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The measurement of the active material volume fraction in composite electrodes of lithium-ion battery cells is difficult due to the small (sub-micrometer) and irregular structure and multi-component composition of the electrodes, particularly in the case of blend electrodes. State-of-the-art experimental methods such as focused ion beam/scanning electron microscopy (FIB/SEM) and subsequent image analysis require expensive equipment and significant expertise. We present here a simple method for identifying active material volume fractions in single-material and blend electrodes, based on the comparison of experimental equilibrium cell voltage curve (open-circuit voltage as function of charge throughput) with active material half-cell potential curves (half-cell potential as function of lithium stoichiometry). The method requires only (i) low-current cycling data of full cells, (ii) cell opening for measurement of electrode thickness and active electrode area, and (iii) literature half-cell potentials of the active materials. Mathematical optimization is used to identify volume fractions and lithium stoichiometry ranges in which the active materials are cycled. The method is particularly useful for model parameterization of either physicochemical (e.g., pseudo-two-dimensional) models or equivalent circuit models, as it yields a self-consistent set of stoichiometric and structural parameters. The method is demonstrated using a commercial LCO–NCA/graphite pouch cell with blend cathode, but can also be applied to other blends (e.g., graphite–silicon anode).
Electrochemical impedance spectroscopy (EIS) is a widely-used diagnostic technique to characterize electrochemical processes. It is based on the dynamic analysis of two electrical observables, that is, current and voltage. Electrochemical cells with gaseous reactants or products (e.g., fuel cells, metal/air cells, electrolyzers) offer an additional observable, that is, the gas pressure. The dynamic coupling of current and/or voltage with gas pressure gives rise to a number of additional impedance definitions, for which we use the term electrochemical pressure impedance. It also gives rise to different experimental probing approaches. In this article we present a model-based study of electrochemical pressure impedance spectroscopy (EPIS). Possible quantifications and realizations of EPIS are discussed. The study of generic cell geometries consisting of gas reservoir, diffusion layer(s) and electrochemically active layer(s) reveals distinct spiral-shaped features in the Nyquist plot. Using the example of a sodium/oxygen (Na/O2) cell, the dynamic spatiotemporal behavior of the state variables is quantified and interpreted. Results are compared to first experimental EPIS measurements by Hartmann et al. [J. Phys. Chem. C118, 1461, 2014]. A sensitivity analysis highlights the properties of EPIS with respect to geometric, transport, and kinetic parameters. We demonstrate that EPIS is sensitive to transport parameters that are not well-accessible with standard EIS.
This article presents the development, parameterization, and experimental validation of a pseudo-three-dimensional (P3D) multiphysics model of a 350 mAh high-power lithium-ion pouch cell with graphite anode and lithium cobalt oxide/lithium nickel cobalt aluminum oxide (LCO/NCA) blend cathode. The model describes transport processes on three different scales: Heat transport on the macroscopic scale (cell), mass and charge transport on the mesoscopic scale (electrode pair), and mass transport on the microscopic scale (active material particles). A generalized description of electrochemistry in blend electrodes is developed, using the open-source software Cantera for calculating species source terms. Very good agreement of model predictions with galvanostatic charge/discharge measurements, electrochemical impedance spectroscopy, and surface temperature measurements is observed over a wide range of operating conditions (0.05C to 10C charge and discharge, 5°C to 35°C). The behavior of internal states (concentrations, potentials, temperatures) is discussed. The blend materials show a complex behavior with both intra-particle and inter-particle non-equilibria during cycling.
Simulation-based degradation assessment of lithium-ion batteries in a hybrid electric vehicle
(2017)
In the dual membrane fuel cell (DM-Cell), protons formed at the anode and oxygen ions formed at the cathode migrate through their respective dense electrolytes to react and form water in a porous composite layer called dual membrane (DM). The DM-Cell concept was experimentally proven (as detailed in Part I of this paper). To describe the electrochemical processes occurring in this novel fuel cell, a mathematical model has been developed which focuses on the DM as the characteristic feature of the DM-Cell. In the model, the porous composite DM is treated as a continuum medium characterized by effective macro-homogeneous properties. To simulate the polarization behavior of the DM-Cell, the potential distribution in the DM is related to the flux of protons and oxygen ions in the conducting phases by introducing kinetic and transport equations into charge balances. Since water pressure may affect the overall formation rate, water mass balances across the DM and transport equations are also considered. The satisfactory comparison with available experimental results suggests that the model provides sound indications on the effects of key design parameters and operating conditions on cell behavior and performance.
Compact solid discharge products enable energy storage devices with high gravimetric and volumetric energy densities, but solid deposits on active surfaces can disturb charge transport and induce mechanical stress. In this Letter, we develop a nanoscale continuum model for the growth of Li2O2 crystals in lithium–oxygen batteries with organic electrolytes, based on a theory of electrochemical nonequilibrium thermodynamics originally applied to Li-ion batteries. As in the case of lithium insertion in phase-separating LiFePO4 nanoparticles, the theory predicts a transition from complex to uniform morphologies of Li2O2 with increasing current. Discrete particle growth at low discharge rates becomes suppressed at high rates, resulting in a film of electronically insulating Li2O2 that limits cell performance. We predict that the transition between these surface growth modes occurs at current densities close to the exchange current density of the cathode reaction, consistent with experimental observations.