<p>Lithium aluminum titanium phosphate (LATP) is well-established as a crystalline electrolyte offering fast Li<sup>+</sup> diffusion pathways. However, when in contact with lithium metal, LATP forms a mixed-conducting interphase, potentially impacting the performance of LATP-based batteries. During lithiation, Ti<sup>4+</sup> is partially reduced to form Ti<sup>3+</sup>, and Li<sup>+</sup> occupies vacant sites within the NaSICON-type structure. Here, we employed <sup>7</sup>Li nuclear magnetic resonance (NMR) to investigate changes in Li<sup>+</sup> diffusivity induced by chemical lithiation using <i>n</i>-butyllithium. Chemical lithiation allowed us to mimic the structural and dynamic changes occurring within a lithium metal battery. Our findings reveal that lithiation does not hinder Li<sup>+</sup> diffusivity; rather, <sup>7</sup>Li NMR relaxation measurements indicate enhanced Li<sup>+</sup> ion hopping processes. Despite the formation of a lithiated interfacial layer that propagates inward, the dynamic properties of LATP—characterized by Li-rich and Li-poor domains—remain resilient. These results highlight that electrochemical degradation does not compromise the intrinsic ion dynamics of LATP.</p><p></p>

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Interfacial lithiation of lithium aluminum titanium phosphate explored by 7Li NMR

  • Annika Marko,
  • Thomas Scheiber,
  • Bernhard Gadermaier,
  • H. Martin R. Wilkening

摘要

Lithium aluminum titanium phosphate (LATP) is well-established as a crystalline electrolyte offering fast Li+ diffusion pathways. However, when in contact with lithium metal, LATP forms a mixed-conducting interphase, potentially impacting the performance of LATP-based batteries. During lithiation, Ti4+ is partially reduced to form Ti3+, and Li+ occupies vacant sites within the NaSICON-type structure. Here, we employed 7Li nuclear magnetic resonance (NMR) to investigate changes in Li+ diffusivity induced by chemical lithiation using n-butyllithium. Chemical lithiation allowed us to mimic the structural and dynamic changes occurring within a lithium metal battery. Our findings reveal that lithiation does not hinder Li+ diffusivity; rather, 7Li NMR relaxation measurements indicate enhanced Li+ ion hopping processes. Despite the formation of a lithiated interfacial layer that propagates inward, the dynamic properties of LATP—characterized by Li-rich and Li-poor domains—remain resilient. These results highlight that electrochemical degradation does not compromise the intrinsic ion dynamics of LATP.