Tailoring Interfaces in Solid-State Batteries Using Interfacial Thermochemistry and Band Alignment

Robert E. Warburton*, Jae Jin Kim, Shane Patel, Jason D. Howard, Larry A. Curtiss, Chris Wolverton, D. Bruce Buchholz, John T. Vaughey, Paul Fenter, Timothy T. Fister, Jeffrey Greeley*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

Solid-state lithium ion batteries have enhanced thermal stability compared to batteries using liquid electrolytes. Although their practical implementation is limited by undesired side reactions between the electrode and electrolyte, different modification strategies have been proposed to stabilize these reactive interfaces. These approaches have been primarily based upon bulk materials properties, however, which may not necessarily be representative of the chemistry at the solid/solid interface. Herein, first-principles calculations and X-ray scattering experiments are used to elucidate molecular-level reactivity and develop design principles for tailored interfaces based on surface and interfacial properties. Because of its well-known instability, the interface between the Li metal anode and the lithium lanthanum titanate (LLTO) solid electrolyte is applied as a model system. Density functional theory calculations are used to describe bulk, surface, and interfacial thermochemistry of the Li/LLTO system, and interfacial reconstruction is probed using ab initio molecular dynamics. These simulations of the Li/LLTO interface demonstrate facile decomposition concomitant with reduction of Ti4+ ions. Based on further insights from computational analysis of the surface band edge positions, La2O3 is proposed as an interlayer coating and is shown to provide an energetic barrier for interfacial charge transfer and decomposition reactions from X-ray reflectivity measurements and theoretical calculations. The findings in this work suggest that design strategies based on surface and interfacial properties can be used to kinetically stabilize electrode/electrolyte interfaces in solid-state batteries.

Original languageEnglish (US)
Pages (from-to)8447-8459
Number of pages13
JournalChemistry of Materials
Volume33
Issue number21
DOIs
StatePublished - Nov 9 2021

Funding

This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.Use of the Center for Nanoscale Materials at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. We acknowledge computational resources from Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory, and the National Energy Research Scientific Computing Center (NERSC). D.B.B. acknowledges the Pulsed Laser Deposition Shared Facility at the Materials Research Center at Northwestern University that is supported, in part, by the CEES-EFRC program, as well as by the National Science Foundation MRSEC program (DMR-1720139) and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205).

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry

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