Role of LaNiO3 in suppressing voltage decay of layered lithium-rich cathode materials

Abstract Lithium-rich cathode materials possess poor cycle stability and severe voltage decay during cycling. The main reason is that they suffer severe structure transformation during (I) Li2MnO3 activation in the initial charge process accompanied with the release of O2 and the extraction of Li-ions from transition metal (TM) layer; (II) the migration of TM-ions (Mn4+, Ni2+) from TM layer to Li layer during cycling. Both of them accelerate phase transformation from the layered to LiNixMn2−xO4 (0 ≤ x ≤ 2) spinel structure. In order to solve this problem, LaNiO3 surface reorganization layer is proposed in this work. In the process of surface modification, the La salts are decomposed and then bond with Ni ions that diffused from the bulk of particles to the surface at high-temperature calcinations. Due to the strong La O bond energy, there is less Li2O removed and less lithium vacancy formed in TM layer during every charge processes. In addition, the stable existing form of Ni3+ in material surface inhibits the migration of TM-ions from TM layer into Li layer. LaNiO3 surface can protect the electrode from the erosion by electrolyte, and effectively impede the electrode/electrolyte interface side reactions. Owing to the positive effects of LaNiO3 surface reorganization layer, the modified Li1.2Mn0.6Ni0.2O2 samples exhibit superior high capacity retention (more than 87.7% after 200 cycles) with a significantly decrease in voltage decay, which exhibit an improvement over the state of art.

[1]  C. Liang,et al.  Probing the initiation of voltage decay in Li-rich layered cathode materials at the atomic scale , 2015 .

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

[3]  Seung M. Oh,et al.  High‐Performance Heterostructured Cathodes for Lithium‐Ion Batteries with a Ni‐Rich Layered Oxide Core and a Li‐Rich Layered Oxide Shell , 2016, Advanced science.

[4]  James C. Knight,et al.  Understanding the effect of Co3+substitution on the electrochemical properties of lithium-rich layered oxide cathodes for lithium-ion batteries , 2014 .

[5]  Xugeng Guo,et al.  The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery , 2008 .

[6]  C. Chen,et al.  Effects of Al substitution for Ni and Mn on the electrochemical properties of LiNi0.5Mn1.5O4 , 2011 .

[7]  D. Xie,et al.  Improved Cycling Stability of Cobalt-free Li-rich Oxides with a Stable Interface by Dual Doping , 2016 .

[8]  Zhaoqi Sun,et al.  Enhanced Electrochemical Performance of Li [ Li0.2Ni0.2Mn0.6 ] O2 Modified by Manganese Oxide Coating for Lithium-Ion Batteries , 2011 .

[9]  Arumugam Manthiram,et al.  High Capacity, Surface-Modified Layered Li [ Li ( 1 − x ) ∕ 3Mn ( 2 − x ) ∕ 3Nix ∕ 3Cox ∕ 3 ] O2 Cathodes with Low Irreversible Capacity Loss , 2006 .

[10]  Feng Wu,et al.  The role of yttrium content in improving electrochemical performance of layered lithium-rich cathode materials for Li-ion batteries , 2013 .

[11]  Feng Wu,et al.  Spinel/Layered Heterostructured Cathode Material for High‐Capacity and High‐Rate Li‐Ion Batteries , 2013, Advanced materials.

[12]  Michael Holzapfel,et al.  Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2. , 2006, Journal of the American Chemical Society.

[13]  Sheng-wu Guo,et al.  Suppressing capacity fading and voltage decay of Li-rich layered cathode material by a surface nano-protective layer of CoF 2 for lithium-ion batteries , 2016 .

[14]  Feng Wu,et al.  High-Rate and Cycling-Stable Nickel-Rich Cathode Materials with Enhanced Li(+) Diffusion Pathway. , 2016, ACS applied materials & interfaces.

[15]  Shi-Gang Sun,et al.  Investigation of layered LiNi1/3Co1/3Mn1/3O2 cathode of lithium ion battery by electrochemical impedance spectroscopy , 2012 .

[16]  J. Colin,et al.  First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries. , 2013, Nano letters.

[17]  D. Abraham,et al.  Local Structure of Layered Oxide Electrode Materials for Lithium‐Ion Batteries , 2010, Advanced materials.

[18]  A. Manthiram,et al.  Smart design of lithium-rich layered oxide cathode compositions with suppressed voltage decay , 2014 .

[19]  Youngsik Kim,et al.  A Novel Surface Treatment Method and New Insight into Discharge Voltage Deterioration for High‐Performance 0.4Li2MnO3–0.6LiNi1/3Co1/3Mn1/3O2 Cathode Materials , 2014 .

[20]  K. Abraham,et al.  A Li-Rich Layered Cathode Material with Enhanced Structural Stability and Rate Capability for Li-on Batteries , 2014 .

[21]  Feng Wu,et al.  Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries , 2014 .

[22]  Feng Wu,et al.  Hierarchical Li1.2Ni0.2Mn0.6O2 Nanoplates with Exposed {010} Planes as High‐Performance Cathode Material for Lithium‐Ion Batteries , 2014, Advanced materials.

[23]  Yunqi Liu,et al.  Transition metal dichalcogenide materials: Solid-state reaction synthesis of nanocrystalline nickel disulfide , 2008 .

[24]  Christopher S. Johnson,et al.  High-energy and high-power Li-rich nickel manganese oxide electrode materials , 2010 .

[25]  Yuanzhen Chen,et al.  Effect of valence states of Ni and Mn on the structural and electrochemical properties of Li1.2NixMn0.8−xO2 cathode materials for lithium-ion batteries , 2016 .

[26]  Miaofang Chi,et al.  Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study , 2011 .

[27]  R. Katiyar,et al.  Synthesis and characterization of Nd doped LiMn2O4 cathode for Li-ion rechargeable batteries , 2007 .

[28]  B. Polzin,et al.  Functioning Mechanism of AlF3 Coating on the Li- and Mn-Rich Cathode Materials , 2014 .

[29]  Stabilizing the structure and suppressing the voltage decay of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode materials for Li-ion batteries via multifunctional Pr oxide surface modification , 2016 .

[30]  A. Manthiram,et al.  Functional surface modifications of a high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode , 2010 .

[31]  Hui Liu,et al.  Formation Mechanism of 1D ZnO Nanowhiskers in Aqueous Solution , 2010 .

[32]  John T. Vaughey,et al.  Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries , 2005 .

[33]  Ning Li,et al.  Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries. , 2014, Nano letters.

[34]  J. Dahn,et al.  Synthesis and Characterization of the Lithium-Rich Core–Shell Cathodes with Low Irreversible Capacity and Mitigated Voltage Fade , 2015 .