Impedance characterization of lithium-ion batteries aging under high-temperature cycling: Importance of electrolyte-phase diffusion

Abstract Lithium-ion batteries experiences impedance rise and therefore power fade during aging. Current understanding toward the impedance rise is yet qualitative, leaving quantification of multiple contributions a challenging gap. To fill in this gap, we combine the distribution of relaxation times method and physics-based modeling to analyze the electrochemical impedance spectroscopy of lithium-ion batteries aged by cycling at 45 °C. We find that the oft-neglected low-frequency diffusion is the largest sole source to the impedance rise. Furthermore, thanks to the advanced physics-based impedance model, we distinguish electrolyte- and solid-phase diffusion, identifying that the former dominates over the latter. This piece of understanding implies novel insights into improving battery lifetime, and the methodology developed is flexible to other battery chemistries.

[1]  Dennis W. Dees,et al.  Application of a lithium-tin reference electrode to determine electrode contributions to impedance rise in high-power lithium-ion cells , 2004 .

[2]  G. Lindbergh,et al.  Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes I. Physically Based Electrochemical Model , 2008 .

[3]  S. Lux,et al.  Impedance change and capacity fade of lithium nickel manganese cobalt oxide-based batteries during calendar aging , 2017 .

[4]  Delphine Riu,et al.  A review on lithium-ion battery ageing mechanisms and estimations for automotive applications , 2013 .

[5]  Kang Xu,et al.  Electrolytes and interphases in Li-ion batteries and beyond. , 2014, Chemical reviews.

[6]  K. Jalkanen,et al.  Cycle aging of commercial NMC/graphite pouch cells at different temperatures , 2015 .

[7]  D. Macdonald.  Reflections on the history of electrochemical impedance spectroscopy , 2006 .

[8]  Jörg Illig,et al.  Understanding the impedance spectrum of 18650 LiFePO4-cells , 2013 .

[9]  Jianqiu Li,et al.  A review on the key issues for lithium-ion battery management in electric vehicles , 2013 .

[10]  Moses Ender,et al.  Separation of Charge Transfer and Contact Resistance in LiFePO4-Cathodes by Impedance Modeling , 2012 .

[11]  M. R. Palacín,et al.  Why do batteries fail? , 2016, Science.

[12]  Jianbo Zhang,et al.  Comparison and validation of methods for estimating heat generation rate of large-format lithium-ion batteries , 2014, Journal of Thermal Analysis and Calorimetry.

[13]  Hui Ye,et al.  Ultra High-Precision Studies of Degradation Mechanisms in Aged LiCoO2/Graphite Li-Ion Cells , 2016 .

[14]  V. Subramanian,et al.  Is There a Benefit in Employing Graded Electrodes for Lithium-Ion Batteries? , 2017 .

[15]  Remus Teodorescu,et al.  Degradation Behavior of Lithium-Ion Batteries During Calendar Ageing—The Case of the Internal Resistance Increase , 2018, IEEE Transactions on Industry Applications.

[16]  W. D. Widanage,et al.  A Comparison between Electrochemical Impedance Spectroscopy and Incremental Capacity-Differential Voltage as Li-ion Diagnostic Techniques to Identify and Quantify the Effects of Degradation Modes within Battery Management Systems , 2017 .

[17]  D. Sauer,et al.  Calendar and cycle life study of Li(NiMnCo)O2-based 18650 lithium-ion batteries , 2014 .

[18]  Chaoyang Wang,et al.  Electrochemical Cycle-Life Characterization of High Energy Lithium-Ion Cells with Thick Li(Ni0.6Mn0.2Co0.2)O2 and Graphite Electrodes , 2017 .

[19]  Zhe Li,et al.  An Agglomerate Model for the Impedance of Secondary Particle in Lithium-Ion Battery Electrode , 2014 .

[20]  M. Dubarry,et al.  Cell degradation in commercial LiFePO4 cells with high-power and high-energy designs , 2014 .

[21]  Göran Lindbergh,et al.  Aging in lithium-ion batteries: Model and experimental investigation of harvested LiFePO4 and mesocarbon microbead graphite electrodes , 2013 .

[22]  Pouyan Shafiei Sabet,et al.  Non-invasive investigation of predominant processes in the impedance spectra of high energy lithium-ion batteries with nickel–cobalt–aluminum cathodes , 2018 .

[23]  Dennis W. Dees,et al.  Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes , 2005 .

[24]  Jian Zhang,et al.  Study of the storage performance of a Li-ion cell at elevated temperature , 2010 .

[25]  Bor Yann Liaw,et al.  Graphical analysis of electrochemical impedance spectroscopy data in Bode and Nyquist representations , 2016 .

[26]  Matthieu Dubarry,et al.  Identify capacity fading mechanism in a commercial LiFePO4 cell , 2009 .

[27]  M. Doyle,et al.  The Impedance Response of a Porous Electrode Composed of Intercalation Particles , 2000 .

[28]  Ralph E. White,et al.  Analytical Expression for the Impedance Response for a Lithium-Ion Cell , 2008 .

[29]  Jianbo Zhang,et al.  Theory of Impedance Response of Porous Electrodes: Simplifications, Inhomogeneities, Non-Stationarities and Applications , 2016 .

[30]  Changhong Liu,et al.  Optimal Design of Li-Ion Batteries through Multi-Physics Modeling and Multi-Objective Optimization , 2017 .

[31]  Robert Dominko,et al.  The Importance of Interphase Contacts in Li Ion Electrodes: The Meaning of the High-Frequency Impedance Arc , 2008 .

[32]  Ellen Ivers-Tiffée,et al.  Electrochemical characterization and post-mortem analysis of aged LiMn2O4–NMC/graphite lithium ion batteries part II: Calendar aging , 2014 .

[33]  Matthieu Dubarry,et al.  Synthesize battery degradation modes via a diagnostic and prognostic model , 2012 .

[34]  H. Schichlein,et al.  Deconvolution of electrochemical impedance spectra for the identification of electrode reaction mechanisms in solid oxide fuel cells , 2002 .

[35]  Zhe Li,et al.  An Analytical Three-Scale Impedance Model for Porous Electrode with Agglomerates in Lithium-Ion Batteries , 2015 .

[36]  Ellen Ivers-Tiffée,et al.  Electrochemical characterization and post-mortem analysis of aged LiMn2O4–Li(Ni0.5Mn0.3Co0.2)O2/graphite lithium ion batteries. Part I: Cycle aging , 2014 .

[37]  G. Lindbergh,et al.  Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes II. Positive Electrode Examination , 2008 .

[38]  Ting Hei Wan,et al.  Influence of the Discretization Methods on the Distribution of Relaxation Times Deconvolution: Implementing Radial Basis Functions with DRTtools , 2015 .

[39]  C. Yap,et al.  Investigation of physico-chemical processes in lithium-ion batteries by deconvolution of electrochemical impedance spectra , 2017 .

[40]  J. Schmidt,et al.  Studies on LiFePO4 as cathode material using impedance spectroscopy , 2011 .

[41]  D. Aurbach,et al.  Impedance of a Single Intercalation Particle and of Non-Homogeneous, Multilayered Porous Composite Electrodes for Li-ion Batteries , 2004 .

[42]  D. Sauer,et al.  Characterization of high-power lithium-ion batteries by electrochemical impedance spectroscopy. II: Modelling , 2011 .

[43]  Andreas Nyman,et al.  Analysis of the Polarization in a Li-Ion Battery Cell by Numerical Simulations , 2010 .

[44]  Dirk Uwe Sauer,et al.  Cycle and calendar life study of a graphite|LiNi1/3Mn1/3Co1/3O2 Li-ion high energy system. Part A: Full cell characterization , 2013 .

[45]  M. Wohlfahrt‐Mehrens,et al.  Ageing mechanisms in lithium-ion batteries , 2005 .

[46]  Z. Fu,et al.  Kinetics of Li + Ion Diffusion into FePO4 and FePON Thin Films Characterized by AC Impedance Spectroscopy , 2007 .

[47]  Ralph E. White,et al.  Capacity Fade Mechanisms and Side Reactions in Lithium‐Ion Batteries , 1998 .

[48]  E. Sarasketa-Zabala,et al.  Understanding Lithium Inventory Loss and Sudden Performance Fade in Cylindrical Cells during Cycling with Deep-Discharge Steps , 2015 .

[49]  K. Maute,et al.  A design optimization methodology for Li+ batteries , 2014 .

[50]  Marc Doyle,et al.  Computer Simulations of the Impedance Response of Lithium Rechargeable Batteries , 2000 .

[51]  L. Gu,et al.  Charge carrier accumulation in lithium fluoride thin films due to Li-ion absorption by titania (100) subsurface. , 2012, Nano letters.

[52]  U. Troeltzsch,et al.  Characterizing aging effects of lithium ion batteries by impedance spectroscopy , 2006 .

[53]  Chaoyang Wang,et al.  Cycling degradation of an automotive LiFePO4 lithium-ion battery , 2011 .

[54]  M. Broussely,et al.  Main aging mechanisms in Li ion batteries , 2005 .

[55]  C. Delacourt,et al.  Postmortem analysis of calendar-aged graphite/LiFePO4 cells , 2013 .

[56]  B. Liaw,et al.  Path dependence of lithium ion cells aging under storage conditions , 2016 .

[57]  Chaoyang Wang,et al.  Cycle-Life Characterization of Automotive Lithium-Ion Batteries with LiNiO2 Cathode , 2009 .

[58]  Francesco Ciucci,et al.  Analysis of Electrochemical Impedance Spectroscopy Data Using the Distribution of Relaxation Times: A Bayesian and Hierarchical Bayesian Approach , 2015 .