Liu Haoyu, Chen Yudan, Chien Po-Hsiu, Amouzandeh Ghoncheh, Hou Dewen, Truong Erica, Oyekunle Ifeoluwa P, Bhagu Jamini, Holder Samuel W, Xiong Hui, Gor'kov Peter L, Rosenberg Jens T, Grant Samuel C, Hu Yan-Yan
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA.
Department of Physics, Florida State University, Tallahassee, FL, USA.
Nat Mater. 2025 Apr;24(4):581-588. doi: 10.1038/s41563-024-02094-6. Epub 2025 Jan 31.
All-solid-state batteries offer high-energy-density and eco-friendly energy storage but face commercial hurdles due to dendrite formation, especially with lithium metal anodes. Here we report that dendrite formation in Li/LiLaZrO/Li batteries occurs via two distinct mechanisms, using non-invasive solid-state nuclear magnetic resonance and magnetic resonance imaging. Tracer-exchange nuclear magnetic resonance shows non-uniform Li plating at electrode-electrolyte interfaces and local Li reduction at LiLaZrO grain boundaries. In situ magnetic resonance imaging reveals rapid dendrite formation via non-uniform Li plating, followed by sluggish bulk dendrite nucleation from Li reduction, with an intervening period of stalled growth. Formation of amorphous dendrites and subsequent crystallization, the defect chemistry of solid electrolytes and battery operating conditions play a critical role in shaping the complex interplay between the two mechanisms. Overall, this work deepens our understanding of dendrite formation in solid-state Li batteries and provides comprehensive insight that might be valuable for mitigating dendrite-related challenges.
全固态电池具有高能量密度和环保储能特性，但由于枝晶形成，尤其是锂金属阳极的枝晶形成，面临着商业化障碍。在此，我们报告通过非侵入性固态核磁共振和磁共振成像发现，Li/LiLaZrO/Li电池中的枝晶形成通过两种不同机制发生。示踪剂交换核磁共振显示在电极-电解质界面处锂镀层不均匀，以及在LiLaZrO晶界处锂发生局部还原。原位磁共振成像揭示了通过不均匀锂镀层快速形成枝晶，随后是由锂还原导致的缓慢的整体枝晶成核，中间有一段生长停滞期。非晶枝晶的形成及随后的结晶、固体电解质的缺陷化学和电池工作条件在塑造这两种机制之间的复杂相互作用中起着关键作用。总体而言，这项工作加深了我们对固态锂电池中枝晶形成的理解，并提供了全面的见解，这对于缓解与枝晶相关的挑战可能具有重要价值。
