systems within this operating temperature range. From the characterized data, modeling of modules based on these materials and segmented legs using LAST(T) with Bi2Te3 have been used to identify the optimal geometry for the individual legs, and the length of the Bi2Te3 segments. We have segmented LAST(T) with Bi2Te3 and achieved contact resistivities of less than 10 μΩ•cm2.

Here we give a detailed presentation on the procedures used in the fabrication of thermoelectric generators based on LAST, LASTT, and segmented with Bi2Te3 materials. We also present the output data on these generators.

Low electrical contact resistance is essential for the fabrication of high efficiency thermoelectric generators in order to convert heat to electricity. These contacts must be stable to high temperatures and through thermal cycling. A ratio of the contact resistance to the leg resistance below 0.1 is the goal for fabrication of a high efficiency thermoelectric power generation device. Here we present the fabrication procedures and characterization of contacts of metal alloys to Pb-Sb-Ag-Te (LAST) and Pb-Sb-Ag-Sn-Te (LASTT) compounds. Contacts were fabricated and measured for both ingot and hot pressed materials. Stainless steel 316 has shown a low resistance contact to these thermoelectric materials when the proper bonding conditions are used. Different time-temperature-pressure conditions for bonding to n-type and to p-type legs are presented. Contact resistances below 10μΩcm2 have been measured. In addition, break tests have shown bond strengths exceeding the semiconductor fracture strength. One of the considerations used in selecting iron alloys for electrical interconnects is the similarity in the coefficient of thermal expansion to the LAST and LASTT materials which is 18 ppm/°C and relatively temperature insensitive. Contacts to the thermoelectric materials were accomplished by diffusion bonding in a furnace developed in our lab at Michigan State University. The furnace is capable of reaching temperatures of up to 1000°C with a controlled atmosphere of a reducing gas. Fabrication procedures and contact data are presented in this paper.

We report the synthesis of nanostructured composite PbTe with excess Pb and Sb metal inclusions. Scanning and transmission electron microscopy reveal these inclusions in both the nano- and macroscales. The electrical conductivity and Seebeck coefficient dependence on temperature show unusual trends which depend on the inclusion Pb/Sb ratio. Several ratios showed marked enhancements in power factor at 700 K. The thermal conductivity of these composites is reported.

Low electrical contact resistance is essential for the fabrication of high efficiency thermoelectric generators. These contacts must be stable to high temperatures and through thermal cycling. Here we present the fabrication procedure and characterization of several contacts to Pb-Sb-Ag-Te (LAST) compounds. Contact materials investigated include tungsten, antimony, tin, nickel, and bismuth antimony based solder. The contacts were typically deposited by an electron beam evaporation method after careful preparation of the sample surface. The resistances were measured by using the transmission line model, and ohmic behavior was verified through current vs. voltage measurements. The best contact resistivities of less than 20 µΩ·cm2 have been measured for annealed antimony to n-type LAST samples. We present these procedures for fabricating low resistance contacts and the use of these procedures towards the fabrication of high efficiency thermoelectric generator modules.

Lead-Antimony-Silver-Tellurium (L-A-S-T) materials, synthesized at Michigan State University, show promising thermoelectric properties at high temperatures for use in power generation applications. Recent scaled-up quantities of L-A-S-T show a ZT=1.4 at 700 K approaching the figure of merit for samples made in small quantities. These materials are of great interest for power generation applications with hot side temperatures in the range of 600-800 K. Developing these materials into working devices requires minimization of the thermal and electrical parasitic contact resistances, so various fabrication methods are under investigation. To examine each method, a new measurement system has been developed to characterize these devices under various load and temperature gradients. An introduction to the system will be presented, as well as results for devices made of the L-A-S-T materials.

The thermoelectric properties of Pb9.6SbyTe10−xSex were investigated in the intermediate temperature range of 300 – 700 K. The effect of the variation of Sb content (y) on the electronic properties of the materials is remarkable. Samples with compositions Pb9.6Sb0.2Te10−xSex (y = 0.2) show the best combination of low thermal conductivity with moderate electrical conductivity and thermopower. For Pb9.6Sb0.2Te8Se2 (x = 2) a maximum figure of merit of ZT ∼ 1.1 was obtained around 700 K. This value is nearly 1.4 times higher than that of PbTe at 700 K. This enhancement of the figure of merit of Pb9.6Sb0.2Te8Se2 derives from its extremely low thermal conductivity (∼0.7 at W/m.K at 700 K). High resolution transmission electron microscopy of Pb9.6Sb0.2Te10−xSex samples shows broadly distributed Sb-rich nanocrystals, which may be the key feature responsible for the suppression of the thermal conductivity.

High efficiency thermoelectric modules are of great interest for power generation applications where hot side temperatures of approximately 800K exist. The fabrication of such modules requires a multidisciplinary effort for the optimization of the material compositions, the engineering of the module systems, modeling and fabrication of the devices, and constant feedback from characterization. Pb-Sb-Ag-Te (LAST) and Pb-Sb-Ag-Sn-Te (LASTT) compounds are among the best known materials for this temperature range. Modeling of these materials and possible cascaded structures shows efficiencies of 14% can be achieved for low resistance contacts. Using antimony we have achieved contact resistivities less than 20 µΩ·cm2. Here we give a detailed presentation on the procedures used in the fabrication of thermoelectric generators based on these new materials. We also present the characterization systems and measurements on these generators.