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Register a new userFaster Lead-Acid Battery Simulations from Porous-Electrode Theory: I. Physical Model
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An isothermal porous-electrode model of a discharging lead-acid battery is presented, which includes an extension of concentrated-solution theory that accounts for excluded-volume effects, local pressure variation, and a detailed microscopic water balance. The approach accounts for three typically neglected physical phenomena: convection, pressure diffusion, and variation of liquid volume with state of charge. Rescaling of the governing equations uncovers a set of fundamental dimensionless parameters that control the batterys response. Total volume change during discharge and nonuniform pressure prove to be higher-order effects in cells where variations occur in just one spatial dimension. A numerical solution is developed and exploited to predict transient cell voltages and internal concentration profiles in response to a range of C-rates. The dependence of discharge capacity on C-rate deviates substantially from Peukerts simple power law: charge capacity is concentration-limited at low C-rates, and voltage-limited at high C-rates. The model is fit to experimental data, showing good agreement.
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Electrochemical and equivalent-circuit modelling are the two most popular approaches to battery simulation, but the former is computationally expensive and the latter provides limited physical insight. A theoretical middle ground would be useful to support battery management, on-line diagnostics, and cell design. We analyse a thermodynamically consistent, isothermal porous-electrode model of a discharging lead-acid battery. Asymptotic analysis of this full model produces three reduced-order models, which relate the electrical behaviour to microscopic material properties, but simulate discharge at speeds approaching an equivalent circuit. A lumped-parameter model, which neglects spatial property variations, proves accurate for C-rates below 0.1C, while a spatially resolved higher-order solution retains accuracy up to 5C. The problem of parameter estimation is addressed by fitting experimental data with the reduced-order models.
We present a porous electrode model for lithium-ion batteries using Butler--Volmer reaction kinetics. We model lithium concentration in both the solid and fluid phase along with solid and liquid electric potential. Through asymptotic reduction, we show that the electric potentials are spatially homogeneous which decouples the problem into a series of time-dependent problems. These problems can be solved on three distinguished time scales, an early time scale where capacitance effects in the electrode dominate, a mid-range time scale where a spatial concentration gradient forms in the electrolyte, and a long-time scale where each of the electrodes saturate and deplete with lithium respectively. The solid-phase concentration profiles are linear functions of time and the electrolyte potential is everywhere zero, which allows the model to be reduced to a system of two uncoupled ordinary differential equations. Analytic and numerical results are compared with full numerical simulations and experimental discharge curves demonstrating excellent agreement.
The rapid charging and/or discharging of electrochemical cells can lead to localized depletion of electrolyte concentration. This depletion can significantly impact the systems time dependent resistance. For systems with porous electrodes, electrolyte depletion can limit the rate of charging and increase energy dissipation. Here we propose a theory to control and avoid electrolyte depletion by tailoring the value and spatial distribution of resistance in a porous electrode. We explore the somewhat counterintuitive idea that increasing local spatial resistances of the solid electrode itself leads to improved charging rate and minimal change in energy loss. We analytically derive a simple expression for an electrode resistance profile that leads to highly uniform electrolyte depletion. We use numerical simulations to explore this theory and simulate spatiotemporal dynamics of electrolyte concentration in the case of a supercapacitor with various tailored electrode resistance profiles which avoid localized depletion. This increases charging rate up to around 2-fold with minimal effect on overall dissipated energy in the system.
A new analytically and numerically manageable model collision operator is developed specifically for turbulence simulations. The like-particle collision operator includes both pitch-angle scattering and energy diffusion and satisfies the physical constraints required for collision operators: it conserves particles, momentum and energy, obeys Boltzmanns H-theorem (collisions cannot decrease entropy), vanishes on a Maxwellian, and efficiently dissipates small-scale structure in the velocity space. The process of transforming this collision operator into the gyroaveraged form for use in gyrokinetic simulations is detailed. The gyroaveraged model operator is shown to have more suitable behavior at small scales in phase space than previously suggested models. A model operator for electron-ion collisions is also presented.
In order for the widely discussed benefits of flow batteries for electrochemical energy storage to be applied at large scale, the cost of the electrochemical stack must come down substantially. One promising avenue for reducing stack cost is to increase the system power density while maintaining efficiency, enabling smaller stacks. Here we report on a membrane-less, hydrogen bromine laminar flow battery as a potential high power density solution. The membrane-less design enables power densities of 0.795 W cm$^{-2}$ at room temperature and atmospheric pressure, with a round-trip voltage efficiency of 92% at 25% of peak power. Theoretical solutions are also presented to guide the design of future laminar flow batteries. The high power density achieved by the hydrogen bromine laminar flow battery, along with the potential for rechargeable operation, will translate into smaller, inexpensive systems that could revolutionize the fields of large-scale energy storage and portable power systems.
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