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    25 views61 pages

    WO2006056809A1

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    HP ghn
    Themoelectic cooling system us patent

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    a2)INTI ERNATIONAL APPLICATION PUBLIS (19) World Intellectual Property Organization International Bureau (43) International Publication Date 1 June 2006 (01.06.2006) ‘THE PATENT COOPERATION TREATY (PCT) an {AE 0 (10) International Publication Number WO 2006/056809 Al (61) International Patent Classification: F25B 21/00 (2006.01) (21) International Application Number: PCT/GH2005/050207 (22) International Filing Date 21 November 2005 (21.11.2005) (25) Fring Language: English (26) Publication Language: English (30) Priority Data: (0426230929 Novemer 2008 (29.11.2004) GB 0682.29, 19 May 2005 (19.05.2005) US. (71) Applicant (jor all designated States except US): CAM BRIDGE. UNIVERSITY TECHNICAL SERVI LIMITED [GB/GB|; The Old Schools, Trinity Lane, Cambridge, Cambridgeshire CB2 1TS (GB). m2) 75) Inventors; and Inventors/Applicants (for US only): [GBIGB); 6 Prenehs Road, Cambri MATHUR, Nell ., Cambridgeshire CB4 3L.A (GB). MISHCHENKO, Alexandr (RUGB}, Churchill College, Cambridge, Cambridgeshire CB3 ODS (By Agent: MARKS & CLERK; 66.68 Hills Road, Cam: bridge, Cambridgeshire CB2 ILA (GB), Designated States (unless otherwise indicated, for every ind of national protection available): SE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EC, HE, BG, ES, FL GH, GM, HR, HU, ID, IL, IN 18, JP, KE, LK,LR, TS, LT, LU, LN, cy «sh ‘s us, SK, SL, SM, SY, TJ, TM, TN, TR, TT, 12, UA, UG, UZ, VC, WN, YU, ZA, ZM, ZW. (84) Designated States (unless otherwise indicated, for every ind of regional protection available}. ARIPO (BW, Gti GM, KE, LS, MW, MZ, NA, SD, SL. SZ, TZ, UG. ZM. ZW), Burasian (AM, AZ, BY, KG, KZ, MD, RU, TI, TM), European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FL [Continued on next page) (G4) Tite: SOLID STATE ELECTROCALORIC COOLING DEVICES AND METHODS WoO 2006/056809 A1 IIIIIIIIII (57) Abstract: A cooling device comprises several elecroesoric ‘working elements 200,210, 220,230) wih working temperatures covering a required temperate range. The elements are sopa rated by heat switehes (100, 110, 120, 130, 140). The number of clectrocalorie elements and heat switches can be diferent in other embodiments. ‘The device can be eascaded or paralleled to pro- vide greater cooling. Thermoclecric heat switches are provided for switching from a heat condueting to & heat insalating state. In some embodiments the thermoelectric switches are replaced by microoleetromechanieal switches, The thermoelectric switches can operate in passive heat conducting mode. In some embodi- iments, the switches can operate in active heat conducting mode ‘with the reverse current passed through the couples in the off eat conduction slate, eleciocalorie elements ean take the form of mul- tilayer capacitors comprised of feroeeetre thin films WO 2006/056809 AX AIIM INANE NIN LINN NN UN HH A GR, HU, TE, 18,11, LT,LU,LV,MC, NL, PL, PT, Fortwo-lettercodes and other abbreviations, refer ta the “Guid ‘SK, TR), OAPI(BE, BJ, CE CG,C1,CM, GA, _ ance Notes om Codes and Abbreviations” appearing at the begin. GN, GQ, GW, ML, MR, NE, SN, TD, TO) hing of each regular issue of he PCT Gazette Published: = with international search report WO 20067056809 PCT/GB2005/050207 M&C Folio: WPP290547 Solid State Electrocaloric Cooling Devices and Methods ‘The present invention relates to solid state electrocaloric cooling devices with heat switches, and to related methods of cooling. Some observers believe the physical limits of silicon will one day slow or halt the steady advance of the computing industry. Today though, a more immediate threat to Moore's law has emerged. The same forces that enable exponential improvements in processor performance are creating enormous problems in another dimension: power. As the transistor density increases, processors consume more power and generate more heat, at an accelerating rate. If past trends continue, with no change in power management, then, over the next decade, high-performance computing devices will surpass the industry's ability to cool them economically (www.intel.comvlabs). Despite the many novel approaches that are being tried now to develop alternative cooling methods, there is a need for improved techniques. Common refrigeration systems use greenhouse gases that are hazardous to the environment. We describe a new reliable active solid state device without moving parts proposed which can offer some advantages over the common approach to refrigeration, both in the electronics and computer industries, and in home and industrial refrigeration systems. Being more efficient, the proposed refrigeration method can help to save energy spent on numerous refrigeration facilities all around the world. An electrocaloric cooling system comprised of a plurality of electrocaloric (EC) working elements (an example of one is depicted in Fig. 1) with a range of working temperatures covering a wide temperature interval was desoribed in Y.V. Sinyavsky and V.M. Brodyansky. Ferroelectrics. 134: p. 321, 1992. and WO 2006/056809 PCT/GB2005/050207 2 AE. Romanov, Ju.V. Sinyavskij, N.D. Pashkov, and G.E. Luganski, "Method of cooling and device for realization of this method", SU Patent No 2075015, 1993. The heat exchange between adjacent electrocaloric working elements as well as heat flow to the ambient and from the cooled body was organised with fluid and gas heat exchangers. The prototype schematic is shown in Fig. 5. The working elements were made of PbScp sT'ao 50s with various thermal treatment so that their working temperatures were different. Variations of ECE versus temperature for different working elements are shown in Fig. 2. The prototype comprised two blocks of working elements 1 and 2 (see Fig. 5), heat load 3, and heat sinks 4. The liquid heat exchanger was pumped through the system with a pump §. Four blocks of PST have been combined into a single shell. Each block had a sandwich type structure comprising a number of PST plates 20 x 10 x 0.3 mm’ each. Each block was 55 mm long with a cross section of 10, x5 mm. The total mass of the PST working material was 35 g. The results of the experiments with the prototype are shown in Fig. 6. Curve 1 shows the ECE of a single EC element, and curve 4 shows the temperature difference between the heat load and the heat sink. The maximum field for Curve 1 is 30 kVcm* and could not be increased due to surface arc (the experiment was carried out in air), Due to the same reason the disclosed prototype with a gas heat exchanger, He, was studied only up to 30 kVem'* (see Curve 2). The ECE effect of a working element placed in pentane, a heat exchanger liquid, is shown by Curve 3. The ECE value is lower due to higher heat capacity of pentane compared to that of a gas. However, the net temperature difference developed between the ends of the whole device with liquid pentane as a heat exchange liquid is much higher and shown by Curve 4. Electrocaloric refrigeration systems for cryogenic temperature ranges (from 20 K and below) are disclosed in L.W. Lawless. "Paraelectric refrigeration method and apparatus”, US Patent No 3436924, 1969. and L.W. Lawless. "Closed- cycle electrocaloric refrigerator and method”, US Patent No 3638440, 1972. An electrocaloric refrigeration system comprising a number of working elements separated by passive unidirectional heat pipes was proposed in A. Basiulis and B.L. Robert. "Solid-state electrocaloric cooling system and method”, US Patent WO 2006/056809 PCT/GB2005/050207 3 No 4757688, 1986. The proposed unidirectional heat pipes work by principle of unidirectional heat transfer accomplished by evaporation of a liquid heat carrier, e.g. No in a cryogenic temperature range. However, such a process is slow and has a large inertia, which makes the realization of such a device difficult. Summary of the Invention Ina first aspect the invention provides a device for transferring heat from a heat source to a heat sink, the device comprising: at least two heat switches, a first to receive heat from the heat source, a second to pass heat to the heat sink; at least one electrocaloric element between two said heat switches and in thermal contact with said two heat switches; and a control input for controlling said at least two heat switches and said electrocaloric element to transfer heat from said source to said sink; and wherein one or both of said heat switches comprise a thermoelectric heat switch, tunnelling heat switch or an electromechanical heat switch. Preferably the device for transferring heat from a heat source to a heat sink is a part of a cascaded system having a plurality of devices for transferring heat from a heat source to a heat sink. More preferably the device for transferring heat from a heat source to a heat sink it is a stacked cascaded system and comprises a parallel system. The control input may comprise one or more electrical connections. Preferred embodiments further comprise a controller to control said heat switches and said at least one electrocaloric element, the controller comprising control means for: cooling said electrocaloric element to a temperature of less than said source or equal to said source; turning said first heat switch on to transfer heat from said source to said electrocaloric element; turning said first heat switch off; warming said electrocaloric element to a temperature of greater than said sink or equal to said sink; turning said second heat switch on to transfer heat from said electrocaloric element to said sink; and turning said second heat switch off. WO 2006/056809 PCT/GB2005/050207 In another aspect the invention provides a method of controlling a heat transfer device for transferring heat from a heat source to a heat sink, the heat transfer device comprising at least one electrocaloric element disposed between a pair of thermoelectric heat switches, a first switch being in thermal contact with said source and a second switch with said sink, the method comprising: cooling said electrocaloric element to a temperature of less than said source or equal to said source; turning said first heat switch on to transfer heat from said source to said electrocaloric element; turning said first heat switch off, warming said electrocaloric element to a temperature of greater than said sink or equal to said sink; turning said second heat switch on to transfer heat from said electrocaloric element to said sink; and turning said second heat switch off, and wherein turing said heat switches off comprises applying a voltage in a first, forward direction to said switches; and wherein turning said switches on comprises applying a voltage in a second, reverse direction to said forward direction to a said switch. ‘There is also provided a controller configured to implement this method. The invention further provides processor control code to implement the above- described controllers and methods, in particular on a data carrier such as a disk, CD- or DVD-ROM, programmed memory such as read-only memory (Firmware), or on a data carrier such as an optical or electrical signal carrier. Code (and/or data) to implement embodiments of the invention may comprise source, object or executable code in a conventional programming language (interpreted or compiled) such as C, or assembly code, code for setting up or controlling an ASIC (Application Specific Integrated Circuit) or FPGA (Field Programmable Gate Array), or code for a hardware description language such as Verilog (Trade Mark) or VHDL (Very high speed integrated circuit Hardware Description Language). As the skilled person will appreciate such code and/or data may be distributed between a plurality of coupled components in communication with one another. WO 2006/056809 PCT/GB2005/050207 Broadly speaking, we will describe a cooling device comprising several electrocaloric working elements with working temperatures covering a required temperature range. The elements are separated by heat switches. The number of electrocaloric elements and heat switches can be different in other embodiments. The device can be cascaded or paralleled to provide greater cooling. Thermoelectric heat switches are provided for switching from a heat conducting to a heat insulating state. In some embodiments, the thermoelectric switches are replaced by microelectromechanical switches. The thermoelectric switches can operate in passive heat conducting mode. In some embodiments, the switches can operate in active heat conducting mode, with the reverse current passed through the couples in the off heat conduction state. electrocaloric elements can take the form of multilayer capacitors comprised of ferroelectric thin films. In some embodiments, the electrocaloric elements can be made from bulk materials. Thermoelectric heat switches can be energized by a direct electrical coupling to a current source or by induction coupling. These and other aspect of the invention will now be further described, by way of example only, with reference to the accompanying figures in which: Figure 1 Shows a schematic of an electrocaloric element. Figure 2 Shows results of the electrocaloric effect measurement of four different samples of PbScosT@os0s used in the prototype shown in Fig. 5. The Curie point, taken as the temperature of the maximum of ECE, can be moved, which allows a much wider temperature interval to be covered than with a single element. Figure 3 Shows the results of the electrocaloric effect measurement of PbosNbo.02(Zro.75Sn02Tio.o5)o.08Os- Figure 4 Shows a thermoelectric couple. WO 2006/056809 PCT/GB2005/050207 Figure 5 Shows a schematic of an electrocaloric fridge prototype. Some characteristics of the prototype are shown in Fig. 6. Figure 6 Shows experimental results obtained with the prototype shown in Figure 5. Figure 7 Shows schematic design of one embodiment of the proposed cooling device comprising one electrocaloric element 200 and two heat switches 100 and 110. Electronic circuits that supply the electrocaloric element and heat switches are not shown here for the sake of clarity. Figure 8 Shows schematic design of one embodiment of the proposed cooling device, a cascaded system comprising 2 electrocaloric elements 200 and 210; 3 heat switches 100, 110 and 120; and electronic circuits that supply the electrocaloric elements and heat switches. The circuits are not shown here for the sake of clarity. Figure9 Shows the working cycles of the cooling sandwich shown in Figure 8. Other embodiments of the proposed device (e.g. cascaded devices comprising 4, 6, etc. electrocaloric elements) can use working cycles of the same principle. Heat exchange between 200 and 210 takes r seconds and between 200 and 10 (210 and 20) - 2: seconds. A label ATT stands for a polarisation of an electrocaloric element (either 200 or 210) that increases its temperature by AT via the electrocaloric effect and a blue label AT, - a depolarisation of an electrocaloric element (either 200 or 210) accompanied by its cooling with AT. See also Fig. 15, later. Figure 10 Shows the schematic design of another embodiment of the proposed cooling device, a cascaded system comprising 4 electrocaloric elements 200, 210, 220 and 230; 5 heat switches 100, 110, 120, 180, and 140; and electronic circuits that supply the electrocaloric elements and heat switches. The circuits are not shown here for the sake of clarity WO 2006/056809 PCT/GB2005/050207 Figure 11. Shows an example thermodynamic cooling cycle of an electrocaloric element (e.g. 200, 210 in Fig. 8). Figure 12 | Shows an example design of a micromechanical heat switch which can be fabricated with a method presented in Fig. 13. Figure 13 Shows microfabrication of a ladder micromechanical heat switch shown in Fig. 12. Figure 14 Shows a schematic design of still another embodiment of the proposed cooling device, a cascaded system comprising 6 electrocaloric elements 200, 210, 220, 230, 240, and 250; 7 heat switches 100, 110, 120, 130, 140, 150, and 160; and electronic circuits that supply the electrocaloric elements and heat switches. The circuits are not shown here for the sake of clarity Figure 15 Shows results of an example calculation of an example cooling cycle of one embodiment of the device - the one comprising 2 electrocaloric elements, shown in Fig. 8, The temperatures of the heat source 20 (Tz0), EC elements 200, 210 (Tzoo, Tz1a) and the heat sink 10 (T1o) are shown. The picture represents equilibrium - 600 cycles have been simulated before these curves are taken. Four stages of a possible refrigeration cycle are highlighted (see Fig. 9). The electrocaloric effect is taken to be the same in both elements: AT)= AT. Figure 16 Shows efficiency and cooling power of one embodiment of the device comprising 4 electrocaloric elements (shown in Fig. 10) versus heat conductivity of the switches. ris the time for heat exchange between any two electrocaloric elements (A.3). Figure 17 Shows efficiency and cooling power of some embodiments of the device (shown in Figs. 7, 8, 10 and 14): cascaded devices comprising 2, 4, and WO 2006/056809 PCT/GB2005/050207 8 6 electrocaloric elements in passive (the reverse current in heat switches is lev = 0 A) and active (Jv = 0.05, 0.1 and 0.2 A) heat conducting modes. The influence of the reverse current on the performance shown in Fig. 18 is calculated at the highlighted temperature differences: 3 K for a cascaded device comprising 2 electrocaloric elements, 6 K for a cascaded device comprising 4 electrocaloric elements, and 10 K for a cascaded device comprising 6 electrocaloric elements. Figure 18 Shows the influence of the heat switches’ reverse current on the performance of some embodiments of the cooling device: cascaded devices comprising 2, 4, and 6 electrocaloric elements, The particular current values can be reduced by increasing the number of couples NV and decreasing the geometrical factor G - a standard approach in design of thermoelectric devices. It should be understood that the values used in the calculations are not fixed, Figure 19 Shows estimated efficiency of some embodiments of the proposed device: cascades comprising 2, 4, and 6 electrocaloric elements and a commercially available thermoelectric cooler. The devices operate in both passive (Irev=0A) and active (Irev = 0.05, 0.1 and 0.2 A) heat conducting modes. The average temperature difference between the hot and the cold ends is about 6—8°C for all curves. Data for the Melcor device is taken from (www.melcor.com, for a device No PT8-7-30 with G = 0.17 om, N = 71, heat resistance riieat = 0.04°CW"). Figure 20 Shows |. Temperature of an electrocaloric element with higher initial temperature (Tie) and an electrocaloric element with lower initial temperature (Tcou) interspaced with a thermoelectric device with a current of 0, 0.05 and 0.2 A versus time. The current is applied at {= 0 s, when Tyo = 305 K and Tos = 300 K; and Il. As above for a current of 0.2 A. Joule heating linear with time manifests on a 10 s timescale. Figure 21 Shows a schematic design of an embodiment of a paralle! configured device for transferring heat from a heat source 20 to a heat sink 10. WO 2006/056809 PCT/GB2005/050207 Introduction It is helpful to first outline features of some preferred embodiments of the invention. We describe a device for transferring heat from a heat source 20 to a heat sink 10, see Fig. 20. The device comprises at least two heat switches 100 and 110, the former to receive heat from the heat source 20, the latter to pass heat to the heat sink 10; at least one electrocaloric (EC) element 200 between the heat switches 100 and 110 and in thermal contact with the heat switches; and a control input for controlling 100, 110, and 200. One or both of the heat switches comprise a thermoelectric heat switch, tunnelling heat switch or an electromechanical heat switch. Preferably, a device described above is a part of a cascaded system having a plurality of the devices for transferring heat from a cold end to a hot end. Some embodiments of a cascaded system are presented in Figs. 7, 9, and 13. Referring to Fig. 7, a cascaded system comprising two electrocaloric elements 200 and 210 and three heat switches 100, 110 and 120 is presented. An electrocaloric element 210 of an additional stage is utilised as a heat source in the previous stage of the cascaded system. In other words, the embodiment of a cascaded system shown in Fig.8 comprises two cooling devices: a first device comprising an electrocaloric element 200 and heat switches 100 and 110 and a second device comprising an electrocaloric element 210 and heat switches 110 and 420. Referring to Fig. 9, a cascaded system comprising four electrocaloric elements 200, 210, 220, and 230 and five heat switches 100, 110, 120, 130, and 140 is presented. Electrocaloric element 210 is utilised as a heat source in the previous stage comprising the electrocaloric element 200. Electrocaloric element 220 is utilised as a heat source in the stage comprising electrocaloric WO 2006/056809 PCT/GB2005/050207 10 elements 200 and 210. Electrocaloric element 230 is utilised as a heat source in the stage comprising electrocaloric elements 200, 210, and 220. In other words, the system comprises four cooling devices: a first device comprising an electrocaloric element 200 and heat switches 100 and 110, a second device comprising an electrocaloric element 210 and heat switches 110 and 120, a third device comprising an electrocaloric element 220 and heat switches 120 and 130, and a fourth device comprising an electrocaloric element 230 and heat switches 130 and 140. The hot end of a fourth device is the cold end of the third device, the hot end of the third device is the cold end of the second device, and the hot end of the second device is the cold end of the first device. Referring to Fig. 13, a cascaded system comprising six electrocaioric elements 200, 210, 220, 230, 240, and 250 and seven heat switches 100, 110, 120, 130, 140, 150, and 160 is presented. It should be understood that cascaded systems comprising any other number of electrocaloric elements and heat switches can be used. Another embodiment of the present invention, a parallel configured device for transferring heat from a heat source 20 to a heat sink 10, is presented in Fig. 21. A plurality of parallel positioned stacks 500, 510, 520 and 530 transfer heat from a heat source 20 to a heat sink 10. The number of stacks can be different. Each stage in each stack 500, 510, 520 and 530 comprises en electrocaloric cooling system presented in one or several embodiments of the present invention. Other configurations and orientations of the elements shown in Fig. 24 may be used, An off state of heat switches comprises applying a voltage in a first, forward direction to the switches, and an on state of the switches comprises applying a voltage in a second, reverse direction to the forward direction to the switches, However, the heat switches do not need to fully reject heat in an off state. WO 2006/056809 PCT/GB2005/050207 ul Embodiments of a device of the present invention also comprise a control input that comprises one or more electrical connections, and means to control heat switches and electrocaloric elements (e.g. a computer program). As previously mentioned, we also describe a method of controlling a heat transfer device for transferring heat from a heat source to a heat sink. As an example, @ method is considered for an embodiment comprising one electrocaioric element 200 and two heat switches 100 and 110, see Fig. 20. The method comprises: cooling electrocaloric element 200 to a temperature of less than source 20 or equal to the source 20; turing the first heat switch 110 on to transfer heat from the source 20 to the electrocaloric element 200; turning the first heat switch 110 off; warming the electrocaloric element 200 to a temperature of greater than the sink 10 or equal to the sink 10; tuming the second heat switch 100 on to transfer heat from the electrocaloric element 200 to the sink 10; and turning the second heat switch 100 off. Turning the heat switches 100 and 110 off comprises applying a voltage in a first, forward direction to the switches, and tuming the switches 100 and 110 on comprises applying a voltage in a second, reverse direction to said forward direction to a said switch. We also describe a method of controlling a cascaded system having a plurality of devices for transferring heat from a cold end to a hot end and wherein the method is repeated for each device for transferring heat from a heat source to a heat sink in the cascaded system. Also, we disclose a method of controlling a parralel and stacked cascaded system having a plurality of devices for transferring heat from a cold end to a hot end wherein the method is repeated for each device for transferring heat from a heat source to a heat sink in said systems, A device embodying aspects of the present invention also comprises a controller configured to implement methods explained above, and a carrier to WO 2006/056809 PCT/GB2005/050207 12 carry a computer program code (e.g. host or disk) to implement methods explained above. The Electrocaloric Effect and Electrocaloric Working Elements The electrocaloric effect is, broadly speaking, a change of a material's temperature upon an application or removal of an electric field. There are some obvious facts that make the electrocaloric effect (ECE) more attractive for applications than magnetocaloric effect (MCE): * itis easier to generate and maintain electric rather than magnetic fields, © itis easier to organise the cycle of energy return after each cycle of the refrigeration, + itis easier to build a cascaded cooling device comprising several working elements separated by heat switches, etc, A standard geometry of an electrocaloric (EC) working element is shown in Fig. 1. It comprises a pair of electrodes 300 and a slab of electrocaloric material 310. So an electrocaloric element is basically a capacitor with an electrocaloric material between its electrodes. The element is energised from a DC or AC voltage source 330, and the voltage is applied by switching 320. So when the switch 320 is tured on, the electrocaloric material 310 polarises and its temperature changes due to the electrocaloric effect. When 320 is turned off, the temperature of 310 returns to its initial value. It should be understood that the Figure is a schematic only and different circuitry can be used, as well as, different structure of the electrodes (e.g. multilayer capacitor structure, similar to that described in M. Togashi. "Multilayer ceramic electronic device", US Patent No 2003/0026059, 2003, for example; layers of electrocaloric material in the multilayer capacitor can be made with thin film deposition techniques, e.g. sol- gel, as disclosed in D.A, Barrow, T.E. Petroff, and M. Sayer. "Method for WO 2006/056809 PCT/GB2005/050207 1B producing thick ceramic films by a sol gel coating process", US Patent No 5585136, 1996, for example). Electrocaloric Materials The best known electrocaloric materials are perovskite ferroelectric materials. The highest electrocaloric effect at room temperature was found in PbScosTao sOs (PST). For a more detailed description of the material see E.H.Birks L.A.Shebanov, K.J.Borman, and A.R.Sternberg. Ferroelectrics. 94: p. 305, 1989, for example. The value of the ECE peaks al the critical temperature Te but remains within 80% of the maximum value within about 10°C region around To. The critical temperature can be adjusted by a special heat treatment of the material during the annealing phase of its manufacturing E.K.H. Birks, L.A. Shebanov, K.Y.A. Bormanis, and M. Dambekalne. "Lead scanotantalate as active element of microcryogenic systems", SU Patent No 1479440, 1989. A typical dependence of ECE for PST after different heat treatments at electric field 25 kVcm' is shown in Fig. 2., which is adapted from Y.V. Sinyavsky, N.D. Pashkov, Y.M. Gorovoi, G.E. Lugansky, and L.A. Shebanov. Ferroelectrics. 90: p. 213, 1989. The highest ECE was found in PbZrTiO; (PZT) doped with Sn and Nb: PbosgNbo.02(Zro.7sSno.2Tio.os)oes03 (B.A. Tuttle. “Polarization reversal and electrocaloric measurements for field-enforced transitions in the system lead zirconate-lead titanate-lead oxide:tin oxide", PhD Thesis at University of Illinois at Urbana-Champaign, 1982). The ECE peaks at about 160°C and has a maximum value of 2.6°C at 30 kVcm". Its dependence upon temperature for samples obtained with different treatments is shown in Fig. 3. Due to the nature of the electrocaloric effect, it is natural that its value grows with the electric field. In practice the maximum field that can be applied to a material is determined by the breakdown voltage. For people acquainted with the state of the art it is well known that thin film materials have much higher breakdown voltages than same compounds in bulk form. A typical breakdown WO 2006/056809 PCT/GB2005/050207 14 value for thin films is 2 MVcm'™ while that for bulk materials is about 30 kV cm” This gives grounds to the prediction that thin film materials will have a much higher electrocaloric effect. Some experimental evidence of this was provided in (L. Shebanovs, K, Borman, W.N. Lawless, and Kalvane A. Ferroelectrics. 273: p. 2515, 2002), Thus, a multilayer capacitor system comprised of a plurality of ferroelectric thin films (deposited by sol gel, for example, as disclosed in D.A. Barrow, T.E. Petroff, and M. Sayer. "Method for producing thick ceramic films by a sol gel coating process", US Patent No 5585136, 1996) separated with electrodes (with a geometry described in M. Togashi. "Multilayer ceramic electronic device’, US Patent No 2003/0026059, 2003, for example) can manifest a much higher ECE than bulk material of the same composition due to the higher electric field applied. The compounds described above can be used in embodiments of the invention either in the form of a multilayer capacitor or in bulk form. However, it should be understood, that any materials with ECE can be used in embodiments of the invention. The inherent efficiency of an electrocaloric element depends on several factors. ‘Among them are hysteresis losses if the material used is ferroelectric and losses due to Joule heating due to finite electrical resistance of the elements. ‘As numerous experiments showed, the inherent efficiency of EC elements is remarkably high — around 98% of the Carnot cycle (Y.V. Sinyavsky, N.D. Pashkov, Y.M. Gorovoi, G.E. Lugansky, and Shebanov L. Ferroelectrics. 91 213, 1980). The efficiency 7 was estimated using the formula: : lm On —Dour™ 2 where Qece is the amount of heat generated in an EC element due to ECE, Qu is electrical energy supplied for the polarization if the EC element, Qour is electrical energy withdrawn from the EC element at its depolarization, and nip is the efficiency of the ideal Carnot refrigeration cycle. The Carnot efficiency is given by: Teou (2) a Thor Tooke WO 2006/056809 PCT/GB2005/050207 15 where Tyor and Toot are temperatures of the hot and cold end respectively. Thus it is supposed in the following that the electrical circuits of the cooling device allow for saving of the electrical energy coming from a depolarization of the working elements. This is easy and straightforward to implement by building RC = circuits for example, where the capacitance element is an electrocaloric element. Heat Switches A heat switch is a device that can be switched between two states — heat conducting and heat insulating. The heat insulating state does not need to be fully insulating. Some examples are given below. Thermoelectric heat switches are important parts of the proposed device in some embodiments, so they will be discussed in more detail here. An example of a thermoelectric couple is presented in Fig. 4. As a rule, it comprises two legs ~ 440 (n-type semiconductor) and 450 (p-type semiconductor), several layers of electrical conducting material 410, several layers of material 400 which is an electrical insulator and heat conductor. When the element is energised with the voltage source 460, it pumps heat from heat source 420 to heat sink 430. The heat pumped at the cold surface 420 Qe (W) is equal to: Qe =2N aT FE ) where N is the number of couples (there is only one in Fig. 4), Toow is the cold surface temperature (K), a is the Seebeck coefficient (VK"), / is the electrical current (A), pis the resistivity of 440 and 450 (Qcm), k is the heat conductivity of 440 and 450 (Wem''K"), AT - the temperature difference between 430 and 420 (K), and G is the ratio of an element's cross-sectional area to its height (cm). The first term in the brackets in (3) describes the Peltier effect, the WO 2006/056809 PCT/GB2005/050207 16 second term describes Joule heating and the third describes parasitic heat flow from 430 to 420. A thermoelectric element can work as @ heat switch, i.e. it can either conduct heat (when / = 0) from the hot to the cold surface (an on state of a heat switch) or not conduct heat (when | = /oy, at which the Peltier cooling just offsets the thermal conductivity and Joule heating — an off state of a heat switch). The value of lo can be found from the equation Qc = 0: (4) It should be understood that the value given by (4) is an example only, and any other close value can be used. Also, a heat insulating state (off state) does not need to be fully heat insulating. ‘A magnetocaloric cooling system using thermoelectric and microelectromechanical (MEMS) heat switches is disclosed in U.S. Ghoshal. "Apparatus and methods for performing switching in magnetic refrigeration systems using thermoelectric switches”, US Patent No 6595004, 2003. Various arrangements of heat switches and working magnetocaloric elements are mentioned. However due to the difficulty in generating a magnetic field, construction of such a device would be complicated. Additionally its efficiency and cooling power would be questionable due to large heat leaks. One of the significant differences between the device and method disclosed in U.S.6595004 and embodiments of the invention is the nature of the working elements — they are electrocaloric in embodiments of the invention, not magnetocaloric as in US6595004. This makes the whole system simpler and allows for direct estimations of the device efficiency with parameters of available materials. High thermodynamic efficiency of thermoelectric heat switches was discussed in length in US6595004. All the discussion along with the conclusions are relevant in the present context. For people acquainted with the field it is well WO 2006/056809 PCT/GB2005/050207 7 known that efficiency of a thermoelectric material sharply increases with decrease of the temperature difference between the hot and cold contacts of a thermocouple. This difference is kept small throughout the whole cooling cycle of the proposed device. An electrocaloric cooling system based on a cascade of electrocaloric working elements separated with piezoelectric heat switches is disclosed in V.M Brodyansky, Yu.V. Sinyavsky, and N.D. Pashkov. "Thermal switch (its versions)", SU Patent No 918770, 1982. A piezoelectric heat switch is similar to the electrocaloric element shown in Fig. 1, but material 310 has high piezoelectric effect in this case, i.e. significant contraction or elongation upon application of electric field, If placed between two electrocaloric elements so that upon elongation it touches both electrocaloric elements, and upon contraction touches none of them, such a piezoelectric element can work as a heat switch. The proposed device does not use bulk piezoelectric heat switches. In some embodiments of the proposed device, microelectromechanical heat switches are used, but their major feature Is a complex surface that increases the surface contact area, which is absent in \V.M. Brodyansky, Yu.V. Sinyavsky, and N.D. Pashkov. "Thermal switch (its versions)", SU Patent No 918770, 1982. Electrocaloric Cooling Technology We next describe some embodiments of the our device and estimation of their characteristics. Description of some embodiments of the device The device comprises at least one electrocaloric working element 200 placed between at least two heat switches 100 and 110, see Fig. 7. Heat switches 100, 410 have thermal contact with a heat sink 10 and heat source 20 respectively. There is also a thermal contact between 100 and 200, 110 and 200. We use WO 2006/056809 PCT/GB2005/050207 18 heat switches which are active elements and require electrical energy to function, In another embodiment, a cascaded system comprising two electrocaloric working elements is proposed. An electrocaloric element 210 of an additional stage is utilised as a heat source in the previous stage of the cascaded system, see Fig. 8. In other words, the embodiment of a cascaded system shown in Fig.8 comprises two cooling devices: a first device comprising an electrocalorio, element 200 and heat switches 100 and 110 and a second device comprising an electrocaloric element 210 and heat switches 110 and 120. Referring to Fig. 8, @ heat source 20 is connected mechanically to the heat switch 120 so that there is a good thermal contact between them. The heat switch 120 is mechanically connected to the working element 210, so that there is good thermal contact between them. However, there is no direct electrical connection between 120 and 210. In a similar fashion electrocaloric element 200 is thermally connected to heat switches 100 and 110 and electrically isolated from them. Elements 210 and 110 as well as 110 and 200 do not contact each other in Fig. 8 for the sake of clarity. Buffer layers. providing thermal contact and electrical insulation between 10 and 100, 100 and 200, 200 and 110, 110 and 210, 210 and 120, and 120 and 20 are also not shown here for clarity. In some embodiments, thermoelectric elements can be used as heat switches, ie. they can be switched between two states — heat insulating and heat conducting. In some embodiments, an on state corresponds to heat flow from the hot to the cold elements by virtue of heat conduction through the thermocouples in passive mode. In other embodiments, the heat flow in an on state is assisted by the application of a reversed current so that the time of heat exchange decreases, and this mode of operation is called active mode. An off state is defined as zero or nearly zero heat transfer to the cold end of a thermoelectric couple/couples. In this state a direct current is passed through the couples so that the thermoelectric cooling effect precisely or almost WO 2006/056809 PCT/GB2005/050207 19 precisely offsets the heat conduction. In some embodiments the current passed through the thermocouples in an off mode can be higher than that required to offset the heat conduction process in order to reduce the time of heat exchange A thermoelectric heat switch incorporated into the proposed device can be energised either directly or by electromagnetic induction, in a similar way to that described in U.S. Ghoshal. "Apparatus and methods for performing switching in magnetic refrigeration systems using thermoelectric switches’, US Patent No 6595004, 2003 in relation to magnetocaloric systems. In another embodiment, thermoelectric switches are replaced by tunneling cooling devices, disclosed in A. Tavkhelidze, L. Koptonashvili, Z. Berishvili, and G. Skhiladze. "Method for making a diode device", US Patent No 6417060, 2002, for example. In these embodiments a proposed device operates in a similar way to that described in the previous paragraph Preferably, thermoelectric heat switches can be manufactured by means of electrolysis disclosed in J.-P. Fleurial, M.A. Ryan, A. Borshchevsky, W. Phillips, EA. Kolawa, GJ. Snyder, T. Caillat, T. Kascich, and P. Mueller. es", US Patent No 6388185, 2002, incorporated by reference in its entirity. The cited patent "Microfabricated thermoelectric power-generation de proposes a thermoelectric device for electrical energy generation, but it can be used for the reverse purpose, ie, heat pumping, due to Onsager relations. Thermocouples made by electrolysis are with a flat geometry, e.g. with 1 mm x 1 mm cross section and 100 um thickness. BiTe is the material used in the cited patent, and it can be used in embodiments of the invention. However, other thermoelectric materials can be used for heat switches as well. From the analysis below it follows that the higher the figure of merit of used thermoelectric materials the higher the efficiency of the whole cooling device. The following estimations show a preferable range of sizes of thermoelectric heat switches. However it should be understood that this is just an example and heat switches of other sizes can-be used. For the cooling device to work WO 2006/056809 PCT/GB2005/050207 20 efficiently, there are preferably two conditions to be satisfied: (i) the heat capacity of each heat switch should be much less than that of an electrocaloric element, and (ii) heat transfer should be accomplished for a reasonable amount of time. Although there is no strict objective limit on this time, 7 = 1s seems a plausible upper value. A time scale of the device operation can be set by the polarisation time (0.1 s), so a heat transfer taking, say, 10 s, is far too slow. These conditions can be expressed as Ceusws = 2NK Gl << C, 3) nicer 2N2kG where C is the heat capacity of an EC element, Cyaisw is total heat capacity of a heat switch, carro is the volume heat capacity of bismuth telluride, a possible material used in thermocouples, NV is the number of thermocouples, his the height of the thermocouples, G is the ratio of the area of one leg of a thermocouple to its height h, k is the heat diffusivity of BiTe. After a simplification one has two inequalities: co. =

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