Constructing a Protective Pillaring Layer by Incorporating Gradient Mn4+ to Stabilize the Surface/Interfacial Structure of LiNi0.815Co0.15Al0.035O2 Cathode.

Nickel-rich layered oxides are regarded as very promising materials as cathodes for lithium-ion batteries because of their environmental benignancy, low cost, and high energy density. However, insufficient cycle performance and poor thermotic characteristics induced by structural degradation at high potentials and elevated temperatures pose challenging hurdles for nickel-rich cathodes. Here, a protective pillaring layer, in which partial Ni2+ ions occupy Li slabs induced by gradient Mn4+, is integrated into the primary particle of LiNi0.815Co0.15Al0.035O2 to stabilize the surface/interfacial structure. With the stable outer surface provided by the enriched Mn4+ gradient concentration and the pillar effect of the NiO-like phase, Mn-incorporated quaternary cathodes show enhanced structural stability and improved Li+ diffusion as well as lithium-storage properties. Compared with the severe capacity fade of a pure layered structure, the cathode with gradient Mn4+ exhibits more stable cycling behavior with a capacity retention of 80.0% after 500 cycles at 5.0 C.

[1]  Seung M. Oh,et al.  Long-Life Nickel-Rich Layered Oxide Cathodes with a Uniform Li2ZrO3 Surface Coating for Lithium-Ion Batteries. , 2017, ACS applied materials & interfaces.

[2]  S. Dou,et al.  Uniform Ni-rich LiNi0.6Co0.2Mn0.2O2 Porous Microspheres: Facile Designed Synthesis and Their Improved Electrochemical Performance , 2016 .

[3]  Jian-hua Wang,et al.  Effect of heat-treatment on the surface structure and electrochemical behavior of AlPO4-coated LiNi1/3Co1/3Mn1/3O2 cathode materials , 2013 .

[4]  Zhixing Wang,et al.  A comprehensive study on electrochemical performance of Mn-surface-modified LiNi0.8Co0.15Al0.05O2 synthesized by an in situ oxidizing-coating method , 2014 .

[5]  Jaephil Cho,et al.  A New High Power LiNi0.81Co0.1Al0.09O2 Cathode Material for Lithium‐Ion Batteries , 2014 .

[6]  Yang-Kook Sun,et al.  Nickel‐Rich and Lithium‐Rich Layered Oxide Cathodes: Progress and Perspectives , 2016 .

[7]  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.

[8]  Ya‐Xia Yin,et al.  Improving the structural stability of Li-rich cathode materials via reservation of cations in the Li-slab for Li-ion batteries , 2017, Nano Research.

[9]  Zhen-guo Wu,et al.  Effect of niobium doping on the structure and electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode materials for lithium ion batteries , 2017 .

[10]  Zhen-guo Wu,et al.  A comparative study of crystalline and amorphous Li0.5La0.5TiO3 as surface coating layers to enhance the electrochemical performance of LiNi0.815Co0.15Al0.035O2 cathode , 2018 .

[11]  Lei Wang,et al.  Copper-substituted Na0.67Ni0.3−xCuxMn0.7O2 cathode materials for sodium-ion batteries with suppressed P2–O2 phase transition , 2017 .

[12]  Chong Seung Yoon,et al.  Advanced Concentration Gradient Cathode Material with Two‐Slope for High‐Energy and Safe Lithium Batteries , 2015 .

[13]  Zhixing Wang,et al.  Investigation on the effect of Na doping on structure and Li-ion kinetics of layered LiNi0.6Co0.2Mn0.2O2 cathode material , 2016 .

[14]  Hun‐Gi Jung,et al.  A nano-LiNbO3 coating layer and diffusion-induced surface control towards high-performance 5 V spinel cathodes for rechargeable batteries , 2017 .

[15]  A. Manthiram,et al.  Role of Mn content on the electrochemical properties of nickel-rich layered LiNi(0.8-x)Co(0.1)Mn(0.1+x)O₂ (0.0 ≤ x ≤ 0.08) cathodes for lithium-ion batteries. , 2015, ACS applied materials & interfaces.

[16]  Jae-won Lee,et al.  Improved electrochemical properties of Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 by surface coating with Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , 2016 .

[17]  Dawei Song,et al.  Understanding the Origin of Enhanced Performances in Core-Shell and Concentration-Gradient Layered Oxide Cathode Materials. , 2015, ACS applied materials & interfaces.

[18]  Zaiping Guo,et al.  Growth of Lithium Lanthanum Titanate Nanosheets and Their Application in Lithium-Ion Batteries. , 2016, ACS applied materials & interfaces.

[19]  Lei Wang,et al.  Research progress on vanadium-based cathode materials for sodium ion batteries , 2018 .

[20]  Ya‐Xia Yin,et al.  Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries. , 2016, ACS applied materials & interfaces.

[21]  Ya‐Xia Yin,et al.  High-Thermal- and Air-Stability Cathode Material with Concentration-Gradient Buffer for Li-Ion Batteries. , 2017, ACS applied materials & interfaces.

[22]  Byung-Beom Lim,et al.  Comparative Study of Ni-Rich Layered Cathodes for Rechargeable Lithium Batteries: Li[Ni0.85Co0.11Al0.04]O2 and Li[Ni0.84Co0.06Mn0.09Al0.01]O2 with Two-Step Full Concentration Gradients , 2016 .

[23]  Lei Wang,et al.  The effect of gradient boracic polyanion-doping on structure, morphology, and cycling performance of Ni-rich LiNi 0.8 Co 0.15 Al 0.05 O 2 cathode material , 2018 .

[24]  Minjoon Park,et al.  Prospect and Reality of Ni‐Rich Cathode for Commercialization , 2018 .

[25]  Jun Chen,et al.  Stable layered Ni-rich LiNi0.9Co0.07Al0.03O2 microspheres assembled with nanoparticles as high-performance cathode materials for lithium-ion batteries , 2017 .

[26]  Feng Wu,et al.  Effect of Ni(2+) content on lithium/nickel disorder for Ni-rich cathode materials. , 2015, ACS applied materials & interfaces.

[27]  Benhe Zhong,et al.  K-doped layered LiNi0.5Co0.2Mn0.3O2 cathode material: Towards the superior rate capability and cycling performance , 2017 .

[28]  Xiqian Yu,et al.  Al2O3 surface coating on LiCoO2 through a facile and scalable wet-chemical method towards high-energy cathode materials withstanding high cutoff voltages , 2017 .

[29]  C. Yoon,et al.  High-Energy Ni-Rich Li[NixCoyMn1–x–y]O2 Cathodes via Compositional Partitioning for Next-Generation Electric Vehicles , 2017 .

[30]  Chong Seung Yoon,et al.  Improvement of long-term cycling performance of Li[Ni0.8Co0.15Al0.05]O2 by AlF3 coating , 2013 .

[31]  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 .

[32]  I. Bobrikov,et al.  Li(Ni,Co,Al)O2 Cathode Delithiation: A Combination of Topological Analysis, Density Functional Theory, Neutron Diffraction, and Machine Learning Techniques , 2017 .

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

[34]  Zhixing Wang,et al.  Metallurgy Inspired Formation of Homogeneous Al2O3 Coating Layer To Improve the Electrochemical Properties of LiNi0.8Co0.1Mn0.1O2 Cathode Material , 2017 .

[35]  Minjoon Park,et al.  Self‐Induced Concentration Gradient in Nickel‐Rich Cathodes by Sacrificial Polymeric Bead Clusters for High‐Energy Lithium‐Ion Batteries , 2017 .

[36]  Ya‐Xia Yin,et al.  High‐Capacity Cathode Material with High Voltage for Li‐Ion Batteries , 2018, Advanced materials.

[37]  M. Whittingham,et al.  Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries , 2017 .

[38]  Min Gyu Kim,et al.  A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles. , 2015, Nano letters.

[39]  Chong Seung Yoon,et al.  Nanostructured high-energy cathode materials for advanced lithium batteries. , 2012, Nature materials.

[40]  Wei Xiang,et al.  Improving cycling performance and rate capability of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode materials by Li4Ti5O12 coating , 2018 .

[41]  Yan‐Bing He,et al.  Deterioration mechanism of LiNi0.8Co0.15Al0.05O2/graphite–SiOx power batteries under high temperature and discharge cycling conditions , 2018 .

[42]  Dawei Song,et al.  A new synthesis strategy towards enhancing the structure and cycle stabilities of the LiNi0.80Co0.15Al0.05O2 cathode material , 2017 .

[43]  Jaephil Cho,et al.  Spinel‐Layered Core‐Shell Cathode Materials for Li‐Ion Batteries , 2011 .

[44]  Min-Joon Lee,et al.  Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries. , 2015, Angewandte Chemie.

[45]  Min-Joon Lee,et al.  The role of nanoscale-range vanadium treatment in LiNi0.8Co0.15Al0.05O2 cathode materials for Li-ion batteries at elevated temperatures , 2015 .