Polymeric nanocomposites for electrocaloric refrigeration

Abstract

Electrocaloric refrigeration represents an alternative solid-state cooling technology that has the potential to reach the ultimate goal of achieving zero-global-warming potential, highly efficient refrigeration, and heat pumps. To date, both polymeric and inorganic oxides have demonstrated giant electrocaloric effect as well as respective cooling devices. Although both polymeric and inorganic oxides have been identified as promising cooling methods that are distinguishable from the traditional ones, they still pose many challenges to more practical applications. From an electrocaloric material point of view, electrocaloric nanocomposites may provide a solution to combine the beneficial effects of both organic and inorganic electrocaloric materials. This article reviews the recent advancements in polymer-based electrocaloric composites and the state-of-the-art cooling devices operating these nanocomposites. From a device point of view, it discusses the existing challenges and potential opportunities of electrocaloric nanocomposites.

Graphical abstract

Keywords

nanocomposites / electrocaloric / refrigeration / polymer

References

[1] Ma R, Zhang Z, Tong K. . Highly efficient electrocaloric cooling with electrostatic actuation. Science, 2017, 357(6356): 1130–1134

[2] Shi J, Han D, Li Z. . Electrocaloric cooling materials and devices for zero-global-warming-potential, high-efficiency refrigeration. Joule, 2019, 3(5): 1200–1225

[3] Qian X, Han D, Zheng L. . High-entropy polymer produces a giant electrocaloric effect at low fields. Nature, 2021, 600(7890): 664–669

[4] Gu H, Qian X, Li X. . A chip scale electrocaloric effect based cooling device. Applied Physics Letters, 2013, 102(12): 122904

[5] Neese B, Chu B, Lu S G. . Large electrocaloric effect in ferroelectric polymers near room temperature. Science, 2008, 321(5890): 821–823

[6] CuiHHeW PeiQ, . Electrocaloric effects in ferroelectric polymers. In: Asadi K, ed. Organic Ferroelectric Materials and Applications.Woodhead Publishing, 2022: 535–570

[7] Qian X, Wu S, Furman E. . Ferroelectric polymers as multifunctional electroactive materials: recent advances, potential, and challenges. MRS Communications, 2015, 5(2): 115–129

[8] Liu Y, Zhang B, Xu W. . Chirality-induced relaxor properties in ferroelectric polymers. Nature Materials, 2020, 19(11): 1169–1174

[9] Lu S G, Rožič B, Zhang Q M. . Organic and inorganic relaxor ferroelectrics with giant electrocaloric effect. Applied Physics Letters, 2010, 97(16): 162904

[10] Qiu J H, Ding J N, Yuan N Y. . Effect of misfit strain on the electrocaloric effect of P(VDF-TrFE) copolymer thin films. European Physical Journal B, 2011, 84(1): 25–28

[11] Li X, Qian X, Gu H. . Giant electrocaloric effect in ferroelectric poly(vinylidenefluoride-trifluoroethylene) copolymers near a first-order ferroelectric transition. Applied Physics Letters, 2012, 101(13): 132903

[12] Chen X, Li X, Qian X. . A polymer blend approach to tailor the ferroelectric responses in P(VDF–TrFE) based copolymers. Polymer, 2013, 54(9): 2373–2381

[13] Moreira R L. Electrocaloric effect in γ-irradiated P(VDF-TrFE) copolymers with relaxor features. Ferroelectrics, 2013, 446(1): 1–8

[14] Qian X, Ye H, Yang T. . Internal biasing in relaxor ferroelectric polymer to enhance the electrocaloric effect. Advanced Functional Materials, 2015, 25(32): 5134–5139

[15] Qian X, Yang T, Zhang T. . Anomalous negative electrocaloric effect in a relaxor/normal ferroelectric polymer blend with controlled nano- and meso-dipolar couplings. Applied Physics Letters, 2016, 108(14): 142902

[16] Prest W M Jr, Luca D J. The formation of the γ phase from the α and β polymorphs of polyvinylidene fluoride. Journal of Applied Physics, 1978, 49(10): 5042–5047

[17] Huang C, Klein R, Feng X. . Poly(vinylidene fluoride-trifluoroethylene) based high performance electroactive polymers. IEEE Transactions on Dielectrics and Electrical Insulation, 2004, 11(2): 299–311

[18] Saranya D, Chaudhuri A R, Parui J. . Electrocaloric effect of PMN-PT thin films near morphotropic phase boundary. Bulletin of Materials Science, 2009, 32(3): 259–262

[19] Bai Y, Zheng G P, Ding K. . The giant electrocaloric effect and high effective cooling power near room temperature for BaTiO₃ thick film. Journal of Applied Physics, 2011, 110(9): 094103

[20] Peng B, Fan H, Zhang Q. A giant electrocaloric effect in nanoscale antiferroelectric and ferroelectric phases coexisting in a relaxor Pb_0.8Ba_0.2ZrO₃ thin film at room temperature. Advanced Functional Materials, 2013, 23(23): 2987–2992

[21] Ye H, Qian X, Jeong D. . Giant electrocaloric effect in BaZr_0.2Ti_0.8O₃ thick film. Applied Physics Letters, 2014, 105(15): 152908

[22] Ye H J, Qian X S, Lu J. . Dielectric and electrocaloric responses of Ba(Zr_0.2Ti_0.8)O₃ bulk ceramics and thick films with sintering aids. IEEE Transactions on Dielectrics and Electrical Insulation, 2015, 22(3): 1501–1505

[23] Hou Y, Yang L, Qian X. . Electrocaloric response near room temperature in Zr- and Sn-doped BaTiO₃ systems. Philosophical Transactions of the Royal Society A, Mathematical, Physical, and Engineering Sciences, 2016, 374(2074): 20160055

[24] Hou Y, Yang L, Qian X. . Enhanced electrocaloric effect in composition gradient bilayer thick films. Applied Physics Letters, 2016, 108(13): 133501

[25] Qian J, Guo M, Jiang J. . Enhanced electrocaloric strength of P(VDF-TrFE-CFE) induced by edge-on lamellae. Journal of Materials Chemistry. C, Materials for Optical and Electronic Devices, 2019, 7(11): 3212–3217

[26] Qian J, Jiang J, Shen Y. Enhanced electrocaloric strength in P(VDF-TrFE-CFE) by decreasing the crystalline size. Journal of Materiomics, 2019, 5(3): 357–362

[27] Li X, Qian X, Lu S G. . Tunable temperature dependence of electrocaloric effect in ferroelectric relaxor poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene terpolymer. Applied Physics Letters, 2011, 99(5): 052907

[28] Li Q, Zhang G, Zhang X. . Relaxor ferroelectric-based electrocaloric polymer nanocomposites with a broad operating temperature range and high cooling energy. Advanced Materials, 2015, 27(13): 2236–2241

[29] Zhang G, Li Q, Gu H. . Ferroelectric polymer nanocomposites for room-temperature electrocaloric refrigeration. Advanced Materials, 2015, 27(8): 1450–1454

[30] Zhang G, Fan B, Zhao P. . Ferroelectric polymer nanocomposites with complementary nanostructured fillers for electrocaloric cooling with high power density and great efficiency. ACS Applied Energy Materials, 2018, 1(3): 1344–1354

[31] Zhang G, Zhang X, Yang T. . Colossal room-temperature electrocaloric effect in ferroelectric polymer nanocomposites using nanostructured barium strontium titanates. ACS Nano, 2015, 9(7): 7164–7174

[32] Zhang G, Weng L, Hu Z. . Nanoconfinement-induced giant electrocaloric effect in ferroelectric polymer nanowire array integrated with aluminum oxide membrane to exhibit record cooling power density. Advanced Materials, 2019, 31(8): 1806642

[33] Jiang Z Y, Zheng X C, Zheng G P. The enhanced electrocaloric effect in P(VDF-TrFE) copolymer with barium strontium titanate nano-fillers synthesized via an effective hydrothermal method. RSC Advances, 2015, 5(76): 61946–61954

[34] Yang L, Qian X, Koo C. . Graphene enabled percolative nanocomposites with large electrocaloric efficient under low electric fields over a broad temperature range. Nano Energy, 2016, 22: 461–467

[35] Qian J, Peng R, Shen Z. . Interfacial coupling boosts giant electrocaloric effects in relaxor polymer nanocomposites: in situ characterization and phase-field simulation. Advanced Materials, 2019, 31(5): e1801949

[36] Lu Y, Yu J, Huang J. . Enhanced electrocaloric effect for refrigeration in lead-free polymer composite films with an optimal filler loading. Applied Physics Letters, 2019, 114(23): 233901

[37] Chen Y, Qian J, Yu J. . An all-scale hierarchical architecture induces colossal room-temperature electrocaloric effect at ultralow electric field in polymer nanocomposites. Advanced Materials, 2020, 32(30): 1907927

[38] Zhang G, Zhang X, Huang H. . Toward wearable cooling devices: highly flexible electrocaloric Ba_0.67Sr_0.33TiO₃ nanowire Arrays. Advanced Materials, 2016, 28(24): 4811–4816

[39] Chen X, Qian X, Li X. . Enhanced electrocaloric effect in poly(vinylidene fluoride-trifluoroethylene)-based terpolymer/copolymer blends. Applied Physics Letters, 2012, 100(22): 222902

[40] Le Goupil F, Coin F, Pouriamanesh N. . Electrocaloric enhancement induced by cocrystallization of vinylidene difluoride-based polymer blends. ACS Macro Letters, 2021, 10(12): 1555–1562

[41] Ullah A, ur Rahman A, Won Ahn C. . Enhancement of dielectric and energy density properties in the PVDF-based copolymer/terpolymer blends. Polymer Engineering and Science, 2015, 55(6): 1396–1402

[42] AziguliHLiu YZhangG, . Tuning the electrocaloric reversibility in ferroelectric copolymers by a blend approach. Europhysics Letters, 2019, 125(5): 57001 (1−6)

[43] Zhang X, Shen Y, Shen Z. . Achieving high energy density in PVDF-based polymer blends: suppression of early polarization saturation and enhancement of breakdown strength. ACS Applied Materials & Interfaces, 2016, 8(40): 27236–27242

[44] Lu S, Zhang Q. Large electrocaloric effect in relaxor ferroelectrics. Journal of Advanced Dielectrics, 2012, 2(3): 1230011

[45] Chen X, Li X, Qian X. . A nanocomposite approach to tailor electrocaloric effect in ferroelectric polymer. Polymer, 2013, 54(20): 5299–5302

[46] Chen J, Xiong X, Zhang Q. . P(VDF-TrFE)/PMMA blended films with enhanced electrowetting responses and superior energy storage performance. Polymers, 2019, 11(3): 526(1–13)

[47] Jung H, Kim J, Lim J. . Energy storage properties of blended polymer films with normal ferroelectric P(VDF-HFP) and relaxor ferroelectric P(VDF-TrFE-CFE). Electronic Materials Letters, 2020, 16(1): 47–54

[48] Shaobo L, Yanqiu L. Research on the electrocaloric effect of PMN/PT solid solution for ferroelectrics MEMS microcooler. Materials Science and Engineering B, 2004, 113(1): 46–49

[49] Kaddoussi H, Gagou Y, Lahmar A. . Ferroelectric phase changes and electrocaloric effects in Ba(Zr_0.1Ti_0.9)_1−xSn_xO₃ ceramics solid solution. Journal of Materials Science, 2016, 51(7): 3454–3462

[50] Chen X, Qian X, Li X. . Enhanced electrocaloric effect in poly(vinylidene fluoride-trifluoroethylene)-based composites. MRS Online Proceedings Library, 2012, 1490: 86–91

[51] TokkanMDemir M MAdemU. Enhanced electrocaloric effect of P(VDF-TrFE)-based nanocomposites with Ca and Sn co-doped BaTiO₃ particles. Materials Science, 2022, doi: 10.2139/ssrn.4091479

[52] De Cicco G, Morten B, Dalmonego D. . Pyroelectricity of PZT-based thick-films. Sensors and Actuators. A, Physical, 1999, 76(1–3): 409–415

[53] Valant M. Electrocaloric materials for future solid-state refrigeration technologies. Progress in Materials Science, 2012, 57(6): 980–1009

[54] Qian X, Ye H, Zhang Y. . Giant electrocaloric response over a broad temperature range in modified BaTiO₃ ceramics. Advanced Functional Materials, 2014, 24(9): 1300–1305

[55] Axelsson A, Le Goupil F, Valant M. . Electrocaloric effect in lead-free Aurivillius relaxor ferroelectric ceramics. Acta Materialia, 2017, 124: 120–126

[56] Kang X, Jia S, Peng J. . Electromagnetic-driven electrocaloric cooling device based on ternary ferroelectric composites. Composites. Part B, Engineering, 2021, 227: 109391

[57] Wang H, Meng Y, Zhang Z. . Self-actuating electrocaloric cooling fibers. Advanced Energy Materials, 2020, 10(12): 1903902

[58] Dang Z, Yuan J, Zha J. . Fundamentals, processes and applications of high-permittivity polymer–matrix composites. Progress in Materials Science, 2012, 57(4): 660–723

[59] Wang J, Wu C, Liu R. . P(VDF–TrFE–CFE)-based percolative composites exhibiting significantly enhanced dielectric properties. Polymer Bulletin, 2013, 70(4): 1327–1335

[60] Tu S, Jiang Q, Zhang X. . Large dielectric constant enhancement in MXene percolative polymer composites. ACS Nano, 2018, 12(4): 3369–3377

[61] Tu S, Jiang Q, Zhang J. . Enhancement of dielectric permittivity of Ti₃C₂T_x MXene/polymer composites by controlling flake size and surface termination. ACS Applied Materials & Interfaces, 2019, 11(30): 27358–27362

[62] Jana S, Garain S, Sen S. . The influence of hydrogen bonding on the dielectric constant and the piezoelectric energy harvesting performance of hydrated metal salt mediated PVDF films. Physical Chemistry Chemical Physics, 2015, 17(26): 17429–17436

[63] Wu X, Kang D, Liu N. . Microstructure manipulation in PVDF/SMA/MWCNTs ultrafiltration membranes: effects of hydrogen bonding and crystallization during the membrane formation. Separation and Purification Technology, 2021, 278: 119523

[64] Li J, Seok S I, Chu B. . Nanocomposites of ferroelectric polymers with TiO₂ nanoparticles exhibiting significantly enhanced electrical energy density. Advanced Materials, 2009, 21(2): 217–221

[65] Shen Z H, Wang J J, Lin Y. . High-throughput phase-field design of high-energy-density polymer nanocomposites. Advanced Materials, 2018, 30(2): 1704380

[66] Dang Z M, Wang L, Yin Y. . Giant dielectric permittivities in functionalized carbon-nanotube/electroactive-polymer nanocomposites. Advanced Materials, 2007, 19(6): 852–857

[67] Nan C. Physics of inhomogeneous inorganic materials. Progress in Materials Science, 1993, 37(1): 66–68

[68] Dan Z, Jiang J, Zhang X. . Interfacial effects of BaTiO₃@TiO₂ nanofibers on dielectric relaxation processes of P(VDF-TrFE-CFE) nanocomposites. Ceramics International, 2020, 46(1): 1119–1123

[69] Zhang Y, Zhang C, Feng Y. . Energy storage enhancement of P(VDF-TrFE-CFE)-based composites with double-shell structured BZCT nanofibers of parallel and orthogonal configurations. Nano Energy, 2019, 66: 104195(1–13)

[70] Morozovska A N, Eliseev E A, Glinchuk M D. . Analytical description of the size effect on pyroelectric and electrocaloric properties of ferroelectric nanoparticles. Physical Review Materials, 2019, 3(10): 104414

[71] Prateek V K, Thakur R K. Recent progress on ferroelectric polymer-based nanocomposites for high energy density capacitors: synthesis, dielectric properties, and future aspects. Chemical Reviews, 2016, 116(7): 4260–4317

[72] Tanaka T, Montanari G C, Mulhaupt R. Polymer nanocomposites as dielectrics and electrical insulation-perspectives for processing technologies, material characterization and future applications. IEEE Transactions on Dielectrics and Electrical Insulation, 2004, 11(5): 763–784

[73] Tanaka T. Dielectric nanocomposites with insulating properties. IEEE Transactions on Dielectrics and Electrical Insulation, 2005, 12(5): 914–928

[74] Lewis T J. Interfaces are the dominant feature of dielectrics at the nanometric level. IEEE Transactions on Dielectrics and Electrical Insulation, 2004, 11(5): 739–753

[75] Gu H, Craven B, Qian X. . Simulation of chip-size electrocaloric refrigerator with high cooling-power density. Applied Physics Letters, 2013, 102(11): 112901

[76] Crossley S, McGinnigle J R, Kar-Narayan S. . Finite-element optimisation of electrocaloric multilayer capacitors. Applied Physics Letters, 2014, 104(8): 082909

[77] Mark J E. Physical Properties of Polymers Handbook. New York: Springer, 2007, 156–159

[78] Plawsky J L. Transport Phenomena Fundamentals. 4th ed. CRC Press, 2009, 96–98

[79] Zeller R C, Pohl R O. Thermal conductivity and specific heat of noncrystalline solids. Physical Review. B, Solid State, 1971, 4(6): 2029–2041

[80] Li M D, Shen X Q, Chen X. . Thermal management of chips by a device prototype using synergistic effects of 3-D heat-conductive network and electrocaloric refrigeration. Nature Communications, 2022, 13(1): 5849(1–8)

[81] Nair B, Usui T, Crossley S. . Large electrocaloric effects in oxide multilayer capacitors over a wide temperature range. Nature, 2019, 575(7783): 468–472

[82] Nouchokgwe Y, Lheritier P, Usui T. . Materials efficiency of electrocaloric lead scandium tantalate multilayer capacitors. Scripta Materialia, 2022, 219: 114873

[83] Guo D, Gao J, Yu Y J. . Design and modeling of a fluid-based micro-scale electrocaloric refrigeration system. International Journal of Heat and Mass Transfer, 2014, 72: 559–564

[84] Meng Y, Zhang Z, Wu H. . A cascade electrocaloric cooling device for large temperature lift. Nature Energy, 2020, 5(12): 996–1002

[85] Bo Y, Zhang Q, Cui H. . Electrostatic actuating double-unit electrocaloric cooling device with high efficiency. Advanced Energy Materials, 2021, 11(13): 2003771

[86] Cui H, Zhang Q, Bo Y. . Flexible microfluidic electrocaloric cooling capillary tube with giant specific device cooling power density. Joule, 2022, 6(1): 258–268

[87] Qian J, Peng R, Shen Z. . Interfacial coupling boosts giant electrocaloric effects in relaxor polymer nanocomposites: in situ characterization and phase-field simulation. Advanced Materials, 2018, 31(5): 1801949

[88] Thakur Y, Zhang T, Iacob C. . Enhancement of the dielectric response in polymer nanocomposites with low dielectric constant fillers. Nanoscale, 2017, 9(31): 10992–10997

[89] Zhang T, Chen X, Zhang Q. . Dielectric enhancement over a broad temperature by nanofiller at ultra-low volume content in poly(ether methyl ether urea). Applied Physics Letters, 2020, 117(7): 072905

[90] Zhang B, Chen X, Lu W. . Morphology-induced dielectric enhancement in polymer nanocomposites. Nanoscale, 2021, 13(24): 10933–10942

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