Dense Freeze‐cast Li_7La_3Zr_2O_(12) Solid Electrolytes with Oriented Open Porosity and Contiguous Ceramic Scaffold

Freeze casting is used for the first time to prepare solid electrolyte scaffolds with oriented porosity and dense ceramic walls made of Li_7La_3Zr_2O_(12) (LLZO), one of the most promising candidates for solid state battery electrolytes. Processing parameters ‐ such as solvent solidification rate, solvent type, and ceramic particle size ‐ are investigated, focusing on their influence on porosity and ceramic wall density. Dendrite‐like porosity is obtained when using cyclohexane and dioxane as solvents. Lamellar porosity is observed in aqueous slurries resulting in a structure with the highest apparent porosity and densest ceramic scaffold but weakest mechanical properties due to the lack of interlamellar support. The use of smaller LLZO particle size in the slurries resulted in lower porosity and denser ceramic walls. The intrinsic ionic conductivity of the oriented LLZ ceramic scaffold is unaffected by the freeze casting technique, providing a promising ceramic scaffold for polymer infill in view of designing new types of ceramic‐polymer composites

Dense Freeze‐cast Li_7La_3Zr_2O_(12) Solid Electrolytes with Oriented Open Porosity and Contiguous Ceramic Scaffold

Freeze casting is used for the first time to prepare solid electrolyte scaffolds with oriented porosity and dense ceramic walls made of Li_7La_3Zr_2O_(12) (LLZO), one of the most promising candidates for solid state battery electrolytes. Processing parameters ‐ such as solvent solidification rate, solvent type, and ceramic particle size ‐ are investigated, focusing on their influence on porosity and ceramic wall density. Dendrite‐like porosity is obtained when using cyclohexane and dioxane as solvents. Lamellar porosity is observed in aqueous slurries resulting in a structure with the highest apparent porosity and densest ceramic scaffold but weakest mechanical properties due to the lack of interlamellar support. The use of smaller LLZO particle size in the slurries resulted in lower porosity and denser ceramic walls. The intrinsic ionic conductivity of the oriented LLZ ceramic scaffold is unaffected by the freeze casting technique, providing a promising ceramic scaffold for polymer infill in view of designing new types of ceramic‐polymer composites

Suspension- and solution-based freeze casting for porous ceramics

Freeze casting of traditional ceramic suspensions and freeze casting of preceramic polymer solutions were directly compared as methods for processing porous ceramics. Alumina and polymethylsiloxane were freeze cast with four different organic solvents (cyclooctane, cyclohexane, dioxane, and dimethyl carbonate) to obtain ceramics with ∼70% porosity. Median pore sizes were smaller for solution freeze casting than for suspension freeze casting under identical processing conditions. The pore structures, which range from foam-like to lamellar, were correlated to the Jackson α-factor of the solvent; solvents with low α-factors yielded nonfaceted pore structures, while high α-factors produced more faceted structures. Intermediate α-factors resulted in dendritic pore structures and were most sensitive to the processing method. Small suspended particles ahead of a solid–liquid interface are hypothesized to destabilize the dendrite tip in suspension freeze casting resulting in more foam-like structures. Differences in processing details were highlighted, particularly regarding the improved freezing front observation possible with solution-based freeze casting

Suspension- and solution-based freeze casting for porous ceramics

Freeze casting of traditional ceramic suspensions and freeze casting of preceramic polymer solutions were directly compared as methods for processing porous ceramics. Alumina and polymethylsiloxane were freeze cast with four different organic solvents (cyclooctane, cyclohexane, dioxane, and dimethyl carbonate) to obtain ceramics with ∼70% porosity. Median pore sizes were smaller for solution freeze casting than for suspension freeze casting under identical processing conditions. The pore structures, which range from foam-like to lamellar, were correlated to the Jackson α-factor of the solvent; solvents with low α-factors yielded nonfaceted pore structures, while high α-factors produced more faceted structures. Intermediate α-factors resulted in dendritic pore structures and were most sensitive to the processing method. Small suspended particles ahead of a solid–liquid interface are hypothesized to destabilize the dendrite tip in suspension freeze casting resulting in more foam-like structures. Differences in processing details were highlighted, particularly regarding the improved freezing front observation possible with solution-based freeze casting

Nucleation-controlled freeze casting of preceramic polymers for uniaxial pores in Si-based ceramics

A grain-selection template was applied to freeze casting to control nucleation of pore-forming crystals and achieve ceramics with highly aligned pore structures. A polymethylsiloxane preceramic polymer was freeze cast with cyclohexane as a solvent to produce dendritic pores in SiOC. Image analysis and permeability measurements were performed to quantify the influence of various templates on sample properties. Results show that the percentage of porosity aligned along the freezing axis increased from 13.9% without a template to 92.6% with an optimal template. The Darcian permeability constant increased by more than 6-fold, from 3.4 × 10^(−12) to 2.1 × 10^(−11) m^2