Highly Reversible Local Structural Transformation Enabled by Native Vacancies in O2-Type Li-Rich Layered Oxides with Anion Redox Activity.

A novel O2-phase Li1.033Ni0.2[□0.1Mn0.5]O2 cathode with native vacancies (denoted as "□") was delicately designed. By a combination of noninvasive 7Li pj-MATPASS NMR and electron paramagnetic resonance measurements, it is unequivocally shown that the reservation of native vacancies enables the fully reversible local structural transformation without the formation of Li in the Li layer (Litet) in Li1.033Ni0.2[□0.1Mn0.5]O2 during the initial and subsequent cycling. In addition, the pernicious in-plane Mn migration that would result in the generation of trapped molecular O2 is effectively mitigated in Li1.033Ni0.2[□0.1Mn0.5]O2. As a result, the cycle stability of Li1.033Ni0.2[□0.1Mn0.5]O2 is significantly enhanced compared to that of the vacancy-free Li1.033Ni0.2Mn0.6O2, showing an extraordinary capacity retention of 102.31% after 50 cycles at a rate of 0.1C (1C = 100 mA g-1). This study defines an efficacious strategy for upgrading the structural stability of O2-type Li-rich layered oxide cathodes with reversible high-voltage anion redox activity.

[1]  Yue Xu,et al.  Modulation of Redox Chemistry of Na2Mn3O7 by Selective Boron Doping Prompted by Na Vacancies. , 2022, ACS applied materials & interfaces.

[2]  K. Stevenson,et al.  Cycling-Driven Electrochemical Activation of Li-Rich NMC Positive Electrodes for Li-Ion Batteries , 2022, ACS Applied Energy Materials.

[3]  Haoshen Zhou,et al.  Reversible anionic redox chemistry in layered Li4/7[□1/7Mn6/7]O2 enabled by stable Li–O-vacancy configuration , 2022, Joule.

[4]  W. Tong,et al.  Coincident formation of trapped molecular O2 in oxygen-redox-active archetypical Li 3d oxide cathodes unveiled by EPR spectroscopy , 2022, Energy Storage Materials.

[5]  P. Arjunan,et al.  Cobalt substituted layered O3 and P2-type Na-Ti-Ni-Co-O anode materials for emerging sodium-ion batteries , 2021 .

[6]  Bei Hu,et al.  What Triggers the Voltage Hysteresis Variation beyond the First Cycle in Li-Rich 3d Layered Oxides with Reversible Cation Migration? , 2021, The journal of physical chemistry letters.

[7]  Zhian Zhang,et al.  Enhanced Activity and Reversibility of Anionic Redox by Tuning Lithium Vacancies in Li-Rich Cathode Materials. , 2021, ACS applied materials & interfaces.

[8]  Chao Li,et al.  Anionic redox reaction in Na-deficient layered oxide cathodes: Role of Sn/Zr substituents and in-depth local structural transformation revealed by solid-state NMR , 2021 .

[9]  C. Li,et al.  Restraining Oxygen Loss and Boosting Reversible Oxygen Redox in a P2-Type Oxide Cathode by Trace Anion Substitution. , 2020, ACS applied materials & interfaces.

[10]  Qingshui Xie,et al.  Recent developments and challenges of Li-rich Mn-based cathode materials for high-energy lithium-ion batteries , 2020 .

[11]  D. Xia,et al.  O2-Type Li0.78[Li0.24Mn0.76]O2 Nanowires for High-Performance Lithium-Ion Battery Cathode. , 2020, Nano letters.

[12]  T. Abe,et al.  Sequential delithiation behavior and structural rearrangement of a nanoscale composite-structured Li1.2Ni0.2Mn0.6O2 during charge–discharge cycles , 2020, Scientific Reports.

[13]  Duho Kim,et al.  Uncovering the Structural Evolution in Na-Excess Layered Cathodes for Rational Use of an Anionic Redox Reaction. , 2020, ACS applied materials & interfaces.

[14]  Sung Kwan Park,et al.  Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes , 2020, Nature Materials.

[15]  L. Gu,et al.  Tuning Oxygen Redox Chemistry in Li‐Rich Mn‐Based Layered Oxide Cathodes by Modulating Cation Arrangement , 2019, Advanced materials.

[16]  Xiqian Yu,et al.  Surface-to-bulk redox coupling through thermally-driven Li redistribution in Li- and Mn-rich layered cathode materials. , 2019, Journal of the American Chemical Society.

[17]  K. Amine,et al.  Injection of oxygen vacancies in the bulk lattice of layered cathodes , 2019, Nature Nanotechnology.

[18]  Jun Lu,et al.  Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness , 2018, Advanced Energy Materials.

[19]  A. Yamada,et al.  Cobalt-Free O2-Type Lithium-Rich Layered Oxides , 2018 .

[20]  Xuanxuan Bi,et al.  Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release , 2018, Nature Energy.

[21]  A. Yamada,et al.  Highly Reversible Oxygen‐Redox Chemistry at 4.1 V in Na4/7−x[□1/7Mn6/7]O2 (□: Mn Vacancy) , 2018 .

[22]  K. Kang,et al.  Suppression of Voltage Decay through Manganese Deactivation and Nickel Redox Buffering in High‐Energy Layered Lithium‐Rich Electrodes , 2018 .

[23]  Jean-Marie Tarascon,et al.  Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries , 2018 .

[24]  J. Tarascon,et al.  Synthesis of Li-Rich NMC: A Comprehensive Study , 2017 .

[25]  J. Colin,et al.  A comparative study of aqueous and organic processed Li1.2Ni0.2Mn0.6O2 Li-rich cathode materials for advanced lithium-ion batteries , 2017 .

[26]  J. Colin,et al.  Li-Rich Mn/Ni Layered Oxide as Electrode Material for Lithium Batteries: A 7Li MAS NMR Study Revealing Segregation into (Nanoscale) Domains with Highly Different Electrochemical Behaviors , 2016 .

[27]  Christopher S. Johnson,et al.  Solid State NMR Studies of Li2MnO3 and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade , 2015 .

[28]  J. Tarascon,et al.  Towards greener and more sustainable batteries for electrical energy storage. , 2015, Nature chemistry.

[29]  C. Grey,et al.  Isotropic high field NMR spectra of Li-ion battery materials with anisotropy >1 MHz. , 2012, Journal of the American Chemical Society.

[30]  Christopher S. Johnson,et al.  Structural and Electrochemical Characterization of Composite Layered-Spinel Electrodes Containing Ni and Mn for Li-Ion Batteries , 2009 .

[31]  M. Armand,et al.  Building better batteries , 2008, Nature.

[32]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[33]  L. Wackett,et al.  Manganese(II)-dependent extradiol-cleaving catechol dioxygenase from Arthrobacter globiformis CM-2. , 1996, Biochemistry.

[34]  P. Hagenmuller,et al.  A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction , 1982 .