- Wu, Erik A;
- Banerjee, Swastika;
- Tang, Hanmei;
- Richardson, Peter M;
- Doux, Jean-Marie;
- Qi, Ji;
- Zhu, Zhuoying;
- Grenier, Antonin;
- Li, Yixuan;
- Zhao, Enyue;
- Deysher, Grayson;
- Sebti, Elias;
- Nguyen, Han;
- Stephens, Ryan;
- Verbist, Guy;
- Chapman, Karena W;
- Clément, Raphaële J;
- Banerjee, Abhik;
- Meng, Ying Shirley;
- Ong, Shyue Ping
Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na3-xY1-xZrxCl6 (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na+) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10-5 S cm-1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl6 rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO2 + NYZC composite cathode, Na3PS4 electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.