Thermoelectric Generators Linking Material Propert PDF
Thermoelectric Generators Linking Material Propert PDF
Thermoelectric Generators Linking Material Propert PDF
a r t i c l e i n f o a b s t r a c t
Article history: Waste-heat recovery with thermoelectric power generators can improve energy efficiency and provide distribut-
Received 24 September 2014 ed electricity generation. New thermoelectric materials and material performance improvements motivate de-
Received in revised form 4 November 2014 velopment of thermoelectric generators for numerous applications with excess exhaust and process heat.
Accepted 13 November 2014
However, thermoelectric generator product development requires solving coupled challenges in materials devel-
Available online 20 November 2014
opment and systems engineering. This review discusses these challenges and indicates ways system-level perfor-
Keywords:
mance relies on more factors than traditional thermoelectric material performance metrics alone. Relevant
Thermoelectric generator thermo-mechanical and chemical material properties, system components such as thermal interface materials
Waste heat recovery and heat exchangers, and system form factors are examined. Manufacturing processes and total system cost com-
Thermoelectric system ponents are evaluated to provide product development and commercial feasibility contexts.
Thermoelectric manufacturing © 2014 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
Thermoelectric power generation (http://creativecommons.org/licenses/by-nc-nd/3.0/).
http://dx.doi.org/10.1016/j.susmat.2014.11.002
2214-9937/© 2014 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
S. LeBlanc / Sustainable Materials and Technologies 1–2 (2014) 26–35 27
Table 1
Approximate waste-heat source temperatures are provided for sample mid- and high-
temperature TEG applications. Temperatures will vary based on TEG position in the sys-
tem, and the temperature at the hot side of the thermoelectric will be lower than the heat
source temperature.
silicon), and oxides are expected to have high temperature stability in filler media for high temperature applications – if they currently exist
air. Notable advancements have been made in both the types of mate- – must also be sufficiently stable and inactive with the TE material. For
rials synthesized and the reported properties. For low temperature ther- example, some materials undergo sublimation within the operating
moelectrics, nanostructured bismuth telluride [27], polymers and temperature range of high temperature applications. Even if the materi-
polymer–inorganic matrices [28–31], and MgAgSb-based materials al properties are sufficient for most of the range or the nominal operat-
[32] have broadened the range of options. The reported material prop- ing temperature, the risk associated with material sublimation during
erties for high temperature thermoelectrics have demonstrated note- any temperature spikes is severe device performance degradation or
worthy gains resulting in ZT values above 1. Hierarchical nano- to even device failure [44]. Hence, reports of ever higher peak thermoelec-
meso-scale structuring [33] and new materials such as tetrahedrites tric material ZT values deceptively allude to more power generation po-
[34] have contributed to the gains. tential which may not be valid given realistic application parameters.
While the materials development progress is promising, the increas- The translation of thermoelectric materials into devices also requires
ing breadth of materials and the reports of ever-increasing ZT mask the consideration of both n- and p-type thermoelectric materials. Although
underlying challenges of employing the materials in devices. Material a thermoelectric unit, or couple is typically composed of n- and p-type
properties are highly temperature-dependent, posing multiple chal- legs, both are not strictly necessary. For instance, if ease of synthesis,
lenges for application-specific materials selection. Few applications material stability, and reliability are challenges for the n- or p-type var-
have heat sources at one single temperature, so matching an application iation of a new material, faster prototype/product development, dem-
temperature with the point of peak ZT in a thermoelectric material is onstration, or commercialization could be achieved with one type (n
unrealistic. Instead, most applications have some degree of thermal or p) coupled with a metal shunt. Using both n- and p-types of materials
fluctuation or cycling. If the heat source is a fluid stream, the tempera- significantly increases the thermopower and thus the open circuit volt-
ture of the fluid varies along the flow direction. The temperature age of the TEG since the total thermopower for a p–n leg couple, Spn,
decreases along the length of each thermoelectric leg, as well. Ways of equals the sum of the magnitude of each leg's thermopower. Again, ad-
combining different materials in one device through cascading, vances in material ZT are thus deceptive. For instance, an increase in the
segmentation, and varying the material in the fluid flow direction ZT of an n-type (p-type) chalcogenide might be achieved, but a similar
have been developed [35–37]. Additionally, peak ZT values for high- increase in the properties of a corresponding p-type (n-type) chalco-
temperature materials often occur at temperatures above 600 °C. How- genide is not. Hence, the overall gain in ZT for the device is not propor-
ever, the temperature at the hot side of the thermoelectric material it- tionally as high as the gain in ZT for the individual material.
self is lower than the heat source temperature because there are Although the topic receives far less attention than thermoelectric
system component thermal resistances between the heat source and properties, mechanical properties of thermoelectric materials are criti-
the thermoelectric material. There are applications with heat sources cal for both device manufacturing and operation. Typical thermoelectric
above 600 °C such as industrial process furnaces and exhaust streams, materials are brittle and behave mechanically like ceramics. Table 2 pro-
and there are many opportunities for thermoelectric power generation vides a perspective of measured parameters which reflect the brittle
in applications with heat sources in the 250–500 °C range [12]. In both quality of these materials. However, it is challenging to characterize
cases, average ZT over the application temperature range is highly rele- the brittleness as measured by hardness, fracture strength, and fracture
vant to material selection and design. Fig. 3 presents ZT values for a high toughness. Characterization results vary based on sample geometry and
peak ZT material as well as materials which have generated commercial testing technique even when the material is held constant [45,46], and
and product development interest and results [38–40]. changes in composition during alloying of the same set of elements
Material stability over the full operating temperature range is rele- can lead to variations in microstructure and mechanical proper-
vant to device engineering. Thermoelectric materials must be stable ties [47].
within the filler medium. If the thermoelectric material is exposed to The coefficient of thermal expansion (CTE) is an important parame-
air, the material must not oxidize within the operating temperature ter due to the high operation temperatures and thermal cycling in po-
range. Devices can be packaged in an inert gas to mediate this problem. tential TEG applications [44,53]. Because each thermoelectric leg is
In low temperature devices, a solid filler is sometimes used, but solid held rigidly in place by a solder joint to the electrical interconnect and
substrate, significant stresses can build up in the material, particularly
at the corners and edges. The CTE mismatch between the TE material,
interface layers, interconnects, and substrates exacerbates the problem
of stress concentration. Proposed solutions involve introduction of com-
pliant interface materials. Examples include liquid metal layers [54] and
novel structures such as carbon nanotube arrays [55].
Table 2
Mechanical properties of selected thermoelectric materials. Measurement error and standard deviations are available in the original references.
Material type Material Young's modulus Hardness Fracture toughness Fracture toughness Fracture strength Reference
E H KIc Kc σf
(GPa) (GPa) (MPa-m1/2) (MPa-m1/2) (MPa)
thermal conductance and the electrical resistance of the TE material at modules have a square or rectangular shape. If the application requires
the module level, and two key features of module geometry, the fill fac- a different form factor, rectangular units are often positioned to accom-
tor and TE leg size, play a large part in this tradeoff. The fill factor is the modate this form factor. There have been limited demonstrations of cy-
ratio of the amount of module surface area occupied by TE material to lindrical modules as shown in Fig. 4 [63,64].
the overall surface area. The total surface area is not necessarily covered The TE module is attached to the exterior system with thermal inter-
by TE material (i.e. the fill factor is not 1) due to performance and/or cost face materials (TIMs) to improve the transfer of heat to and from the hot
optimization [58] and manufacturing constraints like minimum inter- and cold sides of the TE device. The operating temperature, particularly
leg spacing during assembly. Likewise, the tradeoff between thermal on the TE system hot side, creates a critical constraint on the TIM used as
and electrical parameters necessitates an optimization of the TE leg these temperature can be above 200 °C. TIMs come in various forms in-
height. cluding thermal greases or pastes, gap filler pads, and phase change ma-
The materials needs for thermoelectric devices extend beyond the terials [65–67]. However, the typical maximum operating temperature
TE material alone. There are several other device components, some of of most greases or pastes is approximately 150 °C. At high temperatures,
which interact directly with the TE material, affecting overall device greases and pastes dry out leaving air gaps which greatly increase the
performance. For instance, there is a metallurgical bond between the thermal resistance at the interface. Gap filler pads and phase change
TE leg and the metal interconnects. There are engineering consider- materials are more expensive but more reliable for hot side interfaces.
ations which influence the selection of the solder or braze material Carbon-based TIMs are able to operate at higher temperatures with typ-
used to form this bond. The solder/braze material must not diffuse ical maximum operating temperatures near 300 °C, but the thermal
into the TE material; a diffusion barrier placed on the TE material surface conductivity is often anisotropic with the through-plane value being
is typically required [59–62]. The electrical contact resistance between lower. Novel interface materials based on carbon nanotube arrays and
the solder/braze material and TE material must be low. The reflow tem- composites have been proposed and experimentally demonstrated
perature of the solder/braze should be higher than the device operating [55,68–70], and they have the potential to provide an appropriate TIM
temperature to prevent TE leg movement or changes in electrical resis- solution for mid- to high-temperature TEGs.
tance during operation. Additionally, the thermal contact resistance be- Thermoelectric systems for most applications require heat ex-
tween the TE leg and the metal interconnect and between the metal changers on both the hot and cold sides of the device. The heat ex-
interconnect and substrate will affect the temperature drop, and thus changers enable sufficient heat transfer from the heat source to the TE
voltage, achieved across the thermoelectric leg. module hot side as well as heat rejection or cooling on the cold side.
There are challenging materials requirements for the module sub- Therefore, the effectiveness of the heat exchangers directly impacts
strates and geometries. The substrates must be electrically insulating the temperature drop (and thus voltage) across the TE material. The
but thermally conducting. Since the substrate must withstand high tem- overall heat transfer capability of the heat exchanger, often denoted
peratures, particularly on the hot side of the TE leg, the substrates are by an overall heat transfer coefficient U, depends on the exchanger de-
typically ceramic materials, and flexible substrates for high temperature sign and material as well as the heat exchange fluid. The value of U is
TE devices have not been demonstrated. The TE legs are attached to the much higher when the fluid is a liquid, but use of a liquid adds complex-
substrate, so the substrate must have the mechanical strength to sup- ity to the system as a closed-loop system must be implemented. In most
port the legs and interconnects. Module design must incorporate the waste-heat recovery applications, the heat source is a gas stream such as
ability to shape ceramic to the desired design structure, so most flue gas from a chimney or furnace, so a liquid working fluid on the hot
Fig. 4. Cylindrical TEG system produced by Gentherm (a) (figure reproduced from [63]) and cylindrical ingots of doped lead telluride (b) (figure reproduced from [64]).
30 S. LeBlanc / Sustainable Materials and Technologies 1–2 (2014) 26–35
side is unrealistic. The heat exchangers must also be integrated into the
system with the TE module which adds system complexities such as in-
creased weight and size and additional thermal interfaces.
As indicated earlier, the optimization of TEG power output and effi-
ciency depends on TE material properties and dimensions as well as
system-level electrical and thermal resistances. Hence, the selection of
electrical and thermal contact/interface materials, substrates, and heat
exchangers directly impact TEG performance, and the intricacies of
this optimization have been explored through analytical and system
modeling. The impact of asymmetric system-level thermal resistances
on either side of the TE material has been investigated for idealized sys-
tems with constant temperature heat source, fill factor of 1, matched or
averaged n- and p-type material properties, temperature-independent
TE material performance, and negligible electrical contact and parasitic Fig. 5. Thermoelectric material efficiency compared to generator system efficiency simu-
thermal resistance approximations [57,71]. The optimum ratio of lated for three potential applications [76]. The system efficiency is 32%, 33%, and 59%
electrical load to TE internal resistance was shown to take the form lower than material conversion efficiency for the water heater, automotive exhaust, and
industrial furnace applications, respectively. The variation can be reduced by selecting
√(1 + ZT). The optimum ratio between the hot and cold side system- the thermoelectric materials based on each application's operating temperature range.
level thermal resistances took on a value of 1 for maximum power out-
put [57]. A recent study demonstrated the impact of a constant heat flux
versus constant temperature boundary condition, and it included elec- For instance, power is required to blow or pump a cooling fluid through
trical contact resistances to the TE material [72]. A detailed TEG system the cold side heat exchanger. Although a higher mass flow rate of work-
model indicated the optimum hot to cold side thermal resistance ratio ing fluid in the heat exchanger results in the benefit of more effective
must be larger than 10–30 to achieve maximum TEG power output heat exchange, increased pumping power is required to achieve this
[73]. This model was quite extensive in that it incorporated TE material benefit. Additionally, power electronics may be used in a TEG system
property temperature dependence, unmatched (real) n- and p-type or product. For example, these power electronics can be used for
material properties, electrical and thermal contact resistances, parasitic power conversion (e.g. converting DC TEG output to AC input for an
heat loss components, hot and cold side heat exchanger models, and TE electrical grid), and/or they can optimize the electrical load (e.g.
device optimization models. Thus, TEG output and performance is high- matching a variable circuit load resistance to the fixed power source
ly dependent on the link between actual material and system-level electrical resistance to maximize thermoelectric power generated).
parameters. These power electronics can also have a power input requirement for
operation. The net power delivered by the TEG, and thus the power gen-
4. Material vs. system metrics erated for the end user, must account for these parasitic power require-
ments in the system. The end user may have requirements for the
Typical metrics for TEGs are ZT, efficiency, and power output. While minimum net power which must be delivered for the investment in
they are mostly reported in terms of intrinsic material properties, dis- TEG power generation to be worthwhile. This is an important consider-
cussions about system-level performance point out alternative formula- ation to determine the feasibility of TEG power generation in various
tions which account for the contribution of other device and system applications.
components [16,58,74,75]. For instance, while ZT is often reported in The net power generated must also be understood relative to system
terms of TE material properties S, σ, and k, a more relevant formulation sizing features. In most applications, there is limited space and capacity
for a module-level ZT parameter is Spn2T/(KR). The extrinsic parameters available in which to accommodate the TEG. The total surface area and
R and K indicate electrical resistance and thermal conductance of the TE weight of the TEG system influence the ability to integrate it into
material in a couple; these are dependent on the dimensions of the legs. existing systems and architectures, so the power density (power gener-
Thermoelectric efficiency is often reported on a materials basis; it is ated normalized by surface area required or available) and specific
the electrical power generated divided by the thermal energy trans- power (power generated normalized by TEG system mass) are key met-
ferred into the TE material. However, the device- or system-level effi- rics. For example, industrial furnaces have a finite surface area in which
ciency is actually lower since not all of the heat available to the a TEG can be incorporated. Automotive exhaust systems have finite
system is transferred to the TE material. The effectiveness of heat ex- space to accommodate a TEG, and the additional weight of the TEG on
change between the heat source and the TE device, primarily through the vehicle entails a consequential fuel use requirement [78,79].
the heat exchangers, determines the amount of heat transferred to the
TE material. Fig. 5 shows the difference between thermoelectric materi- 5. Manufacturing
al efficiency and TEG system-level efficiency for simulated TE waste-
heat recovery systems in three combustion applications [4,76,77]. The The manufacturing process for thermoelectric devices varies based
TEG system efficiency can be considerably lower than the TE material on the type of thermoelectric material employed. The overview provid-
efficiency which is often reported with material characterization results. ed here applies to bulk materials and the most traditional manufactur-
Only the system parameters were changed in the simulation, and the ing process. It is not comprehensive for all types of TE materials and
selected thermoelectric material was held constant [76]. The difference devices but is provided as a reference to enhance understanding about
between the material and system efficiencies can be reduced if the engineering challenges commonly experienced with materials. A sche-
thermoelectric material selection is optimized for the application matic of a TE device manufacturing process is shown in Fig. 6.
temperature. Process yield is a significant consideration for the manufacture of TE
Frequently, the TEG efficiency is less of a concern than the total devices. As opposed to materials development and characterization
power output since the power generated by the TEG is the valuable where the primary yield concern corresponds to material synthesis
component to the end user. Sufficient understanding of the value of and the number of samples which can be characterized, there are
the power output depends on system-level parameters. There are sys- many more steps in the device manufacturing process. Thermoelectric
tem components which require power input, so the power generated material synthesis is commonly accomplished through ball milling
by the TE device alone is less relevant than the net power, power gener- powders of the constituent elements. While this can be a lengthy pro-
ated less power required for system components, of the entire system. cess, it is fairly repeatable with high yield once a processing recipe is
S. LeBlanc / Sustainable Materials and Technologies 1–2 (2014) 26–35 31
established. However, establishing the process to repeatedly achieve a The advent of thin film thermoelectrics has introduced manufactur-
specific composition can be challenging. Complete mixing is required, ing processes which are commonly associated with the semiconductor
and sufficient energy must be imparted to the powder particles. Ther- industry. Structures such as superlattices and nanowires have been pro-
moelectric materials can also be made through melting processes. posed and are made with deposition, growth, and/or etching micro/
Phase diagrams [80] of TE materials demonstrate the narrow process nanofabrication processes including molecular beam epitaxy, chemical
windows in which each phase is achieved, and the thermoelectric mate- vapor deposition, vapor–liquid–solid growth, and electroless etching
rial properties depend on the phase. For instance, AgSbTe2 is in PbTe- [83]. Additionally, recent demonstrations of thermoelectric materials
based materials such as TAGS and LAST thermoelectric materials in
which microstructures reportedly improve thermoelectric performance
[33,81]. The phase diagram for AgSbTe2 (Fig. 7) demonstrates the com-
plex variations in phase, and thus microstructures, which may arise due
to process parameters [82]. Hence, process fluctuations can result in
variations of phase, microstructure formation, repeatability of the syn-
thesis process, and resulting material properties.
Once the TE material is synthesized in powder or particle form, it is
consolidated into ingots, typically through hot pressing or spark plasma
sintering. As discussed in the materials overview section, sublimation
and stability/reactivity in the process gas environment must be consid-
ered. While a given TE material might be stable at the application's oper-
ating temperature, the consolidation process (or other manufacturing
processes) may occur at a higher temperature in order to densify the
material.
The ingots are then diced to form the thermoelectric legs, and the
material brittleness is a primary concern in this process step. Any
chipping of a thermoelectric leg changes the leg surface area and influ-
ences both the leg's thermal and electrical resistance. This in turn affects
system performance, particularly when the geometry of each leg is not
the same. Chipped legs would not be used in a device, reducing
the manufacturing process yield. Moreover, dicing and subsequent
chipping can lead to crack initiation. These cracks can propagate in sub-
sequent process steps, or worse yet, during TE device operation. Even
microcracks can affect thermal and electrical transport in the TE mate- Fig. 7. Phase diagram of AgSbTe2, a common component in microstructured PbTe-based
thermoelectric materials. The complexity and uncertainties about the bounds of the
rial. The dicing step also constrains the achievable leg dimensions
phase diagram demonstrates how small process fluctuations can affect thermoelectric
since the post-dicing leg dimensions depend on the dicing equipment material formation.
capabilities (e.g. saw blade width, dicing depth). The figure is reproduced from [82].
32 S. LeBlanc / Sustainable Materials and Technologies 1–2 (2014) 26–35
formed through solution processing techniques have been shown for relatively inexpensive material is doped with an expensive element.
both inorganic and organic materials. Since these approaches to making The doping is done to achieve better performance (e.g. higher ZT), so
thin film thermoelectrics are quite varied, a generalizable, standard it is particularly helpful to consider both cost and performance as
manufacturing process flow is not yet available. discussed at the end of this section.
Material characterization during manufacturing poses a unique chal- The standard practice is to synthesize thermoelectric compounds
lenge. Both standard and custom-built equipment exist to characterize with high purity starting materials, and the purity of materials affects
thermoelectric properties of TE materials [84–87]. However, these are cost with higher purity resulting in higher costs. While the effect of ma-
designed to accommodate individual samples of TE material (e.g. an terial purity on TE material properties has not been widely established
ingot or one TE leg), and specialized contacts must be made to the sam- [90–93], and an up-to-date, systematic study would be useful, the pres-
ple. Hence, the techniques are destructive in that the characterization ence of impurities in the TE material likely degrades the properties. The
sample cannot subsequently be used for a TE device. The characteriza- relative difference in material cost based on purity level is demonstrated
tion process is also time-consuming, so it becomes a bottleneck in the in Table 3 for sample materials.
overall manufacturing process stream. Standard, in-line characteriza- While thermoelectric material costs are non-negligible, the system
tion techniques which could be implemented within the manufacturing component costs can overwhelm the material costs. Major contribu-
process would be valuable. They would enable characterization of the tions to system costs are due to the substrates and heat exchangers.
material as it is incorporated into the device as well as the effective Substrates are typically thin ceramic pieces, often alumina-based, with
properties of the material combined with its electrical and thermal con- off-the-shelf costs of approximately $0.10/cm2. The cost of the hot and
tacts to other device components. In-line characterization could also in- cold side heat exchangers is particularly significant. Heat exchangers
crease process yield and reduce waste since defective devices would be have to be customized to the TEG in order to accommodate the form fac-
detected earlier in the manufacturing process. tor of the device and optimize system performance, so it is challenging
to specify cost. However, cost estimates can be determined from off-
6. Cost considerations the-shelf units. Heat exchanger cost generally scales with the overall
heat transfer coefficient [58], or U-value, as shown in Fig. 9.
The thermoelectric materials in established devices are based on bis- Both material and device manufacturing costs are relevant for TEG
muth telluride, lead telluride, and silicon germanium. The high cost of commercialization. Particularly with the advent of nanostructured ther-
tellurium and germanium is touted as a reason to develop thermoelec- moelectric materials, the cost of manufacturing techniques required to
tric materials which do not use expensive elements [88]. The develop- make thermoelectric materials can vary widely. The costs vary based
ment of polymer, silicide, oxide, and tetrahedrite TE materials is on the complexity of the manufacturing process and the maturity of
motivated strongly by the need to lower costs and improve the com- each process step's technology. In particular, the costs associated with
mercial viability of TEGs. Fig. 8 demonstrates the raw materials costs lithographic or epitaxial deposition processes for thick/thin film mate-
associated with sample materials of the main types of TE material clas- rials are orders of magnitude larger than those associated with bulk ma-
sifications. The materials cost depends heavily on material composition. terial processing [75]. While there may be a tradeoff between increased
Within a given classification of material, the cost can vary by a factor of material synthesis cost and assembly cost for thermoelectric thick/thin
two and sometimes even an order of magnitude, particularly when a film materials, such comparisons are not readily available and remain
Fig. 8. Cost of various thermoelectric materials based on the raw material costs [89] of the constituent elements.
The exact cost values and calculations are provided in [75].
S. LeBlanc / Sustainable Materials and Technologies 1–2 (2014) 26–35 33
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