Okur Faruk, Zhang Huanyu, Baumgärtner Julian F, Sivavec Jaka, Klimpel Matthias, Wasser Gregor Paul, Dubey Romain, Jeurgens Lars P H, Chernyshov Dmitry, van Beek Wouter, Kravchyk Kostiantyn V, Kovalenko Maksym V
Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Zürich, CH-8093, Switzerland.
Laboratory for Thin Films and Photovoltaics, Empa, Swiss Federal Laboratories for Materials Science & Technology, Dübendorf, CH-8600, Switzerland.
Adv Sci (Weinh). 2025 Jan;12(2):e2412370. doi: 10.1002/advs.202412370. Epub 2024 Nov 18.
Ultrafast sintering (UFS) is a compelling approach for fabricating LiLaZrO (LLZO) solid-state electrolytes (SSEs), paving the way for advancing and commercializing Li-garnet solid-state batteries. Although this method is commonly applied to the sintering of LLZO ceramics, its use for producing dense, phase-pure LLZO SSEs has thus far been primarily limited to millimeter-thick pellets, which are unsuitable for commercial solid-state batteries. This study presents ultrafast sintering as a highly effective approach for fabricating self-standing, dense, 45 µm-thick LLZO membranes. The chemical and structural evolution of LLZO membranes during the UFS process is characterized through in situ synchrotron X-ray diffraction and thermogravimetric analysis-mass spectrometry, complemented by an in-depth investigation of surface chemistry using X-ray photoelectron spectroscopy. The membranes in Li/LLZO/Li symmetrical cell configuration exhibit a high critical current density of up to 12.5 mA cm and maintain superior cycling stability for 250 cycles at a current density of 1 mA cm, with an areal capacity limit of 1 mAh cm. The electrochemical performance of LLZO membranes is also assessed in full cell configuration using a pyrochlore-type iron (III) hydroxy fluoride cathode.
超快烧结（UFS）是一种用于制备LiLaZrO（LLZO）固态电解质（SSE）的引人注目的方法，为推进锂石榴石固态电池并使其商业化铺平了道路。尽管这种方法通常应用于LLZO陶瓷的烧结，但迄今为止，其用于生产致密、单相纯的LLZO SSE主要限于毫米厚的颗粒，而这些颗粒不适用于商业固态电池。本研究提出超快烧结是一种制备自立式、致密、45μm厚LLZO薄膜的高效方法。通过原位同步辐射X射线衍射和热重分析-质谱对LLZO薄膜在UFS过程中的化学和结构演变进行了表征，并通过X射线光电子能谱对表面化学进行了深入研究加以补充。Li/LLZO/Li对称电池配置中的薄膜表现出高达12.5 mA cm的高临界电流密度，并在1 mA cm的电流密度下保持250次循环的优异循环稳定性，面积容量极限为1 mAh cm。还使用焦绿石型铁（III）羟基氟化物阴极在全电池配置中评估了LLZO薄膜的电化学性能。
