Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics

Abstract

Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create inhomogeneities that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend on the order parameter -- and its gradients, at phase boundaries. This Account presents a general theory of chemical kinetics based on nonequilibrium thermodynamics. The reaction rate is a nonlinear function of the thermodynamic driving force (free energy of reaction) expressed in terms of variational chemical potentials. The Cahn-Hilliard and Allen-Cahn equations are unified and extended via a master equation for non-equilibrium chemical thermodynamics. For electrochemistry, both Marcus and Butler-Volmer kinetics are generalized for concentrated solutions and ionic solids. The theory is applied to intercalation dynamics in the phase separating Li-ion battery material Li${}_x$FePO${}_4$.

arXiv commentresearch account, 17 two-column pages, 12 figs, 78 refs - some typos corrected Accounts of Chemical Research (2013)

References in corpus (11)

• Double layer in ionic liquids: Overscreening vs. crowding
• Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge
• Coherency strain and the kinetics of phase separation in LiFePO4
• Phase field modeling of electrochemistry I: Equilibrium
• Effects of electrostatic correlations on electrokinetic phenomena
• Relationship between Thermodynamic Driving Force and One-Way Fluxes in Reversible Chemical Reactions
• Phase field modeling of electrochemistry II: Kinetics
• Computing Counterion Densities at Intermediate Coupling
• Statistical Kinetics of Phase-Transforming Nanoparticles in LiFePO4 Porous Electrodes
• Theory of Sorption Hysteresis in Nanoporous Solids: II. Molecular condensation
• Topology and shape optimization of induced-charge electro-osmotic micropumps

Cited by in corpus (62)

• Charge Transfer Kinetics at the Solid-Solid Interface in Porous Electrodes
• Performance Metrics for the Objective Assessment of Capacitive Deionization Systems
• Operando optical tracking of single-particle ion dynamics and phase transitions in battery electrodes
• Phase-field simulations of lithium dendrite growth with open-source software
• Electrochemical Ion Insertion: From Atoms to Devices
• Theory of Nucleation in Phase-separating Nanoparticles
• Solid-Electrolyte Interphase During Battery Cycling: Theory of Growth Regimes
• Thermodynamic Stability of Driven Open Systems and Control of Phase Separation by Electro-autocatalysis
• Modeling Nucleation and Growth of Zinc Oxide During Discharge of Primary Zinc-Air Batteries
• Intercalation kinetics in multiphase layered materials
• Over-limiting Current and Control of Dendritic Growth by Surface Conduction in Nanopores
• Theory of Impedance Spectroscopy for Lithium Batteries
• Electrochemical kinetics of SEI growth on carbon black, II: Modeling
• Phase-field study of electrochemical reactions at exterior and interior interfaces in Li-Ion battery electrode particles
• Energetics and cathode voltages of LiMPO${}_4$ olivines (M = Fe, Mn) from extended Hubbard functionals
• Dynamics of Ion Transport in Ionic Liquids
• Theory of phase separation and polarization for dissociated ionic liquids
• Theory of linear sweep voltammetry with diffuse charge: unsupported electrolytes, thin films, and leaky membranes
• Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries
• Zinc Electrode Shape-Change in Secondary Air Batteries: A 2D Modeling Approach
• Electro-Chemo-Mechanical Modeling of Solid-State Batteries
• Autonomous decision making for solid-state synthesis of inorganic materials
• Explaining key properties of lithiation in TiO${}_2$-anatase Li-ion battery electrodes using phase-field modelling
• Interplay of phase boundary anisotropy and electro-autocatalytic surface reactions on the lithium intercalation dynamics in Li${}_X$FePO${}_4$ platelet-like nanoparticles
• A continuum electro-chemo-mechanical gradient theory coupled with damage: Application to Li-metal filament growth in all-solid-state batteries
• Morphological instability during steady electrodeposition at overlimiting currents
• Population dynamics of driven autocatalytic reactive mixtures
• Nonvolatile Electrochemical Random-Access Memory Under Short Circuit
• Capillary stress and structural relaxation in moist granular materials
• Linear stability analysis of transient electrodeposition in charged porous media: suppression of dendritic growth by surface conduction
• Theory of layered-oxide cathode degradation in Li-ion batteries by oxidation-induced cation disorder
• Tuning the stability of Electrochemical Interfaces by Electron Transfer reactions
• The Role of Mobile Point Defects in Two-Dimensional Memristive Devices
• High-Voltage Honeycomb Layered Oxide Positive Electrodes for Rechargeable Sodium Batteries
• Deciphering water-solid reactions during hydrothermal corrosion of SiC
• A sharp-interface model of electrodeposition and ramified growth
• Inferring electrochemical performance and parameters of Li-ion batteries based on deep operator networks
• Image Inversion and Uncertainty Quantification for Constitutive Laws of Pattern Formation
• Interplay between Phase Transformation Instabilities and Spatiotemporal Reaction Heterogeneities in Particulate Intercalation Electrodes
• Scale bridging description of coherent phase equilibria in the presence of surfaces and interfaces
• Ion Solvation in Dipolar Poisson models in a dual view
• Dielectric breakdown by electric-field induced phase separation
• Quantitative Phase Field Model for Electrochemical Systems
• On non-ideal chemical-reaction networks and phase separation
• Theory of voltammetry in charged porous media
• Interfacial resistive switching by multiphase polarization in ion-intercalation nanofilms
• Population Effects Driving Active Material Degradation in Intercalation Electrodes
• Phase separation of stable colloidal clusters
• Chemical reaction motifs driving non-equilibrium behaviors in phase separating materials
• Coulombic Surface-Ion Interactions Induce Nonlinear and Chemistry-Specific Charging Kinetics
• On $\Gamma -$Convergence of a Variational Model for Lithium-Ion Batteries
• Localized Instabilities and Spinodal Decomposition in Driven Systems in the Presence of Elasticity
• Diffusive dynamics of charge regulated macro-ion solutions
• Spinodal decomposition and domain coarsening in a multi-layer Cahn-Hilliard model for lithium intercalation in graphite
• Theory of water desalination with intercalation materials
• The intertwined physics of active chemical reactions and phase separation
• Physical interactions enable energy-efficient Turing patterns
• Externally driven condensates show translation-induced polarization, directed coalescence, and anomalous diffusion in viscoelastic media
• Fluid flow and spatiotemporal chaos in chemically active emulsions
• Structure Matters: A Scale-Resolved Numerical Operando Approach for Lithium-Sulfur Batteries
• Transition between growth of dense and porous films: Theory of dual-layer SEI
• Thermodynamically Consistent Continuum Theory of Magnetic Particles in High-Gradient Fields