Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions
Abstract
The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li7RuO6. Coupling structural and spectroscopic analysis with computational simulations, we show that Li7RuO6 is capable of highly reversible lithiation to Li8RuO6 through the Ru(V)/Ru(IV) redox couple. Further, Li7RuO6 can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.
- Authors:
-
[3];
[2];
[1]
- Univ. of Illinois, Chicago, IL (United States)
- Université Montpellier (France); Centre National de la Recherche Scientifique (CNRS) (France); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1901709
- Grant/Contract Number:
- AC02-06CH11357; DMR-1809372
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 8; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical structure; Electrodes; Oxidation; Oxides; Redox reactions
Citation Formats
Li, Haifeng, Taudul, Beata, Alexander, Grant C. B., Liu, Jue, Freeland, John W., Doublet, Marie-Liesse, and Cabana, Jordi. Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions. United States: N. p., 2022.
Web. doi:10.1021/acs.chemmater.2c00043.
Li, Haifeng, Taudul, Beata, Alexander, Grant C. B., Liu, Jue, Freeland, John W., Doublet, Marie-Liesse, & Cabana, Jordi. Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions. United States. https://doi.org/10.1021/acs.chemmater.2c00043
Li, Haifeng, Taudul, Beata, Alexander, Grant C. B., Liu, Jue, Freeland, John W., Doublet, Marie-Liesse, and Cabana, Jordi. Fri .
"Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions". United States. https://doi.org/10.1021/acs.chemmater.2c00043. https://www.osti.gov/servlets/purl/1901709.
@article{osti_1901709,
title = {Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li7RuO6 via Intercalation Reactions},
author = {Li, Haifeng and Taudul, Beata and Alexander, Grant C. B. and Liu, Jue and Freeland, John W. and Doublet, Marie-Liesse and Cabana, Jordi},
abstractNote = {The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li7RuO6. Coupling structural and spectroscopic analysis with computational simulations, we show that Li7RuO6 is capable of highly reversible lithiation to Li8RuO6 through the Ru(V)/Ru(IV) redox couple. Further, Li7RuO6 can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.},
doi = {10.1021/acs.chemmater.2c00043},
journal = {Chemistry of Materials},
number = 8,
volume = 34,
place = {United States},
year = {Fri Apr 15 00:00:00 EDT 2022},
month = {Fri Apr 15 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013
- Sathiya, M.; Rousse, G.; Ramesha, K.
- Nature Materials, Vol. 12, Issue 9
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Li 7 RuO 6 : As a 4 d Heisenberg Frustrated Magnet
journal, June 2010
- Nakajima, Kanako; Sato, Hirohiko; Fukui, Tomoya
- Journal of the Physical Society of Japan, Vol. 79, Issue 6
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research
journal, June 2020
- Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P.
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 23
Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3
journal, February 2017
- Pearce, Paul E.; Perez, Arnaud J.; Rousse, Gwenaelle
- Nature Materials, Vol. 16, Issue 5
Reversible Anionic Redox Activities in Conventional LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes
journal, March 2020
- Lee, Gi-Hyeok; Wu, Jinpeng; Kim, Duho
- Angewandte Chemie International Edition
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials
journal, April 2018
- Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang
- Nature, Vol. 556, Issue 7700
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016
- Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander
- Nature Chemistry, Vol. 8, Issue 7
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Distinct Oxygen Redox Activities in Li2MO3 (M = Mn, Ru, Ir)
journal, September 2021
- Zhuo, Zengqing; Dai, Kehua; Wu, Jinpeng
- ACS Energy Letters, Vol. 6, Issue 10
Unconventional magnetic order on the hyperhoneycomb Kitaev lattice in : Full solution via magnetic resonant x-ray diffraction
journal, November 2014
- Biffin, A.; Johnson, R. D.; Choi, Sungkyun
- Physical Review B, Vol. 90, Issue 20
Decoupling Cationic–Anionic Redox Processes in a Model Li-Rich Cathode via Operando X-ray Absorption Spectroscopy
journal, November 2017
- Assat, Gaurav; Iadecola, Antonella; Delacourt, Charles
- Chemistry of Materials, Vol. 29, Issue 22
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials
journal, July 2019
- Radin, Maxwell D.; Vinckeviciute, Julija; Seshadri, Ram
- Nature Energy, Vol. 4, Issue 8
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries
journal, January 2017
- Xie, Y.; Saubanère, M.; Doublet, M. -L.
- Energy & Environmental Science, Vol. 10, Issue 1
Elucidating Anionic Redox Chemistry in P3 Layered Cathode for Na-Ion Batteries
journal, August 2020
- Jia, Min; Li, Haifeng; Qiao, Yu
- ACS Applied Materials & Interfaces, Vol. 12, Issue 34
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
The lithium-ion battery: State of the art and future perspectives
journal, June 2018
- Zubi, Ghassan; Dufo-López, Rodolfo; Carvalho, Monica
- Renewable and Sustainable Energy Reviews, Vol. 89
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems
journal, January 2019
- Lebens-Higgins, Zachary W.; Faenza, Nicholas V.; Radin, Maxwell D.
- Materials Horizons, Vol. 6, Issue 10
CoO2, The End Member of the LixCoO2 Solid Solution
journal, January 1996
- Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
- Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123
Origin of voltage decay in high-capacity layered oxide electrodes
journal, December 2014
- Sathiya, M.; Abakumov, A. M.; Foix, D.
- Nature Materials, Vol. 14, Issue 2
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Ligand K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand-Metal Bonding: Charge Donation and Covalency in Copper-Chloride Systems
journal, September 1994
- Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O.
- Inorganic Chemistry, Vol. 33, Issue 19
Competition between Metal Dissolution and Gas Release in Li-Rich Li 3 Ru y Ir 1– y O 4 Model Compounds Showing Anionic Redox
journal, October 2018
- Jacquet, Quentin; Iadecola, Antonella; Saubanère, Matthieu
- Chemistry of Materials, Vol. 30, Issue 21
Electrochemical and In Situ X‐Ray Diffraction Studies of Lithium Intercalation in LixCoO2
journal, January 1992
- Reimers, Jan N.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 139, Issue 8, p. 2091-2097
High-capacity electrode materials for rechargeable lithium batteries: Li 3 NbO 4 -based system with cation-disordered rocksalt structure
journal, June 2015
- Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries
journal, June 2019
- Jacquet, Quentin; Iadecola, Antonella; Saubanère, Matthieu
- Journal of the American Chemical Society, Vol. 141, Issue 29
Interplay between Cation and Anion Redox in Ni-Based Disordered Rocksalt Cathodes
journal, August 2021
- Yue, Yuan; Ha, Yang; Huang, Tzu-Yang
- ACS Nano, Vol. 15, Issue 8
Elucidation of Active Oxygen Sites upon Delithiation of Li 3 IrO 4
journal, December 2020
- Li, Haifeng; Perez, Arnaud J.; Taudul, Beata
- ACS Energy Letters, Vol. 6, Issue 1
Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material
journal, April 2020
- Ramakrishnan, Srinivasan; Park, Byungchun; Wu, Jue
- Journal of the American Chemical Society, Vol. 142, Issue 18
Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 114, Issue 23
Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4
journal, December 2017
- Perez, Arnaud J.; Jacquet, Quentin; Batuk, Dmitry
- Nature Energy, Vol. 2, Issue 12
Bethe-Salpeter equation calculations of core excitation spectra
journal, March 2011
- Vinson, J.; Rehr, J. J.; Kas, J. J.
- Physical Review B, Vol. 83, Issue 11
Efficient implementation of core-excitation Bethe–Salpeter equation calculations
journal, December 2015
- Gilmore, K.; Vinson, John; Shirley, E. L.
- Computer Physics Communications, Vol. 197
A Relativistic Equation for Bound-State Problems
journal, December 1951
- Salpeter, E. E.; Bethe, H. A.
- Physical Review, Vol. 84, Issue 6
Quantifying the Capacity Contributions during Activation of Li 2 MnO 3
journal, January 2020
- Rana, Jatinkumar; Papp, Joseph K.; Lebens-Higgins, Zachary
- ACS Energy Letters, Vol. 5, Issue 2
Efficient pseudopotentials for plane-wave calculations
journal, January 1991
- Troullier, N.; Martins, José Luriaas
- Physical Review B, Vol. 43, Issue 3
Lithium Rich Composition of Li 2 RuO 3 and Li 2 Ru 1-x Ir x O 3 Layered Materials as Li-Ion Battery Cathode
journal, January 2014
- Sarkar, S.; Mahale, P.; Mitra, S.
- Journal of The Electrochemical Society, Vol. 161, Issue 6
First-Principles Investigation of Phase Stability in the O2-LiCoO 2 System
journal, July 2003
- Carlier, D.; Van der Ven, A.; Delmas, C.
- Chemistry of Materials, Vol. 15, Issue 13
Revealing Electronic Signatures of Lattice Oxygen Redox in Lithium Ruthenates and Implications for High-Energy Li-Ion Battery Material Designs
journal, September 2019
- Yu, Yang; Karayaylali, Pinar; Nowak, Stanisław H.
- Chemistry of Materials, Vol. 31, Issue 19
The Li 3 Ru y Nb 1– y O 4 (0 ≤ y ≤ 1) System: Structural Diversity and Li Insertion and Extraction Capabilities
journal, May 2017
- Jacquet, Quentin; Perez, Arnaud; Batuk, Dmitry
- Chemistry of Materials, Vol. 29, Issue 12
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
A reflection on lithium-ion battery cathode chemistry
journal, March 2020
- Manthiram, Arumugam
- Nature Communications, Vol. 11, Issue 1
Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes
journal, December 2019
- House, Robert A.; Maitra, Urmimala; Pérez-Osorio, Miguel A.
- Nature, Vol. 577, Issue 7791
Enumeration as a Tool for Structure Solution: A Materials Genomic Approach to Solving the Cation-Ordered Structure of Na 3 V 2 (PO 4 ) 2 F 3
journal, September 2020
- Mattei, Gerard S.; Dagdelen, John M.; Bianchini, Matteo
- Chemistry of Materials, Vol. 32, Issue 20
The rechargeable revolution: A better battery
journal, March 2014
- Van Noorden, Richard
- Nature, Vol. 507, Issue 7490
Cationic and anionic redox in lithium-ion based batteries
journal, January 2020
- Li, Matthew; Liu, Tongchao; Bi, Xuanxuan
- Chemical Society Reviews, Vol. 49, Issue 6
Oxygen Contribution on Li-Ion Intercalation−Deintercalation in LiCoO 2 Investigated by O K-Edge and Co L-Edge X-ray Absorption Spectroscopy
journal, March 2002
- Yoon, Won-Sub; Kim, Kwang-Bum; Kim, Min-Gyu
- The Journal of Physical Chemistry B, Vol. 106, Issue 10
Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992
- Perdew, John P.; Wang, Yue
- Physical Review B, Vol. 45, Issue 23, p. 13244-13249
Ground State of the Electron Gas by a Stochastic Method
journal, August 1980
- Ceperley, D. M.; Alder, B. J.
- Physical Review Letters, Vol. 45, Issue 7, p. 566-569
Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V
journal, June 2019
- Zhang, Jie-Nan; Li, Qinghao; Ouyang, Chuying
- Nature Energy, Vol. 4, Issue 7
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017
- Gent, William E.; Lim, Kipil; Liang, Yufeng
- Nature Communications, Vol. 8, Issue 1
Definition of Redox Centers in Reactions of Lithium Intercalation in Li 3 RuO 4 Polymorphs
journal, April 2020
- Li, Haifeng; Ramakrishnan, Srinivasan; Freeland, John W.
- Journal of the American Chemical Society, Vol. 142, Issue 18
Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li 2 MnO 3 , studied by soft X-ray absorption spectroscopy
journal, January 2016
- Oishi, Masatsugu; Yamanaka, Keisuke; Watanabe, Iwao
- Journal of Materials Chemistry A, Vol. 4, Issue 23
Synthesis and Electrochemical Activity of Some Na(Li)‐Rich Ruthenium Oxides with the Feasibility to Stabilize Ru 6+
journal, February 2019
- Otoyama, Misae; Jacquet, Quentin; Iadecola, Antonella
- Advanced Energy Materials, Vol. 9, Issue 15
LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density
journal, June 1980
- Mizushima, K.; Jones, P. C.; Wiseman, P. J.
- Materials Research Bulletin, Vol. 15, Issue 6
High Performance Li 2 Ru 1– y Mn y O 3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding
journal, March 2013
- Sathiya, M.; Ramesha, K.; Rousse, G.
- Chemistry of Materials, Vol. 25, Issue 7
Crystal Structures, Dimorphism and Lithium Mobility of Li7MO6 (M = Bi, Ru, Os)
journal, September 2005
- Mühle, Claus; Karpov, Andrey; Verhoeven, Aswin
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 631, Issue 12