Fabricating Heterostructures for Boosting the Structure Stability of Li-Rich Cathodes

Li-rich Mn-based oxides are regarded as the most promising new-generation cathode materials, but their practical application is greatly hindered by structure collapse and capacity degradation. Herein, a rock salt phase is epitaxially constructed on the surface of Li-rich Mn-based cathodes through Mo doping to improve their structural stability. The heterogeneous structure composed of a rock salt phase and layered phase is induced by Mo6+ enriched on the particle surface, and the strong Mo–O bonding can enhance the TM–O covalence. Therefore, it can stabilize lattice oxygen and inhibit the side reaction of the interface and structural phase transition. The discharge capacity of 2% Mo-doped samples (Mo 2%) displays 279.67 mA h g–1 at 0.1 C (vs 254.39 mA h g–1 (pristine)), and the discharge capacity retention rate of Mo 2% is 79.4% after 300 cycles at 5 C (vs 47.6% (pristine)).

[1]  Hangchao Wang,et al.  Entropy Stabilization Strategy for Enhancing the Local Structural Adaptability of Li‐Rich Cathode Materials , 2022, Advanced materials.

[2]  T. Brezesinski,et al.  Tailoring the LiNbO 3 coating of Ni-rich cathode materials for stable and high-performance all-solid-state batteries , 2022, Nano Research Energy.

[3]  Tongchao Liu,et al.  Origin of structural degradation in Li-rich layered oxide cathode , 2022, Nature.

[4]  K. An,et al.  Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy , 2022, Nature communications.

[5]  Yi‐Chun Lu,et al.  Design strategies for low temperature aqueous electrolytes , 2022, Nano Research Energy.

[6]  Wenxi Zhao,et al.  An exquisite branch-leaf shaped metal sulfoselenide composites endowing ultrastable sodium-storage lifespan over 10000 cycles , 2022, Journal of Materials Chemistry A.

[7]  Jing Mao,et al.  Lithium-rich manganese-based cathode materials with highly stable lattice and surface enabled by perovskite-type phase-compatible layer , 2021 .

[8]  F. Pan,et al.  Modifying Li@Mn6 Superstructure Units by Al Substitution to Enhance the Long‐Cycle Performance of Co‐Free Li‐Rich Cathode , 2021, Advanced Energy Materials.

[9]  Zhen-guo Wu,et al.  A simple Gas-solid treatment for surface modification in Li-rich oxides cathode. , 2021, Angewandte Chemie.

[10]  Yanjie Hu,et al.  Surface enrichment and diffusion enabling gradient-doping and coating of Ni-rich cathode toward Li-ion batteries , 2021, Nature Communications.

[11]  Abdullah M. Asiri,et al.  In situ tailoring bimetallic–organic framework-derived yolk–shell NiS2/CuS hollow microspheres: an extraordinary kinetically pseudocapacitive nanoreactor for an effective sodium-ion storage anode , 2021, Journal of Materials Chemistry A.

[12]  Qinghua Zhang,et al.  Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands , 2021, Nature Communications.

[13]  G. Cui,et al.  How Do Polymer Binders Assist Transition Metal Oxide Cathodes to Address the Challenge of High-Voltage Lithium Battery Applications? , 2021, Electrochemical Energy Reviews.

[14]  C. Su,et al.  Metal–Organic Frameworks and Their Derivatives as Cathodes for Lithium-Ion Battery Applications: A Review , 2021, Electrochemical Energy Reviews.

[15]  P. He,et al.  Ion‐Exchange: A Promising Strategy to Design Li‐Rich and Li‐Excess Layered Cathode Materials for Li‐Ion Batteries , 2021, Advanced Energy Materials.

[16]  I. Belharouak,et al.  Valuation of Surface Coatings in High-Energy Density Lithium-ion Battery Cathode Materials , 2021 .

[17]  Tae-Hee Kim,et al.  Promoting the Reversible Oxygen Redox Reaction of Li‐Excess Layered Cathode Materials with Surface Vanadium Cation Doping , 2021, Advanced science.

[18]  Jun Chen,et al.  Recent breakthroughs and perspectives of high-energy layered oxide cathode materials for lithium ion batteries , 2020 .

[19]  Hong Dong,et al.  Enhanced Structural Stability of Boron-Doped Layered@Spinel@Carbon Heterostructured Lithium-Rich Manganese-Based Cathode Materials , 2020, ACS Sustainable Chemistry & Engineering.

[20]  H. Wang,et al.  Surface Modification of Li 1.144 Ni 0.136 Co 0.136 Mn 0.544 O 2 by Hybrid Protection Layer with Enhanced Rate Capability , 2020 .

[21]  K. An,et al.  The effect of oxygen vacancy and spinel phase integration on both anionic and cationic redox in Li-rich cathode materials , 2020 .

[22]  F. Kang,et al.  A Simple Dual-Ion Doping Method to Stabilize Li-Rich Materials and Suppress Voltage Decay. , 2020, ACS applied materials & interfaces.

[23]  Evan M. Erickson,et al.  High-nickel layered oxide cathodes for lithium-based automotive batteries , 2020 .

[24]  S. Trabesinger,et al.  Impact of Nickel Substitution into Model Li-Rich Oxide Cathode Materials for Li-Ion Batteries , 2019, Chemistry of Materials.

[25]  M. Whittingham,et al.  Li-Nb-O coating/substitution enhances the electrochemical performance of LiNi0.8Mn0.1Co0.1O2 (NMC 811) Cathode. , 2019, ACS applied materials & interfaces.

[26]  Zhen-guo Wu,et al.  Highly Stabilized Ni-Rich Cathode Material with Mo Induced Epitaxially Grown Nanostructured Hybrid Surface for High-Performance Lithium-Ion Batteries. , 2019, ACS applied materials & interfaces.

[27]  Qinghua Zhang,et al.  Stabilizing the Oxygen Lattice and Reversible Oxygen Redox Chemistry through Structural Dimensionality in Lithium-Rich Cathode Oxides. , 2019, Angewandte Chemie.

[28]  Qiaobao Zhang,et al.  Enhanced Electrochemical Performance of Li-Rich Layered Cathode Materials by Combined Cr Doping and LiAlO2 Coating , 2019, ACS Sustainable Chemistry & Engineering.

[29]  M. Zubair,et al.  Electrochemical Kinetics and Cycle Stability Improvement with Nb Doping for Lithium-Rich Layered Oxides , 2018, ACS Applied Energy Materials.

[30]  Hun‐Gi Jung,et al.  Improved Cycling Stability of Li[Ni0.90Co0.05Mn0.05]O2 Through Microstructure Modification by Boron Doping for Li‐Ion Batteries , 2018, Advanced Energy Materials.

[31]  Jaephil Cho,et al.  A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries , 2018 .

[32]  Seung M. Oh,et al.  Site‐Selective In Situ Electrochemical Doping for Mn‐Rich Layered Oxide Cathode Materials in Lithium‐Ion Batteries , 2018 .

[33]  Jun Lu,et al.  Elucidating anionic oxygen activity in lithium-rich layered oxides , 2018, Nature Communications.

[34]  Alicia Koo,et al.  Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al 2 O 3 and LiAlO 2 coatings on LiNi 0.6 Co 0.2 Mn 0.2 O 2 , 2018 .

[35]  C. Graf Cathode materials for lithium-ion batteries , 2018 .

[36]  Kei Mitsuhara,et al.  Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries , 2016, Nature Communications.

[37]  S. Passerini,et al.  Lithium‐ and Manganese‐Rich Oxide Cathode Materials for High‐Energy Lithium Ion Batteries , 2016 .

[38]  Tongchao Liu,et al.  Aligned Li+ Tunnels in Core-Shell Li(NixMnyCoz)O2@LiFePO4 Enhances Its High Voltage Cycling Stability as Li-ion Battery Cathode. , 2016, Nano letters.

[39]  K. Edström,et al.  Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. , 2016, Nature chemistry.

[40]  Ya‐Xia Yin,et al.  Enhancing the Kinetics of Li‐Rich Cathode Materials through the Pinning Effects of Gradient Surface Na+ Doping , 2016 .

[41]  A. Grimaud,et al.  Anionic redox processes for electrochemical devices. , 2016, Nature materials.

[42]  Donghai Wang (Invited) Ti-Substituted Li[Li 0.26 Mn 0.6- X Ti x Ni 0.07 Co 0.07 ]O 2 Layered Cathode Material with Improved Structural Stability and Suppressed Voltage Fading , 2015 .

[43]  Zi-kui Liu,et al.  Ti-substituted Li[Li0.26Mn0.6−xTixNi0.07Co0.07]O2 layered cathode material with improved structural stability and suppressed voltage fading , 2015 .

[44]  Jaephil Cho,et al.  Countering Voltage Decay and Capacity Fading of Lithium‐Rich Cathode Material at 60 °C by Hybrid Surface Protection Layers , 2015 .

[45]  Haoshen Zhou,et al.  New Insights into Improving Rate Performance of Lithium‐Rich Cathode Material , 2015, Advanced materials.

[46]  K Ramesha,et al.  Origin of voltage decay in high-capacity layered oxide electrodes. , 2015, Nature materials.

[47]  B. Hwang,et al.  Understanding the Role of Ni in Stabilizing the Lithium-Rich High-Capacity Cathode Material Li[NixLi(1–2x)/3Mn(2–x)/3]O2 (0 ≤ x ≤ 0.5) , 2014 .

[48]  Qi Li,et al.  K(+)-doped Li(1.2)Mn(0.54)Co(0.13)Ni(0.13)O2: a novel cathode material with an enhanced cycling stability for lithium-ion batteries. , 2014, ACS applied materials & interfaces.

[49]  Bin Chen,et al.  Enhanced rate performance of molybdenum-doped spinel LiNi0.5Mn1.5O4 cathode materials for lithium ion battery , 2014 .

[50]  Yongyao Xia,et al.  Improving the electrochemical performance of layered lithium-rich transition-metal oxides by controlling the structural defects , 2014 .

[51]  B. Hwang,et al.  Direct in situ observation of Li2O evolution on Li-rich high-capacity cathode material, Li[Ni(x)Li((1-2x)/3)Mn((2-x)/3)]O2 (0 ≤ x ≤ 0.5). , 2014, Journal of the American Chemical Society.

[52]  B. Hwang,et al.  3 Mn ( 2 − x ) / 3 ] O 2 ( 0 ≤ x ≤ 0 . 5 ) , 2014 .

[53]  Liquan Chen,et al.  Atomic Structure of Li2MnO3 after Partial Delithiation and Re‐Lithiation , 2013 .

[54]  Jaephil Cho,et al.  A new type of protective surface layer for high-capacity Ni-based cathode materials: nanoscaled surface pillaring layer. , 2013, Nano letters.

[55]  K. Kang,et al.  Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries , 2012 .

[56]  Bruno Scrosati,et al.  The Role of AlF3 Coatings in Improving Electrochemical Cycling of Li‐Enriched Nickel‐Manganese Oxide Electrodes for Li‐Ion Batteries , 2012, Advanced materials.

[57]  沈晞,et al.  Lithium ion battery , 2012 .

[58]  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.

[59]  Christopher S. Johnson,et al.  Anomalous capacity and cycling stability of xLi2MnO3 · (1 − x)LiMO2 electrodes (M = Mn, Ni, Co) in lithium batteries at 50 °C , 2007 .