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The ferroelectric analyzed herein belongs to a family of electrolytes that allow energy harvesting and storage as part of its self\u2010charging features when thermally activated. The Na<jats:sub>2.99<\/jats:sub>Ba<jats:sub>0.005<\/jats:sub>ClO electrolyte shows quasi\u2010adiabatic 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\u00a0C\u00a0m<jats:sup>\u22122<\/jats:sup> \u00b0C<jats:sup>\u22121<\/jats:sup> from \u22125 to 46 \u00b0C. The emergence occurs via negative resistance and capacitance. The glass transition is found to have its origins in the sharp depolarization at 46 \u2013 48 \u00b0C. Above \u201310 \u00b0C, at \u2248 \u20135 \u00b0C, another thermal anomaly may rely on the topologic characteristics of the A<jats:sub>3\u20132x<\/jats:sub>Ba<jats:sub>x<\/jats:sub>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<jats:sup>+<\/jats:sup>\u2010ion\u2010ion electrolytes.<\/jats:p>","DOI":"10.1002\/adfm.202212344","type":"journal-article","created":{"date-parts":[[2022,12,21]],"date-time":"2022-12-21T08:48:56Z","timestamp":1671612536000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Giant Polarization in Quasi\u2010Adiabatic Ferroelectric Na<sup>+<\/sup> Electrolyte for Solid\u2010State Energy Harvesting and Storage"],"prefix":"10.1002","volume":"33","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8933-2751","authenticated-orcid":false,"given":"Manuela","family":"Carvalho Baptista","sequence":"first","affiliation":[{"name":"Engineering Physics Department, Engineering Faculty University of Porto  4200\u2013465 Porto Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6683-7936","authenticated-orcid":false,"given":"Hesham","family":"Khalifa","sequence":"additional","affiliation":[{"name":"Engineering Physics Department, Engineering Faculty University of Porto  4200\u2013465 Porto Portugal"},{"name":"Department of Physics, Faculty of Science Damanhour University  Damanhur 22511 Egypt"}]},{"given":"Ad\u00e3o","family":"Ara\u00fajo","sequence":"additional","affiliation":[{"name":"Norleq \u2013 Equipamentos e Servi\u00e7os, Lda.  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