In Situ Atomic‐Scale Imaging of Phase Boundary Migration in FePO4 Microparticles During Electrochemical Lithiation

The electrochemical lithiation of FePO4 particles is investigated by in situ high-resolution transmission electron microscopy (HRTEM), and the anisotropic lithiation mechanism is directly observed. For the first time and in contrast to the previous post mortem HRTEM observations, a sharp (010) phase boundary between LiFePO4 and FePO4 is observed, which migrates along the [010] direction during lithiation.

[1]  Yang Liu,et al.  Anisotropic swelling and fracture of silicon nanowires during lithiation. , 2011, Nano letters.

[2]  Y. Chiang Building a Better Battery , 2010, Science.

[3]  Daniel A. Cogswell,et al.  Suppression of phase separation in LiFePO₄ nanoparticles during battery discharge. , 2011, Nano letters.

[4]  Peter R. Slater,et al.  Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO4 Olivine-Type Battery Material , 2005 .

[5]  K. Kanamura,et al.  Particle morphology, crystal orientation, and electrochemical reactivity of LiFePO4 synthesized by the hydrothermal method at 443 K , 2007 .

[6]  Rahul Malik,et al.  Particle size dependence of the ionic diffusivity. , 2010, Nano letters.

[7]  Charles Delacourt,et al.  Study of the LiFePO4/FePO4 Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy , 2006 .

[8]  Hsiao-Ying Shadow Huang,et al.  Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries , 2007 .

[9]  Milo R. Dorr,et al.  Anisotropic Phase Boundary Morphology in Nanoscale Olivine Electrode Particles , 2011 .

[10]  Wolfgang Dreyer,et al.  The thermodynamic origin of hysteresis in insertion batteries. , 2010, Nature materials.

[11]  Y. Chiang,et al.  Modeling the competing phase transition pathways in nanoscale olivine electrodes , 2010 .

[12]  W. Craig Carter,et al.  Overpotential-Dependent Phase Transformation Pathways in Lithium Iron Phosphate Battery Electrodes , 2010 .

[13]  Martin Z. Bazant,et al.  Nonequilibrium Thermodynamics of Porous Electrodes , 2012, 1204.2934.

[14]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[15]  Ruhul Amin,et al.  Phase boundary propagation in large LiFePO4 single crystals on delithiation. , 2012, Journal of the American Chemical Society.

[16]  Daniel A. Cogswell,et al.  Coherency strain and the kinetics of phase separation in LiFePO4 nanoparticles. , 2011, ACS nano.

[17]  Dane Morgan,et al.  Li Conductivity in Li x MPO 4 ( M = Mn , Fe , Co , Ni ) Olivine Materials , 2004 .

[18]  Li-Jun Wan,et al.  LiFePO4 Nanoparticles Embedded in a Nanoporous Carbon Matrix: Superior Cathode Material for Electrochemical Energy‐Storage Devices , 2009, Advanced materials.

[19]  Venkat Srinivasan,et al.  Discharge Model for the Lithium Iron-Phosphate Electrode , 2004 .

[20]  C. Delmas,et al.  Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model. , 2008, Nature materials.

[21]  Ting Zhu,et al.  Ultra-strength materials , 2010 .

[22]  John P. Sullivan,et al.  In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode , 2010, Science.

[23]  Ting Zhu,et al.  In Situ TEM Experiments of Electrochemical Lithiation and Delithiation of Individual Nanostructures , 2012 .

[24]  M. Bazant Phase-Field Theory of Ion Intercalation Kinetics , 2012 .

[25]  John O. Thomas,et al.  The source of first-cycle capacity loss in LiFePO4 , 2001 .

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

[27]  Montse Casas-Cabanas,et al.  Room-temperature single-phase Li insertion/extraction in nanoscale Li(x)FePO4. , 2008, Nature materials.

[28]  Thomas J. Richardson,et al.  Electron Microscopy Study of the LiFePO4 to FePO4 Phase Transition , 2006 .

[29]  Alain Mauger,et al.  Study of the Li-insertion/extraction process in LiFePO4/FePO4 , 2009 .

[30]  Yet-Ming Chiang,et al.  Electronically conductive phospho-olivines as lithium storage electrodes , 2002, Nature materials.

[31]  Sung-Wook Nam,et al.  Electrical Wind Force–Driven and Dislocation-Templated Amorphization in Phase-Change Nanowires , 2012, Science.

[32]  Rahul Malik,et al.  Kinetics of non-equilibrium lithium incorporation in LiFePO4. , 2011, Nature materials.

[33]  Byoungwoo Kang,et al.  Battery materials for ultrafast charging and discharging , 2009, Nature.

[34]  Jeff Wolfenstine,et al.  Kinetic Study of the Electrochemical FePO 4 to LiFePO 4 Phase Transition , 2007 .

[35]  Martin Z. Bazant,et al.  Intercalation dynamics in rechargeable battery materials : General theory and phase-transformation waves in LiFePO4 , 2008 .

[36]  Lin Gu,et al.  Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution. , 2011, Journal of the American Chemical Society.