Nie Bo, Wang Ta-Wei, Lee Seok Woo, Sun Hongtao
The Harold and Inge Marcus Department of Industrial and Manufacturing Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
ACS Appl Mater Interfaces. 2024 Dec 11;16(49):67635-67641. doi: 10.1021/acsami.4c13031. Epub 2024 Nov 26.
All-solid-state batteries (ASSBs) have attracted increasing attention for next-generation electrochemical energy storage due to their high energy density and enhanced safety, achieved through the use of nonflammable solid-state electrolytes (SSEs). Oxide-based SSEs, such as LiAlTi(PO) (LATP), are notable for their high ionic conductivity and excellent chemical and electrochemical oxidation stability. Nevertheless, their brittle mechanical properties and poor interface contact with electrode materials necessitate high-temperature and long-duration sintering or postcalcination processes, limiting their processability for real-world applications. Additionally, the formation of secondary phases can detrimentally affect the ionic conductivity of LATP electrolytes. Emerging halide-based SSEs offer reliable deformation for practical processing while maintaining high ionic conductivity. In this work, we report a transient liquid-assisted cold sintering process to integrate oxide-based LATP as the matrix and halide-based LiInCl as the conductive boundary phase into a halide-in-oxide ceramic composite electrolyte at a low processing temperature of 150 °C. This composite structure significantly reduces interface resistance, effectively addressing ion-transport depletion across the boundaries between LATP particles. Consequently, the cosintered LATP-LiInCl composite SSE exhibits a high ionic conductivity of 1.4 × 10 S cm at ambient temperature. Furthermore, the symmetric Li|LATP-LiInCl·DMF|Li cell demonstrates stable stripping and plating processes for 1600 h at 55 °C (0.1 mA cm) and 1200 h at 100 °C (1 mA cm). This work represents the first demonstration of halide-oxide ceramic composite SSEs that combine the advantages of oxides and halides for high-performance SSBs.
全固态电池（ASSB）因其高能量密度和增强的安全性而在下一代电化学储能领域受到越来越多的关注，这是通过使用不可燃的固态电解质（SSE）实现的。基于氧化物的SSE，如LiAlTi(PO)（LATP），以其高离子电导率以及优异的化学和电化学氧化稳定性而著称。然而，其脆性的机械性能以及与电极材料较差的界面接触需要高温和长时间的烧结或煅烧后处理工艺，这限制了它们在实际应用中的可加工性。此外，次生相的形成会对LATP电解质的离子电导率产生不利影响。新兴的基于卤化物的SSE在保持高离子电导率的同时，为实际加工提供了可靠的变形能力。在这项工作中，我们报道了一种瞬态液体辅助冷烧结工艺，该工艺在150°C的低温加工条件下，将基于氧化物的LATP作为基体与基于卤化物的LiInCl作为导电边界相结合，制成一种氧化物-卤化物陶瓷复合电解质。这种复合结构显著降低了界面电阻，有效解决了LATP颗粒之间边界处的离子传输损耗问题。因此，共烧结的LATP-LiInCl复合SSE在室温下表现出1.4×10 S cm的高离子电导率。此外，对称的Li|LATP-LiInCl·DMF|Li电池在55°C（0.1 mA cm）下可稳定进行1600小时的剥离和电镀过程，在100°C（1 mA cm）下可稳定进行1200小时。这项工作首次展示了结合氧化物和卤化物优点的用于高性能全固态电池的卤化物-氧化物陶瓷复合SSE。
