Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo₃O₈
Abstract
Electrode materials for Li⁺-ion batteries require optimization along several disparate axes related to cost, performance, and sustainability. One of the important performance axes is the ability to retain structural integrity though cycles of charge/discharge. Metal–metal bonding is a distinct feature of some refractory metal oxides that has been largely underutilized in electrochemical energy storage, but that could potentially impact structural integrity. Here LiScMo₃O₈, a compound containing triangular clusters of metal–metal bonded Mo atoms, is studied as a potential anode material in Li⁺-ion batteries. Electrons inserted though lithiation are localized across rigid Mo₃ triangles (rather than on individual metal ions), resulting in minimal structural change as suggested by operando diffraction. The unusual chemical bonding allows this compound to be cycled with Mo atoms below a formally +4 valence state, resulting in an acceptable voltage regime that is appropriate for an anode material. Several characterization methods including potentiometric entropy measurements indicate two-phase regions, which are attributed through extensive first-principles modeling to Li⁺ ordering. This study of LiScMo₃O₈ provides valuable insights for design principles for structural motifs that stably and reversibly permit Li⁺ (de)insertion.
Additional Information
© 2022 American Chemical Society. Received 15 November 2021. Published online 25 March 2022. This work was supported as part of the Center for Synthetic Control Across Length scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE SC0019381. This research used computational resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231, and shared facilities of the UC Santa Barbara Materials Research Science and Engineering Center (MRSEC, NSF DMR 1720256), a member of the Materials Research Facilities Network (www.mrfn.org). We also acknowledge use of the shared computing facilities of the Center for Scientific Computing at UC Santa Barbara, supported by NSF CNS-1725797, and the NSF MRSEC at UC Santa Barbara, NSF DMR 1720256. C.D. and Y.M.E. thank the German Research Foundation (DFG, Deutsche Forschungsgemeinschaft) under Germany's Excellence Strategy -2082/1-390761711 for financial support. 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. J.L.K. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Advanced Scientific Computing Research, Department of Energy Computational Science Graduate Fellowship under Award Number DE-FG02-97ER25308. J.J.Z. has been supported by the National Science Foundation Graduate Research Fellowship under DGE-1745301. R.C.V. has been supported by the National Science Foundation Graduate Research Fellowship under DGE-1650114. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. We thank Jue Liu of the Oak Ridge National Laboratory and Anna Kallistova of the UC Santa Barbara Materials Research Laboratory for helpful discussions regarding refinement of the X-ray diffraction data. We additionally thank Miguel Zepeda of the UC Santa Barbara Materials Research Laboratory for the help with operando X-ray diffraction. The authors declare no competing financial interest.Attached Files
Supplemental Material - ja1c12070_si_001.pdf
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Additional details
- Alternative title
- Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo<sub>3</sub>O<sub>8</sub>
- Eprint ID
- 114135
- Resolver ID
- CaltechAUTHORS:20220401-183452006
- DE-SC0019381
- Department of Energy (DOE)
- DE-AC02-05CH11231
- Department of Energy (DOE)
- DMR-1720256
- NSF
- CNS-1725797
- NSF
- 2082/1-390761711
- Deutsche Forschungsgemeinschaft (DFG)
- DE-AC02-06CH11357
- Department of Energy (DOE)
- DE-FG02-97ER25308
- Department of Energy (DOE) Computational Science Graduate Fellowship Program
- DGE-1745301
- NSF Graduate Research Fellowship
- DGE-1650114
- NSF Graduate Research Fellowship
- Created
-
2022-04-01Created from EPrint's datestamp field
- Updated
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2022-04-25Created from EPrint's last_modified field