The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X-Ray Spectroscopy and Theory

Abate, Iwnetim; Kim, Se Young; Pemmaraju, C. Das; Toney, Michael F.; Yang, Wanli; Devereaux, Thomas P.; Chueh, William C.; Nazar, Linda F.

doi:10.1002/anie.202012205

The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X-Ray Spectroscopy and Theory

Journal Article · Tue Mar 30 00:00:00 EDT 2021 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202012205· OSTI ID:1781060

Abate, Iwnetim ^[1]; Kim, Se Young ^[2]; Pemmaraju, C. Das ^[3]; Toney, Michael F. ^[4]; Yang, Wanli ^[5]; Devereaux, Thomas P. ^[1]; Chueh, William C. ^[1]; ^[2]

Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Waterloo, ON (Canada)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Stanford Univ., CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

We investigate high-valent oxygen redox in the positive Na-ion electrode P2-Na_0.67-x[Fe_0.5Mn_0.5]O₂ (NMF) where Fe is partially substituted with Cu (P2-Na_0.67-x[Mn_0.66Fe_0.20Cu_0.14]O₂, NMFC) or Ni (P2-Na_0.67-x[Mn_0.65Fe_0.20Ni_0.15]O₂, NMFN). From combined analysis of resonant inelastic X-ray scattering and X-ray near-edge structure with electrochemical voltage hysteresis and X-ray pair distribution function profiles, we correlate structural disorder with high-valent oxygen redox and its improvement by Ni or Cu substitution. Density of states calculations elaborate considerable anionic redox in NMF and NMFC without the widely accepted requirement of an A-O-A' local configuration in the pristine materials (where A=Na and A'=Li, Mg, vacancy, etc.). We also show that the Jahn–Teller nature of Fe⁴⁺ and the stabilization mechanism of anionic redox could determine the extent of structural disorder in the materials. These findings shed light on the design principles in TM and anion redox for positive electrodes to improve the performance of Na-ion batteries.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; AC02-05CH11231; AC02-05CH11231

OSTI ID:: 1781060

Alternate ID(s):: OSTI ID: 1786120

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 19 Vol. 60; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials Chen, Xi; Hwang, Sooyeon; Chisnell, Robin Advanced Functional Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adfm.201803896	journal	July 2018
High-Performance P2-Type Na _2/3 (Mn _1/2 Fe _1/4 Co _1/4 )O ₂ Cathode Material with Superior Rate Capability for Na-Ion Batteries Liu, Lei; Li, Xin; Bo, Shou-Hang Advanced Energy Materials, Vol. 5, Issue 22 https://doi.org/10.1002/aenm.201500944	journal	September 2015
Computational Design and Preparation of Cation-Disordered Oxides for High-Energy-Density Li-Ion Batteries Urban, Alexander; Matts, Ian; Abdellahi, Aziz Advanced Energy Materials, Vol. 6, Issue 15 https://doi.org/10.1002/aenm.201600488	journal	May 2016
Highly Reversible Oxygen-Redox Chemistry at 4.1 V in Na _4/7− _x [□ _1/7 Mn _6/7 ]O ₂ (□: Mn Vacancy) Mortemard de Boisse, Benoit; Nishimura, Shin-ichi; Watanabe, Eriko Advanced Energy Materials, Vol. 8, Issue 20 https://doi.org/10.1002/aenm.201800409	journal	April 2018
Anionic Redox Activity in a Newly Zn-Doped Sodium Layered Oxide P2-Na _2/3 Mn ₁₋ _y Zn _y O ₂ (0 < y < 0.23) Bai, Xue; Sathiya, Mariyappan; Mendoza-Sánchez, Beatriz Advanced Energy Materials, Vol. 8, Issue 32 https://doi.org/10.1002/aenm.201802379	journal	October 2018
Anionic Redox Activity Regulated by Transition Metal in Lithium‐Rich Layered Oxides Song, Jun‐Hyuk; Yoon, Gabin; Kim, Byunghoon Advanced Energy Materials https://doi.org/10.1002/aenm.202001207	journal	June 2020
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage Kundu, Dipan; Talaie, Elahe; Duffort, Victor Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410376	journal	February 2015
Layered P2-Na _0.66 Fe _0.5 Mn _0.5 O ₂ Cathode Material for Rechargeable Sodium-Ion Batteries Xu, Jiantie; Chou, Shu-Lei; Wang, Jian-Li ChemElectroChem, Vol. 1, Issue 2 https://doi.org/10.1002/celc.201300026	journal	August 2013
Sodium deintercalation from sodium iron oxide Takeda, Yasuo; Nakahara, Kazuaki; Nishijima, Motoaki Materials Research Bulletin, Vol. 29, Issue 6 https://doi.org/10.1016/0025-5408(94)90122-8	journal	June 1994
Layered Na[Ni1/3Fe1/3Mn1/3]O2 cathodes for Na-ion battery application Kim, Donghan; Lee, Eungje; Slater, Michael Electrochemistry Communications, Vol. 18 https://doi.org/10.1016/j.elecom.2012.02.020	journal	January 2012
NaFe0.5Co0.5O2 as high energy and power positive electrode for Na-ion batteries Yoshida, Hiroaki; Yabuuchi, Naoaki; Komaba, Shinichi Electrochemistry Communications, Vol. 34 https://doi.org/10.1016/j.elecom.2013.05.012	journal	September 2013
P2-type Na0.67Mn0.65Fe0.2Ni0.15O2 Cathode Material with High-capacity for Sodium-ion Battery Yuan, Dingding; Hu, Xiaohong; Qian, Jiangfeng Electrochimica Acta, Vol. 116 https://doi.org/10.1016/j.electacta.2013.10.211	journal	January 2014
Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode Rong, Xiaohui; Liu, Jue; Hu, Enyuan Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.10.008	journal	January 2018
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions Dai, Kehua; Wu, Jinpeng; Zhuo, Zengqing Joule, Vol. 3, Issue 2 https://doi.org/10.1016/j.joule.2018.11.014	journal	February 2019
Design Rules for High-Valent Redox in Intercalation Electrodes Gent, William E.; Abate, Iwnetim Iwnetu; Yang, Wanli Joule, Vol. 4, Issue 7 https://doi.org/10.1016/j.joule.2020.05.004	journal	July 2020
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering Yang, Wanli; Devereaux, Thomas P. Journal of Power Sources, Vol. 389 https://doi.org/10.1016/j.jpowsour.2018.04.018	journal	June 2018
Stabilizing the oxygen lattice and reversible oxygen redox in Na-deficient cathode oxides Zheng, Wei; Liu, Qiong; Wang, Zhenyu Journal of Power Sources, Vol. 439 https://doi.org/10.1016/j.jpowsour.2019.227086	journal	November 2019
Harbinger of hysteresis in lithium-rich oxides: Anionic activity or defect chemistry of cation migration Croy, Jason R.; Garcia, Juan C.; Iddir, Hakim Journal of Power Sources, Vol. 471 https://doi.org/10.1016/j.jpowsour.2020.228335	journal	September 2020
Iron migration and oxygen oxidation during sodium extraction from NaFeO2 Li, Yejing; Gao, Yurui; Wang, Xuefeng Nano Energy, Vol. 47 https://doi.org/10.1016/j.nanoen.2018.03.007	journal	May 2018
Uptake of CO ₂ in Layered P2-Na _0.67 Mn _0.5 Fe _0.5 O ₂ : Insertion of Carbonate Anions Duffort, Victor; Talaie, Elahe; Black, Robert Chemistry of Materials, Vol. 27, Issue 7 https://doi.org/10.1021/acs.chemmater.5b00097	journal	March 2015
High-Performance P2-Phase Na _2/3 Mn _0.8 Fe _0.1 Ti _0.1 O ₂ Cathode Material for Ambient-Temperature Sodium-Ion Batteries Han, Man Huon; Gonzalo, Elena; Sharma, Neeraj Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03276	journal	December 2015
Lithium Extraction Mechanism in Li-Rich Li ₂ MnO ₃ Involving Oxygen Hole Formation and Dimerization Chen, Hungru; Islam, M. Saiful Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b02870	journal	September 2016
Structural Evolution and Redox Processes Involved in the Electrochemical Cycling of P2–Na _0.67 [Mn _0.66 Fe _0.20 Cu _0.14 ]O ₂ Talaie, Elahe; Kim, Se Young; Chen, Ning Chemistry of Materials, Vol. 29, Issue 16 https://doi.org/10.1021/acs.chemmater.7b01146	journal	July 2017
Anionic Redox Activity as a Key Factor in the Performance Degradation of NaFeO ₂ Cathodes for Sodium Ion Batteries Susanto, Dieky; Cho, Min Kyung; Ali, Ghulam Chemistry of Materials, Vol. 31, Issue 10 https://doi.org/10.1021/acs.chemmater.9b00149	journal	May 2019
Full Energy Range Resonant Inelastic X-ray Scattering of O ₂ and CO ₂ : Direct Comparison with Oxygen Redox State in Batteries Zhuo, Zengqing; Liu, Yi-sheng; Guo, Jinghua The Journal of Physical Chemistry Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jpclett.0c00423	journal	March 2020
Spectroscopic Signature of Oxidized Oxygen States in Peroxides Zhuo, Zengqing; Pemmaraju, Chaitanya Das; Vinson, John The Journal of Physical Chemistry Letters, Vol. 9, Issue 21 https://doi.org/10.1021/acs.jpclett.8b02757	journal	October 2018
Electrospun P2-type Na _2/3 (Fe _1/2 Mn _1/2 )O ₂ Hierarchical Nanofibers as Cathode Material for Sodium-Ion Batteries Kalluri, Sujith; Seng, Kuok Hau; Pang, Wei Kong ACS Applied Materials & Interfaces, Vol. 6, Issue 12 https://doi.org/10.1021/am502343s	journal	June 2014
P2-Na _x Mn _1/2 Fe _1/2 O ₂ Phase Used as Positive Electrode in Na Batteries: Structural Changes Induced by the Electrochemical (De)intercalation Process Mortemard de Boisse, Benoit; Carlier, Dany; Guignard, Marie Inorganic Chemistry, Vol. 53, Issue 20 https://doi.org/10.1021/ic5017802	journal	September 2014
Re-entrant Lithium Local Environments and Defect Driven Electrochemistry of Li- and Mn-Rich Li-Ion Battery Cathodes Dogan, Fulya; Long, Brandon R.; Croy, Jason R. Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/ja511299y	journal	February 2015
Exploring Oxygen Activity in the High Energy P2-Type Na _0.78 Ni _0.23 Mn _0.69 O ₂ Cathode Material for Na-Ion Batteries Ma, Chuze; Alvarado, Judith; Xu, Jing Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b00164	journal	March 2017
Unraveling Oxygen Evolution in Li-Rich Oxides: A Unified Modeling of the Intermediate Peroxo/Superoxo-like Dimers Chen, Zhenlian; Li, Jun; Zeng, Xiao Cheng Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b03710	journal	June 2019
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Role of Ligand-to-Metal Charge Transfer in O3-Type NaFeO ₂ –NaNiO ₂ Solid Solution for Enhanced Electrochemical Properties Wang, Xianfen; Liu, Guandong; Iwao, Tatsumi The Journal of Physical Chemistry C, Vol. 118, Issue 6 https://doi.org/10.1021/jp411382r	journal	January 2014
A cost and resource analysis of sodium-ion batteries Vaalma, Christoph; Buchholz, Daniel; Weil, Marcel Nature Reviews Materials, Vol. 3, Issue 4 https://doi.org/10.1038/natrevmats.2018.13	journal	March 2018
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials Seo, Dong-Hwa; Lee, Jinhyuk; Urban, Alexander Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2524	journal	May 2016
Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2 Maitra, Urmimala; House, Robert A.; Somerville, James W. Nature Chemistry, Vol. 10, Issue 3 https://doi.org/10.1038/nchem.2923	journal	January 2018
Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11397	journal	April 2016
P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi Nature Materials, Vol. 11, Issue 6 https://doi.org/10.1038/nmat3309	journal	April 2012
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides Gent, William E.; Lim, Kipil; Liang, Yufeng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02041-x	journal	December 2017
Elucidating anionic oxygen activity in lithium-rich layered oxides Xu, Jing; Sun, Meiling; Qiao, Ruimin Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03403-9	journal	March 2018
Coulombic self-ordering upon charging a large-capacity layered cathode material for rechargeable batteries Mortemard de Boisse, Benoit; Reynaud, Marine; Ma, Jiangtao Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09409-1	journal	May 2019
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries Assat, Gaurav; Tarascon, Jean-Marie Nature Energy, Vol. 3, Issue 5 https://doi.org/10.1038/s41560-018-0097-0	journal	April 2018
Probing the thermal effects of voltage hysteresis in anionic redox-based lithium-rich cathodes using isothermal calorimetry Assat, Gaurav; Glazier, Stephen L.; Delacourt, Charles Nature Energy, Vol. 4, Issue 8 https://doi.org/10.1038/s41560-019-0410-6	journal	July 2019
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides Hong, Jihyun; Gent, William E.; Xiao, Penghao Nature Materials, Vol. 18, Issue 3 https://doi.org/10.1038/s41563-018-0276-1	journal	February 2019
Unified picture of anionic redox in Li/Na-ion batteries Ben Yahia, Mouna; Vergnet, Jean; Saubanère, Matthieu Nature Materials, Vol. 18, Issue 5 https://doi.org/10.1038/s41563-019-0318-3	journal	March 2019
Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes House, Robert A.; Maitra, Urmimala; Pérez-Osorio, Miguel A. Nature, Vol. 577, Issue 7791 https://doi.org/10.1038/s41586-019-1854-3	journal	December 2019
Synthesis and characterization of pure P2- and O3-Na _2/3 Fe _2/3 Mn _1/3 O ₂ as cathode materials for Na ion batteries Gonzalo, E.; Han, M. H.; López del Amo, J. M. J. Mater. Chem. A, Vol. 2, Issue 43 https://doi.org/10.1039/C4TA03991B	journal	January 2014
Structure of the high voltage phase of layered P2-Na _2/3−z [Mn _1/2 Fe _1/2 ]O ₂ and the positive effect of Ni substitution on its stability Talaie, Elahe; Duffort, Victor; Smith, Hillary L. Energy & Environmental Science, Vol. 8, Issue 8 https://doi.org/10.1039/C5EE01365H	journal	January 2015
Exploring reversible oxidation of oxygen in a manganese oxide Du, Ke; Zhu, Jinyou; Hu, Guorong Energy & Environmental Science, Vol. 9, Issue 8 https://doi.org/10.1039/C6EE01367H	journal	January 2016
Identification and characterisation of high energy density P2-type Na _2/3 [Ni _1/3−y/2 Mn _2/3−y/2 Fe _y ]O ₂ compounds for Na-ion batteries Somerville, J. W.; House, R. A.; Tapia-Ruiz, N. Journal of Materials Chemistry A, Vol. 6, Issue 13 https://doi.org/10.1039/C7TA09607K	journal	January 2018
A comparison of destabilization mechanisms of the layered NaxMO2 and LixMO2 compounds upon alkali de-intercalation Kim, Sangtae; Ma, Xiaohua; Ong, Shyue Ping Physical Chemistry Chemical Physics, Vol. 14, Issue 44 https://doi.org/10.1039/c2cp43377j	journal	January 2012
Oxygen and transition metal involvement in the charge compensation mechanism of LiNi1/3Mn1/3Co1/3O2 cathodes Petersburg, Cole F.; Li, Zheng; Chernova, Natasha A. Journal of Materials Chemistry, Vol. 22, Issue 37 https://doi.org/10.1039/c2jm33392a	journal	January 2012
Novel copper redox-based cathode materials for room-temperature sodium-ion batteries Xu, Shu-Yin; Wu, Xiao-Yan; Li, Yun-Ming Chinese Physics B, Vol. 23, Issue 11 https://doi.org/10.1088/1674-1056/23/11/118202	journal	November 2014
Electrochemical Properties of NaCuO2 for Sodium-Ion Secondary Batteries Ono, Y.; Yui, Y.; Hayashi, M. ECS Transactions, Vol. 58, Issue 12 https://doi.org/10.1149/05812.0033ecst	journal	February 2014
The Interaction between Cu and Fe in P2-Type Na _x TMO ₂ Cathodes for Advanced Battery Performance Zhang, Yangning; Kim, Sooran; Feng, Guangyuang Journal of The Electrochemical Society, Vol. 165, Issue 7 https://doi.org/10.1149/2.0171807jes	journal	January 2018
Structural and Electrochemical Characterizations of P2 and New O3-Na _x Mn _1-y Fe _y O ₂ Phases Prepared by Auto-Combustion Synthesis for Na-Ion Batteries Mortemard de Boisse, B.; Carlier, D.; Guignard, M. Journal of The Electrochemical Society, Vol. 160, Issue 4 https://doi.org/10.1149/2.032304jes	journal	January 2013
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering Wu, Jinpeng; Li, Qinghao; Sallis, Shawn Condensed Matter, Vol. 4, Issue 1 https://doi.org/10.3390/condmat4010005	journal	January 2019

Similar Records

The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X‐Ray Spectroscopy and Theory

Journal Article · Tue Mar 30 00:00:00 EDT 2021 · Angewandte Chemie · OSTI ID:1780181

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anion redox
ligand metal charge transfer
nonbonding O 2p state
sodium ion batteries
structure-redox coupling

The Role of Metal Substitution in Tuning Anion Redox in Sodium Metal Layered Oxides Revealed by X-Ray Spectroscopy and Theory

Citation Formats

References (57)

Similar Records

Related Subjects