Ceramic-in-Polymer Hybrid Electrolytes with Enhanced Electrochemical Performance.

Polymer electrolytes are attractive candidates to boost the application of rechargeable lithium metal batteries. Single-ion conducting polymers may reduce polarization and lithium dendrite growth, though these materials could be mechanically overly rigid, thus requiring ion mobilizers such as organic solvents to foster transport of Li ions. An inhomogeneous mobilizer distribution and occurrence of preferential Li transport pathways eventually yield favored spots for Li plating, thereby imposing additional mechanical stress and even premature cell short circuits. In this work, we explored ceramic-in-polymer hybrid electrolytes consisting of polymer blends of single-ion conducting polymer and PVdF-HFP, including EC/PC as swelling agents and silane-functionalized LATP particles. The hybrid electrolyte features an oxide-rich layer that notably stabilizes the interphase toward Li metal, enabling single-side lithium deposition for over 700 h at a current density of 0.1 mA cm-2. The incorporated oxide particles significantly reduce the natural solvent uptake from 140 to 38 wt % despite maintaining reasonably high ionic conductivities. Its electrochemical performance was evaluated in LiNi0.6Co0.2Mn0.2O2 (NMC622)||Li metal cells, exhibiting impressive capacity retention over 300 cycles. Notably, very thin LiNbO3 coating of the cathode material further boosts the cycling stability, resulting in an overall capacity retention of 78% over more than 600 cycles, clearly highlighting the potential of hybrid electrolyte concepts.

Spray Flame Synthesis (SFS) of Lithium Lanthanum Zirconate (LLZO) Solid Electrolyte.

A spray-flame reaction step followed by a short 1-h sintering step under O2 atmosphere was used to synthesize nanocrystalline cubic Al-doped Li7La3Zr2O12 (LLZO). The as-synthesized nanoparticles from spray-flame synthesis consisted of the crystalline La2Zr2O7 (LZO) pyrochlore phase while Li was present on the nanoparticles' surface as amorphous carbonate. However, a short annealing step was sufficient to obtain phase pure cubic LLZO. To investigate whether the initial mixing of all cations is mandatory for synthesizing nanoparticulate cubic LLZO, we also synthesized Li free LZO and subsequently added different solid Li precursors before the annealing step. The resulting materials were all tetragonal LLZO (I41/acd) instead of the intended cubic phase, suggesting that an intimate intermixing of the Li precursor during the spray-flame synthesis is mandatory to form a nanoscale product. Based on these results, we propose a model to describe the spray-flame based synthesis process, considering the precipitation of LZO and the subsequent condensation of lithium carbonate on the particles' surface.