Fast Lithium Ion Conduction in Lithium Phosphidoaluminates

Solid electrolyte materials are crucial for the development of high‐energy‐density all‐solid‐state batteries (ASSB) using a nonflammable electrolyte. In order to retain a low lithium‐ion transfer resistance, fast lithium ion conducting solid electrolytes are required. We report on the novel superionic conductor Li9AlP4 which is easily synthesised from the elements via ball‐milling and subsequent annealing at moderate temperatures and which is characterized by single‐crystal and powder X‐ray diffraction. This representative of the novel compound class of lithium phosphidoaluminates has, as an undoped material, a remarkable fast ionic conductivity of 3 mS cm−1 and a low activation energy of 29 kJ mol−1 as determined by impedance spectroscopy. Temperature‐dependent 7Li NMR spectroscopy supports the fast lithium motion. In addition, Li9AlP4 combines a very high lithium content with a very low theoretical density of 1.703 g cm−3. The distribution of the Li atoms over the diverse crystallographic positions between the [AlP4]9− tetrahedra is analyzed by means of DFT calculations. Leicht und mit schneller Li‐Ionenleitung: Feste Elektrolyte mit schneller Ionenleitung sind entscheidend für Festkörperbatterien. Das neue Material Li9AlP4 vereint einen hohen Lithiumgehalt und eine hohe Ionenleitfähigkeit von 3 mS cm−1 bei 25 °C mit einer sehr geringen theoretischen Dichte von 1.703 g cm−3.