DataVXACS Energy LettersPaper
journal article·2021-01-08Open access

Elucidation of Active Oxygen Sites upon Delithiation of Li3IrO4

Haifeng Li, Arnaud J. Perez, Beata Taudul, Teak D. Boyko, John W. Freeland, Marie-Liesse Doublet, Jean-Marie Tarascon, Jordi Cabana

ACS Energy Letters· Volume 6· Issue 1
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Source abstract

Abstract

Transformational increases in the storage capacity of battery cathodes could be achieved by tapping into the redox activity at oxide ligands in addition to conventional transition metal couples. However, the key signatures that govern such lattice oxygen redox (LOR) have not been ascertained. Li3IrO4 has the largest reversible LOR, rendering it a unique model system. Here, X-ray spectroscopy and computational simulations reveal that LOR in Li3IrO4 is selectively compensated via O sites with three lone pairs, which are activated by Li/Ir disorder. The two-electron LOR can be reversed to regenerate the initial state without unlocking competing bulk reactions observed in many other compounds. We uncover an intricate interplay between stoichiometry, O coordination, and nonbonding states in LOR and pinpoint spectroscopic signatures. This interplay is indispensable for designing materials with 3d metals that fulfill the promise of LOR to overcome the bottlenecks of current cathodes for future implementation in practical batteries.
Source: openalex_inverted_index · Quality: baseline

Research context

Energy storage

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Transition Metal Oxide Nanomaterials

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

Affiliations

Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States

Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France

Sorbonne Université, 4 Place Jussieu, F-75005 Paris, France

Institut Charles Gerhardt, Univ. Montpellier, CNRS, ENSCM, 34095 Montpellier, France

Réseau sur le Stockage Electrochimique de l’Energie (RS2E) CNRS FR3459, 33 rue Saint Leu, 80039 Amiens Cedex, France

Canadian Light Source, University of Saskatchewan, Saskatoon, Saskatchewan S7N 2V3, Canada

Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States

Funding

Canadian Institutes of Health Research · National Research Council Canada · Canada Foundation for Innovation · Natural Sciences and Engineering Research Council of Canada · Division of Materials Research · Government of Saskatchewan

References (49)

Show source-provided references
1. 10.1126/science.121274110.1126/science.1212741 ↗
2. 10.1021/cm901452z10.1021/cm901452z ↗
3. 10.1016/0025-5408(80)90012-410.1016/0025-5408(80)90012-4 ↗
4. 10.1149/1.141318210.1149/1.1413182 ↗
5. 10.1246/cl.2001.64210.1246/cl.2001.642 ↗
6. 10.1016/j.jpowsour.2007.06.15310.1016/j.jpowsour.2007.06.153 ↗
7. 10.1149/1.140799410.1149/1.1407994 ↗
8. 10.1016/j.elecom.2004.08.00210.1016/j.elecom.2004.08.002 ↗
9. 10.1016/j.elecom.2006.06.03010.1016/j.elecom.2006.06.030 ↗
10. 10.1039/b702425h10.1039/b702425h ↗
11. 10.1021/cm801245r10.1021/cm801245r ↗
12. 10.1149/2.0111514jes10.1149/2.0111514jes ↗
13. 10.1039/C6TA00174B10.1039/C6TA00174B ↗
14. 10.1038/nchem.247110.1038/nchem.2471 ↗
15. 10.1021/ja108588y10.1021/ja108588y ↗
16. 10.1021/jacs.8b1141310.1021/jacs.8b11413 ↗
17. 10.1038/s41467-017-02291-910.1038/s41467-017-02291-9 ↗
18. 10.1126/science.aac826010.1126/science.aac8260 ↗
19. 10.1038/s41560-017-0042-710.1038/s41560-017-0042-7 ↗
20. 10.1038/nmat486410.1038/nmat4864 ↗
21. 10.1038/nchem.252410.1038/nchem.2524 ↗
22. 10.1039/C5EE03048J10.1039/C5EE03048J ↗
23. 10.1038/s41467-017-02041-x10.1038/s41467-017-02041-x ↗
24. 10.1038/s41563-018-0276-110.1038/s41563-018-0276-1 ↗
25. 10.1039/C6EE02328B10.1039/C6EE02328B ↗
26. 10.1038/s41563-019-0318-310.1038/s41563-019-0318-3 ↗
27. 10.1038/s41467-018-03403-910.1038/s41467-018-03403-9 ↗
28. 10.1016/j.jpowsour.2018.04.01810.1016/j.jpowsour.2018.04.018 ↗
29. 10.1371/journal.pone.004918210.1371/journal.pone.0049182 ↗
30. 10.1103/PhysRevLett.112.05640210.1103/PhysRevLett.112.056402 ↗
31. 10.1103/PhysRevB.96.06443610.1103/PhysRevB.96.064436 ↗
32. 10.1021/ic00097a00910.1021/ic00097a009 ↗
33. 10.1016/j.ccr.2004.03.02010.1016/j.ccr.2004.03.020 ↗
34. 10.1016/j.jpowsour.2012.08.02310.1016/j.jpowsour.2012.08.023 ↗
35. 10.1073/pnas.150490111210.1073/pnas.1504901112 ↗
36. 10.1021/jacs.9b1243810.1021/jacs.9b12438 ↗
37. 10.1038/s41560-018-0207-z10.1038/s41560-018-0207-z ↗
38. 10.1021/acs.jpcc.9b0129810.1021/acs.jpcc.9b01298 ↗
39. 10.1038/s41586-019-1854-310.1038/s41586-019-1854-3 ↗
40. 10.1038/s41560-020-00697-210.1038/s41560-020-00697-2 ↗
41. 10.1021/acs.chemmater.8b0459110.1021/acs.chemmater.8b04591 ↗
42. 10.1016/j.joule.2020.05.00410.1016/j.joule.2020.05.004 ↗
43. 10.1039/C9MH00765B10.1039/C9MH00765B ↗
44. 10.1021/acsenergylett.9b0214710.1021/acsenergylett.9b02147 ↗
45. 10.1038/nmat369910.1038/nmat3699 ↗
46. 10.1038/nmat413710.1038/nmat4137 ↗
47. 10.1021/acsenergylett.9b0279910.1021/acsenergylett.9b02799 ↗
48. 10.1021/acs.chemmater.8b0295510.1021/acs.chemmater.8b02955 ↗
49. 10.1039/b207282c10.1039/b207282c ↗