Taking advantage of electrode thicknesses well beyond conventional dimensions allowed us to follow the surface plasmonic THz frequency phenomenon with vacuum wavelengths of 100 μm to 1 mm, only to scrutinize them within millimeters-thicknesses insulators. Here, we analyze an Al/insulator/Cu cell in which the metal electrodes-collectors were separated by a gap that was alternatively filled by SiO₂, MgO, Li₂O, Na₃Zr₂Si₂PO₁₂–NASICON, Li_1.5Al_0.5Ge_1.5(PO₄)₃–LAGP, and Li_2.99Ba_0.005ClO–Li⁺ glass. A comparison was drawn using experimental surface chemical potentials, cyclic voltammetry (I-V plots), impedance spectroscopy, and theoretical approaches such as structure optimization, simulation of the electronic band structures, and work functions. The analysis reveals an unexpected common emergency from the cell’s materials to align their surface chemical potential, even in operando when set to discharge under an external resistor of 1842 Ω.cm_insulator. A very high capability of the metal electrodes to vary their surface chemical potentials and specific behavior among dielectric oxides and solid electrolytes was identified. Whereas LAGP and Li₂O behaved as p-type semiconductors below 40 °C at OCV and while set to discharge with a resistor in agreement with the Li⁺ diffusion direction, NASICON behaved as a quasi n-type semiconductor at OCV, as MgO, and as a quasi p-type semiconductor while set to discharge. The capacity to behave as a p-type semiconductor may be related to the ionic conductivity of the mobile ion. The ferroelectric behavior of Li_2.99Ba_0.005ClO has shown surface plasmon polariton (SPP) waves in the form of surface propagating solitons, as in complex phenomena, as well as electrodes’ surface chemical potentials inversion capabilities (i.e., χ (Al) − χ (Cu) > 0 to χ (Al) − χ (Cu) < 0 vs. E_vacuum = 0 eV) and self-charge (ΔV_cell ≥ +0.04 V under a 1842 Ω.cm_insulator resistor). The multivalent 5.5 mm thick layer cell filled with Li_2.99Ba_0.005ClO was the only one to display a potential bulk difference of 1.1 V. The lessons learned in this work may pave the way to understanding and designing more efficient energy harvesting and storage devices.

Anode-less batteries are a promising innovation in energy storage technology, eliminating the need for traditional anodes and offering potential improvements in efficiency and capacity. Here, we have fabricated and tested two types of anode-less pouch cells, the first using solely a copper negative current collector and the other the same current collector but coated with a nucleation seed ZnO layer. Both types of cells used the same all-solid-state electrolyte, Li_2.99Ba_0.005ClO composite, in a cellulose matrix and a LiFePO₄ cathode. Direct and indirect methods confirmed Li metal anode plating after charging the cells. The direct methods are X-ray photoelectron spectroscopy (XPS) and laser-induced breakdown spectroscopy (LIBS), a technique not divulged in the battery world but friendly to study the surface of the negative current collector, as it detects lithium. The indirect methods used were electrochemical cycling and impedance and scanning electron microscopy (SEM). It became evident the presence of plated Li on the surface of the current collector in contact with the electrolyte upon charging, both directly and indirectly. A maximum average lithium plating thickness of 2.9 µm was charged, and 0.13 µm was discharged. The discharge initiates from a maximum potential of 3.2 V, solely possible if an anode-like high chemical potential phase, such as Li, would form while plating. Although the ratings and energy densities are minor in this study, it was concluded that a layer of ZnO, even at 25 °C, allows for higher discharge power for more hours than plain Cu. It was observed that where Li plates on ZnO, Zn is not detected or barely detected by XPS. The present anode-less cells discharge quickly initially at higher potentials but may hold a discharge potential for many hours, likely due to the ferroelectric character of the electrolyte.

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_2.99Ba_0.005ClO 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_3–2xBa_xClO (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.