Glass, unlike a crystalline solid, contains atoms and molecules that do not occupy fixed positions. A glass that contains molecules that attract one another can age with time. We report such a glass that contains A 2 O and (OA) − electric dipoles (A = Li or Na). At a temperature T < 1.2T g ≈ 110 • C (T g is the glass transition temperature) the electric dipoles coalesce with time into clusters within which, unlike in ice, some dipoles condense into ferroelectric, negatively charged molecules locally charge-compensated by weakly attracted A + ions. In an applied electric field, the dipoles are oriented and, over time depending on the T < 110 • C, are aligned parallel to the field axis to yield a solid A + electrolyte with an ionic conductivity σ i > 10 −2 S cm −1 and a huge dielectric constant that makes it suitable for many applications, including safe rechargeable batteries of high energy density and long cycle life. The A-glass electrolytes (A = Li or Na) formed from A 2.99 Ba 0.005 ClO + xH 2 O (x < 1) exhibit an unusually high dielectric constant as well as an alkali-ion conductivity σ i > 10 −2 S cm −1 at 25• C after the glass has been conditioned. 1 The solvated water leaves the glass as HCl during heating to 250• C; and most, if not all, of the residual OH − are evaporated as H 2 O above 230Measurement of the inverse loss tangent, tan −1 δ = ε /ε , as a function of frequency at different temperatures showed two resonant frequencies that were coupled to one another. We interpret these resonances to be due to rotational vibrations of the A 2 O and OA − electric dipoles. The vibrations were coupled in the temperature interval 70 < T < 90• C at a frequency 10 < f < 500 Hz, and a chronopotentiometric measurement of the dc current in a symmetric Li/Ca doped Li-glass/Li cell at 44• C 1,2 showed an increase with time of the lithium conductivity in the as-prepared Li-glass. The as-prepared glasses were furnace cooled, not quenched, to 25• C. In this paper we investigate the frequency and temperature dependences of the dielectric constant and how the activation enthalpy H m for a Na + hop in an Au/Na-glass/Au cell is conditioned by an orientation of electric dipoles. We show that a designed thermal history under an applied ac electric field can provide a rapid increase of dc cation conductivity to a σ i > 10 −2 S cm −1 and decrease of an activation energy of mobility to H m = 0.06 eV at 25• C. Materials and MethodsSynthesis.-Nominal glass/amorphous solid electrolytes Na 2.99 Ba 0.005 O 1+x Cl 1-2x were processed in a wet synthesis as described previously 1 from the commercial precursors NaCl (99.9%, Merck), Na(OH) (>99%, Merck), and Ba(OH) 2 · 8H 2 O (98.5%, Merck). The glass products were dried by HCl evaporation at lower temperatures and the loss of the OH − by the reaction 2OH − = O 2− + H 2 O↑ above 230• C as previously shown in Ref. 1; the reaction leaves a glass/amorphous solid containing electric dipoles. Samples "as prepared" were slowly cooled down to room temperature. Some samples were subject to heating ...

Materials having a high dielectric constant are needed for a variety of electrical applications from transistors to capacitors. Ferroelectric amorphous-oxide (glass) alkali-ion electrolytes of composition A2.99Ba0.005ClO (A = Li, Na) are shown by two different types of measurement and different consistent analyses to have extraordinarily high dielectric constants, varying from 109 at 25 °C to 1010 at 220 °C if the glass is properly conditioned. These anomalously high dielectric properties coexist with alkali-ion conductivities at 25 °C that are equivalent to those of the best organic-liquid electrolytes of a Li-ion cell, and cyclic voltammetry (CV) in a Au/glass electrolyte/Au cell is stable from −10 to +10 V. A model to interpret microscopically all the key features of the CV curves shows that the electric-double-layer capacitors that form at the gold/electrolyte interfaces in the Au/glass electrolyte/Au heterojunction reverse polarization at an applied voltage V = ±2.1 V, resulting in three almost equivalent discharging capacitances for a single physical capacitor from −10 to +10 V.

The dependence of modern society on the energy stored in a fossil fuel is not sustainable. An immediate challenge is to eliminate the polluting gases emitted from the roads of the world by replacing road vehicles powered by the internal combustion engine with those powered by rechargeable batteries. These batteries must be safe and competitive in cost, performance, driving range between charges, and convenience. The competitive performance of an electric car has been demonstrated, but the cost of fabrication, management to ensure safety, and a short cycle life have prevented large-scale penetration of the all-electric road vehicle into the market. Low-cost, safe all-solid-state cells from which dendrite-free alkali-metal anodes can be plated are now available; they have an operating temperature range from -20 °C to 80 °C and they permit the design of novel high-capacity, high-voltage cathodes providing fast charge/discharge rates. Scale-up to large multicell batteries is feasible.

Solid-state electrolytes are a promising family of materials for the next generation of high-energy rechargeable lithium batteries. Polymer electrolytes (PEs) have been widely investigated due to their main advantages, which include easy processability, high safety, good mechanical flexibility, and low weight. This review presents recent scientific advances in the design of versatile polymer-based electrolytes and composite electrolytes, underlining the current limitations and remaining challenges while highlighting their technical accomplishments. The recent advances in PEs as a promising application in structural batteries are also emphasized.