Abstract
For many lithium-ion cathode materials, transition metal (TM) dissolution into the electrolyte contributes to cell degradation. Cathode coatings can limit TM dissolution by containing TMs in cathode materials. We perform density functional theory calculations to evaluate cathode/coating pairs for TM containment, specifically focusing on reactive stability of coating/cathode pairs as well as TM solubility in the coating materials. We consider stability and containment of materials at both synthesis and operating conditions. We find that many cathode/coating pairs are reactive when lithiated, while other cathode-coating pairs are stable when lithiated but become reactive following delithiation. Of all the coatings that we considered, Li3 PO4 occupies a unique chemical position, in that its coatings on oxide cathode materials maintained equilibrium under both lithiated and delithiated conditions. Furthermore, for oxide cathode materials, the Li3 PO4 coatings exhibit low TM solubilities across all cathode states of charge. Our results demonstrate that Li3 PO4 is a promising candidate for stable coatings on oxide cathode materials to limit TM dissolution into the electrolyte.
| Original language | English (US) |
|---|---|
| Pages (from-to) | A2054-A2064 |
| Journal | Journal of the Electrochemical Society |
| Volume | 163 |
| Issue number | 9 |
| DOIs | |
| State | Published - 2016 |
Funding
The authors are grateful to M. Thackeray, J. Bhattacharya, S. Hao, S. Kim, Z. Lu, and Z. Yao for helpful discussions. D. S. contributed all DFT calculations and thermodynamic analysis, and led writing of the manuscript. S. K. contributed the OQMD high-throughput DFT database and edited the manuscript. M. A. and C. W. assisted with the OQMD database and interpretation of results, and edited the manuscript. D. S. acknowledges support from The Ford Motor Company and S. K. as part of the Center for Electrochemical Energy Science (CEES), an Energy Frontier Research Center (EFRC) funded by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences (Award No. DE-AC02-06CH11357). D. S. also acknowledges fellowship support from Northwestern's Hierarchical Materials Cluster Program and from the Institute for Sustainability and Energy at Northwestern (ISEN). M. A. and C. W. were supported by The Dow Chemical Company. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U. S. Department of Energy under Contract No. DE-AC02-05CH11231 as well as the Northwestern University Quest computing resources.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Renewable Energy, Sustainability and the Environment
- Condensed Matter Physics
- Surfaces, Coatings and Films
- Electrochemistry
- Materials Chemistry
