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Abstract

The electrocaloric effects in various types of materials, including inorganic perovskites, organic perovskites, organic polymers, molecular ferroelectrics and two-dimensional ferroelectric materials, possess great potential in realizing solid-state cooling devices due to the advantages of low-cost, high-efficiency and environmental friendly. Different ferroelectric materials have distinct characteristics in terms of phase transition and electrocaloric response. The mechanism for enhancing the electrocaloric effect currently remains elusive. Here, typical inorganic perovskite BaTiO ₃, PbTiO ₃and BiFeO ₃, organic perovskite [MDABCO](NH ₄)I ₃, organic polymer P(VDF-TrFE), molecular ferroelectric ImClO ₄and two-dimensional ferroelectric CuInP ₂S ₆are selected to analyze the origins of their electrocaloric effects based on the Landau-Devonshire theory. The temperature-dependent pyroelectric coefficients and electrocaloric performances of different ferroelectric materials indicate that the first-order phase transition material MDABCO and the second-order phase transition material ImClO ₄have excellent performances for electrocaloric refrigeration. The predicted results also strongly suggest that near the phase transition point of the ferroelectric material, the variation rate of free energy barrier height with temperature contributes to the polarizability change with temperature, resulting in enhanced electrocaloric effect. This present work provides a theoretical basis and a new insight into the further development of ferroelectric materials with high electrocaloric response.

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Authors and contacts

Corresponding author:Huang Hou-Bing,hbhuang@bit.edu.cn

Funds:Project supported by the National Natural Science Foundation of China (Grant No. 51972028) and the National Key R&D Program of China (Grant No. 2019YFA0307900).

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Coefficients	BaTiO₃^[45]	PbTiO₃^[46]	BiFeO₃^[47]	ImClO₄^[43]	[MDABCO] (NH₄)I₃^[42]	CuInP₂S₆^[41]	P(VDF-TrFE)^[26]
α₁/C^–2·m²·N	$\begin{array}{cc} & 5.0 \times 10^5 \times 160 \times\\& \Big[{\rm Coth}\Big(\dfrac{160}{T} \Big)–{\rm Coth} \Big(\dfrac{160}{390}\Big)\Big] \end{array}$	3.8 × 10⁵× (T– 752)	4.646 × 10⁵× (T– 1103)	7.533 × 10⁷× (T– 373)	4.01 × 10⁶× (T– 437)	1.76 × 10⁷× (T– 315)	1.412 × 10⁷× (T– 315)
α₁₁/C^–4·m⁶·N	–1.154×10⁸	–0.73×10⁸	2.290×10⁸	1.5×10¹¹	–7.032×10⁹	1.38×10¹¹	–1.842×10¹¹
α₁₂/C^–4·m⁶·N	6.530×10⁸	7.5×10⁸	3.064×10⁸		1.124×10⁸
α₁₁₁/C^–6·m¹⁰·N	–2.106×10⁹	2.6×10⁸	5.99×10⁹	2×10¹²	α₁₁₁(T)	6.81×10¹³	2.585×10¹³
α₁₁₂/C^–6·m¹⁰·N	4.091×10⁹	6.1×10⁸	–3.340×10⁸		0
α₁₂₃/C^–6·m¹⁰·N	–6.688×10⁹	–3.7×10⁹	–1.778×10⁹		–2.018×10¹⁰
α₁₁₁₁/C^–8·m¹⁴·N	7.590×10¹⁰
α₁₁₁₂/C^–8·m¹⁴·N	–2.193×10¹⁰
α₁₁₂₂/C^–8·m¹⁴·N	–2.221×10¹⁰
α₁₁₂₃/C^–8·m¹⁴·N	2.416× 10¹⁰
注:α₁₁₁(T):T>T₀(437 K),α₁₁₁= 3×10¹¹;T≤T₀,α₁₁₁= –3.5085×10⁹× 55$\left[{\rm Coth}\left(\dfrac{55}{T}\right) \right.$ –Coth$\left.\left(\dfrac{55}{523}\right)\right]$.

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Parameters	BaTiO₃^[35,37,42]	PbTiO₃^[36,48,49]	BiFeO₃^[20]	ImClO₄^[43]	[MDABCO](NH₄)I₃^[42]	CuInP₂S₆^[41]	P(VDF-TrFE)^[50,51]
ρ/kg·m^–3	6020	8300	8346	1719	4039	3405	1886
C/J·m^–3·K^–1	3.05 × 10⁶	3.9 × 10⁶	2.88 × 10⁶	2.423 × 10⁶	4.039 × 10⁶	1.896 × 10⁶	2.244 × 10⁶

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Vol. 69, Issue 21 - 2020-11-05

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