Enhanced Activity and Reversibility of Anionic Redox by Tuning Lithium Vacancies in Li-Rich Cathode Materials.

Li-rich Mn-based layered oxide cathodes (LLOs) are considered to be the most promising cathode candidates for lithium-ion batteries owing to their high-voltage platform and ultrahigh specific capacity originating from anionic redox. However, anionic redox results in many problems including irreversible oxygen release, voltage hysteresis, and so on. Although many efforts have been made to regulate anionic redox, a fundamental issue, the effect of lithium vacancies on anionic redox, is still unclear. Herein, we synthesized a series of LLO materials with different lithium vacancy contents by controlling the amount of lithium salt. Specifically, lithium-vacancy-type LLOs Li1.11Ni0.18Co0.18Mn0.53O2 with a pompon morphology exhibit an ultrahigh specific capacity (293.9 mA h g-1 at 0.1 C), an outstanding long-term cycling stability (173.5 mA h g-1 after 300 cycles at 1 C), and an excellent rate performance (106 mA h g-1 at 10 C). It reveals that lithium vacancy is a key factor to enhance anionic redox activity and reversibility. Lithium vacancies exhibit different inductive effects on the structure of the surface and bulk. Abundant surface oxygen vacancies and a surface spinel phase layer induced by lithium vacancies suppress irreversible oxygen release, while the bulk phase transformation and cation disorder combined with sufficient lithium vacancies in the bulk stabilize structure and improve anionic redox kinetic. The findings offer a significant theoretical guidance for the practical application of LLO materials.

[1]  Zhaoping Liu,et al.  Boosting energy efficiency of Li-rich layered oxide cathodes by tuning oxygen redox kinetics and reversibility , 2021 .

[2]  P. Bruce,et al.  The role of O2 in O-redox cathodes for Li-ion batteries , 2021, Nature Energy.

[3]  Shengwen Zhong,et al.  Na-substitution induced oxygen vacancy achieving high transition metal capacity in commercial Li-rich cathode , 2021 .

[4]  Y. Kimura,et al.  Oxygen defect engineering for the Li-rich cathode material Li1.2Ni0.13Co0.13Mn0.54O2−δ , 2021 .

[5]  M. Winter,et al.  Li-rich cathodes for rechargeable Li-based batteries: reaction mechanisms and advanced characterization techniques , 2020 .

[6]  Jason A. Weeks,et al.  Stabilization of a Highly Ni-Rich Layered Oxide Cathode through Flower-Petal Grain Arrays. , 2020, ACS nano.

[7]  K. Amine,et al.  Full Concentration Gradient‐Tailored Li‐Rich Layered Oxides for High‐Energy Lithium‐Ion Batteries , 2020, Advanced materials.

[8]  Yang Zhao,et al.  Composite Nanostructure Construction on the Grain Surface of Li‐Rich Layered Oxides , 2020, Advanced materials.

[9]  F. Pan,et al.  Enhanced long-term cyclability in Li-Rich layered oxides by electrochemically constructing a LixTM3-xO4-type spinel shell , 2020 .

[10]  Ruifeng Zhang,et al.  Achieving high structure and voltage stability in cobalt-free Li-rich layered oxide cathodes via selective dual-cation doping , 2020 .

[11]  Joseph K. Papp,et al.  Enabling Facile Anionic Kinetics through Cationic Redox Mediator in Li-Rich Layered Cathodes , 2020 .

[12]  X. Sun,et al.  Decoupling the Voltage Hysteresis of Li‐Rich Cathodes: Electrochemical Monitoring, Modulation Anionic Redox Chemistry and Theoretical Verifying , 2020, Advanced Functional Materials.

[13]  P. Bruce,et al.  First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk , 2020, Nature Energy.

[14]  Y. Kimura,et al.  Impact of Oxygen Defects on Electrochemical Processes and Charge Compensation of Li-Rich Cathode Material Li1.2Mn0.6Ni0.2O2−δ , 2020 .

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

[16]  Weifeng Wei,et al.  Heteroepitaxial oxygen-buffering interface enables a highly stable cobalt-free Li-rich layered oxide cathode , 2020 .

[17]  Jun Lu,et al.  Potassium Prussian blue-coated Li-rich cathode with enhanced lithium ion storage property , 2020 .

[18]  Xiaokai Ding,et al.  Accurate control of initial Coulombic efficiency for Li-rich Mn-based layered oxides by surface multicomponent integration. , 2020, Angewandte Chemie.

[19]  L. Gu,et al.  Fully Exploited Oxygen Redox Reaction by the Inter‐Diffused Cations in Co‐Free Li‐Rich Materials for High Performance Li‐Ion Batteries , 2020, Advanced science.

[20]  J. Fransaer,et al.  Oxygen redox activity with small voltage hysteresis in Na0.67Cu0.28Mn0.72O2 for sodium-ion batteries , 2020 .

[21]  G. Wen,et al.  Spherical layered Li-rich cathode material: Unraveling the role of oxygen vacancies on improving lithium ion conductivity , 2020, Journal of Power Sources.

[22]  Qian Sun,et al.  Size-Mediated Recurring Spinel Sub-nanodomains in Li and Mn-rich Layered Cathode Materials. , 2020, Angewandte Chemie.

[23]  A. Cao,et al.  Dielectric Polarization in Inverse Spinel‐Structured Mg2TiO4 Coating to Suppress Oxygen Evolution of Li‐Rich Cathode Materials , 2020, Advanced materials.

[24]  A. Nakao,et al.  Activation and stabilization mechanisms of anionic redox for Li storage applications: Joint experimental and theoretical study on Li2TiO3–LiMnO2 binary system , 2020 .

[25]  Huixian Xie,et al.  An Ultra‐Long‐Life Lithium‐Rich Li 1.2 Mn 0.6 Ni 0.2 O 2 Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries , 2020, Angewandte Chemie.

[26]  Tongchao Liu,et al.  Cationic and anionic redox in lithium-ion based batteries. , 2020, Chemical Society reviews.

[27]  Qinghua Zhang,et al.  Atomic-scale structural evolution of electrode materials in Li-ion batteries: a review , 2020, Rare Metals.

[28]  Bin Luo,et al.  Faster Activation and Slower Capacity/Voltage Fading: A Bifunctional Urea Treatment on Lithium‐Rich Cathode Materials , 2020, Advanced Functional Materials.

[29]  Xianluo Hu,et al.  Stabilizing Li-rich layered cathode materials by nanolayer-confined crystal growth for Li-ion batteries , 2020 .

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

[31]  Guohua Chen,et al.  An appropriate amount of new spinel phase induced by control synthesis for the improvement of electrochemical performance of Li-rich layered oxide cathode material , 2020 .

[32]  L. Zan,et al.  Mitigation of voltage decay in Li-rich layered oxides as cathode materials for lithium-ion batteries , 2019, Nano Research.

[33]  Yancheng Liu,et al.  3D Cube‐Maze‐Like Li‐Rich Layered Cathodes Assembled from 2D Porous Nanosheets for Enhanced Cycle Stability and Rate Capability of Lithium‐Ion Batteries , 2019, Advanced Energy Materials.

[34]  P. Bruce,et al.  Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes , 2019, Nature.

[35]  Jinhyuk Lee,et al.  Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment , 2019 .

[36]  Zhian Zhang,et al.  Bifunctional nano-ZrO2 modification of LiNi0·92Co0·08O2 cathode enabling high-energy density lithium ion batteries , 2019, Journal of Power Sources.

[37]  M. Kuenzel,et al.  Elucidating the Effect of Iron Doping on the Electrochemical Performance of Cobalt‐Free Lithium‐Rich Layered Cathode Materials , 2019, Advanced Energy Materials.

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

[39]  Yongsheng Chen,et al.  A facile gaseous sulfur treatment strategy for Li-rich and Ni-rich cathode materials with high cycling and rate performance , 2019, Nano Energy.

[40]  Yunjiao Li,et al.  Li4V2Mn(PO4)4-stablized Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode materials for lithium ion batteries , 2019, Nano Energy.

[41]  Qingshui Xie,et al.  Enhanced electrochemical performances of layered-spinel heterostructured lithium-rich Li1.2Ni0.13Co0.13Mn0.54O2 cathode materials , 2019, Chemical Engineering Journal.

[42]  A. Van der Ven,et al.  Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials , 2019, Nature Energy.

[43]  Liquan Chen,et al.  Li–Ti Cation Mixing Enhanced Structural and Performance Stability of Li‐Rich Layered Oxide , 2019, Advanced Energy Materials.

[44]  Z. Wen,et al.  Towards improved structural stability and electrochemical properties of a Li-rich material by a strategy of double gradient surface modification , 2019, Nano Energy.

[45]  Hong Zhang,et al.  Lithium Deficiencies Engineering in Li-Rich Layered Oxide Li1.098Mn0.533Ni0.113Co0.138O2 for High Stability Cathode. , 2019, Journal of the American Chemical Society.

[46]  L. Mai,et al.  Double-shell Li-rich layered oxide hollow microspheres with sandwich-like carbon@spinel@layered@spinel@carbon shells as high-rate lithium ion battery cathode , 2019, Nano Energy.

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

[48]  Jian Wang,et al.  Co-regulating the surface and bulk structure of Li-rich layered oxides by a phosphor doping strategy for high-energy Li-ion batteries , 2019, Journal of Materials Chemistry A.

[49]  Jun Lu,et al.  30 Years of Lithium‐Ion Batteries , 2018, Advanced materials.

[50]  P. He,et al.  Direct Visualization of the Reversible O2−/O− Redox Process in Li‐Rich Cathode Materials , 2018, Advanced materials.

[51]  Evan M. Erickson,et al.  Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries , 2018 .

[52]  Wangda Li,et al.  High-voltage positive electrode materials for lithium-ion batteries. , 2017, Chemical Society reviews.

[53]  Rahul Malik,et al.  The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. , 2016, Nature chemistry.

[54]  K Ramesha,et al.  Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. , 2013, Nature materials.

[55]  K. Kubota,et al.  Direct synthesis of oxygen-deficient Li2MnO3−x for high capacity lithium battery electrodes , 2012 .

[56]  Shinichi Komaba,et al.  Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2. , 2011, Journal of the American Chemical Society.

[57]  Gary M. Koenig,et al.  Identification of LiNi0.5Mn1.5O4 spinel in layered manganese enriched electrode materials , 2011 .

[58]  P. Bruce,et al.  Overcharging manganese oxides: Extracting lithium beyond Mn4+ , 2005 .

[59]  Zhonghua Lu,et al.  Synthesis, Structure, and Electrochemical Behavior of Li [ Ni x Li1 / 3 − 2x / 3Mn2 / 3 − x / 3 ] O 2 , 2002 .

[60]  Bing Sun,et al.  Towards high-energy-density lithium-ion batteries: Strategies for developing high-capacity lithium-rich cathode materials , 2021 .

[61]  X. Sun,et al.  In-situ surface chemical and structural self-reconstruction strategy enables high performance of Li-rich cathode , 2021, Nano Energy.

[62]  Zhenyu Wang,et al.  Insights into the chemical and structural evolution of Li-rich layered oxide cathode materials , 2020 .

[63]  Y. Okamoto.  Ambivalent Effect of Oxygen Vacancies on Li2MnO3: A First-Principles Study , 2011 .