Probing lithium mobility at a solid electrolyte surface

Clarisse Woodahl; Sasawat Jamnuch; Angelique Amado; Can B Uzundal; Emma Berger; Paul Manset; Yisi Zhu; Yan Li; Dillon D Fong; Justin G Connell; Yasuyuki Hirata; Yuya Kubota; Shigeki Owada; Kensuke Tono; Makina Yabashi; Suzanne G E Te Velthuis; Sanja Tepavcevic; Iwao Matsuda; Walter S Drisdell; Craig P Schwartz; John W Freeland; Tod A Pascal; Alfred Zong; Michael Zuerch

doi:10.1038/s41563-023-01535-y

Probing lithium mobility at a solid electrolyte surface

Nat Mater. 2023 Jul;22(7):848-852. doi: 10.1038/s41563-023-01535-y. Epub 2023 Apr 27.

Authors

Clarisse Woodahl^#^{1

2}, Sasawat Jamnuch^#³, Angelique Amado^{2

4}, Can B Uzundal^{2

4}, Emma Berger^{2

4}, Paul Manset⁵, Yisi Zhu⁶, Yan Li⁶, Dillon D Fong⁶, Justin G Connell⁶, Yasuyuki Hirata⁷, Yuya Kubota^{8

9}, Shigeki Owada^{8

9}, Kensuke Tono^{8

9}, Makina Yabashi^{8

9}, Suzanne G E Te Velthuis⁶, Sanja Tepavcevic⁶, Iwao Matsuda^{10

11}, Walter S Drisdell^{12

13}, Craig P Schwartz¹⁴, John W Freeland¹⁵, Tod A Pascal^{16

17

18}, Alfred Zong^{2

4}, Michael Zuerch^{19

20

21

22}

Affiliations

¹ University of Florida, Gainesville, FL, USA.
² Department of Chemistry, University of California, Berkeley, CA, USA.
³ ATLAS Materials Science Laboratory, Department of Nano Engineering and Chemical Engineering, University of California, San Diego, La Jolla, CA, USA.
⁴ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁵ École Normale Supérieure - PSL, Paris, France.
⁶ Materials Science Division, Argonne National Laboratory, Lemont, IL, USA.
⁷ National Defense Academy of Japan, Yokosuka, Japan.
⁸ RIKEN SPring-8 Center, Sayo, Hyogo, Japan.
⁹ Japan Synchrotron Radiation Research Institute, Sayo, Hyogo, Japan.
¹⁰ Institute for Solid State Physics, The University of Tokyo, Kashiwa, Japan.
¹¹ Trans-scale Quantum Science Institute, The University of Tokyo, Tokyo, Japan.
¹² Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
¹³ Joint Center for Artificial Photosynthesis, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
¹⁴ Nevada Extreme Conditions Laboratory, University of Nevada, Las Vegas, Las Vegas, NV, USA.
¹⁵ X-ray Science Division, Argonne National Laboratory, Lemont, IL, USA.
¹⁶ ATLAS Materials Science Laboratory, Department of Nano Engineering and Chemical Engineering, University of California, San Diego, La Jolla, CA, USA. tpascal@ucsd.edu.
¹⁷ Materials Science and Engineering, University of California San Diego, La Jolla, CA, USA. tpascal@ucsd.edu.
¹⁸ Sustainable Power and Energy Center, University of California San Diego, La Jolla, CA, USA. tpascal@ucsd.edu.
¹⁹ Department of Chemistry, University of California, Berkeley, CA, USA. mwz@berkeley.edu.
²⁰ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. mwz@berkeley.edu.
²¹ Fritz Haber Institute of the Max Planck Society, Berlin, Germany. mwz@berkeley.edu.
²² Friedrich Schiller University Jena, Jena, Germany. mwz@berkeley.edu.

^# Contributed equally.

Abstract

Solid-state electrolytes overcome many challenges of present-day lithium ion batteries, such as safety hazards and dendrite formation^1,2. However, detailed understanding of the involved lithium dynamics is missing due to a lack of in operando measurements with chemical and interfacial specificity. Here we investigate a prototypical solid-state electrolyte using linear and nonlinear extreme-ultraviolet spectroscopies. Leveraging the surface sensitivity of extreme-ultraviolet-second-harmonic-generation spectroscopy, we obtained a direct spectral signature of surface lithium ions, showing a distinct blueshift relative to bulk absorption spectra. First-principles simulations attributed the shift to transitions from the lithium 1 s state to hybridized Li-s/Ti-d orbitals at the surface. Our calculations further suggest a reduction in lithium interfacial mobility due to suppressed low-frequency rattling modes, which is the fundamental origin of the large interfacial resistance in this material. Our findings pave the way for new optimization strategies to develop these electrochemical devices via interfacial engineering of lithium ions.

MeSH terms

Electric Power Supplies
Electrolytes*
Engineering
Lithium*
Software

Substances

Lithium
Electrolytes

Abstract

MeSH terms

Substances

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