Ambient‐Pressure Relithiation of Degraded LixNi0.5Co0.2Mn0.3O2 (0 < x < 1) via Eutectic Solutions for Direct Regeneration of Lithium‐Ion Battery Cathodes

With the rapid growth of the lithium‐ion battery (LIBs) market, recycling and re‐use of end‐of‐life LIBs to reclaim lithium (Li) and transition metal (TM) resources (e.g., Co, Ni), as well as eliminating pollution from disposal of waste batteries, has become an urgent task. Here, for the first time the ambient‐pressure relithiation of degraded LiNi0.5Co0.2Mn0.3O2 (NCM523) cathodes via eutectic Li+ molten‐salt solutions is successfully demonstrated. Combining such a low‐temperature relithiation process with a well‐designed thermal annealing step, NCM523 cathode particles with significant Li loss (≈40%) and capacity degradation (≈50%) can be successfully regenerated to achieve their original composition and crystal structures, leading to effective recovery of their capacity, cycling stability, and rate capability to the levels of the pristine materials. Advanced characterization tools including atomic resolution electron microscopy imaging and electron energy loss spectroscopy are combined to demonstrate that NCM523's original layered crystal structure is recovered. For the first time, it is shown that layer‐to‐rock salt phase change on the surfaces and subsurfaces of the cathode materials can be reversed if lithium can be incorporated back to the material. The result suggests the great promise of using eutectic Li+ molten–salt solutions for ambient‐pressure relithiation to recycle and remanufacture degraded LIB cathode materials.

[1]  Doron Aurbach,et al.  Structural and Electrochemical Aspects of LiNi0.8Co0.1Mn0.1O2 Cathode Materials Doped by Various Cations , 2019, ACS Energy Letters.

[2]  F. Sprei,et al.  Assessing the progress toward lower priced long range battery electric vehicles , 2019, Energy Policy.

[3]  V. Aravindan,et al.  Burgeoning Prospects of Spent Lithium‐Ion Batteries in Multifarious Applications , 2018, Advanced Energy Materials.

[4]  Li Li,et al.  Toward sustainable and systematic recycling of spent rechargeable batteries. , 2018, Chemical Society reviews.

[5]  Jun Lu,et al.  The Recycling of Spent Lithium-Ion Batteries: a Review of Current Processes and Technologies , 2018, Electrochemical Energy Reviews.

[6]  Linda Gaines,et al.  Lithium-ion battery recycling processes: Research towards a sustainable course , 2018, Sustainable Materials and Technologies.

[7]  Y. Meng,et al.  Urea-based hydrothermal synthesis of LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery , 2018, Journal of Power Sources.

[8]  Shengkui Zeng,et al.  Remaining capacity estimation of lithium-ion batteries based on the constant voltage charging profile , 2018, PloS one.

[9]  Yang Shi,et al.  Resolving the Compositional and Structural Defects of Degraded LiNixCoyMnzO2 Particles to Directly Regenerate High-Performance Lithium-Ion Battery Cathodes , 2018, ACS Energy Letters.

[10]  Feng Lin,et al.  Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials. , 2018, Nano letters.

[11]  Wolfgang Haselrieder,et al.  Current status and challenges for automotive battery production technologies , 2018 .

[12]  Yang Shi,et al.  Effective regeneration of LiCoO2 from spent lithium-ion batteries: a direct approach towards high-performance active particles , 2018 .

[13]  Hongbin Cao,et al.  A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries , 2018 .

[14]  M. Winter,et al.  Running out of lithium? A route to differentiate between capacity losses and active lithium losses in lithium-ion batteries. , 2017, Physical chemistry chemical physics : PCCP.

[15]  Joeri Van Mierlo,et al.  Cost Projection of State of the Art Lithium-Ion Batteries for Electric Vehicles Up to 2030 , 2017 .

[16]  Martin Winter,et al.  Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density , 2017, Journal of Solid State Electrochemistry.

[17]  Chen Li,et al.  Failure statistics for commercial lithium ion batteries: A study of 24 pouch cells , 2017 .

[18]  Doron Aurbach,et al.  Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes I. Nickel-Rich, LiNixCoyMnzO2 , 2017 .

[19]  M. Winter,et al.  Best Practice: Performance and Cost Evaluation of Lithium Ion Battery Active Materials with Special Emphasis on Energy Efficiency , 2016 .

[20]  K. Kubota,et al.  Lithium Molten Salt Battery at Near Room Temperature Using Low-Melting Alkali Metal Melts , 2016 .

[21]  Yan Chen,et al.  Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries , 2016, Nature Communications.

[22]  Y. Meng,et al.  Ultrathin Al2O3 Coatings for Improved Cycling Performance and Thermal Stability of LiNi0.5Co0.2Mn0.3O2 Cathode Material , 2016 .

[23]  Betar M. Gallant,et al.  A Molten Salt Lithium-Oxygen Battery. , 2016, Journal of the American Chemical Society.

[24]  Yang-Tse Cheng,et al.  Electrode Side Reactions, Capacity Loss and Mechanical Degradation in Lithium-Ion Batteries , 2015 .

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

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

[27]  Wei Xie,et al.  An Integrated Probabilistic Approach to Lithium-Ion Battery Remaining Useful Life Estimation , 2015, IEEE Transactions on Instrumentation and Measurement.

[28]  Helmut Ehrenberg,et al.  Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches , 2015 .

[29]  Xiqian Yu,et al.  Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy. , 2014, ACS applied materials & interfaces.

[30]  Jianqiu Li,et al.  Cycle Life of Commercial Lithium-Ion Batteries with Lithium Titanium Oxide Anodes in Electric Vehicles , 2014 .

[31]  Feng Lin,et al.  Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries , 2014, Nature Communications.

[32]  Haegyeom Kim,et al.  Understanding the Degradation Mechanisms of LiNi0.5Co0.2Mn0.3O2 Cathode Material in Lithium Ion Batteries , 2014 .

[33]  Chong Seung Yoon,et al.  Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries , 2013 .

[34]  Debasish Mohanty,et al.  Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction , 2013 .

[35]  D. Mohanty,et al.  Microstructural investigation of LixNi1/3Mn1/3Co1/3O2 (x ≤ 1) and its aged products via magnetic and diffraction study , 2012 .

[36]  Y. Koyama,et al.  Defect Chemistry in Layered LiMO2 (M = Co, Ni, Mn, and Li1/3Mn2/3) by First-Principles Calculations , 2012 .

[37]  T. Wanger.  The Lithium future—resources, recycling, and the environment , 2011 .

[38]  Xu Yu,et al.  Synthesis of LiNi1/3Co1/3Al1/3O2 cathode material with eutectic molten salt LiOH-LiNO3 , 2011 .

[39]  S. Garimella,et al.  Molten-salt thermal energy storage in thermoclines under different environmental boundary conditions , 2010 .

[40]  D. Wexler,et al.  Basic molten salt process-A new route for synthesis of nanocrystalline Li4Ti5O12-TiO2 anode material for Li-ion batteries using eutectic mixture of LiNO3-LiOH-Li2O2 , 2010 .

[41]  A. Majee,et al.  Zwitterionic-type molten salt-catalyzed syn-selective aza-Henry reaction: solvent-free one-pot synthesis of β-nitroamines , 2009 .

[42]  Ralph E. White,et al.  Capacity fade analysis of a lithium ion cell , 2008 .

[43]  Qi Lu,et al.  Preferred Orientation of Crystals and the Intensity Ratios of XRD Peaks of Cathode Material LiCoO 2 , 2007 .

[44]  G. Ceder,et al.  Factors that affect Li mobility in layered lithium transition metal oxides , 2006 .

[45]  G. Rao,et al.  Synthesis by molten salt and cathodic properties of Li (Ni1/3Co1/3Mn1/3 )O2 , 2006 .

[46]  L. Wen,et al.  Molten salt synthesis of spherical LiNi0.5Mn1.5O4 cathode materials , 2006 .

[47]  Michel Armand,et al.  Room temperature molten salts as lithium battery electrolyte , 2004 .

[48]  John W. Kelton,et al.  Testing of Thermocline Filler Materials and Molten-Salt Heat Transfer Fluids for Thermal Energy Storage Systems in Parabolic Trough Power Plants , 2004 .

[49]  B. Fultz,et al.  White lines and d-band occupancy for the 3d transition-metal oxides and lithium transition-metal oxides , 2004 .

[50]  Nancy J. Dudney,et al.  Preferred Orientation of Polycrystalline LiCoO2 Films , 2000 .