journal article·2024-01-12Open access

Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Krishna Prasad Koirala, Lin Jiang, Shripad Patil, Paolo Longo, Zhao Liu, Bert Freitag, Juri Barthel, Ethan C. Self, Yingge Du, Lee Pullan, Ted Tessner, Leslie J. Allen, Wu Xu, Wei Tong, Jagjit Nanda, Chongmin Wang

ACS Energy Letters· Volume 9· Issue 1

Abstract

Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li 1.2 Mn 0.7 Ti 0.1 O 1.7 F 0.3 and Li 1.15 Ni 0.45 Ti 0.3 Mo 0.1 O 1.85 F 0.15 . We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation–anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Electron and X-Ray Spectroscopy Techniques

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States

Thermo Fisher Scientific, 5350 NE Dawson Creek Drive, Hillsboro, Oregon 97124, United States

Bredesen Center for Interdisciplinary Research and Education, University of Tennessee Knoxville, Knoxville, Tennessee 37996, United States

Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States

Thermo Fisher Scientific, Achtseweg Noord 5, 5651 GG Eindhoven, The Netherlands

Ernst Ruska-Center (ER-C-2), Forschungszentrum, 52428 Julich, Germany

School of Physics, University of Melbourne, Parkville, Victoria 3010, Australia

Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99354, United States

Energy Storage and Distribute Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Applied Energy Division, SLAC National Laboratory, Menlo Park, California 94025, United States

Materials Science and Engineering, Stanford University, Stanford, California 94305, United States

Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States

Funding

Vehicle Technologies Office

References (40)

Show source-provided references
1. 10.1016/j.mattod.2014.10.04010.1016/j.mattod.2014.10.040 ↗
2. 10.1021/acsaem.0c0083910.1021/acsaem.0c00839 ↗
3. 10.1039/D0TA12179G10.1039/D0TA12179G ↗
4. 10.1002/adma.20210625610.1002/adma.202106256 ↗
5. 10.1021/acsami.1c0788210.1021/acsami.1c07882 ↗
6. 10.1002/aenm.20210305010.1002/aenm.202103050 ↗
7. 10.1002/aenm.20220042610.1002/aenm.202200426 ↗
8. 10.1038/s41563-020-00816-010.1038/s41563-020-00816-0 ↗
9. 10.1002/aenm.20230022110.1002/aenm.202300221 ↗
10. 10.1021/acsami.3c0480510.1021/acsami.3c04805 ↗
11. 10.1021/ja062027+10.1021/ja062027+ ↗
12. 10.1038/ncomms1381410.1038/ncomms13814 ↗
13. 10.1039/C5EE02329G10.1039/C5EE02329G ↗
14. 10.1021/acs.chemmater.5b0353010.1021/acs.chemmater.5b03530 ↗
15. 10.1002/aenm.20170153310.1002/aenm.201701533 ↗
16. 10.1038/s41467-017-01115-010.1038/s41467-017-01115-0 ↗
17. 10.1016/j.chempr.2019.10.00110.1016/j.chempr.2019.10.001 ↗
18. 10.1021/acs.chemmater.8b0379410.1021/acs.chemmater.8b03794 ↗
19. 10.1038/s41586-018-0015-410.1038/s41586-018-0015-4 ↗
20. 10.1002/aenm.20180295910.1002/aenm.201802959 ↗
21. 10.1039/C9EE02803J10.1039/C9EE02803J ↗
22. 10.1002/aenm.20190324010.1002/aenm.201903240 ↗
23. 10.1039/C7EE03195E10.1039/C7EE03195E ↗
24. 10.1002/adfm.20210188810.1002/adfm.202101888 ↗
25. 10.1002/adfm.20220597210.1002/adfm.202205972 ↗
26. 10.1002/advs.20150012810.1002/advs.201500128 ↗
27. Pennycook S. J. · 201110.1007/978-1-4419-7200-2 ↗
28. 10.1002/aenm.20200167110.1002/aenm.202001671 ↗
29. 10.3389/fchem.2019.0010710.3389/fchem.2019.00107 ↗
30. 10.1002/aenm.20210020410.1002/aenm.202100204 ↗
31. 10.1126/science.218.4567.4910.1126/science.218.4567.49 ↗
32. 10.1111/j.1365-2818.1983.tb04213.x10.1111/j.1365-2818.1983.tb04213.x ↗
33. 10.1021/acsnano.1c0328910.1021/acsnano.1c03289 ↗
34. 10.1002/aenm.20220320710.1002/aenm.202203207 ↗
35. 10.1107/S002188980300287510.1107/S0021889803002875 ↗
36. 10.1021/acs.chemmater.2c0147410.1021/acs.chemmater.2c01474 ↗
37. 10.1080/1478643031000160347210.1080/14786430310001603472 ↗
38. 10.1016/0304-3991(94)90060-410.1016/0304-3991(94)90060-4 ↗
39. 10.1016/S0304-3991(03)00095-010.1016/S0304-3991(03)00095-0 ↗
40. 10.1021/acs.chemmater.2c0382710.1021/acs.chemmater.2c03827 ↗