Journal of ELECTRONIC MATERIALS, Vol. 38, No.

7, 2009

Special Issue Paper

DOI: 10.1007/s11664-009-0680-z 2009 TMS

Automotive Applications of Thermoelectric Materials

JIHUI YANG1,3 and FRANCIS R. STABLER2
1.Materials and Processes Lab, GM R&D Center, Warren, MI 48090, USA. 2.Future Tech, LLC, 2096 Cameo Drive, Troy, MI 48098-2409, USA. 3.e-mail: jihui.yang@gm.com

This report reviews several existing and potential automotive applications of thermoelectric technology. Material and device issues related to automotive applications are discussed. Challenges for automotive thermoelectric applications are highlighted. Key words: Thermoelectric materials, automotive waste heat recovery, thermoelectric applications

INTRODUCTION Automotive applications for thermoelectric materials are growing in importance, driven by the customers desire for high efciency and for more features. Most thermoelectric applications can be divided into one of two segments. One segment is based on the Peltier effect and is focused on various applications of heating or cooling. The other segment is based on the Seebeck effect and is focused on power generation, primarily from waste heat. The heating and cooling applications will be addressed rst because some of these applications are already in production. PELTIER EFFECT APPLICATIONS: HEATING AND COOLING While vehicle customers need and expect high efciency from vehicles, there is a competing demand for additional features for comfort and convenience. Thermoelectric materials can offer vehicle owners several unique features by providing heating and cooling for various items on the vehicle. Seats with thermoelectric heating and cooling are available today and have been in production for almost a decade in many luxury vehicles. Cup holders that keep beverages hot or cold are available on a few models. Small thermoelectric refrigerators or wine coolers are available as features for limousines and recreational vehicles. Numerous after-market manufacturers are producing warmercooler units for

automotive use. These units can be set to cool or heat food and drink using the 12-V power from a vehicle. Many of these warmercooler units are portable and can be used in any location where electric power is available. All of these thermoelectric systems offer the benet of being small, relatively lightweight, and silent in operation. These unique features make thermoelectric technology very attractive even though the efciency is low. The most promising area for application of the Peltier effect has been discussed in numerous patents, papers, and presentations, but has not reached production yet. This delay in production application has been due in part to the relatively low efciency of thermoelectric materials (low ZT and low coefcient of performance). The impact on the vehicle design has been an additional part of the delay. Thermoelectric materials have the potential to revolutionize automotive heating, ventilation, and air-conditioning (HVAC) systems. Improved thermoelectric materials can enable the production of HVAC systems with several very desirable and unique features:  No Greenhouse gases required for refrigerant  Silent operation  Faster operation, especially faster delivery of warm air on cold starts  Potentially lighter weight systems  Potential of more energy-efcient cooling  Ability to heat or cool the passenger compartment without engine operation (hybrids, engine off when vehicle stops, remote HVAC activation without engine start, etc.)  Increased reliability and durability due to no or few moving parts
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(Received July 30, 2008; accepted January 15, 2009; published online February 13, 2009)

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HVAC systems based on thermoelectric modules can contribute to the acceptance of hybrid, electric, or fuel cell vehicles where quiet operation without the need for mechanical input is a needed capability. There are at least two distinctly different approaches for thermoelectric HVAC systems: direct replacement or a new distributed system. Direct Replacement of Existing HVAC Systems The direct replacement approach would retain the single-point HVAC system where one unit in the vehicle rewall distributes heated or cooled air through a vent system in the instrument panel. The thermoelectric modules would provide the heating or cooling of the air, eliminating the need for the current heater core, compressor-evaporator system, pipes, and AC radiator, and much of the engine compartment complexity. There is the possibility that engine coolant will be needed to provide or remove heat from the thermoelectric modules. This simplies the packaging of the HVAC components and has limited impact on the passenger cabin. Figure 1 provides one possible embodiment of a thermoelectric HVAC system. This approach may save some mass and operating power (depending on the performance of the available materials). As vehicles become more efcient, both gasoline and diesel engines take much longer to warm up and provide adequate coolant temperature to warm the passenger compartment. Thermoelectric systems can offer a solution to this problem by heating air to the passenger compartment within seconds of activation. While this design would be relatively easy to package and has several benets, it does not take full advantage of features offered by thermoelectric systems. Distributed HVAC System A completely new vehicle cabin design to incorporate a distributed HVAC system would be a much more difcult project; however, it has the potential to offer much more for the customer. It would offer all of the features mentioned above plus several unique ones. A distributed design has the potential to offer the following:
Major Thermoelectric HVAC Functions
Fluid In Source Side Heat Exchanger Thermoelectric Modules Air In Cabin Side Heat Exchanger Fluid Out Electric Power Air Out
Vehicle Coolant Hot for heating, cold for cooling Added pumps / flow controls

 Faster cooling and heating than either current HVAC systems or a new direct replacement system  Lower power requirements and ultimately increased fuel efciency  Less wasted energy by heating or cooling only the passengers, not empty seats  Lighter weight system and better packaging, especially less impact on the instrument panel  Ability to provide individual temperature control for each passenger or sector of the vehicle (partially available today with conventional systems)  Better temperature control, especially for rearseat passengers To design a successful distributed HVAC system, much research is needed on how people perceive a comfortable temperature for their environment. Air temperature, air movement, surface temperatures, and other subtle factors all play a part in achieving the desired result for all passengers. Thermoelectric modules would offer a designer the ability to cool or heat surfaces the passengers touch in addition to controlling air temperature. This is the downside of the distributed system. Much of the passenger cabin would have to be redesigned and many passive components such as seats, arm rests, steering wheel, and possibly the head liner would become active parts of the HVAC system. The heated and cooled seats offered in some current cars are an initial example of this capability. Even control of air temperature could change since it would be possible to have many small sources of air ow rather than a central source. Using a system similar to or shared with the airbag system, the distributed HVAC system could activate only the portions needed to provide a comfortable environment for the passengers, not empty areas. The success of these features depends on the efciency of the thermoelectric modules used for heating and cooling and even more importantly on the availability of economical modules. It is desirable to have high-performance materials because they allow higher efciency (less electric power demand from the vehicle) and smaller systems (lighter, easier to package systems). Specic design of thermoelectric components for a distributed system will require signicant interior component redesign, many that are vehicle specic, to have an efcient system. The general design will be small units similar to that shown in Fig. 1 with air being the source in some cases and some vehicle surfaces being cooled or heated instead of cabin air. There are other applications of the Peltier effect on automobiles that would not be features directly observed by the customer, but important to vehicle performance and durability. These involve controlling the temperature of certain vehicle systems to keep them within the desired temperature range for proper, reliable operation. Some of the applications could include the following:

Power Source & Vehicle Interface

Cabin Air

Current flow to TE modules in one direction for heating cabin air and reversed for cooling

Fig. 1. Major TE functions of a direct-replacement HVAC system.

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Thermoelectric Generator (TEG) Functions
Hot Fluid In
(Exhaust Gas or Coolant)

 Warming or cooling the lead-acid starter battery to improve its durability and ability to accept a charge at very low or high ambient temperatures1  Assisting in temperature management of the catalytic converter for optimum life and emissions after-treatment performance2  Temperature management for the battery packs of hybrid vehicles  Cooling critical electronics to prevent damage due to high-temperature conditions Not all of these applications will be implemented, but there are likely many more applications not listed here. The cost of thermoelectric units added to systems for increased durability will have to be justied by the added value provided to those systems. SEEBECK EFFECT APPLICATIONS: POWER GENERATION The world currently faces numerous problems relating to transportation energy. The global demand for oil is continuing to increase with record high prices for a barrel of oil. In most countries, the price of a liter or gallon of gasoline or diesel fuel is at record highs and increasing. There is growing concern about the effect of greenhouse gases, especially carbon dioxide, on the environment. All of these issues are driving the demand for obtaining more useful energy from every gallon of fuel burned. Many new engine, transmission, and vehicle technologies are being produced or are in development to make vehicle transportation more fuel efcient. All of these technologies are missing one important issue: much of the energy from a gallon of fuel will still be unusable heat in the vehicle exhaust or cooling system (Fig. 2). Thermoelectrics represent a technology that can make use of this waste heat. By converting some of a vehicles waste heat to electric power, the electric generators mechanical load on the engine can be reduced or eliminated, improving vehicle fuel efciency. Additional fuel efciency may be achievable through weight reduction or

Hot Side Heat Exchanger Thermoelectric Modules Cold Side Heat Exchanger

Hot Fluid Out

Electric Power

Power Conditioning & Vehicle Interface

Cold Fluid In
(Coolant or Air)

Cold Fluid Out

Fig. 3. Major functions of a TEG.

more efcient operation of the HVAC system as discussed above. An automotive thermoelectric generator (TEG), using waste heat as its energy source, consists of several general components (Fig. 3): 1. A heat exchanger to take heat from the exhaust gases or engine coolant and deliver it to the hot side of the thermoelectric modules 2. Thermoelectric modules with good conversion efciency (heat to electricity) in the available temperature range 3. A heat exchanger to maintain the cold side of the thermoelectric modules by taking heat from the modules and radiating it to a liquid coolant or to the air 4. An electrical power conditioning and interface unit to match the power output of the thermoelectric modules to the vehicle electrical system Additional items and functions may be required by the system depending on the design and the vehicle application. Examples of this could include items such as the following:  An electronic unit to monitor and control the operation of the TEG and possibly interface with the engine control unit and/or the generator  An electric pump to control the ow of coolant to the TEG  Sensors for temperatures and ow rates to improve control of the TEG

Vehicle Operation Combustion 30% Engine 25% Mobility & Accessories

Gasoline

Gasoline

Gasoline

100%

5% Friction & Parasitic Losses 30% Coolant

40% Exhaust Gas

Fig. 2. Typical energy path for vehicles with gasoline-fueled internal combustion engines.

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 An exhaust ow control to bypass the TEG when the gases are too hot  Added valves to control the coolant ow to and from the engine or radiator  Additional fans for air cooling the radiator or the cold side of the TEG  Incorporating the mufer function into an exhaust system TEG or using the system to help manage catalytic converter temperature2 When designing a TEG, the thermoelectric modules must be selected to have optimum (high) ZT (the gure of merit for thermoelectric materials, which will be dened later) in the typically available temperature range, which will vary somewhat with the type of vehicle and engine. The design must also provide protection for the modules in the event of temperature extremes that can be found on a vehicle. If a sufciently efcient TEG can be designed, it may be desirable to include a fuel combustion unit to provide heat to generate electric power from the TEG when waste heat is not available.3 This could benet conventional vehicles that turn off the engine for fuel savings on deceleration and when stopped since the alternative is to operate from inefcient batteries during these events. The use of the power from a TEG may seem simple, but how a vehicle uses electric power must be considered. In most US government emission and fuel economy tests, a vehicle is tested with all optional systems turned off, limiting electrical usage to 250 W to 350 W. This is far different from the more typical 300 W to 1500 W of electrical power used by a customers vehicle in general use. To achieve fuel economy based on government testing, additional vehicle modications will be needed to use the electrical power generated by a TEG with output greater than about 300 W. The modications should reduce or remove some mechanical loads from the engine and could include items such as electric water or oil pumps. In normal driving, the typical customer will have electrical loads that are greater than the TEG output; therefore, any electrical power generated from waste heat will improve real-world fuel economy. The more electrical power generated by a TEG, the better for the customer and the world, because less fuel will be burned. Use of a TEG on a hybrid electric vehicle is an especially desirable conguration if large amounts of electrical power can be generated (>1 kW or 2 kW). MATERIALS REQUIREMENTS The performance of a thermoelectric material is determined by the dimensionless thermoelectric gure of merit4 ZT S2 T qj (1)

thermal conductivity, which includes a lattice (jL) and an electronic (je) component. The efciency of a TEG can be estimated by4 p TH TC 1 ZT 1 e (2) p T ; TH 1 ZT T C
H

where TH and TC are the hot-side and cold-side temperatures of the thermoelectric materials, respectively. The maximum coefcient of performance COPmax (the heat absorption rate versus the input electrical power) of a thermoelectric cooler is approximately given by4 p T 1 ZT H TC p TC : (3) COPmax TH TC 1 ZT 1 It is therefore evident that higher material ZT values would lead to higher TEG efciency and higher COP. A thermoelectric cooler with ZT > 2 materials could have higher COP values than a mechanical compressor-based air-conditioning unit.5 In the case of TEG, the efciency improvement is much more signicant between ZT = 1 and 2 than between ZT = 2 and 3.5 The entire thermoelectric cooling industry currently uses ZT  1 materials; however, materials with ZT 2 would certainly facilitate bringing many potential thermoelectric applications, including automotive applications, into practical reality. In the past decade, we have witnessed signicant ZT increases in various materials,5,6 some of which will be discussed in a later section. Higher ZT values in the operational temperature range, however, are not the only concerns. The materials need to be chemically stable and mechanically robust at elevated temperatures or with large temperature gradients; for example, the materials used for radioisotope TEGs in space applications often experience hot-side sublimation,5 which could lead to substantial cross-sectional area decrease, electrical power output reduction, and mechanical failure. For almost all known high-ZT materials, their ZT versus T curves peak slightly lower than the material degradation (melting, sublimation, etc.) temperatures. We are hence left with the dilemma that, from the performance point of view, one would like to optimize the materials so that their highest ZT values fall in the temperature range of the applications. On the other hand, the materials highest ZT values usually occur near the degradation temperatures. Over the years many techniques, such as inert-gas environment and various coatings, have been developed to mitigate materials sublimation over the service period.5,7 In the case of automotive exhaust waste heat recovery, the average exhaust temperature for various vehicles is between 500C and 600C, with maximum values up to 1000C under certain operating conditions. Therefore, proper measures on the device and subsystem levels need to be in place to protect materials from deterioration.

where S is the Seebeck coefcient, q the electrical resistance, T the absolute temperature, and j the

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4 PbSexTe1-x/PbTe quantum dots 3 Bi2Te3/Sb2Te3 superlattices

Another potential issue is the mechanical strength of thermoelectric materials. In the automotive thermoelectric applications, thermal gradient, thermal cycling, and vibration will impose stress on the thermoelectric materials. In addition, most thermoelectric materials are brittle semiconductors; therefore, fracture strength and fracture toughness are critical for determining mechanical failure mechanisms.8 In addition, elastic properties such as the Youngs modulus, shear modulus, Poissons ratio, and thermal expansion coefcient are needed for TE module design and optimization. There has been very limited data published on mechanical properties of thermoelectric materials, let alone their temperature dependence.812 Successful thermoelectric technology development will require mechanical property characterization and understanding, and materials synthesis processes to improve materials mechanical integrity, such as grain size, aw size, and edge aw controls.8 Furthermore, thermoelectric modules are made of both p- and n-type thermoelectric materials. It is ideal to have the same type of materials on the n- and p-legs with similar ZT curves. This will allow maximum module performance, reduce stress induced by the unbalanced thermal expansion coefcients of the two legs, and simplify the module manufacturing process by using the same diffusion barriers and electrical contact materials. DEVICE CONSIDERATIONS The choice of interconnect materials at the hot and cold sides are critical for device fabrication. First, the interconnect materials and the thermoelectric materials should have comparable thermal expansion coefcients to minimize stress at the joints. Second, the interconnect materials should have high electrical and thermal conductivity values at operating temperatures to minimize electrical and thermal contact resistance. Third, the interconnect materials should not be easily oxidized. Fourth, the interconnect materials and the thermoelectric materials should not react chemically. Finally, the diffusion layer between the two should be a few microns thick to ensure good contact and should be stable at the hotside temperature over time. Details of interconnect materials development for thermoelectric coolers and generators have been presented elsewhere.1317 RECENT MATERIALS DEVELOPMENT Many recent materials research advances have invigorated worldwide interest not only in materials research but also in technology development, including the automotive applications. Figure 4 shows the ZT versus T curves for many state-of-thepractice and state-of-the-art materials. All state-ofthe-practice materials have maximum ZT values 1. Almost all ZTmax > 1 materials were developed in the past 15 years. Many recent reviews have been devoted to new thermoelectric materials progress.6,18

AgPb18SbTe20
Yb0.19Co4Sb12 (n-type)

ZT

2
Ba0.08Yb0.09Co4Sb12 (n-type) La CoFe Sb
0.9 3

BiSb 1 Bi2Te3

12

(p-type)

SiGe

PbTe

200

400

600

800

1000

1200

1400

T (K)
Fig. 4. ZT versus T for state-of-the-practice (symbols with lines) and state-of-the-art materials (lines only).

Here we only focus on a few of the latest ones, and their relevance to automotive applications. Nanostructured Materials In 1993, Hicks and Dresselhaus proposed that low dimensionality in materials could result in enhanced electronic density of states near the Fermi energy. This could lead to larger Seebeck coefcients, and in nanostructured materials boundary scattering can affect phonons more than electrons.19 Subsequent works have shown signicant ZT improvement in Bi2Te3/Sb2Te3 superlattices, PbSexTe1x/PbTe quantum dot superlattices, and two-dimensional electron gas in SrTiO3.2023 Of particular interest are high-efciency bulk (PbTe)1x(AgSbTe2)x (x @ 0.05) nanocomposites that have achieved very high ZT @ 2.1 at 800 K (shown in Fig. 4),24 since nanostructured bulk materials have the advantage of being scalable for practical energy conversion. These high ZT values were attributed to nanoprecipitates observed in the materials. This suggests that it may be possible to achieve high ZT values of superlattices and quantum dots in bulk materials, if the results can be independently reproduced. Though Seebeck coefcient enhancement was postulated,19 most of the ZT gains in recent materials come from thermal conductivity reduction. This is certainly the case for recent work on Si nanowires and nanograin Bi2Te3 alloys.2527 In addition, real-world vehicle applications require materials to be stable over a long period of time (several to 10 years) under elevated temperatures. Nanostructured materials thermal stability under various application temperature ranges needs to be investigated and addressed. Bulk Semiconductors Filled skutterudites, semiconducting clathrates, and complex chalcogenides are amongst a few

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Fig. 5. Temperature dependence of ZT for Ba0.08Yb0.09Co4Sb12.12, BaxNi0.05Co3.95Sb12,33 and (AgSbTe2)0.85(GeTe)0.15.34

prospective bulk materials for advance applications.2830 In particular, lled skutterudites have the advantage of high ZT values in the temperature range of automotive exhaust heat (Fig. 4), availability of both n- and p-type material, and mechanical robustness. Based on the idea of multiple-frequency phonon resonant scattering,31 signicant ZT enhancement has been achieved for double-lled skutterudites.32 Figure 5 shows that ZT values in (Ba0.08Yb0.09Co4Sb12.12) are almost 0.2 higher than those of n-type skutterudite BaxNi0.05Co3.95Sb1233 over the entire temperature range investigated. Also, the ZT of this material is twice as high as that of optimized (AgSbTe2)0.15(GeTe)0.8534 at room temperature, and 0.2 higher near 800 K. Complex Oxides Several layered hexagonal cobalt oxides discovered by various Japanese groups have shown very good thermoelectric performance at elevated temperatures.3537 A common feature of these materials is the presence of hexagonal CoO2 layers. The high Seebeck coefcients observed are attributed to spin entropy contributions. Oxide materials are very attractive for practical applications because of their stability at elevated temperatures, low-cost raw materials, and relatively simple synthesis methods. Interestingly, a 140-couple oxide TEG module was successfully constructed which demonstrated reasonable power output.38 The development of high-performance n-type oxides, however, remains challenging. If successful, an oxide-based TEG could be very attractive for automotive applications. CHALLENGES FOR TEG APPLICATIONS The demonstrated long-term durability of thermoelectric power generators is very impressive with

20 years to 30 years of continuous operation in spacecraft and remote monitor applications. These applications, however, have been continuous operation with little or no thermal cycling and no vibration. A major challenge to automotive powergeneration applications will be the thermal cycling and severe mechanical vibration that could degrade the thermoelectric modules. Signicant testing will be required to validate the durability of thermoelectric modules in automotive applications. In addition, cost and efciency are competing issues. Higher-ZT materials are needed to get more electrical power, but they typically cost more. The challenge for researchers is to nd materials that balance cost against efciency. Matching the temperature of the heat source to the proper thermoelectric module type will be difcult. Part of the problem is that the temperature across a heat exchanger could drop between input and output. Additionally, the vehicle source temperature varies with vehicle operating cycle and time. An additional issue is the need to have an efcient material (high ZT) in the nominal temperature range while avoiding module damage at peak temperatures. As additional technologies are added to engines to improve fuel efciency, the amount of waste heat will be reduced and exhaust temperatures will be lowered. This will require more efciency from TEGs to make them cost effective. TEG use on hybrid electric vehicles will face additional challenges of intermittent engine operation under various driving cycles and lower total waste heat relative to a conventional vehicle. Efcient operation of the TEG heat exchangers over the life of 10 years to 30 years of a vehicle is a concern. The effect of material buildup on the heat exchanger surfaces from exhaust gas, coolant, or air is basically unknown and needs research to ensure that it does not excessively degrade system operation. Automotive manufacturers need the availability of economical thermoelectric modules in sufcient quantities to support automotive production volume if HVAC and TEG applications grow rapidly. Even a relatively small 10% penetration of the worlds automotive production by thermoelectric technology would require an estimated 6 9 109 W of electric power generating capacity from TEG each year, and twice that for power cooling and heating. There are competing technologies that could be cost competitive for TEGs if economical efcient thermoelectric materials cannot be developed for production quickly. These technologies include generators driven by small Rankine cycle engines, Stirling engines, or turbos, all operating from exhaust heat or ow. SUMMARY Automotive applications for heating and cooling have started with currently available thermoelectric

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modules. The low efciency of these units is offset by the unique features they provide. As advanced thermoelectric materials become available with volume production quantities and economics, the improved efciency has the potential to rapidly expand automotive applications. For both HVAC and electric power-generation applications, environmental issues will play a signicant part in selection of thermoelectric technology, but the real measure will be in cents per watt in high volume at the material, module, and system levels. ACKNOWLEDGEMENTS J. Yang wants to thank Drs. Jan F. Herbst and Mark W. Verbrugge for continuous support and encouragement. The work is supported by GM and by DOE under corporate agreement DE-FC2604NT42278. REFERENCES
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