Liquid-Like Li-Ion Conduction in Oxides Enabling Anomalously Stable Charge Transport across the Li/Electrolyte Interface in All-Solid-State Batteries.

The softness of sulfur sublattice and rotational PS4 tetrahedra in thiophosphates result in liquid-like ionic conduction, leading to enhanced ionic conductivities and stable electrode/thiophosphate interfacial ionic transport. However, the existence of liquid-like ionic conduction in rigid oxides remains unclear, and modifications are deemed necessary to achieve stable Li/oxide solid electrolyte interfacial charge transport. In this study, by combining the neutron diffraction survey, geometrical analysis, bond valence site energy analysis, and ab initio molecular dynamics simulation, 1D liquid-like Li-ion conduction is discovered in LiTa2 PO8 and its derivatives, wherein Li-ion migration channels are connected by four- or five-fold oxygen-coordinated interstitial sites. This conduction features a low activation energy (0.2 eV) and short mean residence time (<1 ps) of Li ions on the interstitial sites, originating from the Li-O polyhedral distortion and Li-ion correlation, which are controlled by doping strategies. The liquid-like conduction enables a high ionic conductivity (1.2 mS cm-1 at 30 °C), and a 700 h anomalously stable cycling under 0.2 mA cm-2 for Li/LiTa2 PO8 /Li cells without interfacial modifications. These findings provide principles for the future discovery and design of improved solid electrolytes that do not require modifications to the Li/solid electrolyte interface to achieve stable ionic transport.

Electrochemical and Structural Property of TiSiNb TFSOC on Affordable Interconnects in Proton Exchange Membrane Fuel Cell Applications.

High cost and low electrochemical stability of the interconnection in Proton Exchange Membrane Fuel Cell (PEMFC) in the presence of H2SO4 are one of the main issues hindering the commercialization of these devices. This manuscript presents the utilization of cost-effective steel in an attempt to minimize the PEMFC interconnection costs with a thin-film solid oxide coating (TFSOC) providing sufficient corrosion resistance for efficient long-term operation. Novel Ti0.50-y/2Si0.50-y/2Nby1,2O2 as TFSOC was deposited on the C45E steel as a metal interconnect utilizing a sol-gel process at various annealing temperatures. The analysis of the phase and surface morphology demonstrates that lower annealing temperatures developed nanometric crystallite size of 68 nm, more uniform structure and higher corrosion resistance. Under standard test conditions, the TFSOC demonstrated high polarization resistance (1.3 kΩ cm2) even after 720 hours (h). Electrical conductivity of the TFSOC as low as 1.4 × 10-2 (Ω m)-1 and activation energy of 0.20 eV were achieved, which helps to maintain the PEMFC output power.

Anomalies in Bulk Ion Transport in the Solid Solutions of Li7La3M2O12 (M = Hf, Sn) and Li5La3Ta2O12.

Cubic Li7La3Zr2O12(LLZO), stabilized by supervalent cations, is one of the most promising oxide electrolyte to realize inherently safe all-solid-state batteries. It is of great interest to evaluate the strategy of supervalent stabilization in similar compounds and to describe its effect on ionic bulk conductivity σ'bulk. Here, we synthesized solid solutions of Li7-x La3M2-x Ta x O12 with M = Hf, Sn over the full compositional range (x = 0, 0.25...2). It turned out that Ta contents at x of 0.25 (M = Hf, LLHTO) and 0.5 (M = Sn, LLSTO) are necessary to yield phase pure cubic Li7-x La3M2-x Ta x O12. The maximum in total conductivity for LLHTO (2 × 10-4 S cm-1) is achieved for x = 1.0; the associated activation energy is 0.46 eV. At x = 0.5 and x = 1.0, we observe two conductivity anomalies that are qualitatively in agreement with the rule of Meyer and Neldel. For LLSTO, at x = 0.75 the conductivity σ'bulk turned out to be 7.94 × 10-5 S cm-1 (0.46 eV); the almost monotonic decrease of ion bulk conductivity from x = 0.75 to x = 2 in this series is in line with Meyer-Neldel's compensation behavior showing that a decrease in E a is accompanied by a decrease of the Arrhenius prefactor. Altogether, the system might serve as an attractive alternative to Al-stabilized (or Ga-stabilized) Li7La3Zr2O12 as LLHTO is also anticipated to be highly stable against Li metal.

Highly Conductive Garnet-Type Electrolytes: Access to Li6.5La3Zr1.5Ta0.5O12 Prepared by Molten Salt and Solid-State Methods.

Tantalum-doped garnet (Li6.5La3Zr1.5Ta0.5O12, LLZTO) is a promising candidate to act as a solid electrolyte in all-solid-state batteries owing to both its high Li+ conductivity and its relatively high robustness against the Li metal. Synthesizing LLZTO using conventional solid-state reaction (SSR) requires, however, high calcination temperature (>1000 °C) and long milling steps, thereby increasing the processing time. Here, we report on a facile synthesis route to prepare LLZTO using a molten salt method (MSS) at lower reaction temperatures and shorter durations (900 °C, 5 h). Additionally, a thorough analysis on the properties, i.e., morphology, phase purity, and particle size distribution of the LLZTO powders, is presented. LLZTO pellets, either prepared by the MSS or the SSR method, that were sintered in a Pt crucible showed Li+ ion conductivities of up to 0.6 and 0.5 mS cm-1, respectively. The corresponding activation energy values are 0.37 and 0.38 eV, respectively. The relative densities of the samples reached values of approximately 96%. For comparison, LLZTO pellets sintered in alumina crucibles or with γ-Al2O3 as sintering aid revealed lower ionic conductivities and relative densities with abnormal grain growth. We attribute these observations to the formation of Al-rich phases near the grain boundary regions and to a lower Li content in the final garnet phase. The MSS method seems to be a highly attractive and an alternative synthetic approach to SSR route for the preparation of highly conducting LLZTO-type ceramics.