Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide

Qiao, Yu; Guo, Shaohua; Zhu, Kai; Liu, Pan; Li, Xiang; Jiang, Kezhu; Sun, Cheng-Jun; Chen, Mingwei; Zhou, Haoshen

doi:10.1039/C7EE03554C

Title: Reversible anionic redox activity in Na₃RuO₄ cathodes: a prototype Na-rich layered oxide

Abstract

Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li₂MnO₃, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na₃RuO₄ (Ru⁵⁺), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.

Authors:

^[1];

^[2];

^[3];

^[4]; Li, Xiang ^[1]; Jiang, Kezhu ^[2]; Sun, Cheng-Jun ^[5];

^[4];

^[6]

National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering
Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures
National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.
Shanghai Jiao Tong Univ. (China). State Key Lab. of Metal Matrix Composites. School of Material Science and Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Nanjing Univ. (China). Center of Energy Storage Materials & Technology. College of Engineering and Applied Sciences. National Lab. of Solid State Microstructures. Collaborative Innovation Center of Advanced Microstructures; National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Energy Technology Research Inst.; Univ. of Tsukuba (Japan). Graduate School of System and Information Engineering

Publication Date:: Fri Jan 26 00:00:00 EST 2018

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States); National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Nanjing Univ. (China); Shanghai Jiao Tong Univ. (China)

Sponsoring Org.:: USDOE Office of Science (SC); Japan Science and Technology Agency (JST); National Basic Research Program of China; National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jiangsu Province (China); China Scholarship Council (CSC)

OSTI Identifier:: 1471523

Grant/Contract Number:: AC02-06CH11357; 2014CB932300; 21373111; 21633003; 51602144; BK20170630

Resource Type:: Accepted Manuscript

Journal Name:: Energy & Environmental Science

Additional Journal Information:: Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1754-5692

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE

Citation Formats


                    Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide.  United States: N. p., 2018. 
Web.  doi:10.1039/C7EE03554C.

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                    Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, & Zhou, Haoshen. Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide.  United States.  https://doi.org/10.1039/C7EE03554C

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                    Qiao, Yu, Guo, Shaohua, Zhu, Kai, Liu, Pan, Li, Xiang, Jiang, Kezhu, Sun, Cheng-Jun, Chen, Mingwei, and Zhou, Haoshen. Fri .  
"Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide".  United States.  https://doi.org/10.1039/C7EE03554C.  https://www.osti.gov/servlets/purl/1471523.

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@article{osti_1471523,

  title        = {Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide},

  author       = {Qiao, Yu and Guo, Shaohua and Zhu, Kai and Liu, Pan and Li, Xiang and Jiang, Kezhu and Sun, Cheng-Jun and Chen, Mingwei and Zhou, Haoshen},

  abstractNote = {Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. In this paper, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Finally, our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.},

  doi          = {10.1039/C7EE03554C},

  journal      = {Energy & Environmental Science},

  number       = 2,

  volume       = 11,

  place        = {United States},

  year         = {Fri Jan 26 00:00:00 EST 2018},

  month        = {Fri Jan 26 00:00:00 EST 2018}

}

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Figure 1: Structure of as-prepared Na₃RuO₄ layered Na-rich oxide: (a) XRD patterns with SEM image inset; (b) Schematic of crystal structure; (c) Scanning area electron diffraction (SAED) patterns; (d) High-angle annular dark field (HAADF) STEM images. The corresponding crystal structure is inset for clarity.

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Title: Reversible anionic redox activity in Na3RuO4 cathodes: a prototype Na-rich layered oxide

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Citation Formats

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Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal, July 2013

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A 3.8-V earth-abundant sodium battery electrode journal, July 2014

Reactions in the Rechargeable Lithium–O 2 Battery with Alkyl Carbonate Electrolytes journal, May 2011

Isolated spin 3/2 plaquettes in Na3RuO4 journal, June 2005

Anionic redox processes for electrochemical devices journal, January 2016

X-ray Photoemission Spectroscopy Study of Cationic and Anionic Redox Processes in High-Capacity Li-Ion Battery Layered-Oxide Electrodes journal, January 2016

Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2 journal, February 2015

Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 journal, August 2016

Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization journal, September 2016

The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries journal, January 2016

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries journal, May 2014

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries journal, January 2016

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2 journal, March 2011

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode journal, January 2018

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode journal, April 2016

Shell-isolated nanoparticle-enhanced Raman spectroscopy journal, March 2010

A New High-Energy Cathode for a Na-Ion Battery with Ultrahigh Stability journal, September 2013

Layered Na2RuO3 as a cathode material for Na-ion batteries journal, August 2013

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes journal, November 2015

Direct In situ Observation of Li 2 O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤0.5) journal, January 2014

Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries journal, April 2015

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries journal, December 2016

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

Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li 2 MnO 3 ·(1 − x )LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 ≤ x ≤ 0.7) journal, October 2008

Exploring reversible oxidation of oxygen in a manganese oxide journal, January 2016

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

Research Development on Sodium-Ion Batteries journal, October 2014

Exposing {010} Active Facets by Multiple-Layer Oriented Stacking Nanosheets for High-Performance Capacitive Sodium-Ion Oxide Cathode journal, August 2018

Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries journal, May 2019

A New Type of Li‐Rich Rock‐Salt Oxide Li 2 Ni 1/3 Ru 2/3 O 3 with Reversible Anionic Redox Chemistry journal, January 2019

Synthesis and characterization of Ru doped NaNi0.5Mn0.3Ti0.2O2 cathode material with improved electrochemical performance for sodium-ion batteries journal, January 2019

Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S journal, October 2019

Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials journal, July 2019

Na 2 Ru 1−x Mn x O 3 as the cathode for sodium-ion batteries journal, January 2019

Correlation between Ru–O hybridization and the oxygen evolution reaction in ruthenate epitaxial thin films journal, January 2019

Simultaneously tuning cationic and anionic redox in a P2-Na 0.67 Mn 0.75 Ni 0.25 O 2 cathode material through synergic Cu/Mg co-doping journal, January 2019

Na 2 SeO 3 : A Na-Ion Battery Positive Electrode Material with High Capacity journal, November 2018

Understanding Oxygen Redox in Cu-Doped P2-Na 0.67 Mn 0.8 Fe 0.1 Co 0.1 O 2 Cathode Materials for Na-Ion Batteries journal, January 2018

Air-Stable NaxTMO2 Cathodes for Sodium Storage journal, May 2019

Title: Reversible anionic redox activity in Na₃RuO₄ cathodes: a prototype Na-rich layered oxide

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes
journal, July 2013

Study of the nanosized Li2MnO3: Electrochemical behavior, structure, magnetic properties, and vibrational modes
journal, May 2013

Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3
journal, February 2017

Anionic Redox in Rechargeable Lithium Batteries
journal, June 2017

Understanding and Controlling Anionic Electrochemical Activity in High-Capacity Oxides for Next Generation Li-Ion Batteries
journal, January 2017

Redox Potential Paradox in Na _x MO ₂ for Sodium-Ion Battery Cathodes
journal, February 2016

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges
journal, January 2015

Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂
journal, June 2006

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries
journal, March 2010

The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials
journal, May 2016

Lattice vibrations of materials for lithium rechargeable batteries III. Lithium manganese oxides
journal, June 2003

Improving Energy Density and Structural Stability of Manganese Oxide Cathodes for Na-Ion Batteries by Structural Lithium Substitution
journal, December 2016

Mechanistic Insight into the Superoxide Induced Ring Opening in Propylene Carbonate Based Electrolytes using in Situ Surface-Enhanced Infrared Spectroscopy
journal, March 2016

A 3.8-V earth-abundant sodium battery electrode
journal, July 2014

Reactions in the Rechargeable Lithium–O ₂ Battery with Alkyl Carbonate Electrolytes
journal, May 2011

Isolated spin 3/2 plaquettes in Na3RuO4
journal, June 2005

Anionic redox processes for electrochemical devices
journal, January 2016

X-ray Photoemission Spectroscopy Study of Cationic and Anionic Redox Processes in High-Capacity Li-Ion Battery Layered-Oxide Electrodes
journal, January 2016

Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2
journal, February 2015

Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li _0.2 Ni _0.2 Mn _0.6 ]O ₂
journal, August 2016

Lithium Extraction Mechanism in Li-Rich Li ₂ MnO ₃ Involving Oxygen Hole Formation and Dimerization
journal, September 2016

The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
journal, May 2014

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries
journal, January 2016

Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li ₂ MnO ₃ −LiCo _1/3 Ni _1/3 Mn _1/3 O ₂
journal, March 2011

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode
journal, January 2018

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode
journal, April 2016

Shell-isolated nanoparticle-enhanced Raman spectroscopy
journal, March 2010

A New High-Energy Cathode for a Na-Ion Battery with Ultrahigh Stability
journal, September 2013

Layered Na2RuO3 as a cathode material for Na-ion batteries
journal, August 2013

Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi _0.5 Mn _1.5 O ₄ Electrodes
journal, November 2015

Direct In situ Observation of Li ₂ O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni _x Li _{(1–2 x )/3} Mn _{(2– x )/3} ]O ₂ (0 ≤ x ≤0.5)
journal, January 2014

Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries
journal, April 2015

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries
journal, December 2016

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

Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li ₂ MnO ₃ ·(1 − x )LiMn _0.333 Ni _0.333 Co _0.333 O ₂ (0 ≤ x ≤ 0.7)
journal, October 2008

Exploring reversible oxidation of oxygen in a manganese oxide
journal, January 2016

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

Research Development on Sodium-Ion Batteries
journal, October 2014

Exposing {010} Active Facets by Multiple-Layer Oriented Stacking Nanosheets for High-Performance Capacitive Sodium-Ion Oxide Cathode
journal, August 2018

Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries
journal, May 2019

A New Type of Li‐Rich Rock‐Salt Oxide Li 2 Ni 1/3 Ru 2/3 O 3 with Reversible Anionic Redox Chemistry
journal, January 2019

Synthesis and characterization of Ru doped NaNi0.5Mn0.3Ti0.2O2 cathode material with improved electrochemical performance for sodium-ion batteries
journal, January 2019

Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S
journal, October 2019

Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials
journal, July 2019

Na ₂ Ru _1−x Mn _x O ₃ as the cathode for sodium-ion batteries
journal, January 2019

Correlation between Ru–O hybridization and the oxygen evolution reaction in ruthenate epitaxial thin films
journal, January 2019

Simultaneously tuning cationic and anionic redox in a P2-Na _0.67 Mn _0.75 Ni _0.25 O ₂ cathode material through synergic Cu/Mg co-doping
journal, January 2019

Na ₂ SeO ₃ : A Na-Ion Battery Positive Electrode Material with High Capacity
journal, November 2018

Understanding Oxygen Redox in Cu-Doped P2-Na _0.67 Mn _0.8 Fe _0.1 Co _0.1 O ₂ Cathode Materials for Na-Ion Batteries
journal, January 2018

Air-Stable NaxTMO2 Cathodes for Sodium Storage
journal, May 2019