Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Xin Xu^#^{1

2

3}, Teng Cui^#⁴, Geoff McConohy^#^{5

6}, Harsh D Jagad^#⁷, Samuel S Lee^#^{6

4}, Sunny Wang^{6

8}, Celeste Melamed⁵, Yufei Yang⁵, Edward Barks^{5

6}, Emma Kaeli⁵, Leah Narun⁵, Yi Cui⁵, Zewen Zhang⁵, Hye Ryoung Lee^{6

9}, Rong Xu⁵, Melody M Wang⁵, Levi Hoogendoorn⁵, Ajai Romana⁵, Alexis Geslin^{5

10}, Robert Sinclair⁵, Yi Cui^{5

6

10}, Yue Qi¹¹, X Wendy Gu¹², William C Chueh^{13

14

15}

Affiliations

¹ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA. xxu@asu.edu.
² Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. xxu@asu.edu.
³ The Polytechnic School, Ira A. Fulton Schools of Engineering, Arizona State University, Mesa, AZ, USA. xxu@asu.edu.
⁴ Department of Mechanical Engineering, Stanford University, Stanford, CA, USA.
⁵ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA.
⁶ Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
⁷ School of Engineering, Brown University, Providence, RI, USA.
⁸ Department of Chemistry, Stanford University, Stanford, CA, USA.
⁹ Geballe Laboratory for Advanced Materials, Stanford University, Stanford, CA, USA.
¹⁰ Department of Energy Science and Engineering, Stanford University, Stanford, CA, USA.
¹¹ School of Engineering, Brown University, Providence, RI, USA. yueqi@brown.edu.
¹² Department of Mechanical Engineering, Stanford University, Stanford, CA, USA. xwgu@stanford.edu.
¹³ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA. wchueh@stanford.edu.
¹⁴ Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. wchueh@stanford.edu.
¹⁵ Department of Energy Science and Engineering, Stanford University, Stanford, CA, USA. wchueh@stanford.edu.

^# Contributed equally.

PMID: 41545651
DOI: 10.1038/s41563-025-02465-7

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Xin Xu et al. Nat Mater. 2026.

. 2026 Jan 16.

doi: 10.1038/s41563-025-02465-7. Online ahead of print.

Authors

Affiliations

¹ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA. xxu@asu.edu.
² Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. xxu@asu.edu.
³ The Polytechnic School, Ira A. Fulton Schools of Engineering, Arizona State University, Mesa, AZ, USA. xxu@asu.edu.
⁴ Department of Mechanical Engineering, Stanford University, Stanford, CA, USA.
⁵ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA.
⁶ Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
⁷ School of Engineering, Brown University, Providence, RI, USA.
⁸ Department of Chemistry, Stanford University, Stanford, CA, USA.
⁹ Geballe Laboratory for Advanced Materials, Stanford University, Stanford, CA, USA.
¹⁰ Department of Energy Science and Engineering, Stanford University, Stanford, CA, USA.
¹¹ School of Engineering, Brown University, Providence, RI, USA. yueqi@brown.edu.
¹² Department of Mechanical Engineering, Stanford University, Stanford, CA, USA. xwgu@stanford.edu.
¹³ Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA. wchueh@stanford.edu.
¹⁴ Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. wchueh@stanford.edu.
¹⁵ Department of Energy Science and Engineering, Stanford University, Stanford, CA, USA. wchueh@stanford.edu.

^# Contributed equally.

PMID: 41545651
DOI: 10.1038/s41563-025-02465-7

Abstract

Lithium dendrite intrusion in solid-state batteries limits fast charging and causes short-circuiting, yet the underlying regulating mechanisms are not well-understood. Here we discover that heterogeneous Ag⁺ doping dramatically affects lithium intrusion into Li_6.6La₃Zr_1.6Ta_0.4O₁₂ (LLZO), a brittle solid electrolyte. Nanoscale Ag⁺ doping is achieved by thermally annealing a 3-nm-thick metallic coating on LLZO, inducing Ag-Li ion exchange and Ag diffusion into grains and grain boundaries. Density functional theory calculations and experimental characterization show negligible impact on the electronic properties and surface wettability from Ag⁺ incorporation. Mechanically, nanoindentation experiments show a fivefold increase in the mechanical force required to fracture the surface Ag⁺-doped LLZO, indicating substantial doping-induced surface toughening. Operando microprobe scanning electron microscopy experiments show that the Ag⁺-doped LLZO surface exhibits improved lithium plating at >250 mA cm^-2 and an electroplating diameter that is expanded by over fourfold, even under an extreme indentation stress of 3 GPa. This demonstrates enhanced defect tolerance in LLZO, rather than electronic or adhesion effects. Our study reveals a chemo-mechanical mechanism via surface heterogeneous doping, complementing present bulk design rules to minimize mechanical failures in solid-state batteries.

PubMed Disclaimer

Conflict of interest statement

Competing interests: The authors declare no competing interests.

References

1. Cao, D. et al. Lithium dendrite in all-solid-state batteries: growth mechanisms, suppression strategies, and characterizations. Matter 3, 57–94 (2020). - DOI
1. Janek, J. & Zeier, W. G. Challenges in speeding up solid-state battery development. Nat. Energy 8, 230–240 (2023). - DOI
1. Zhang, H., Ren, Y., Wu, X. & Wang, N. An interface-modified solid-state electrochemical device for lithium extraction from seawater. J. Power Sources 482, 228938 (2021). - DOI
1. Xiong, Y. et al. Electrochemical lithium extraction from aqueous sources. Matter 5, 1760–1791 (2022). - DOI
1. Teprovich, J. A. Jr et al. Electrochemical extraction of hydrogen isotopes from Li/LiT mixtures. Fusion Eng. Des. 139, 1–6 (2019). - DOI

Grants and funding

LinkOut - more resources

Full Text Sources
- Nature Publishing Group

Save citation to file

Email citation

Add to Collections

Add to My Bibliography

Your saved search

Create a file for external citation management software

Your RSS Feed

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Affiliations

Heterogeneous doping via nanoscale coating impacts the mechanics of Li intrusion in brittle solid electrolytes

Authors

Affiliations

Abstract

Conflict of interest statement

References

Grants and funding

LinkOut - more resources

Full Text Sources