A TEM study of morphological and structural degradation phenomena in LiFePO4‐CB cathodes

Summary LiFePO4-based cathodes suffer from various degradation mechanisms, which influences the battery performance. In this paper, morphological and structural degradation phenomena in laboratory cathodes made of LiFePO4 mixed with carbon black (CB) in a 1 mol/L LiPF6 in EC : DMC (1:1 by weight) electrolyte are investigated by transmission electron microscopy at various preparation, assembling, storage, and cycling stages. High-resolution transmission electron microscopy imaging shows that continuous SEI layers are formed on the LiFePO4 particles and that both storage and cycling affect the formation. Additionally, loss of CB crystallinity, CB aggregation, and agglomeration is observed. Charge–discharge curves and impedance spectra measured during cycling confirm that these degradation mechanisms reduce the cathode conductivity and capacity. Copyright © 2016 John Wiley & Sons, Ltd.

[1]  F. Gao,et al.  Kinetic behavior of LiFePO4/C cathode material for lithium-ion batteries , 2008 .

[2]  M. Verbrugge,et al.  Aging Mechanisms of LiFePO4 Batteries Deduced by Electrochemical and Structural Analyses , 2010 .

[3]  Haiyan Gao,et al.  High rate capability of Co-doped LiFePO4/C , 2013 .

[4]  A. Hollenkamp,et al.  Carbon properties and their role in supercapacitors , 2006 .

[5]  David B. Williams,et al.  Transmission Electron Microscopy: A Textbook for Materials Science , 1996 .

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

[7]  D. Ugarte Curling and closure of graphitic networks under electron-beam irradiation , 1992, Nature.

[8]  Gang Liu,et al.  Influence of AlF3 coating on the electrochemical properties of LiFePO4/graphite Li-ion batteries , 2009 .

[9]  Danna Qian,et al.  Recent progress in cathode materials research for advanced lithium ion batteries , 2012 .

[10]  Claus Daniel,et al.  Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes. , 2013, Journal of colloid and interface science.

[11]  Venkat R. Subramanian,et al.  Model-Based SEI Layer Growth and Capacity Fade Analysis for EV and PHEV Batteries and Drive Cycles , 2014 .

[12]  Daniel A. Cogswell,et al.  Theory of coherent nucleation in phase-separating nanoparticles. , 2013, Nano letters.

[13]  Xiaozhen Liao,et al.  Electrochemical behavior of LiFePO4/C cathode material for rechargeable lithium batteries , 2005 .

[14]  Feng Wu,et al.  Enhanced electrochemical performance of LiFePO4 cathode with the addition of fluoroethylene carbonate in electrolyte , 2013, Journal of Solid State Electrochemistry.

[15]  Chao Luo,et al.  Comparison of electrochemical performances of olivine NaFePO4 in sodium-ion batteries and olivine LiFePO4 in lithium-ion batteries. , 2013, Nanoscale.

[16]  Andrew L. Hector,et al.  Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries , 2014, The journal of physical chemistry. C, Nanomaterials and interfaces.

[17]  Michael Fowler,et al.  Li‐ion battery performance and degradation in electric vehicles under different usage scenarios , 2016 .

[18]  David B. Williams,et al.  Transmission Electron Microscopy , 1996 .

[19]  Phl Peter Notten,et al.  Modeling the SEI-Formation on Graphite Electrodes in LiFePO4 Batteries , 2015 .

[20]  K. Edström,et al.  Analysis of the Interphase on Carbon Black Formed in High Voltage Batteries , 2015 .

[21]  P. S. Jørgensen,et al.  Electron microscopy investigations of changes in morphology and conductivity of LiFePO4/C electrodes , 2016 .

[22]  K. S. Nanjundaswamy,et al.  Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries , 1997 .

[23]  YoungJung Chang,et al.  Electrochemical Impedance Analysis for Lithium Ion Intercalation into Graphitized Carbons , 2000 .

[24]  Xiaofeng Qian,et al.  In situ observation of random solid solution zone in LiFePO₄ electrode. , 2014, Nano letters.

[25]  John D Sherwood,et al.  A review of the terms agglomerate and aggregate with a recommendation for nomenclature used in powder and particle characterization. , 2002, Journal of pharmaceutical sciences.

[26]  Kazuo Yamamoto,et al.  Dynamic visualization of the electric potential in an all-solid-state rechargeable lithium battery. , 2010, Angewandte Chemie.

[27]  R. V. Vander Wal,et al.  Analysis of HRTEM images for carbon nanostructure quantification , 2004 .

[28]  Paul K. Chu,et al.  Characterization of amorphous and nanocrystalline carbon films , 2006 .

[29]  K. Ostrikov,et al.  Graphitization of nanocrystalline carbon microcoils synthesized by catalytic chemical vapor deposition , 2008 .

[30]  J. Belt,et al.  Development and Use of a Lithium-Metal Reference Electrode in Aging Studies of Lithium-Ion Batteries , 2014 .

[31]  M. Armand,et al.  Surface chemistry of carbon-treated LiFePO4 particles for Li-ion battery cathodes studied by PES , 2003 .

[32]  Guangchuan Liang,et al.  The cycling performance of LiFePO4/C cathode materials , 2009 .

[33]  D. Goers,et al.  Development of carbon conductive additives for advanced lithium ion batteries , 2011 .

[34]  W. Han,et al.  In Situ AFM Imaging of Solid Electrolyte Interfaces on HOPG with Ethylene Carbonate and Fluoroethylene Carbonate-Based Electrolytes. , 2015, ACS applied materials & interfaces.

[35]  N. Kwon The effect of carbon morphology on the LiCoO2 cathode of lithium ion batteries , 2013 .

[36]  Chia‐Chin Chang,et al.  Tris(pentafluorophenyl) borane as an electrolyte additive for LiFePO4 battery , 2009 .

[37]  Ann Marie Sastry,et al.  Particle Interaction and Aggregation in Cathode Material of Li-Ion Batteries: A Numerical Study , 2011 .

[38]  Chang Liu,et al.  New insight into the solid electrolyte interphase with use of a focused ion beam. , 2005, The journal of physical chemistry. B.

[39]  Seung M. Oh,et al.  Effect of carbon additive on electrochemical performance of LiCoO2 composite cathodes , 2002 .

[40]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[41]  Pontus Svens,et al.  Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis , 2014 .

[42]  Ilke Arslan,et al.  Direct visualization of initial SEI morphology and growth kinetics during lithium deposition by in situ electrochemical transmission electron microscopy. , 2014, Chemical communications.

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

[44]  T. Tyliszczak,et al.  High-resolution chemical analysis on cycled LiFePO4 battery electrodes using energy-filtered transmission electron microscopy , 2014 .

[45]  A. Manthiram,et al.  In situ Raman spectroscopy of LiFePO4: size and morphology dependence during charge and self-discharge , 2013, Nanotechnology.

[46]  Sylvain Franger,et al.  LiFePO4 Synthesis Routes for Enhanced Electrochemical Performance , 2002 .

[47]  Jou-Hyeon Ahn,et al.  for Rechargeable Lithium Batteries , 2009 .

[48]  Claudia Felser,et al.  On the influence of bandstructure on transport properties of magnetic tunnel junctions with Co2Mn1−xFexSi single and multilayer electrode , 2008 .

[49]  M. Mastragostino,et al.  Reduced Graphene Oxide in Cathode Formulations Based on LiNi0.5Mn1.5O4 , 2015 .

[50]  X. Sun,et al.  the remaining challenges for future energy storage , 2015 .

[51]  Sai-Cheong Chung,et al.  Optimized LiFePO4 for Lithium Battery Cathodes , 2001 .

[52]  Jiajun Wang,et al.  Olivine LiFePO4: the remaining challenges for future energy storage , 2015 .

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

[54]  E. A. Belenkov Formation of Graphite Structure in Carbon Crystallites , 2001 .

[55]  C. Medaglia,et al.  A Numerical Study , 2005 .