<p>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/Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub>/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<sup>+</sup> reduction at Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> grain boundaries. In situ magnetic resonance imaging reveals rapid dendrite formation via non-uniform Li plating, followed by sluggish bulk dendrite nucleation from Li<sup>+</sup> 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.</p>

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Dendrite formation in solid-state batteries arising from lithium plating and electrolyte reduction

  • Haoyu Liu,
  • Yudan Chen,
  • Po-Hsiu Chien,
  • Ghoncheh Amouzandeh,
  • Dewen Hou,
  • Erica Truong,
  • Ifeoluwa P. Oyekunle,
  • Jamini Bhagu,
  • Samuel W. Holder,
  • Hui Xiong,
  • Peter L. Gor’kov,
  • Jens T. Rosenberg,
  • Samuel C. Grant,
  • Yan-Yan Hu

摘要

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/Li7La3Zr2O12/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 Li7La3Zr2O12 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.