Co-existence of large negative & positive electrocaloric effects and

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Co-existence of large negative & positive electrocaloric effects and energystorage performance in LiNbO doped K Na NbO nanocrystalline ceramics 3

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Raju Kumar, Ashish Kumar, and Satyendra Singh ACS Appl. Electron. Mater., Just Accepted Manuscript • DOI: 10.1021/acsaelm.9b00033 • Publication Date (Web): 04 Mar 2019 Downloaded from http://pubs.acs.org on March 5, 2019

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ACS Applied Electronic Materials

Co-existence of large negative & positive electrocaloric effects and energy-storage performance in LiNbO3 doped K0.5Na0.5NbO3 nanocrystalline ceramics Raju kumar, Ashish kumar, and Satyendra singh∗ Special Centre for Nanoscience, Jawaharlal Nehru University, New Delhi-110067, India. E-mail: [email protected]

Abstract The electrocaloric effect (ECE) has been investigated in (1-x)K0.5 Na0.5 NbO3 -xLiNbO3 (KNN-xLiN) nanocrystalline ceramics with compositions in the range of 0.01 ≤ x ≤ 0.05 by the indirect measurement using Maxwell’s approach. The coexistence of the negative and positive ECEs has been achieved in all samples. The maximum value of negative and positive ECE were found to be -0.40 K and 0.24 K for x = 0.01, -0.23 K & 0.18 K for x = 0.03, and -0.13 K & 0.29 K for x = 0.05, respectively. The maximum recoverable energy densities were found to be 0.12, 0.13, and 0.128 J/cm3 with energy storage efficiencies of 30, 50 and 51% at an electric field of 45 kV/cm for x = 0.01, 0.03, and 0.05, respectively. The co-existence of the negative and positive ECEs with a high recoverable energy density in one material makes it a promising candidate for highly efficient, environmentally friendly cooling device and energy-storage device applications.

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Keywords: Lead-free ferroelectrics, Electrocaloric responsivity, Electrocaloric effect, Energy storage, Dielectrics, Electrocaloric cycle.

Introduction Recently, environmentally friendly and low cost electrocaloric (EC) refrigeration technology have attracted a lot of attention to replace the traditional vapor compression based cooling (VCC) technology. 1 The existing VCC technology uses Chlorofluorocarbon which is hazardous and it also contributes the major part of CO2 emission to the environment. The EC refrigeration is one of the best solutions for cooling application due to its advantages of feasible manipulation, easy miniaturization, and higher efficiency. 2–4 The caloric effect, in which entropy change (∆S) and the reversible temperature change (∆T ), appears under application or removal of the electric field on ferroelectric material called the electrocaloric effect (ECE). 5–8 An external field applied to ferroelectric/antiferroelectric material, lowers its specific dipolar entropy which heat the material under adiabatic condition. In rare condition, adiabatic cooling has also been observed under the applied electric field. The inverse (negative) ECE has enormous potential in enhancing the overall caloric responses, which attracts further interest of the scientific community. Interestingly, two types of ECEs (i.e. positive (∆T >0) and negative (∆T 0 upon its removal and in above discussion application & removal interchange to give the explanation of negative ECE application. The present investigated material shows the unique and rare combination of the negative and positive ECE. For the case of 2nd order phase transition, latent heat is absent, but the external field align electric dipole parallel to the electric field direction with lower symmetry. This alignment reduces the disorder compared to the active state of disorderness where the dipoles are randomly oriented. The alignment reduces the entropy (∆S), subsequently also the heat (∆Q), since ∆Q = T.∆S, which results in the lattice vibration increases and increases the temperature. Conclusively, first and the third step of applying and removing an external field is the unique properties of the ferroelectric material. Both types of phase transition is important for electrocaloric purposes. A larger entropy change appeared in the 1st order phase transition and effective near the TC . In general, the 1st order phase transition occurs with the hysteresis loops with the hysteresis losses that reduce cooling of performance (COP). Whereas the 2nd order phase transition demonstrates the lower entropy change with no hysteresis loops and can be used in a broader temperature scale. A rare and major challenge observed with the material with both type of ECE, but surely with the separated boundary of 1st & 2nd order phase transitions.

Conclusions In summary, lead-free KNN-xLiN nanocrystalline ceramics were prepared and their EC responses were systematically studied using Maxwell’s approach. Coexistence of negative and positive electrocaloric effects were observed over a broad temperature range. It displays good electrocaloric responsivity, electrical energy density, and efficiency. Presence of negative and

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positive ECE with a high recoverable electrical energy storage density makes it a highly potential candidate for applications in electrocaloric cooling and high energy-storage density devices with clean energy solution.

Notes The authors declare no competing financial interest.

Acknowledgement We acknowledge Advanced Instrumentation Research Facility, JNU, New Delhi for extending the instrumental research facilities. S. Singh acknowledges the financial support from SERB (EEQ/2016/000256), DST (PURSE-II) and UGC (Project # 33, UPE-II), Govt. of India. R. Kumar acknowledges the award of the junior research fellowship of UGC.

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