Monitoring the Local Coordination Evolutions in Li-Rich Cathode Materials via In Situ Raman Spectroscopy

Yanfang Wang; Yingzhi Li; Zhiqiang Li; Ning Qin; Feng Wu; Joshua W. Makepeace; Fucai Zhang; Phoebe K. Allan; Zhouguang Lu

doi:10.1021/acsenergylett.3c02109

Monitoring the Local Coordination Evolutions in Li-Rich Cathode Materials via In Situ Raman Spectroscopy

Yanfang Wang, Yingzhi Li, Zhiqiang Li, Ning Qin, Feng Wu, Joshua W. Makepeace, Fucai Zhang^*, Phoebe K. Allan^*, Zhouguang Lu^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Letter › peer-review

Abstract

Although consensus has been reached that the lattice oxygen (O²–) could be ultimately oxidized to molecular O2 in lithium-rich cathode materials (LRCMs), monitoring the local coordination evolutions around oxygen in real time is still demanding. Herein, we demonstrate the potential of using in situ Raman spectroscopy to decipher the local environment changes upon de-/lithiation in Li₂RuO₃. Evolutions of both the Ru–Ru motions and Ru–O vibrations have been captured by in situ Raman tests and interpreted in combination with multimodal characterizations. Uniquely, triggering the anion redox reactions (ARRs) produces a Raman band (∼500 cm^–1), which upon careful examination is attributed to the Ru–O₂^n– (0 < n < 4) coordination and suggested as the indicator of O–O dimerization. Considering its nondestructivity and high sensitivity to lattice vibrations, this work could shed new light on utilizing Raman spectroscopy to investigate the local coordination evolutions in LRCMs and other materials.

Original language	English
Pages (from-to)	4888–4894
Number of pages	7
Journal	ACS Energy Letters
Volume	8
Issue number	11
Early online date	27 Oct 2023
DOIs	https://doi.org/10.1021/acsenergylett.3c02109
Publication status	Published - 10 Nov 2023

Bibliographical note

Acknowledgments:
This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20220818100418040), Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (ZDSYS20200421111401738), and the National Natural Science Foundation of China (U22A20439, 21875097, 12074167). The authors thank beamline scientists at BL02U (SSRF) for the sXAS measurement. The authors acknowledge Y.H.Z. and S.X.H. for support of in situ XRD tests. The authors acknowledge the assistance of SUSTech Core Research Facilities (CRF).

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@article{c00a2fab746a498bb944591120d9df6a,

title = "Monitoring the Local Coordination Evolutions in Li-Rich Cathode Materials via In Situ Raman Spectroscopy",

abstract = "Although consensus has been reached that the lattice oxygen (O2–) could be ultimately oxidized to molecular O2 in lithium-rich cathode materials (LRCMs), monitoring the local coordination evolutions around oxygen in real time is still demanding. Herein, we demonstrate the potential of using in situ Raman spectroscopy to decipher the local environment changes upon de-/lithiation in Li2RuO3. Evolutions of both the Ru–Ru motions and Ru–O vibrations have been captured by in situ Raman tests and interpreted in combination with multimodal characterizations. Uniquely, triggering the anion redox reactions (ARRs) produces a Raman band (∼500 cm–1), which upon careful examination is attributed to the Ru–O2n– (0 < n < 4) coordination and suggested as the indicator of O–O dimerization. Considering its nondestructivity and high sensitivity to lattice vibrations, this work could shed new light on utilizing Raman spectroscopy to investigate the local coordination evolutions in LRCMs and other materials.",

author = "Yanfang Wang and Yingzhi Li and Zhiqiang Li and Ning Qin and Feng Wu and Makepeace, {Joshua W.} and Fucai Zhang and Allan, {Phoebe K.} and Zhouguang Lu",

note = "Acknowledgments: This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20220818100418040), Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (ZDSYS20200421111401738), and the National Natural Science Foundation of China (U22A20439, 21875097, 12074167). The authors thank beamline scientists at BL02U (SSRF) for the sXAS measurement. The authors acknowledge Y.H.Z. and S.X.H. for support of in situ XRD tests. The authors acknowledge the assistance of SUSTech Core Research Facilities (CRF).",

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doi = "10.1021/acsenergylett.3c02109",

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T1 - Monitoring the Local Coordination Evolutions in Li-Rich Cathode Materials via In Situ Raman Spectroscopy

AU - Wang, Yanfang

AU - Li, Yingzhi

AU - Li, Zhiqiang

AU - Qin, Ning

AU - Wu, Feng

AU - Makepeace, Joshua W.

AU - Zhang, Fucai

AU - Allan, Phoebe K.

AU - Lu, Zhouguang

N1 - Acknowledgments: This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (JCYJ20220818100418040), Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (ZDSYS20200421111401738), and the National Natural Science Foundation of China (U22A20439, 21875097, 12074167). The authors thank beamline scientists at BL02U (SSRF) for the sXAS measurement. The authors acknowledge Y.H.Z. and S.X.H. for support of in situ XRD tests. The authors acknowledge the assistance of SUSTech Core Research Facilities (CRF).

PY - 2023/11/10

Y1 - 2023/11/10

N2 - Although consensus has been reached that the lattice oxygen (O2–) could be ultimately oxidized to molecular O2 in lithium-rich cathode materials (LRCMs), monitoring the local coordination evolutions around oxygen in real time is still demanding. Herein, we demonstrate the potential of using in situ Raman spectroscopy to decipher the local environment changes upon de-/lithiation in Li2RuO3. Evolutions of both the Ru–Ru motions and Ru–O vibrations have been captured by in situ Raman tests and interpreted in combination with multimodal characterizations. Uniquely, triggering the anion redox reactions (ARRs) produces a Raman band (∼500 cm–1), which upon careful examination is attributed to the Ru–O2n– (0 < n < 4) coordination and suggested as the indicator of O–O dimerization. Considering its nondestructivity and high sensitivity to lattice vibrations, this work could shed new light on utilizing Raman spectroscopy to investigate the local coordination evolutions in LRCMs and other materials.

AB - Although consensus has been reached that the lattice oxygen (O2–) could be ultimately oxidized to molecular O2 in lithium-rich cathode materials (LRCMs), monitoring the local coordination evolutions around oxygen in real time is still demanding. Herein, we demonstrate the potential of using in situ Raman spectroscopy to decipher the local environment changes upon de-/lithiation in Li2RuO3. Evolutions of both the Ru–Ru motions and Ru–O vibrations have been captured by in situ Raman tests and interpreted in combination with multimodal characterizations. Uniquely, triggering the anion redox reactions (ARRs) produces a Raman band (∼500 cm–1), which upon careful examination is attributed to the Ru–O2n– (0 < n < 4) coordination and suggested as the indicator of O–O dimerization. Considering its nondestructivity and high sensitivity to lattice vibrations, this work could shed new light on utilizing Raman spectroscopy to investigate the local coordination evolutions in LRCMs and other materials.

U2 - 10.1021/acsenergylett.3c02109

DO - 10.1021/acsenergylett.3c02109

M3 - Letter

SN - 2380-8195

VL - 8

SP - 4888

EP - 4894

JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 11

ER -

Monitoring the Local Coordination Evolutions in Li-Rich Cathode Materials via In Situ Raman Spectroscopy

Abstract

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