NMR Studies of Multivalent-ion Electrode Materials for Next Generation Multivalent-Ion Batteries
EMSL Project ID
49405
Abstract
Lithium-ion batteries are currently the rechargeable battery systems of choice in any high energy density application. Existing materials are unable to keep up with the ever growing demands of the modern way of life (mainly transportation and grid). Therefore new, low cost, safe materials with superior performances are still urgently required. Multivalent-ion batteries promise breakthrough advances in battery performance, energy density and cost for next generation energy storage systems. This is due to the difference in the chemistry, which utilize a multi-electron transfer phenomenon instead of just one electron transfer (as is the case for Li-ion oxidation/redox). In this proposed study, Mg+2/Mg0 multivalent intercalation redox system is to be studied in detail because of its immediate application potential. According to previous reports on candidate electrode and electrolyte systems, there are a number of roadblocks preventing the development of Mg-ion, namely; the stability of the Grignard based electrolytes with Mg metal anodes, the lack of a stable reference electrode, and the lack of high voltage cathode materials. Furthermore little is known about insertion/intercalation of Mg-ion electrode systems. Therefore, structural characterization (long and short range) tools need to be established for this system prior to successful implementation of Mg-ion batteries. Solid-state NMR is a powerful tool to investigate short order changes in solids. However, the specific nuclei to be studied (Mg and other multivalent) require high magnetic fields. The proposed work will focus on application of high field 25Mg solid state NMR to gain insights on the types of Mg local coordinations and the correlation of these local structures with long range order and with the electrochemical performances. Oxyfluorides, Chevrel phases and high voltage transition metal oxides will be investigated as cathode candidates. Transition metal oxides such as V2O5 and MnO2 can also be used effectively as baseline material for cathodes as well as suitable Chevrel phases. This will show the differences in intercalation phenomenon in an electron rich system in contrast to electron poor systems (TM-oxides, titanium being the poorest). Ex-situ state of charge 25Mg NMR studies for these intercalation cathodes is aimed to gather insights on the general Mg intercalation phenomenon in different hosts and the primary differences between structure and host transition metal effects.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2016-10-01
End Date
2018-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Bayliss R.D., B. Key, G. Sai Gautam, P. Canepa, B.J. Kwon, S.H. Lapidus, and F. Dogan, et al. 2020. "Probing Mg Migration in Spinel Oxides." Chemistry of Materials 32, no. 2:663-670. PNNL-SA-129154. doi:10.1021/acs.chemmater.9b02450
Bayliss R.D., B. Key, G. Sai Gautam, P. Canepa, S.H. Lapidus, F. Dogan, and A.A. Adil, et al. 2017. "Mg Mobility in Spinel Oxides." Nature Materials. PNNL-SA-129154. [Unpublished]
Han B., B. Key, A.S. Lipton, J. Vaughey, B. Hughes, J. Trevey, and F. Dogan. 2019. "Influence of Coating Protocols on Alumina-coated Cathode Material: Atomic Layer Deposition versus Wet-chemical Coating." Journal of the Electrochemical Society 166, no. 15:A3679-A3684. PNNL-SA-145484. doi:10.1149/2.0681915jes
Wustrow A.E., B. Key, P.J. Phillips, N. Sa, A.S. Lipton, R.F. Klie, and J. Vaughey, et al. 2018. "Synthesis and Characterization of MgCr2S4 Thiospinel as a Potential Magnesium Cathode." Inorganic Chemistry 57, no. 14:8634–8638. PNNL-SA-135174. doi:10.1021/acs.inorgchem.8b01417