INTERNATIONAL JOURNAL OF ENERGY RESEARCH Int. J. Energy Res. 2004; 28:753–768 (DOI: 10.1002/er.991) Improving the coefficient of performance of thermoelectric cooling systems: a review S. B. Riffatn,y and Xiaoli Ma Institute of Building Technology, School of the Built Environment, University of Nottingham, Nottingham, NG7 2RD, U.K. SUMMARY This paper reviews research carried out to improve the coefficient of performance of thermoelectric cooling systems during the past decade. This includes development of new materials for thermoelectric modules, optimisation of module design and fabrication, system analysis and heat exchange efficiency. Several conclusions are drawn. Copyright # 2004 John Wiley & Sons, Ltd. KEY WORDS: thermoelectric cooling system; coefficient of performance; optimisation 1. INTRODUCTION Thermoelectric modules are solid state heat pumps that utilize the Peltier effect. During operation, DC current flows through the thermoelectric module, causing heat to be transferred from one side of the thermoelectric device to other, creating a cold and hot side. A single-stage thermoelectric module can achieve a temperature difference up to 708C, or can transfer heat at an utmost rate of 125 W under the extreme conditions. A thermoelectric cooling system incorporates a power source to provide a direct current through the electrical circuit, a thermoelectric module with at least one heat sink and at least one heat source, and a control assembly. The basic arrangement of a thermoelectric module in a cooling system is shown in Figure 1. Thermoelectric technology has existed for about 40 years and thermoelectric systems are employed as cooling devices in many applications including military, aerospace, industrial and commercial. The main drawback of this technology however, is low coefficient of performance (COP), particularly in larger capacity applications. The emphasis of recent research has therefore been the improvement of the COP of thermoelectric cooling systems by means of developing new materials for thermoelectric modules, optimization of module system design and fabrication and improvement of the heat exchange (heat sink and heat rejector) efficiency. Advances in areas are described in the following sections. n y Correspondence to: S. B. Riffat, Institute of Building Technology, School of the Built Environment, University of Nottingham, Nottingham, NG7 2RD, U.K. E-mail: saffa.riffat@nottingham.ac.uk Copyright # 2004 John Wiley & Sons, Ltd. Received 24 July 2003 Accepted 22 September 2003 754 S. B. RIFFAT AND XIAOLI MA Q1 Cold side heat sink Thermoelectric device P Hot side heat sink Q2 Figure 1. Conventional arrangement for thermoelectric cooler. Q1 is the heat to be pumped, P is the electrical power supplied and Q2 is the heat dissipated to the ambient. Qc Tc Qsb Th 1/2QJ 1/2QJ Qcd _ + Qh Figure 2. Schematic diagram of a thermoelectric couple. 2. THERMOELECTRIC MODULE PERFORMANCE This section provides a basic understanding of the performance of a thermoelectric module. Thermoelectric heat pumping (Peltier effect) at the cold end of a thermal couple, as shown in Figure 2, is given by Qab ¼ aITc ð1Þ The term a is the average Seebeck coefficient of the thermoelectric material. It is seen from this relation that heat is pumped when current flows through the couple. However, the heat pumped may include other unwanted heat sources. These heat sources are described in the following sections. Joule heat: Current flow generates resistive or Joule heating (QJ) in the thermoelectric material. It can be shown that 50 per cent of the Joule heat goes to the cold end and 50 per cent goes to the hot end. The Joule heating is given by QJ ¼ I 2 R ð2Þ where R is the resistivity of the couple. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 755 Conducted heat: During operation, heat is conducted from the hot end to the cold end through the thermoelectric material. The rate of heat conduction is given by Qcd ¼ kðTh Tc Þ ¼ kDT ð3Þ where k is the thermal conductivity of thermocouple. Equation (3) shows that Qcd increases with the temperature difference across the couple. Combining Equations (1), (2), and (3) into an energy balance at the end of the thermoelectric couple gives the following: Qc ¼ Qsb 0:5QJ Qcd ¼ aITc 0:512 R kDT ð4Þ Equation (4) is the standard equation of thermal module performance. This equation shows that a thermoelectric module no longer operates (Qc=0) when the sum of one half the Joule heat (0.5QJ) and the conducted heat (Qcd) equals the Peltier heat (Qsb). The electrical energy consumption of the couple is given by QE ¼ I 2 R þ aIDT ð5Þ Equation (5) shows that the electrical power consumption of a thermoelectric couple is used to generate the Joule heat and overcome the Seebeck effect, which generates power due to the temperature difference between the two junctions of the couple. The COP of the thermoelectric module for cooling is given by e ¼ Qc =QE ¼ aITc kDT 0:5I 2 R I 2 R þ aIDT ð6Þ It is seen that the COP is a function of the material dimension property of thermocouple, the temperature of the hot side and cold side Th, Tc and the current input. There exists an optimum current for maximum COP, if Th, Tc and the thermoelectric material are fixed. Solving the equation @e=@I ¼ 0; the optimum current for the maximum (optimum) COP can be given by aDT =R Iopt ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 þ ZTm 1 ð7Þ Replace I in Equation (6) by Iopt, the optimum COP can be given by pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Th 1 þ ZT m Tc Tc pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi eopt ¼ ðTh Tc Þ ð 1 þ ZTm þ 1Þ ð8Þ where Tm ¼ 1=2ðTh þ Tc Þ ð9Þ Z ¼ a2 =kR ð10Þ It is seen that the optimum COP under the optimum current is a function of Th, Tc and the figure of merit of thermoelectric material. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 756 S. B. RIFFAT AND XIAOLI MA 3. DEVELOPMENT OF NEW THERMOELECTRIC MATERIALS Equation (10) express the performance of a thermoelectric materials: Z ¼ a2 =kR ð10Þ where Z is a figure of merit, a the Seebeck coefficient, R the electric resistivity and k the thermal conductivity. Z depends only on material properties and should be maximized to increase the module efficiency. This parameter may be made dimensionless by multiplying by T (average temperature of the hot side and cold side of the thermoelectric module, K): ZT ¼ a2 T =kR ð11Þ Over the past four decades, improvement in the conversion efficiency has been marginal. The challenge has been the development of thermoelectric materials with an improved dimensionless figure of merit. Effort has been concentrated on improving the performance of the thermocouple materials. Currently, bismuth telluride (Bi2 Te3 ), which is the best low temperature thermoelectric material and is widely employed in thermoelectric generators and coolers. Bi2Te3 possess a maximum value of ZT1 (Min et al., 2002). If the ZT could be raised to 2 or 3, the thermoelectric cooling device would be competitive with vapour compression cooling systems. Furthermore, if the ZT could be raised to 6, thermoelectric devices would be able to cool to cryogenic temperature (77 K) from room temperature. Recent advances have indicated the possibility of overcoming classical limitations and increasing the figure of merit significantly. Most of the advances involve tailoring the microstructure of a material to increase phonon scattering in order to decrease thermal conductivity. These materials include skutterudites, clathrates, half-Heusler alloys and chalcogenides. Another approach to the problem is to reduce the dimensionality of the material so that quantum size-effects alter the ratio between the electrical and thermal conductivity. A reported calculation for 2D quantum well structures, as well as 1D quantum ( . In addition, experiments wires, predicted values of ZT beyond 10 for wire diameters below 10 A carried out on quantum wells synthesized by molecular beam epitaxy showed that the Seebeck coefficient (times the carrier concentration) increased as the well thickness decreased (Hillhouse et al., 2001). Many other new approaches to the design of improved thermoelectric materials have also been suggested. However, these are yet to be realised in practice. Entrique Macia (in press) presented a theoretical study into the possible use of quasicrystals as potential thermoelectric materials. By considering a suitable model for the spectral conductivity, it was shown high values of the thermoelectric figure of merit, well beyond the practical upper limit ZT ¼ 1; may be expected for certain quasicrystalline alloys. Anatychuk et al. (1996) gave a number of examples supporting the concept of using inhomogeneous materials (with functional gradients) to improve the module efficiency. Development of thin-film thermoelectric materials offers many advantages including extending the possibility of a variety of designs for lower heat-flux modules; enabling mass production; reducing manufacturing costs; and performance enhancement. Venkatasubramanian et al. (2001) reported thin-film thermoelectric materials that demonstrated a significant enhancement in ZT at 300 K, compared to state-of-the-art bulk Bi2 Te3 alloys. This amounts to a maximum observed factor of approximately 2.4 for p-type Bi2 Te3 =Sb2 Te3 superlattice devices. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 757 The enhancement is achieved by controlling the transport of phonons and electrons in the superlattices. At present, this thin-film thermoelectric material has only been used in electronic device cooling. 4. OPTIMIZATION OF MODULE DESIGN AND FABRICATION One approach to improve the COP of thermoelectric modules is to examine all the aspects of their design and fabrication that affect the overall performance of the thermoelectric system. Recent investigations have demonstrated the effect of size of the thermoelements the COP of the thermoelectric module. Min et al. (2000) has developed an improved theoretical model of a Peltier module which takes into account both the electrical and thermal contact resistances (conventional module theory neglects contact resistances). Instead of the conventional performance formula, as given in Equation (8), the COP of a Peltier module, which takes into account both electrical and thermal contact resistances, may be given by l Tc b Th =Tc rlc eopt ¼ ð12Þ l þ 2rlc Th Tc 1 þ b l where lZTM 1=2 b¼ 1þ nþl n¼ 2Rc R r¼ k kc TM ¼ ðTh þ Tc Þ=2 ð13Þ Theoretical calculations based on this model indicate that both the COP and heat pumping capacity are dependent on thermoelement length. This dependence becomes increasingly significant with a decrease in thermoelement length. As a result, a relatively long thermoelement is required to obtain a large COP, while a relatively short thermoelement is desirable for achieving maximum heat pumping capacity. It is apparent that the optimum module design will be a compromise between the requirements of COP and heat pumping capacity. Min also showed that reducing the contact resistances, in particular, the thermal contact resistance, is an essential requirement to achieve a further improvement in both COP and heat pumping capacity. In addition, a precise manufacturing technique is required to provide high quality thermoelectric modules, with high performance. Precise manufacturing technique requires exact determination of module parameters. The requirements include: precision measurement of each module internal resistance at the ambient temperature; consideration of the resistance of the module supply leads; determination of optimum current and voltage of each module; determination of thermal efficiency of each module; calculation of temperature difference Tmax, maximum cooling capacity Qmax according to the measurement results and figure of merit Z; certification of the module main parameters, values of internal resistance Rmin, Rmax and Tmin, Qmax, etc. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 758 S. B. RIFFAT AND XIAOLI MA Methods for precise and rapid determination of parameters governing the performance of thermoelectric cooling and generation modules, as well as software and hardware used in the realization of these measurements are reviewed by Anatychuk et al. (1998). 5. OPTIMIZATION OF THE DESIGN OF THERMOELECTRIC COOLING SYSTEMS AND NOVEL METHODOLOGY FOR SYSTEM ANALYSIS The methodology of system design and system analysis is very important to the design of highperformance thermoelectric cooling systems. 5.1. Exact system design method The design procedure of a thermoelectric cooling system usually follows the performance curves of the thermoelectric module provided by the manufacturer. Usually, the design of a thermoelectric cooling system starts from a given temperature difference across the hot and cold sides of the module DT (=THTL) and the required cooling capacity QL. The current I for the thermoelectric module is determined from a measured DT–I curve at a fixed QL. The V–I curves at zero cooling capacity (QL=0) and at zero temperature difference (DT=0) are then used to determine the voltages V. The required thermal resistance of the heat sink is then evaluated. An iteration procedure is necessary since the heat sink design may not be feasible and the assumed DT may not be practical. In addition, this design method only determines the range of the applied voltage. The actual value of V needs to be determined experimentally. In general, this method is more suitable for the selection of the thermoelectric module as it does not take into account the effect of the thermal resistance of heat sink (Huang et al., 2000). In addition, the above design procedure can give rise to several difficulties. Most manufacturers do not supply the performance curves of the thermoelectric module. Furthermore, the thermal performance of a thermoelectric module depends on physical properties such as the Seebeck coefficient a; the electric resistance R, and the thermal conductivity K. In general, these properties may vary with operating temperature. Manufacturers of thermoelectric module do not usually provide this type of data for their customer, or if provided, the data are not accurate due to variations in the manufacturing process (Huang et al., 2000). A high quality design procedure is therefore required for the design of high-performance thermoelectric cooling systems. Huang et al. (2000) developed novel system design method for thermoelectric cooling systems. The performance curve and the basic physical properties of a thermoelectric module were first measured from a module test. An automatic test apparatus was designed and built to carry out the testing. System analysis was then carried out using the measured results and a computer model was developed to assist system design. The thermal resistance of the heat sink was selected as one of the key parameters in design of a thermoelectric cooling system. This eliminated the need to carry out the complicated heat transfer analysis of a heat sink during the system analysis and thus simplified the system design procedure. This system design method allows the derivation of more accurate relations for determining the optimum COP and optimum cooling capacity, (it was found that the extreme value of COP represents the design Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 759 limit which corresponds to heat exchanger thermal resistance Re=0). The main drawback of this method is that it needs an automated test apparatus and therefore may not be convenient to use. 5.2. Convenient optimization thermoelectric system design form It is important to design a system so that it operates with a maximum COP for a specified heat exchanger thermal resistance and at a constant temperature difference. There have been several investigations into optimum design to maximize the COP of a thermoelectric cooling system, but many methods are not in a convenient form to allow simulation of the optimum thermoelectric cooling system. The present interest is to develop a form convenient for this type of simulation. Yamanashi et al. (1996) investigated an optimum design to maximize the COP of a thermoelectric cooling system when the thermal resistances of the heat exchangers are given and the system operates under a constant temperature difference. The optimization was performed using non-dimensional entropy flow equations, which are an extension of the heat balance equations of a thermoelectric cooling system. The thermoelectric cooling system absorbs the heat flow (Qc) at the cold side and emits the heat flow (Qh) at the hot side. Therefore, the entropy flows at the cold and hot sides are Qc/Tc and Qh/Th, respectively. The non-dimensional entropy flows at the cold and hot side are derived from normalizing these entropy flows by the thermal conductance of the thermoelectric module. The non-dimensional thermal resistances of the hot side and the cold side heat exchangers are the ratio of the thermal resistances of the hot side and the cold side heat exchangers to the thermal resistance of the thermoelectric module. In these equations, the COP becomes a function of the non-dimensional thermal resistance of the cold side heat exchanger, and the non-dimensional entropy flow at the cold side of the thermoelectric cooling system. Therefore, the COP of the thermoelectric cooling system can be shown as a contour graph based on these two variables. This graph allows not only determination of the thermoelectric cooling design parameters for the maximum COP of the thermoelectric cooling system, but also evaluation of the degrading effect on the COP of the thermal resistance of the system. The maximum COP was found to decrease rapidly as the ratio of the cold side thermal resistance and the hot side thermal resistance increased. In these simulations, the thermoelectric properties of thermoelements are based on values determined from the average operating temperature of the thermoelectric module. This convenient design method is therefore an approximate method. 5.3. Novel system analysis method Chen et al. (1996) investigated the heat transfer rate and efficiency of thermoelectric cooling systems. The study focused on the use of large-scale thermoelectric refrigerators for air conditioning applications. A one-dimensional heat transfer analysis was performed to determine the cooling power and electricity consumption of the thermoelectric elements. The constantproperty results were in good agreement with the variable-property solutions for the thermoelectric materials and temperatures typical for air conditioning applications. A heat transfer analysis was also carried out for thermoelectric refrigerators equipped with a heat exchanger. Both parallel- and counter-flow heat exchangers were considered. Fluid temperature variations of these two flow arrangements were found to be quite different, but the efficiencies and cold fluid exit temperatures differed only slightly when a uniform current was used for all thermoelectric elements. If the length of the heat exchanger exceeds an optimum value, the cold Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 760 S. B. RIFFAT AND XIAOLI MA fluid temperature begins to rise and the efficiency drops for both parallel- and counter-flow arrangements. The second law of thermodynamics was applied to the optimization of thermoelectric refrigerators operating between two constant-temperature reservoirs and between two flowing fluids. It was found that if a thermoelectric cooling system incorporates a heat exchanger, a non-uniform current distribution should be used to achieve the maximum efficiency and the lowest cold fluid temperature. The optimization results for thermoelectric refrigerators operating between two constant-temperature reservoirs are not applicable to thermoelectric cooling systems operating between two flowing fluids. Heat transfer at a finite rate, and electrical resistive losses, are necessarily irreversible processes and unavoidable in a thermoelectric device. Go. ktun et al. (1995) suggested that the internal and external irreversibilities in a thermoelectric refrigerator might be characterised by a single parameter named the device-design parameter. The presence of this parameter in the equations for the refrigeration effect and the maximum input power, shows that a real refrigerator has a smaller cooling capacity and needs more input power than an ideal refrigerator. 6. IMPROVEMENT OF EFFICIENCY OF THE HEAT EXCHANGE SYSTEM As described previously, the COP of a thermoelectric module (the optimum COP on the condition of optimum current) can be expressed by Equation (8). This indicates that the COP of a specific thermoelectric module is a function of module’s hot and cold side temperatures, i.e, Th and Tc, respectively. Increasing the Tc and decreasing the Th will improve the COP. For a fixed Th or Tc, the COP of a thermoelectric module typically decreases with an increase in the temperature difference between the module’s hot and cold side. Figure 3 shows the calculated COP of a commercially available module as a function of temperature difference between the hot and cold side, at a hot side temperature of 300 K, which is a typical condition for domestic refrigeration. For a typical domestic refrigerator, a temperature difference between the ambient and the cabinet of about 25–30 K at Th=300 K is usually required to achieve satisfactory cooling performance. This indicates that the maximum COP of a thermoelectric refrigerator comprised of a commercially available module is around 0.9–1.2, as shown in Figure 3. However, the practical COP of a thermoelectric refrigerator is much lower than this because the temperature difference between the hot and cold side of the thermoelectric module is larger than the temperature difference between the ambient and the cabinet. In other words, the hot side temperature is higher than the ambient and the cold side temperature is lower than the cabinet temperature. For a practical thermoelectric cooling system, the hot side heat exchanger rejects the heat produced on the hot side of the thermoelectric module to the ambient and so reduces the hot side temperature. The cold side heat exchanger removes the heat from the cold region to the cold side of thermoelectric module and so increases the temperature of the cold side. Because the thermoelectric module is very high heat intensity equipment, the high efficiency thermoelectric heat exchangers is necessity. The efficiency of the heat exchange system strongly influences the COP of the thermoelectric cooling system. If the efficiency of the heat exchange system is high, the temperature difference between hot and cold side of the thermoelectric cooling system may be reduced significantly, and Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 761 IMPROVING THE COEFFICIENT OF PERFORMANCE 3 Th =300K Z=2.8×10-3K-1 2.5 COP 2 1.5 1 0.5 0 0 5 10 15 20 25 30 35 40 45 50 Temperature difference, Th-Tc, (K) Figure 3. COP as a function of temperature difference across the module at hot side temperature Th=300 K. the COP will be increased. If the efficiency of the heat exchange system is low, the temperature difference between hot and cold side will be greater, and the COP will be lower. Heat is rejected from the hot side across a heat exchanger to the ambient. Heat exchanger thermal resistance is defined by Qh ¼ Th Ta Re or Th ¼ Qh Re þ Ta ð14Þ As shown in Equation (14), the hot side temperature may be calculated as a function of the heat exchanger thermal resistance, Re under specific heat flow at hot side Qh and ambient temperature Ta. The Re determines how high the thermoelectric cooling system rises above the ambient temperature. In principle, heat exchangers in thermoelectric cooling systems should be designed to minimise their thermal resistance under restrictions such as the size of the system and heat transfer method and system design method, because as the thermal resistance of the heat exchangers increases, the efficiency of thermoelectric cooling systems decreases. Typical heat exchanger designs include natural convection, and forced convection heat exchangers for heat rejection to air, and forced convection heat exchangers for heat rejection to water flow, as shown in Figure 4. Of these common types of heat exchanger, shown in Figure 4, the liquid cooled system is the most efficient. The typical heat exchanger thermal resistance for a 45 45 mm square thermoelectric module is: (1) Natural convection: 0.853–13.075 m2 K kW1, depending on the fin density and the ratio of the heat exchanger base plate area to the thermoelectric module area. Higher ratios of the Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 762 S. B. RIFFAT AND XIAOLI MA Figure 4. Common heat exchanger designs: (a) natural air convection, (b) forced air convection (heat sink not shown for clarity) and (c) water-cooled forced convection. heat exchanger base plate area to the thermoelectric module area result in a lower thermal resistance; (2) Forced air convection: 0.531–5.759 m2 K kW1, depending on the air flow rate. Larger air flow rates result in a lower thermal resistance; (3) Water-cooled exchanger: 0.348–0.737 m2 K kW1, depending on the water flow rate. Larger water flow rates result in a lower thermal resistance. A ducted, forced-air, convection system has a higher performance than an un-ducted system. The data provided by Melcor shows the typical allowances of temperature difference between the hot side and ambient, with respect to the heat exchange mode. That is: (1) Natural convection 20–408C; (2) Forced air convection: 10–158C. (3) Liquid exchangers: 2–58C above liquid temperature. Since the heat flux densities on the cold side of the system are considerably lower than those on the hot side, an allowance of about 50% on the afore-mentioned hot side data can be used. Various types of heat pipe may be used to conduct heat from the small ceramic area to the convection surface, which is an alternate to the metal heat spreader plate. A heat pipe may also be used to assist the distribution of heat within the spreader plate. A heat pipe system must still reject heat to air or water. Hence, it must use one of the previously discussed convective heat rejection systems. Assuming a 12.7 mm diameter aluminum/methanol heat pipe, and using a high performance wick structure, one can have a heat pipe resistance as low as 0.02 K W1. Coupling this with a liquid heat exchanger with a thermal resistance of 0.172 K W1 will result in a heat pipe/convection resistance of 0.132 K W1. Use of a heat pipe will not be of benefit for natural convection, because the dominant thermal resistance in this case is the convection resistance (Webb et al., 1998). As mentioned previously, water-cooled forced convection heat exchangers have excellent performance. The main drawback of a water-cooled heat exchanger is that it needs a convenient Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 763 source of cooling water. Without a source of cooling water, a forced convection water heat exchanger would require a pump and radiator and associated fittings and tubing. The added resistance of the radiator would increase the overall resistance. Air-cooled systems are therefore often more desirable. Many heat exchange systems based on the afore-mentioned forced air convection exchangers and the use of heat pipes have been reported. Sofrata (1996) reported that using a double fan in an appropriate position could significantly increase the efficiency of the forced air exchanger compared to using the single fan in a refrigerator. A long chimney for a natural-convection heat exchanger may also improve the performance of the refrigerator without the need to use fans that, of course, require the electrical power input. A novel, air-cooled thermosyphon reboiler-condenser system has been reported (Webb et al., 1998) and has been used as a heat exchanger of a thermoelectric refrigerator (Gilley et al., 1999). This system is capable of providing very low heat sink resistance values with aircooling and a thermal resistance as low as 0.0194–0.0505 K W1 was obtained for cooling a 45 mm square module. The system promises significantly higher COP for thermoelectric coolers than is possible using existing heat exchange technology. The high performance is obtained using of enhanced heat transfer surfaces and its operation is summarised as follows. As shown in Figure 5(a), the heat exchanger includes a boiling chamber, and a condensing chamber. The boiling surface inside the boiling chamber has a porous metal coating to enhance its heat transfer. The working fluid, which has been heated in boiling chamber to its vapour phase, can flow upwardly through the hollow tube into the condensing tube in condensing chamber. As shown in Figure 5(b), each condensing tube includes partitions, which provide the required structural strength for respective tubes and also increase the total surface area contained within each condensing tube. Enhanced heat transfer surfaces are preferably formed on the interior surface of each condensing tube. The working fluid that has been condensed into its liquid phase in the condensing chamber will flow through the hollow tube downward into the boiling chamber. Riffat et al. (2001) have reported a thermoelectric refrigeration system, which employs a phase change material (PCM) as a cold side heat exchanger for cooling storage and improvement of the COP. The refrigeration system was first fabricated and tested using a conventional heat sink system (bonded fin heat sink system) at the cold heat sink. In order to improve the performance and storage capability, the system was reconstructed and tested using an encapsulated phase change material (PCM) as a cold sink. Both configurations used heat pipe embedded fins as the heat sink on the hot side, as shown in Figure 6. Results of tests on the latter system showed an increased performance. This was because the PCM had a large storage capacity allowing most of the cooling energy to be absorbed by the PCM, and therefore the cold side temperature fell more slowly than when the PCM was not used. During the phase change process, the temperature of the refrigeration system was almost constant until the phase change process was complete. This helped to keep the temperature difference across the thermoelectric module to a minimum, thus improving its performance. In general, thermoelectric modules are very high heat intensity equipment, which need high efficiency heat exchangers to lower the hot side temperature and increase the cold side temperature in order to improve the COP. Use of a greater number of modules would also improve the COP of the system. Use of more modules would reduce the heat load on each module, and so lower the heat flux densities of both the hot and cold side of each module. The Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 764 S. B. RIFFAT AND XIAOLI MA Figure 5. (a) Air cooled, thermosyphon reboiler-condenser assembly, and (b) cross-section of the hollow condensing tube with enhanced heat transfer surface. Figure 6. Schematic description of an experimental thermoelectric refrigeration system. hot side temperature could therefore be reduced more by the heat exchange system. The main disadvantage of this is however, that the use of many modules would increase both cost and space requirements. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 765 7. OTHER APPROACHES 7.1. Multistage thermoelectric cooling system The COP of a thermoelectric cooling system decreases rapidly with increasing temperature difference but its performance can be improved by the use of multistage thermoelectric modules. Figure 7 shows typical designs of a single-stage module and a multistage module. Lindler (1998) investigated the improvement in performance that could be obtained using a multistage module. The results showed a comparison of COP as a function of hot side temperature (with a fixed cold side temperature of 208C) for a single, commercially available CP 1.0-17-08L module, and two CP 1.0-17-08L cascaded modules. For a hot side temperature around 508C (temperature difference of 308C), the improvement in COP was too small to justify the added cost of a second module. For a hot side temperature of 608C, the single module operated at a COP of 0.670 compared to a COP of 0.719 for the cascaded module. This represents a 7.3% improvement in COP. For hot side temperature above 908C, the improvement in COP is significant. At a hot side temperature of 1008C, the single module COP is 0.151 compared to 0.232 for the cascaded module. This represents a 54% improvement in COP. The results also show that a cascaded system consisting of a CP1.0-17-08L module on the cold side with a CP 1.0-31-08L module on the hot side, yielded essentially the same COP as two CP 1.017-08L modules cascaded for hot side temperatures less than 908C. For higher hot side temperatures, the cascaded system with a CP 1.0-31-08L module on the hot side outperformed the cascaded system consisting of two CP 1.0-17-08L modules. It has also been reported that at low temperature cooling (200–250 K) and for a given temperature difference, using a multistage module with an appropriate number of stages may lead to sharp increase in the cooling efficiency (Anatychuk et al., 1996). Optimum temperature staging has been investigated to minimise entropy generation in a multi-stage cryogenic refrigeration cycle (Jeong et al., 1994). It was found that the best intermediate temperature distribution was to have the same high to low temperature ratio at each stage of the system. As an example, the result could be applied to the design of a cryogenic cascade thermoelectric cooling system to find the optimum size distribution of each stage. 7.2. Optimization of module location Welling et al. (1997) reported an experiment designed to evaluate the effect of thermoelectric module location on cooling system efficiency. An experimental device was conceived, which was to employ thermoelectric modules in the duct attached to an enclosure with a heat load, similar in function to an automobile air conditioner. The hot air flowed through the duck and it was found that the positions of the thermoelectric modules in the duct had an effect on the air Figure 7. Typical thermoelectric module designs. (a) single-stage module and (b) multistage module. Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 766 S. B. RIFFAT AND XIAOLI MA cooling rate. It can therefore be concluded that it is important to optimise module location in order to increase system efficiency and reduce operating costs. 7.3. Further investigation Buist et al. (1996) reported a theoretical analysis of thermoelectric cooling performance enhancement via thermal and electrical pulsing. The cooling enhancement was by virtue of the fact that Peltier cooling is a surface effect and extremely concentrated at the cold junction, whereas, Joule heating is a volume effect and is distributed throughout the volume of the thermoelement. As a result, most of the Joule heat takes a longer time to reach the cold side, than heat from the Peltier effect. This phenomenon was demonstrated theoretically by modelling a high-current pulse applied after the minimum steady-state cold side temperature had been established. Calculations showed that cold side temperatures could be reduced by 16 K compared to temperatures achieved by steady-state means. These transient enhancements are admittedly short-lived and have limited effectiveness. However, the results presented suggest that further investigation of the fundamental differences between Peltier and Joule heat may be useful. 8. CONCLUSIONS (1) Recent advances have indicated the possibility of overcoming classical limitations and increasing the figure of merit of the thermoelectric materials significantly. The investigations include the following aspects: tailoring the microstructure of a material to increase phonon scattering in order to decrease thermal conductivity; reducing the dimensionality of the material so that quantum size-effects alter the ratio between the electrical and thermal conductivity; use of quasicrystals as potential thermoelectric materials; use of inhomogeneous materials (with functional gradients) and development of thin-film thermoelectric materials which has achieved a figure of merit of approximate 2.4. (2) Investigations have demonstrated the effect of size of the thermoelements on the COP and heat pumping capacity of the thermoelectric module. A relatively long thermoelement is required to obtain a large COP, while a relatively short thermoelement is desirable for achieving maximum heat pumping capacity. The optimum module design will be a compromise between the requirements of COP and heat pumping capacity. The investigations also showed that reducing the contact resistances, is an essential requirement to achieve a further improvement in both COP and heat pumping capacity of a thermoelectric module. (3) The new methodologies of system design and system analysis to the design of high-performance thermoelectric cooling systems include the following main points: use of the performance curve and the basic physical properties of a thermoelectric module measured from an accurate module test; use of non-dimensional entropy flow equations to determine the thermoelectric cooling design parameters for the maximum COP of the thermoelectric cooling system; one-dimensional heat transfer analysis; use of the ‘‘device-design parameter’’ which characterise the internal and external irreversibilities in a thermoelectric refrigerator. (4) Of the common types of heat exchanger for thermoelectric cooling systems, water-cooled forced convection heat exchangers have excellent performance. The air-cooled heat exchange Copyright # 2004 John Wiley & Sons, Ltd. Int. J. Energy Res. 2004; 28:753–768 IMPROVING THE COEFFICIENT OF PERFORMANCE 767 systems are however generally the most desirable at present due to its convenience to use. And some novel air-cooled heat exchangers with higher performance have been developed. (5) For large temperature temperature difference applications, the COP can be improved significantly by use of multistage thermoelectric modules. NOMENCLATURE Qab a I QJ R Qcd K Th Tc DT Qc Qh QE e Iopt eopt Z Rc l lc kc Ta Re = = = = = = = = = = = = = = = = = = = = = = = Peltier heat pumping rate (W) seebeck coefficient of thermoelectric material (W/A-K) current (A) joule heat generation rate (W) electrical resistivity of the thermocouple (V A1) heat conduction from the hot end to cold end (W) thermal conductivity of thermocouple (W m-K1) hot end temperature (8C) cold end temperature (8C) temperature difference between hot and cold end (8C) heat flow at cold side (W) heat flow at hot side (W) power consumption (W) COP of the thermoelectric couple optimum current (A) optimum COP of the thermoelectric couple figure of merit of thermoelectric material (K1) electrical contact resistivity between the thermoelements and copper strips (R) thermoelement length (mm) thickness of contact layers between thermoelements and copper strips (mm) thermal conductivity of the contact layers (W m-K1) ambient temperature (8C) heat exchanger thermal resistance (K W1) REFERENCES Anatychuk LI et al. 1996. 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