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Here, N-doped Li6Zr2O7 (LZON) is investigated using first-principles density functional theory (DFT) methods to evaluate its (electro)chemical stability and Li-ion transport properties for its novel design as a practical dual-use Li ionic conductor, both as a cathode-coating layer (CCL) and solid electrolyte (SE) in all-solid-state Li-ion batteries (ASSBs). Thermodynamic free energy calculations showed that LZO, as CCL and SE, is chemically stable versus most known cathode materials. Focusing on LiCoO2 (LCO) cathode, explicit hetero-interface modeling analysis of the low-energy LCO(104)|LZO(001) interface revealed that LZO can form a strongly adhered and a low-strain contact with LCO. The electronic structure of this interface has LCO-side states (Co-3d, O-2p) occupying the highest occupied states, thereby facilitating a stable cell charging. Climbing-image nudged elastic band calculations results suggested that the LCO(104)|LZO(001) interface also has interface-normal diffusion pathways with low Li ion migration energy. Meanwhile, ab-initio- and machine-learning-based molecular dynamics simulation results confirmed that Li diffusivity in bulk LZO can be greatly enhanced by several orders of magnitude via aliovalent N-doping with Li interstitial addition. For the LCO(104)|LZON(001) interface, the N dopant is determined to energetically prefer the LZON bulk region, the corresponding interface electronic structure that can also facilitate a stable ASSB cell charging.

Rights:

• Creative Commons BY-NC Attribution-NonCommercial 4.0 International
  

Keyword: all solid state batteries, lithium ion conductors, solid electrolytes, cathode coatings, first-principles calculations, molecular dynamics simulations, machine learning interatomic potentials, solid hetero-interface modeling

Date published: 2025-10-01

Publisher: Wiley

Journal:

• Small Methods (ISSN: 23669608) vol. 9 issue. 11 e01289

Funding:

• Ministry of Education, Culture, Sports, Science and Technology JPMXP1020230325
• Japan Society for the Promotion of Science JP21K14729
• Japan Science and Technology Agency JPMJGX23S2
• Ministry of Education, Culture, Sports, Science and Technology JPMXP0219207397

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.6027

First published URL: https://doi.org/10.1002/smtd.202501289

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Updated at: 2025-12-19 08:30:58 +0900

Published on MDR: 2025-12-18 19:08:19 +0900