Giant Polarization in Quasi‐Adiabatic Ferroelectric Na⁺ Electrolyte for Solid‐State Energy Harvesting and Storage

Abstract

The advent of new solid-state energy storage devices to tackle the electrical revolution requires the usage of nonlinear behavior leading to emergent phenomena. The ferroelectric analyzed herein belongs to a family of electrolytes that allow energy harvesting and storage as part of its self-charging features when thermally activated. The Na 2.99 Ba 0.005 ClO electrolyte shows quasi-adiabatic behavior with a continuous increase in polarization upon cycling, displaying almost no hysteresis. The maximum polarization obtained at a weak electric field is giant and similar to the remanent polarization. It depends on the temperature with a pyroelectric coefficient of 5.37 C m −2 °C−1 from −5 to 46 °C. The emergence occurs via negative resistance and capacitance. The glass transition is found to have its origins in the sharp depolarization at 46 -48 °C. Above -10 °C, at ≈ -5 °C, another thermal anomaly may rely on the topologic characteristics of the A 3-2x Ba x ClO (A = Li, Na, K) glass electrolytes enabling positive feedback of the current of electrons throughout the surface of the inner cell. The phenomena may pave the way toward a better understanding of dipolar nanodomain fragile glasses with exceptional ferroelectric characteristics to architect energy harvesting and storage devices based on multivalent thermally activated Na + -ion-ion electrolytes.

Cork: Enabler of sustainable and efficient coaxial structural batteries

“…At the same time, the conduction of ions through the bulk electrolyte in the opposite direction allows for the occurrence of “limitless" cycles, portrayed by the emergent event of self-charging and self-cycling. This behavior has been systematically observed in several cells, confirming their self-charging capabilities [ [3] , [9] ].…”

“…The ionic movement, leading to polarization, is co-responsible for energy storage in the ferroelectric solid-state cell [ 8 , 9 ]. In typical conditions, the electrolyte should be an electrical insulator to avoid leakage of electrons through the battery's inner cell, propitiating spurious reactions such as those leading to forming a solid electrolyte interphase layer, SEI.…”

“…The no flammability and improved durability broaden their high-performance applications [ 2 , 10 ]. Sodium-ion-based ferroelectric Na 2.99 Ba 0.005 ClO electrolytes [ 4 , 9 , 11 ] have proven essential in the structural cells illustrated in Fig. 1 (a–d).…”

Li, Na, K, Mg, Zn, Al, and Ca Anode Interface Chemistries Developed by Solid‐State Electrolytes

“…Incorporation of ferroelectric phases such as (BaTiO 3 , K 0.5 Na 0.5 NbO 3, and others) to NASICON SIEs and A 3-2x Ba x ClO (A = Li, Na, K, x = 0.005-0.01) accelerates the Na + (others)-migrations and uniform distributions of charges for the Na//NASICON or Na//A 3-2x Ba x ClO interfaces during cycling illustrating the dense Na-/other-metals electrodepositions with high CCD. [422,424,425] Na//NASICON-3BTO shows flat and dense morphology, whereas wattle-like Na-metal for NASICON only (Figure 21ch), verifying the superior interface that ascribes to the even Nadepositions persuaded by dynamically self-adaptive interfaces. Ferroelectric phase BTO provides the conformal and switchable electric polarization for ordered distributions of charge carriers.…”

“…Incorporation of ferroelectric phases such as (BaTiO 3 , K 0.5 Na 0.5 NbO 3, and others) to NASICON SIEs and A 3‐2x Ba x ClO (A = Li, Na, K, x = 0.005–0.01) accelerates the Na + (others)‐migrations and uniform distributions of charges for the Na//NASICON or Na//A 3‐2x Ba x ClO interfaces during cycling illustrating the dense Na‐/other‐metals electrodepositions with high CCD. [ 422,424,425 ]…”