Direct Precursor Route for the Fabrication of LLZO Composite Cathodes for Solid-State Batteries.

Solid-state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium-ion batteries. However, the large-scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one-step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050 °C, eliminating the time- and energy-consuming synthesis of preformed LLZO powders. In addition, performance-optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase-pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85 µm, a relative density of 95%, and an industrial relevant LCO loading of 15 mg show an initial capacity of 82 mAh g-1 (63% of the theoretical capacity of LCO) in a solid-state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future.

Structure-activity correlation of thermally activated graphite electrodes for vanadium flow batteries.

Thermal activation of graphite felts has proven to be a valuable technique for electrodes in vanadium flow batteries to improve their sluggish reaction kinetics. In the underlying work, a novel approach is presented to describe the morphological, microstructural, and chemical changes that occur as a result of the activation process. All surface properties were monitored at different stages of thermal activation and correlated with the electrocatalytic activity. The subsequently developed model consists of a combined ablation and damaging process observed by Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. Initially, the outermost layer of adventitious carbon is removed and sp2 layers of graphite are damaged in the oxidative atmosphere, which enhances the electrocatalytic activity by introducing small pores with sharp edges. In later stages, the concentration of reaction sites does not increase further, but the defect geometry changes significantly, leading to lower activity. This new perspective on thermal activation allows several correlations between structural and functional properties of graphite for the vanadium redox couple, describing the importance of structural defects over surface chemistry.