Using atomic layer deposition to hinder solvent decomposition in lithium ion batteries: first principles modeling and experimental studies

Abstract

Passivating lithium ion battery electrode surfaces to prevent electrolyte decomposition is critical for battery operations. Recent work on conformal atomic layer deposition (ALD) coating of anodes and cathodes has shown significant technological promise. ALD further provides well-characterized model platforms for understanding electrolyte decomposition initiated by electron tunneling through a passivating layer. First principles calculations reveal two regimes of electron transfer to adsorbed ethylene carbonate molecules (EC, a main component of commercial electrolyte) depending on whether the electrode is alumina-coated. On bare Li metal electrode surfaces, EC accepts electrons and decomposes within picoseconds. In contrast, constrained density functional theory calculations in an ultra-high vacuum setting show that, with the oxide coating, e- tunneling to the adsorbed EC falls within the non-adiabatic regime. Here the molecular reorganization energy, computed in the harmonic approximation, plays a key role in slowing down electron transfer. Ab initio molecular dynamics simulations conducted at liquid EC-electrode interfaces are consistent with the view that reactions and electron transfer occur right at the interface. Microgravimetric measurements demonstrate that the ALD coating decreases electrolyte decomposition and corroborate the theoretical predictions.

40 pages, 7 figures

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Cited by in corpus (7)

• Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries
• Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries
• Two-electron reduction of ethylene carbonate: a quantum chemistry re-examination of mechanisms
• First Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li(x)Mn(2)O(4) (100) Surfaces
• Ab-initio modeling of electrolyte molecule Ethylene Carbonate decomposition reaction on Li(Ni,Mn,Co)O2 cathode surface
• Towards First Principles prediction of Voltage Dependences of Electrolyte/Electrolyte Interfacial Processes in Lithium Ion Batteries
• Galvanic Corrosion and Electric Field in Lithium Anode Passivation Films: Effects on Self-Discharge