Kinetics-Controlled Degradation Reactions at Crystalline LiPON/Li(x)CoO(2) and Crystalline LiPON/Li-metal Interfaces

Abstract

Detailed understanding of solid-solid interface structure-function relations is critical for the improvement and wide deployment of all solid-state batteries. The interfaces between lithium phosphorous oxynitride ("LiPON") solid electrolyte material and lithium metal anode, between LiPON and Li(x)CoO(2) cathode surfaces, have been reported to generate solid electrolyte interphase ("SEI")-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models with atomic-layer-deposition-like stoichiometry, we predict LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Li(x)CoO(2) (104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON motifs that readily react with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures.

arXiv comment35 pages, 9 figures

References in corpus (8)

• Maximally-localized generalized Wannier functions for composite energy bands
• Joint Density-Functional Theory of the Electrode-Electrolyte Interface: Application to Fixed Electrode Potentials, Interfacial Capacitances, and Potentials of Zero Charge
• Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces
• Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries
• Nanoscale Solid State Batteries Enabled By Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte
• First Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li(x)Mn(2)O(4) (100) Surfaces
• First Principles Modeling of Mn(II) Migration above and Dissolution from Li(x)Mn(2)O(4) (001) Surfaces
• Ab-initio modeling of electrolyte molecule Ethylene Carbonate decomposition reaction on Li(Ni,Mn,Co)O2 cathode surface

Cited by in corpus (5)

• Unveiling the Stable Nature of the Solid Electrolyte Interphase between Lithium Metal and LiPON via Cryogenic Electron Microscopy
• First-principles prediction of potentials and space-charge layers in all-solid-state batteries
• DFT Modelling of Explicit Solid-Solid Interfaces in Batteries: Methods and Challenges
• Interfacial Effects on Solid Electrolyte Interphase in Lithium-ion Batteries
• Galvanic Corrosion and Electric Field in Lithium Anode Passivation Films: Effects on Self-Discharge