Mechanochemical synthesis of Li-argyrodite Li6PS5X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application

• Published in: Solid state ionics 2012-08, Vol.221, p.1-5
• Main Authors: Boulineau, Sylvain, Courty, Matthieu, Tarascon, Jean-Marie, Viallet, Virginie
• Format: Article
• Language: English
• Subjects: All solid state batteries; Argyrodite; Ball milling; Conductivity; Electrolytes; Ionic conductivity; Lithium batteries; Lithium battery; Mechanical milling; Optimization; Resistivity; Solid electrolytes; Solid state
• ISSN: 0167-2738; 1872-7689
• DOI: 10.1016/j.ssi.2012.06.008

Highly ion-conductive Li6PS5X (X=Cl, Br, I) Li-argyrodites were prepared through a high‐energy ball milling. Electrical and electrochemical properties were investigated. Ball-milled compounds exhibit a high conductivity between 2 and 7×10−4S/cm with an activation energy of 0.3–0.4eV for conduction. These attractive properties were attributed to the spontaneous formation of crystallized Li-argyrodite during ball-milling. An optimization of milling time led to a conductivity of 1.33×10−3S/cm for the Li6PS5Cl phase with an electrochemical stability up to 7V vs. lithium. An all solid state LiCoO2/Elec./In lithium ion battery using ball-milled Li6PS5Cl as electrolyte was successfully assembled, and its room temperature performance is reported. ► Revisited synthesis of sulfur-based solid electrolyte for all solid state batteries. ► Argyrodite phase formed by high-energy ball milling synthesis. ► Wide electrochemical stability window from 0 to 7V vs. Li. ► High ionic conductivity of 1.33×10−3S/cm for ball-milled Li6PS5Cl sample at room temperature. ► Reversible capacity of 100mAh/g using LiCoO2 in all solid state battery.