The availability of materials with high electrocaloric (EC) strengths is critical to enabling EC refrigeration in practical applications. Although large EC entropy changes, ΔSEC , and temperature changes, ΔTEC , have been achieved in traditional thin-film ceramics and polymer ferroelectrics, they require the application of very high electric fields and thus their EC strengths ΔSEC /ΔE and ΔTEC /ΔE are too low for practical applications. Here, a fundamental thermodynamic description is developed, and extraordinarily large EC strengths of a metal-free perovskite ferroelectric [MDABCO](NH4 )I3 (MDABCO) are predicted. The predicted EC strengths: isothermal ΔSEC /ΔE and adiabatic ΔTEC /ΔE for MDABCO are 18 J m kg-1 K-1 MV-1 and 8.06 K m MV-1 , respectively, more than three times the largest reported values in BaTiO3 single crystals. These predictions strongly suggest the metal-free ferroelectric family of materials as the best candidates among existing materials for EC applications. The present work not only presents a general approach to developing thermodynamic potential energy functions for ferroelectric materials but also suggests a family of candidate materials with potentially extremely high EC performance.
Keywords: electrocaloric effect; ferroelectrics; metal-free perovskites; thermodynamic potential.
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