Ferroelectricity and Piezoelectric Energy Harvesting of Hybrid A2BX4-Type Halogenocuprates Stabilized by Phosphonium Cations

Supriya Sahoo; Thangavel Vijayakanth; Premkumar Kothavade; Prashant Dixit; Jan K Zaręba; Kadhiravan Shanmuganathan; Ramamoorthy Boomishankar

doi:10.1021/acsmaterialsau.1c00046

Ferroelectricity and Piezoelectric Energy Harvesting of Hybrid A₂BX₄-Type Halogenocuprates Stabilized by Phosphonium Cations

ACS Mater Au. 2021 Nov 8;2(2):124-131. doi: 10.1021/acsmaterialsau.1c00046. eCollection 2022 Mar 9.

Authors

Supriya Sahoo¹, Thangavel Vijayakanth¹, Premkumar Kothavade^{2

3}, Prashant Dixit⁴, Jan K Zaręba⁵, Kadhiravan Shanmuganathan^{2

3}, Ramamoorthy Boomishankar^{1

1}

Affiliations

¹ Department of Chemistry and Centre for Energy Science, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pune 411008, India.
² Polymer Science and Engineering Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India.
³ Academy of Scientific and Innovative Research, Ghaziabad 201002, India.
⁴ PZT Centre, Armament Research and Development Establishment, Dr. Homi Bhabha Road, Pune 411021, India.
⁵ Advanced Materials Engineering and Modelling Group, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.

Abstract

Perovskite-structured compounds containing organic cations and inorganic anions have gained prominence as materials for next-generation electronic and energy devices. Hybrid materials possessing ferro- and piezoelectric properties are in recent focus for mechanical energy harvesting (nanogenerator) applications. Here, we report the ferroelectric behavior of A₂BX₄-type halogenocuprate materials supported by heteroleptic phosphonium cations. These lead-free discrete Cu(II) halides [Ph₃MeP]₂[CuCl₄] (1) and [Ph₃MeP]₂[CuBr₄] (2) exhibit a remnant polarization (P _r) of 17.16 and 26.02 μC cm^-2, respectively, at room temperature. Furthermore, flexible polymer films were prepared with various weight percentage (wt %) compositions of 1 in thermoplastic polyurethane (TPU) and studied for mechanical energy harvesting applications. A highest peak-to-peak voltage output of 25 V and power density of 14.1 μW cm^-2 were obtained for the optimal 15 wt % 1-TPU composite film. The obtained output voltages were utilized for charging a 100 μF electrolytic capacitor that reaches its maximum charging point within 30 s with sizable stored energies and accumulated charges.