CO₂ Laser Sintering of Garnet-Type Solid-State Electrolytes

The processing of garnet-type solid-state electrolytes remains challenging as densification conventionally requires high sintering temperatures and long processing times, which can result in severe Li loss, the formation of secondary phases, and thus high porosity and low ionic conductivity. Here, we report an ultrafast sintering method based on CO2 laser scanning with the assistance of a heating stage. We demonstrate the rapid densification of low-packing-density Li6.4La3Zr1.4Ta0.6O12 (LLZTO) films, which are difficult to densify by conventional furnace sintering methods. This unique approach has three fingerprint characteristics: (1) mitigation of Li loss through ultrafast sintering (dwelling time ≪1 s); (2) a unique anisotropic shrinkage behavior that greatly reduces film thickness; (3) wave-like surface topology from point scanning strategy that enables 3D interfacial contacts with electrode materials. Herein, highly dense (95.68%) and highly conductive (0.26 mS·cm–1 at 25 °C) LLZTO films are obtained through CO2 laser sintering. This work provides a unique, scalable, and widely applicable ultrarapid laser sintering technique to overcome the difficulties associated with classic methods for the integration of SSEs for practical all-solid-state Li-metal battery applications.