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Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides

Journal Article · · Nature Materials
 [1];  [2];  [3];  [1];  [4];  [5];  [6];  [7];  [7];  [8];  [7];  [7];  [9];  [10];  [11];  [12];  [13]
  1. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource. Stanford Inst. for Materials & Energy Sciences. Applied Energy Division
  2. Stanford Univ., CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Advanced Light Source
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  4. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials & Energy Sciences; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Advanced Light Source
  6. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  8. Argonne National Lab. (ANL), Argonne, IL (United States). The Advanced Photon Source
  9. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Advanced Light Source
  10. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
  11. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  12. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource. Applied Energy Division
  13. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials & Energy Sciences. Applied Energy Division
+ Show Author Affiliations

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal here that this structure–redox coupling arises from the local stabilization of short approximately 1.8 Å metal–oxygen π bonds and approximately 1.4 Å O–O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF) (United States)
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231; AC02-06CH11357; SC0012583
OSTI ID:
1494840
Alternate ID(s):
OSTI ID: 1503542
OSTI ID: 1594911
Journal Information:
Nature Materials, Journal Name: Nature Materials Vol. 18; ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (15)

Cation insertion to break the activity/stability relationship for highly active oxygen evolution reaction catalyst journal March 2020
Tuning Oxygen Redox Chemistry in Li‐Rich Mn‐Based Layered Oxide Cathodes by Modulating Cation Arrangement journal September 2019
Insight of a Phase Compatible Surface Coating for Long‐Durable Li‐Rich Layered Oxide Cathode journal July 2019
Fundamental Insights from a Single‐Crystal Sodium Iridate Battery journal March 2020
Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries journal April 2019
Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy journal November 2019
Reversible Oxygen Redox Chemistry in Aqueous Zinc‐Ion Batteries journal May 2019
Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy journal November 2019
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials journal July 2019
Ultrahigh power and energy density in partially ordered lithium-ion cathode materials journal March 2020
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes journal January 2020
A paradigm of storage batteries journal January 2019
Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes journal January 2020
Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes journal January 2019
Charge-transfer descriptor for the cycle performance of β-Li 2 MO 3 cathodes: role of oxygen dimers journal January 2020

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