Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3% lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism and the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation compounds in general and can help guide the design of better electrodes. Lithium transport and phase transformation kinetics in olivine LiFePO4 electrode remain not fully understood. Here the authors show that microsized olivine particles possess 2D lithium diffusivity and exhibit a possible hybrid mode of phase boundary migration upon cycling.

• Publication year

  2017

• Venue

  Nature Communications

• Publication date

  2017-10-01

• Fields of study

  Medicine, Materials Science

• Identifiers
  DOI 10.1038/s41467-017-01315-8PMID 29084965PMCID 5662729
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Direct visualization of hydrogen absorption dynamics in individual palladium nanoparticles

  2017cited by this paper
• Thermodynamic stability of driven open systems and control of phase separation by electro-autocatalysis.

  2017cited by this paper
• Feeling the strain: enhancing ionic transport in olivine phosphate cathodes for Li- and Na-ion batteries through strain effects

  2016cited by this paper
• [100]-Oriented LiFePO4 Nanoflakes toward High Rate Li-Ion Battery Cathode.

  2016cited by this paper
• Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles

  2016cited by this paper
• enhancing ionic transport in olivine phosphate cathodes for Li-and Naion batteries through strain e ff ects †

  2016cited by this paper
• Visualization of anisotropic-isotropic phase transformation dynamics in battery electrode particles

  2016cited by this paper
• Defects, Entropy, and the Stabilization of Alternative Phase Boundary Orientations in Battery Electrode Particles

  2016cited by this paper
• Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in LixFePO₄.

  2015cited by this paper
• Tracking Non‐Uniform Mesoscale Transport in LiFePO4 Agglomerates During Electrochemical Cycling

  2015cited by this paper
• Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

  2015cited by this paper
• Phase evolution in single-crystalline LiFePO4 followed by in situ scanning X-ray microscopy of a micrometre-sized battery

  2015cited by this paper
• Size-dependent surface phase change of lithium iron phosphate during carbon coating

  2014cited by this paper
• Particle-size and morphology dependence of the preferred interface orientation in LiFePO4 nano-particles

  2014cited by this paper
• Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes

  2014cited by this paper
• Rate-induced solubility and suppression of the first-order phase transition in olivine LiFePO4.

  2014cited by this paper
• Current-induced transition from particle-by-particle to concurrent intercalation in phase-separating battery electrodes.

  2014cited by this paper
• In operando tracking phase transformation evolution of lithium iron phosphate with hard X-ray microscopy

  2014cited by this paper
• A Critical Review of the Li Insertion Mechanisms in LiFePO4 Electrodes

  2013cited by this paper
• Transient phase change in two phase reaction between LiFePO4 and FePO4 under battery operation

  2013cited by this paper
• Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation.

  2013cited by this paper
• Intercalation pathway in many-particle LiFePO4 electrode revealed by nanoscale state-of-charge mapping.

  2013cited by this paper
• Screw dislocation driven growth of nanomaterials.

  2013cited by this paper
• In Situ Atomic‐Scale Imaging of Phase Boundary Migration in FePO4 Microparticles During Electrochemical Lithiation

  2013cited by this paper
• Free Energy of a Nonuniform System. I. Interfacial Free Energy and Free Energy of a Nonuniform System. III. Nucleation in a Two‐Component Incompressible Fluid

  2013cited by this paper
• Kinetically Controlled Lithium-Staging in Delithiated LiFePO4 Driven by the Fe Center Mediated Interlayer Li–Li Interactions

  2012cited by this paper
• Direct evidence of concurrent solid-solution and two-phase reactions and the nonequilibrium structural evolution of LiFePO4.

  2012cited by this paper
• Surface modes of coherent spinodal decomposition.

  2012cited by this paper
• Phase boundary propagation in large LiFePO4 single crystals on delithiation.

  2012cited by this paper
• Suppression of phase separation in LiFePO₄ nanoparticles during battery discharge.

  2011cited by this paper
• Coherency strain and the kinetics of phase separation in LiFePO4 nanoparticles.

  2011cited by this paper
• Study of antisite defects in hydrothermally prepared LiFePO₄ by in situ X-ray diffraction.

  2011cited by this paper
• Kinetics of non-equilibrium lithium incorporation in LiFePO4.

  2011cited by this paper
• Anisotropic Phase Boundary Morphology in Nanoscale Olivine Electrode Particles

  2011cited by this paper
• Particle size dependence of the ionic diffusivity.

  2010cited by this paper
• An Electrochemical Cell for Operando Study of Lithium Batteries Using Synchrotron Radiation

  2010cited by this paper
• Galvanostatic Intermittent Titration Technique for Phase-Transformation Electrodes

  2010cited by this paper
• Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines

  2009cited by this paper
• Investigation on diffusion behavior of Li+ in LiFePO4 by capacity intermittent titration technique (CITT)

  2009cited by this paper
• Comparative Study of Lithium Transport Kinetics in Olivine Cathodes for Li-ion Batteries†

  2009cited by this paper
• Battery materials for ultrafast charging and discharging

  2009cited by this paper
• Study of the Li-insertion/extraction process in LiFePO4/FePO4

  2009cited by this paper
• Li-ion diffusion kinetics in LiFePO4 thin film prepared by radio frequency magnetron sputtering

  2009cited by this paper
• Intercalation dynamics in rechargeable battery materials : General theory and phase-transformation waves in LiFePO4

  2008cited by this paper
• What is spinodal decomposition

  2008cited by this paper
• Study on dynamics of structural transformation during charge/discharge of LiFePO4 cathode

  2008cited by this paper
• Ionic and electronic transport in single crystalline LiFePO4 grown by optical floating zone technique

  2008cited by this paper
• TEM Study of Fracturing in Spherical and Plate-like LiFePO4 Particles

  2008cited by this paper
• Size-Dependent Lithium Miscibility Gap in Nanoscale Li1 − x FePO4

  2007cited by this paper
• Strain Accommodation during Phase Transformations in Olivine‐Based Cathodes as a Materials Selection Criterion for High‐Power Rechargeable Batteries

  2007cited by this paper
• A Discharge Model for Phase Transformation Electrodes: Formulation, Experimental Validation, and Analysis

  2007cited by this paper
• Electron Microscopy Study of the LiFePO4 to FePO4 Phase Transition

  2006cited by this paper
• Ab initio study of the migration of small polarons in olivine Li x FePO 4 and their association with lithium ions and vacancies

  2006cited by this paper
• Study of the LiFePO4/FePO4 Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy

  2006cited by this paper
• Room-temperature miscibility gap in LixFePO4

  2006cited by this paper
• Kinetics of Materials: Balluffi/Kinetics

  2005cited by this paper
• Discharge Model for the Lithium Iron-Phosphate Electrode

  2004cited by this paper
• Li Conductivity in Li x MPO 4 ( M = Mn , Fe , Co , Ni ) Olivine Materials

  2004cited by this paper
• Electronically conductive phospho-olivines as lithium storage electrodes

  2002cited by this paper
• Determination of the chemical diffusion coefficient of lithium in LiFePO4

  2002cited by this paper
• Reactivity, stability and electrochemical behavior of lithium iron phosphates

  2002cited by this paper
• Optimized LiFePO4 for Lithium Battery Cathodes

  2001cited by this paper
• Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates

  2001cited by this paper
• Phospho‐olivines as Positive‐Electrode Materials for Rechargeable Lithium Batteries

  1997cited by this paper
• Mass transport in the presence of internal defect reactions. Concept of conservative ensembles. III, Trapping effect of dopants on chemical diffusion

  1993cited by this paper
• Mass Transport in the Presence of Internal Defect Reactions—Concept of Conservative Ensembles: I, Chemical Diffusion in Pure Compounds

  1993cited by this paper
• Free Energy of a Nonuniform System. I. Interfacial Free Energy

  1958cited by this paper
• Supplementary Figures Supplementary Figure 1 | Construction of Chemical Phase Maps Using Improved Data Processing Method

  year unknowncited by this paper

• Direct repair of spent LiFePO4 via a closed-loop deep eutectic solvent process

  2026cites this paper
• Consecutive intra-particle phase transitions in the LiFePO 4 battery electrode material

  2026cites this paper
• A novel strategy to synthesize LiFePO4 by recovering heterosite FePO4 from spent lithium batteries and reloading lithium

  2026cites this paper
• Surface Antisite Defect-Induced Three-Dimensional Li+ Diffusion Enables Stable and Kinetic-Enhanced LiFe1-xMnxPO4 Cathodes.

  2026cites this paper
• Homogenization‐confined‐repair regeneration of spent LiFePO4 cathodes via tunable pre‐oxidization and microencapsulation strategy

  2025cites this paper
• In operando and in situ characterization tools for advanced rechargeable batteries: Effects of electrode origin and electrolyte

  2025cites this paper
• Repurposing spent LiFePO4 batteries for sustainable photothermal-upcycling of polyesters

  2025cites this paper
• A critical review on the direct regeneration technologies of cathode materials from spent lithium iron phosphate batteries

  2025cites this paper
• Progress and prospect of spent lithium iron phosphate cathode materials recycling: A review

  2025cites this paper
• Probing the Effect of Electrode Thermodynamics on Reaction Heterogeneity in Thick Battery Electrodes

  2025cites this paper
• Direct and Low‐Temperature Regeneration of Degraded LiFePO₄ Cathodes at Ambient Conditions Using Green and Sustainable Deep Eutectic Solvent

  2025cites this paper
• Disordered Rocksalts as High‐Energy and Earth‐Abundant Li‐Ion Cathodes

  2025cites this paper
• Troubleshooting Carbon Nanotube Bundling Using Electrostatic Energy-Driven Dispersion for LiFePO4 Bimodal Thick Electrode in Lithium-Ion Batteries.

  2025cites this paper
• Direct Recycling of Spent LiFePO4 Cathodes Through Photocatalytic Correction of Anti‐Site Defects

  2025cites this paper
• Enhancement of Cathode Superior Kinetics and Li-Storage Properties of LiMn0.5Fe0.5PO4@C Cathode Materials by Ni Doping Strategy

  2025cites this paper
• Investigating the Reductive Phosphatization Reaction Pathway in the Synthesis of Transition Metal Phosphates: A Case Study on Titanium Phosphates

  2025cites this paper
• Study of thermodynamic and kinetic behaviours of tin anode and its variation with state of charge, state of health and operating current rates of the battery

  2025cites this paper
• Unveiling Residual Charge Effects in the Direct Regeneration of Spent LiFePO4.

  2025cites this paper
• Sustainable and efficient strategies for recovering spent LiFePO4-based lithium-ion batteries

  2025cites this paper
• Molecular engineering strategies of ammonium vanadates for advanced zinc-ion storage

  2025cites this paper
• Phase Transitions and Ion Transport in Lithium Iron Phosphate by Atomic‐Scale Analysis to Elucidate Insertion and Extraction Processes in Li‐Ion Batteries

  2024cites this paper
• Scalable Top-Down Approach for Recycling Highly Degraded Spent LiFePO4 via Lattice Fragmentation-Regeneration.

  2024cites this paper
• Setting the standard for machine learning in phase field prediction: a benchmark dataset and baseline metrics

  2024cites this paper
• Direct Regeneration of Industrial LiFePO4 Black Mass Through A Glycerol-Enabled Granule Reconstruction Strategy.

  2024cites this paper
• Hystimator: DRT‐based hysteresis modelling for accurate SoC estimation in LFP battery cells

  2024cites this paper
• How dispersed LLZTO enhances ionic conductivity in LiFePO4 composite cathodes for solid-state batteries

  2024cites this paper
• Direct regeneration of LiFePO4 cathode by inherent impurities in spent lithium-ion batteries.

  2024cites this paper
• Electrochemical Relithiation in Spent LiFePO4 Slurry for Regeneration of Lithium-Ion Battery Cathode.

  2024cites this paper
• Diffusion of ferrocene through vanadyl phosphate by density functional theory.

  2024cites this paper
• Enhancing the Mn Redox Kinetics of LiMn0.5Fe0.5PO4 Cathodes Through a Synergistic Co-Doping with Niobium and Magnesium for Lithium-Ion Batteries.

  2024cites this paper
• Selection of Li-Ion Batteries Used On Electric Vehicles

  2024cites this paper
• Ammonia-free synthesis of lithium manganese iron phosphate cathodes via a co-precipitation reaction

  2024cites this paper
• Toward Sustainable Lithium Iron Phosphate in Lithium‐Ion Batteries: Regeneration Strategies and Their Challenges

  2024cites this paper
• Investigation of the Single‐Particle Scale Structure–Activity Relationship Providing New Insights for the Development of High‐Performance Batteries

  2024cites this paper
• Combined study of phase transitions in the P2-type Na_XNi_1/3Mn_2/3O_2 cathode material: experimental, ab-initio and multiphase-field results

  2024cites this paper
• Towards Greener Recycling: Direct Repair of Cathode Materials in Spent Lithium-Ion Batteries

  2024cites this paper
• Based on N, F, and P co-doping biomass carbon to construct 3D porous carbon coated LiFePO4 for preparing lithium-ion batteries

  2024cites this paper
• Fluorine Chemistry in Rechargeable Batteries: Challenges, Progress, and Perspectives.

  2024cites this paper
• A high Li-ion diffusion kinetics in multidimensional and compact-structured electrodes via vacuum filtration casting

  2024cites this paper
• Progress in doping and crystal deformation for polyanions cathode based lithium-ion batteries

  2024cites this paper
• Phase-field electrochemical simulations of reconstructed graphite electrodes

  2024cites this paper
• Research on green recycling of lithium-ion batteries cathode waste powder

  2024cites this paper
• Strengthen metal-O interaction toward high ionic mobility on doping LiFePO4

  2024cites this paper
• A Li-rich strategy towards advanced Mn-doped triphylite cathodes for Li-ion batteries

  2023cites this paper
• Electrochemical Restoration of Battery Materials Guided by Synchrotron Radiation Technology for Sustainable Lithium‐Ion Batteries

  2023cites this paper
• Polyacrylonitrile-Derived Carbon Nanocoating for Long-Life High-Power Phosphate Electrodes

  2023cites this paper
• Direct regeneration of degraded lithium-ion battery cathodes with a multifunctional organic lithium salt

  2023cites this paper
• A Multifunctional Amino Acid Enables Direct Recycling of Spent LiFePO4 Cathode Material

  2023cites this paper
• The decisive role of electrostatic interactions in transport mode and phase segregation of lithium ions in LiFePO4

  2023cites this paper
• Advantages of a Solid Solution over Biphasic Intercalation for Vanadium-Based Polyanion Cathodes in Na-Ion Batteries.

  2023cites this paper
• Defluorination and directional conversion to light fuel by lithium synergistic vacuum catalytic co-pyrolysis for electrolyte and polyvinylidene fluoride in spent lithium-ion batteries.

  2023cites this paper
• Dynamic surface phases controlling asymmetry of high-rate lithiation and delithiation in phase-separating electrodes

  2023cites this paper
• Physics-Based Simulation of Electrochemical Impedance Spectroscopy of Complex Electrode Microstructures Using Smoothed Boundary Method

  2022cites this paper
• Chemical Redox of Lithium-Ion Solid Electroactive Material in a Packed Bed Flow Reactor

  2022cites this paper
• Dynamic Investigation of Battery Materials via Advanced Visualization: From Particle, Electrode to Cell Level

  2022cites this paper
• Solvent Control of the Nucleation-Induced Voltage Hysteresis in Li-Rich Lifepo4 Materials

  2022cites this paper
• Reaction Heterogeneity in LiFePO4 Agglomerates and the Role of Intercalation-Induced Stress

  2022cites this paper
• Modeling intercalation in cathode materials with phase-field methods: Assumptions and implications using the example of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si26.svg"><mml:mrow><mml:mtext>Li</mml:mtext><mml:msub><mml:mtext>FePO</mml:mtext><mml:mn>4</mml:mn></mml:msub></mm

  2022cites this paper
• Recent Research Progress of Silicon‐Based Anode Materials for Lithium‐Ion Batteries

  2022cites this paper
• A Convergent Understanding of Charged Defects

  2022cites this paper
• Recent progress in Mn and Fe-rich cathode materials used in Li-ion batteries

  2022cites this paper
• Electrochemical dynamics in hybrid graphite–carbon electrodes

  2022cites this paper
• Direct recovery: A sustainable recycling technology for spent lithium-ion battery

  2022cites this paper
• Nanostructuring‐Promoted Non‐Equilibrium Phase Transformation of Bi Anodes Toward Diffusion‐Controlled Reaction for K‐Ion Batteries

  2022cites this paper
• Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study.

  2021cites this paper
• Entering Voltage Hysteresis in Phase Separating Materials: Revealing the Thermodynamic Origin of a Newly Discovered Phenomenon and Its Impact on the Electric Response of a Battery

  2021cites this paper
• Probing lattice defects in crystalline battery cathode using hard X-ray nanoprobe with data-driven modeling

  2021cites this paper
• Crystal Structures of Two Titanium Phosphate-Based Proton Conductors: Ab Initio Structure Solution and Materials Properties

  2021cites this paper
• L-Lysine-assisted solvothermal synthesis of hollow-like structure LiFePO4/C powders as cathode materials for Li-ion batteries

  2021cites this paper
• Understanding solid electrolyte interphases: Advanced characterization techniques and theoretical simulations

  2021cites this paper
• Recycled cathode materials enabled superior performance for lithium-ion batteries

  2021cites this paper
• Structural and chemical evolution in layered oxide cathodes of lithium-ion batteries revealed by synchrotron techniques

  2021cites this paper
• Facile synthesis of novel, known, and low-valent transition metal phosphates via reductive phosphatization

  2021cites this paper
• Absolute Local Quantification of Li as Function of State-of-Charge in All-Solid-State Li Batteries via 2D MeV Ion-Beam Analysis

  2021cites this paper
• Oxygen Defects Engineering of VO2·xH2O Nanosheets via In Situ Polypyrrole Polymerization for Efficient Aqueous Zinc Ion Storage

  2021cites this paper
• P3-Type K0.45Co1/12Mg1/12Mn5/6O2 as a superior cathode material for potassium-ion batteries with high structural reversibility ensured by Co–Mg Co-substitution

  2021cites this paper
• Advanced electrochemical analysis of metal-ion battery materials for rationalizing and improving battery performance

  2021cites this paper
• Efficient Simulation of Chemical–Mechanical Coupling in Battery Active Particles

  2021cites this paper
• Hydrothermal synthesis of olivine phosphates in the presence of excess phosphorus: a case study of LiMn0.8Fe0.19Mg0.01PO4

  2021cites this paper
• Self-supervised learning and prediction of microstructure evolution with convolutional recurrent neural networks

  2021cites this paper
• Pseudocapacitance-Dominated Li-Ion Capacitors Showing Remarkable Energy Efficiency by Introducing Amorphous LiFePO4 in the Cathode

  2021cites this paper
• Hydrothermally synthesized nanostructured LiMnxFe1−xPO4 (x = 0–0.3) cathode materials with enhanced properties for lithium-ion batteries

  2021cites this paper
• Multiphase-field modeling of spinodal decomposition during intercalation in an Allen-Cahn framework

  2021cites this paper
• DFT simulation of NaFeSnO4 structure, electronic and electrochemical properties validated by experimental results

  2021cites this paper
• Three‐stage kinetics of laser‐induced LiFePO 4 decomposition

  2020cites this paper
• Phase boundary propagation mode in nano-sized electrode materials evidenced by potentiostatic current transients analysis: Li-rich LiFePO4 case study

  2020cites this paper
• Simultaneous Monitoring of Structural Changes and Phase Distribution of LiFePO4 Along the Cathode Thickness of Li Metal Polymer Battery

  2020cites this paper
• Efficient Direct Recycling of Lithium-Ion Battery Cathodes by Targeted Healing

  2020cites this paper
• Application of phase-field method in rechargeable batteries

  2020cites this paper
• Mechanisms and Applications of Steady-State Photoluminescence Spectroscopy in Two-Dimensional Transition-Metal Dichalcogenides.

  2020cites this paper
• Intelligent optimization methodology of battery pack for electric vehicles: A multidisciplinary perspective

  2020cites this paper
• Atomic-Scale Analysis of Biphasic Boundaries in the Lithium-Ion Battery Cathode Material LiFePO4

  2020cites this paper
• Phase boundary propagation kinetics predominately limit the rate capability of NASICON-type Na3+xMnxV2-x(PO4)3 (0≤x≤1) materials

  2020cites this paper
• Polaron transport mechanism in maricite NaFePO4: A combined experimental and simulation study

  2020cites this paper
• Synthesis of (Li2Fe1-yMny)SO Antiperovskites with Comprehensive Investigations of (Li2Fe0.5Mn0.5)SO as Cathode in Li-ion Batteries.

  2020cites this paper
• b-axis phase boundary movement induced (020) plane cracking in LiFePO4.

  2020cites this paper
• A scaling law to determine phase morphologies during ion intercalation

  2020cites this paper
• Extra Li-ion storage of LiFePO4/C composite materials synthesized with Fe1.5P

  2020cites this paper
• Quantifying redox heterogeneity in single-crystalline LiCoO2 cathode particles.

  2020cites this paper
• Three-dimensional phase evolution and stress-induced non-uniform Li intercalation behavior in lithium iron phosphate

  2020cites this paper