Polyanion and cation co-doping stabilized Ni-rich Ni–Co–Al material as cathode with enhanced electrochemical performance for Li-ion battery

Abstract Layered Ni-rich transition metal oxides exert great potential as high-capacity cathode materials for lithium-ion batteries. However, structural degradation during lithiation/delithiation hinders the cathode materials for commercial utilization. Herein, PO43− polyanion and Mn4+ cation are co-doped into Ni-rich LiNi0.80Co0.15Al0.05O2 cathode to improve the structural stability and electrochemical performance. The effects of PO43− and Mn4+ co-existence on phase, crystal structure, element valence state, electrochemical performance and phase transition during lithiation/delithihation are systematically investigated. The results show that moderate content of PO43− and Mn4+ co-doping can enlarge the channel for Li+ lithiation/delithiation, lower the cationic mixing, and suppress the structural degradation during cycling. With the stabilization role of Mn4+ and PO43−, the material with moderate amount of dopants shows remarkable enhanced electrochemical performance, especially at harsh condition. In the cell potential of 2.7–4.3 V, the 3% PO43− and Mn4+ co-doped cathode shows a reversible discharge capacity of 204 mAh g−1 at 0.1C, outstanding cycling stability with a capacity of 174 mAh g−1 and capacity retention of 85.5% at 1C after 100 cycles, especially, a superior discharge capacity of 157.8 mAh g−1 at 5C. Even at elevated temperature of 55 °C, the cathode retains 80.9% of initial capacity (195 mAh g−1) at 1C after 100 cycles.

[1]  James A. Gilbert,et al.  Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells , 2017 .

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

[3]  Evan M. Erickson,et al.  From Surface ZrO2 Coating to Bulk Zr Doping by High Temperature Annealing of Nickel‐Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries , 2018 .

[4]  Hyunchul Kim,et al.  New Insight into Ni‐Rich Layered Structure for Next‐Generation Li Rechargeable Batteries , 2018 .

[5]  Ji‐Guang Zhang,et al.  Effect of calcination temperature on the electrochemical properties of nickel-rich LiNi0.76Mn0.14Co0.10O2 cathodes for lithium-ion batteries , 2018, Nano Energy.

[6]  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 .

[7]  H. Wang,et al.  Effects of fluorine doping on structure, surface chemistry, and electrochemical performance of LiNi0.8Co0.15Al0.05O2 , 2015 .

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

[9]  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 .

[10]  S. George,et al.  Coating Solution for High-Voltage Cathode: AlF3 Atomic Layer Deposition for Freestanding LiCoO2 Electrodes with High Energy Density and Excellent Flexibility. , 2017, ACS applied materials & interfaces.

[11]  Wangda Li,et al.  Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover. , 2017, ACS nano.

[12]  Enhanced electrochemical performances of Li-rich layered oxides by surface modification with reduced graphene oxide/AlPO4 hybrid coating , 2014 .

[13]  Feng Wu,et al.  Lithium-active molybdenum trioxide coated LiNi0.5Co0.2Mn0.3O2 cathode material with enhanced electrochemical properties for lithium-ion batteries , 2014 .

[14]  Wei Liu,et al.  Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling. , 2017, ACS nano.

[15]  Qinghua Zhang,et al.  Improving the electrochemical performances of Li-rich Li 1.20 Ni 0.13 Co 0.13 Mn 0.54 O 2 through a cooperative doping of Na + and PO 4 3− with Na 3 PO 4 , 2018 .

[16]  Li Chen,et al.  Excellent high rate capability and high voltage cycling stability of Y2O3-coated LiNi0.5Co0.2Mn0.3O2 , 2014 .

[17]  Yong Liu,et al.  Surface Structural Transition Induced by Gradient Polyanion‐Doping in Li‐Rich Layered Oxides: Implications for Enhanced Electrochemical Performance , 2016 .

[18]  Xueping Gao,et al.  Na-Doped LiNi0.8Co0.15Al0.05O2 with Excellent Stability of Both Capacity and Potential as Cathode Materials for Li-Ion Batteries , 2018, ACS Applied Energy Materials.

[19]  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.

[20]  Zhen-guo Wu,et al.  Construction of homogeneously Al3+ doped Ni rich Ni-Co-Mn cathode with high stable cycling performance and storage stability via scalable continuous precipitation , 2018, Electrochimica Acta.

[21]  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 .

[22]  Yuji Kojima,et al.  Effect of Mg-doping on the degradation of LiNiO2-based cathode materials by combined spectroscopic methods , 2012 .

[23]  Peter Lamp,et al.  Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives , 2017 .

[24]  Xueping Gao,et al.  The Effect of Polyanion-Doping on the Structure and Electrochemical Performance of Li-Rich Layered Oxides as Cathode for Lithium-Ion Batteries , 2015 .

[25]  K. Du,et al.  Enhanced electrochemical performance and thermal stability of LiNi0.80Co0.15Al0.05O2 via nano-sized LiMnPO4 coating , 2016 .

[26]  Xiaoxiong Xu,et al.  Structure Integrity Endowed by a Ti-Containing Surface Layer towards Ultrastable LiNi0.8Co0.15Al0.05O2 for All-Solid-State Lithium Batteries , 2016 .

[27]  R. Huggins,et al.  Investigations of a number of alternative negative electrode materials for use in lithium cells , 2001 .

[28]  Qingbing Xia,et al.  The Effect of Boron Doping on Structure and Electrochemical Performance of Lithium-Rich Layered Oxide Materials. , 2016, ACS applied materials & interfaces.

[29]  Wei Xiang,et al.  Constructing a Protective Pillaring Layer by Incorporating Gradient Mn4+ to Stabilize the Surface/Interfacial Structure of LiNi0.815Co0.15Al0.035O2 Cathode. , 2018, ACS applied materials & interfaces.