Ambient‐Pressure Relithiation of Degraded Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (0 &lt; x &lt; 1) via Eutectic Solutions for Direct Regeneration of Lithium‐Ion Battery Cathodes

Shi, Yang; Zhang, Minghao; Meng, Ying Shirley; Chen, Zheng

doi:10.1002/aenm.201900454

Ambient‐Pressure Relithiation of Degraded Li _x Ni _0.5 Co _0.2 Mn _0.3 O ₂ (0 < x < 1) via Eutectic Solutions for Direct Regeneration of Lithium‐Ion Battery Cathodes

Journal Article · Mon Apr 08 00:00:00 EDT 2019 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201900454· OSTI ID:1505652

Shi, Yang ^[1]; Zhang, Minghao ^[1]; Meng, Ying Shirley ^[2]; ^[3]

Department of NanoEngineering University of California San Diego La Jolla CA 92093 USA
Department of NanoEngineering University of California San Diego La Jolla CA 92093 USA, Sustainable Power &, Energy Center (SPEC) University of California San Diego La Jolla CA 92093 USA
Department of NanoEngineering University of California San Diego La Jolla CA 92093 USA, Sustainable Power &, Energy Center (SPEC) University of California San Diego La Jolla CA 92093 USA, Program of Chemical Engineering University of California San Diego La Jolla CA 92093 USA

Abstract

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 LiNi _0.5 Co _0.2 Mn _0.3 O ₂ (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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1505652

Alternate ID(s):: OSTI ID: 23098857

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 20 Vol. 9; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (50)

Understanding the Degradation Mechanisms of LiNi _0.5 Co _0.2 Mn _0.3 O ₂ Cathode Material in Lithium Ion Batteries Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300787	journal	August 2013
Burgeoning Prospects of Spent Lithium-Ion Batteries in Multifarious Applications Natarajan, Subramanian; Aravindan, Vanchiappan Advanced Energy Materials, Vol. 8, Issue 33 https://doi.org/10.1002/aenm.201802303	journal	October 2018
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries Liu, Wen; Oh, Pilgun; Liu, Xien Angewandte Chemie International Edition, Vol. 54, Issue 15 https://doi.org/10.1002/anie.201409262	journal	March 2015
Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density Placke, Tobias; Kloepsch, Richard; Dühnen, Simon Journal of Solid State Electrochemistry, Vol. 21, Issue 7 https://doi.org/10.1007/s10008-017-3610-7	journal	May 2017
The Recycling of Spent Lithium-Ion Batteries: a Review of Current Processes and Technologies Li, Li; Zhang, Xiaoxiao; Li, Matthew Electrochemical Energy Reviews, Vol. 1, Issue 4 https://doi.org/10.1007/s41918-018-0012-1	journal	September 2018
Molten-salt thermal energy storage in thermoclines under different environmental boundary conditions Yang, Zhen; Garimella, Suresh V. Applied Energy, Vol. 87, Issue 11 https://doi.org/10.1016/j.apenergy.2010.04.024	journal	November 2010
Room temperature molten salts as lithium battery electrolyte Garcia, Béatrice; Lavallée, Serge; Perron, Gérald Electrochimica Acta, Vol. 49, Issue 26 https://doi.org/10.1016/j.electacta.2004.04.041	journal	October 2004
Molten salt synthesis of spherical LiNi0.5Mn1.5O4 cathode materials Wen, Lei; Lu, Qi; Xu, Guoxiang Electrochimica Acta, Vol. 51, Issue 21 https://doi.org/10.1016/j.electacta.2005.12.018	journal	June 2006
Ultrathin Al2O3 Coatings for Improved Cycling Performance and Thermal Stability of LiNi0.5Co0.2Mn0.3O2 Cathode Material Shi, Yang; Zhang, Minghao; Qian, Danna Electrochimica Acta, Vol. 203 https://doi.org/10.1016/j.electacta.2016.03.185	journal	June 2016
Assessing the progress toward lower priced long range battery electric vehicles Nykvist, Björn; Sprei, Frances; Nilsson, Måns Energy Policy, Vol. 124 https://doi.org/10.1016/j.enpol.2018.09.035	journal	January 2019
Synthesis by molten salt and cathodic properties of Li(Ni1/3Co1/3Mn1/3)O2 Reddy, M. V.; Rao, G. V. Subba; Chowdari, B. V. R. Journal of Power Sources, Vol. 159, Issue 1 https://doi.org/10.1016/j.jpowsour.2006.04.134	journal	September 2006
Capacity fade analysis of a lithium ion cell Zhang, Qi; White, Ralph E. Journal of Power Sources, Vol. 179, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.01.028	journal	May 2008
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 Rahman, M. M.; Wang, Jia-Zhao; Hassan, Mohd Faiz Journal of Power Sources, Vol. 195, Issue 13 https://doi.org/10.1016/j.jpowsour.2010.01.073	journal	July 2010
Microstructural investigation of LixNi1/3Mn1/3Co1/3O2 (x ≤ 1) and its aged products via magnetic and diffraction study Mohanty, D.; Gabrisch, H. Journal of Power Sources, Vol. 220 https://doi.org/10.1016/j.jpowsour.2012.08.005	journal	December 2012
Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction Mohanty, Debasish; Kalnaus, Sergiy; Meisner, Roberta A. Journal of Power Sources, Vol. 229 https://doi.org/10.1016/j.jpowsour.2012.11.144	journal	May 2013
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 Noh, Hyung-Joo; Youn, Sungjune; Yoon, Chong Seung Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2013.01.063	journal	July 2013
Failure statistics for commercial lithium ion batteries: A study of 24 pouch cells Harris, Stephen J.; Harris, David J.; Li, Chen Journal of Power Sources, Vol. 342 https://doi.org/10.1016/j.jpowsour.2016.12.083	journal	February 2017
Urea-based hydrothermal synthesis of LiNi0.5Co0.2Mn0.3O2 cathode material for Li-ion battery Shi, Yang; Zhang, Minghao; Fang, Chengcheng Journal of Power Sources, Vol. 394 https://doi.org/10.1016/j.jpowsour.2018.05.030	journal	August 2018
Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H. Materials Science and Engineering: B, Vol. 192 https://doi.org/10.1016/j.mseb.2014.11.014	journal	February 2015
Synthesis of LiNi1/3Co1/3Al1/3O2 cathode material with eutectic molten salt LiOH-LiNO3 Chang, Zhao-Rong; Yu, Xu; Tang, Hong-Wei Powder Technology, Vol. 207, Issue 1-3 https://doi.org/10.1016/j.powtec.2010.11.025	journal	February 2011
Lithium-ion battery recycling processes: Research towards a sustainable course Gaines, Linda Sustainable Materials and Technologies, Vol. 17 https://doi.org/10.1016/j.susmat.2018.e00068	journal	September 2018
Zwitterionic-type molten salt-catalyzed syn-selective aza-Henry reaction: solvent-free one-pot synthesis of β-nitroamines Kundu, Dhiman; Debnath, Rajib Kumar; Majee, Adinath Tetrahedron Letters, Vol. 50, Issue 50 https://doi.org/10.1016/j.tetlet.2009.09.153	journal	December 2009
Best Practice: Performance and Cost Evaluation of Lithium Ion Battery Active Materials with Special Emphasis on Energy Efficiency Meister, Paul; Jia, Haiping; Li, Jie Chemistry of Materials, Vol. 28, Issue 20 https://doi.org/10.1021/acs.chemmater.6b02895	journal	October 2016
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials Mu, Linqin; Lin, Ruoqian; Xu, Rong Nano Letters, Vol. 18, Issue 5 https://doi.org/10.1021/acs.nanolett.8b01036	journal	April 2018
Effect of Ni ²⁺ Content on Lithium/Nickel Disorder for Ni-Rich Cathode Materials Wu, Feng; Tian, Jun; Su, Yuefeng ACS Applied Materials & Interfaces, Vol. 7, Issue 14 https://doi.org/10.1021/acsami.5b00645	journal	April 2015
Resolving the Compositional and Structural Defects of Degraded LiNi _x Co _y Mn _z O ₂ Particles to Directly Regenerate High-Performance Lithium-Ion Battery Cathodes Shi, Yang; Chen, Gen; Liu, Fang ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b00833	journal	June 2018
Structural and Electrochemical Aspects of LiNi _0.8 Co _0.1 Mn _0.1 O ₂ Cathode Materials Doped by Various Cations Weigel, Tina; Schipper, Florian; Erickson, Evan M. ACS Energy Letters, Vol. 4, Issue 2 https://doi.org/10.1021/acsenergylett.8b02302	journal	January 2019
A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries Lv, Weiguang; Wang, Zhonghang; Cao, Hongbin ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 2 https://doi.org/10.1021/acssuschemeng.7b03811	journal	December 2017
Structural Changes and Thermal Stability of Charged LiNi _x Mn _y Co _z O ₂ Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning ACS Applied Materials & Interfaces, Vol. 6, Issue 24 https://doi.org/10.1021/am506712c	journal	December 2014
Defect Chemistry in Layered Li M O ₂ ( M = Co, Ni, Mn, and Li _1/3 Mn _2/3 ) by First-Principles Calculations Koyama, Yukinori; Arai, Hajime; Tanaka, Isao Chemistry of Materials, Vol. 24, Issue 20 https://doi.org/10.1021/cm3018314	journal	October 2012
A Molten Salt Lithium–Oxygen Battery Giordani, Vincent; Tozier, Dylan; Tan, Hongjin Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b11744	journal	February 2016
Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries Qiu, Bao; Zhang, Minghao; Wu, Lijun Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12108	journal	July 2016
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
Current status and challenges for automotive battery production technologies Kwade, Arno; Haselrieder, Wolfgang; Leithoff, Ruben Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0130-3	journal	April 2018
Running out of lithium? A route to differentiate between capacity losses and active lithium losses in lithium-ion batteries Holtstiege, Florian; Wilken, Andrea; Winter, Martin Physical Chemistry Chemical Physics, Vol. 19, Issue 38 https://doi.org/10.1039/C7CP05405J	journal	January 2017
Effective regeneration of LiCoO ₂ from spent lithium-ion batteries: a direct approach towards high-performance active particles Shi, Yang; Chen, Gen; Chen, Zheng Green Chemistry, Vol. 20, Issue 4 https://doi.org/10.1039/C7GC02831H	journal	January 2018
Toward sustainable and systematic recycling of spent rechargeable batteries Zhang, Xiaoxiao; Li, Li; Fan, Ersha Chemical Society Reviews, Vol. 47, Issue 19 https://doi.org/10.1039/C8CS00297E	journal	January 2018
White lines and d -band occupancy for the 3 d transition-metal oxides and lithium transition-metal oxides Graetz, Jason; Ahn, Channing C.; Ouyang, Hao Physical Review B, Vol. 69, Issue 23 https://doi.org/10.1103/PhysRevB.69.235103	journal	June 2004
Factors that affect Li mobility in layered lithium transition metal oxides Kang, Kisuk; Ceder, Gerbrand Physical Review B, Vol. 74, Issue 9 https://doi.org/10.1103/PhysRevB.74.094105	journal	September 2006
An Integrated Probabilistic Approach to Lithium-Ion Battery Remaining Useful Life Estimation No authors listed IEEE Transactions on Instrumentation and Measurement, Vol. 64, Issue 3 https://doi.org/10.1109/TIM.2014.2348613	journal	March 2015
The Lithium future-resources, recycling, and the environment: The Lithium future Wanger, Thomas Cherico Conservation Letters, Vol. 4, Issue 3 https://doi.org/10.1111/j.1755-263X.2011.00166.x	journal	March 2011
Testing of Thermocline Filler Materials and Molten-Salt Heat Transfer Fluids for Thermal Energy Storage Systems in Parabolic Trough Power Plants Brosseau, Doug; Kelton, John W.; Ray, Daniel Journal of Solar Energy Engineering, Vol. 127, Issue 1 https://doi.org/10.1115/1.1824107	journal	February 2005
Lithium Molten Salt Battery at Near Room Temperature Using Low-Melting Alkali Metal Melts Kubota, K.; Matsumoto, H. ECS Transactions, Vol. 73, Issue 1 https://doi.org/10.1149/07301.0095ecst	journal	August 2016
Preferred Orientation of Polycrystalline LiCoO[sub 2] Films Bates, J. B.; Dudney, N. J.; Neudecker, B. J. Journal of The Electrochemical Society, Vol. 147, Issue 1 https://doi.org/10.1149/1.1393157	journal	January 2000
Electrode Side Reactions, Capacity Loss and Mechanical Degradation in Lithium-Ion Batteries Xu, Jiagang; Deshpande, Rutooj D.; Pan, Jie Journal of The Electrochemical Society, Vol. 162, Issue 10 https://doi.org/10.1149/2.0291510jes	journal	January 2015
Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes: I. Nickel-Rich, LiNi Schipper, Florian; Erickson, Evan M.; Erk, Christoph Journal of The Electrochemical Society, Vol. 164, Issue 1 https://doi.org/10.1149/2.0351701jes	journal	December 2016
Remaining capacity estimation of lithium-ion batteries based on the constant voltage charging profile Wang, Zengkai; Zeng, Shengkui; Guo, Jianbin PLOS ONE, Vol. 13, Issue 7 https://doi.org/10.1371/journal.pone.0200169	journal	July 2018
Cost Projection of State of the Art Lithium-Ion Batteries for Electric Vehicles Up to 2030 Berckmans, Gert; Messagie, Maarten; Smekens, Jelle Energies, Vol. 10, Issue 9, p. 1314 https://doi.org/10.3390/en10091314	journal	September 2017
Cycle Life of Commercial Lithium-Ion Batteries with Lithium Titanium Oxide Anodes in Electric Vehicles Han, Xuebing; Ouyang, Minggao; Lu, Languang Energies, Vol. 7, Issue 8 https://doi.org/10.3390/en7084895	journal	July 2014
Preferred Orientation of Crystals and the Intensity Ratios of XRD Peaks of Cathode Material LiCoO₂ Yong-Chong, Chen; Xing-Jun, Xu; Hong-Zhi, Cui Acta Physico-Chimica Sinica, Vol. 23, Issue 12 https://doi.org/10.3866/PKU.WHXB20071222	journal	January 2007

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Ambient‐Pressure Relithiation of Degraded Li _x Ni _0.5 Co _0.2 Mn _0.3 O ₂ (0 < x < 1) via Eutectic Solutions for Direct Regeneration of Lithium‐Ion Battery Cathodes