Arnulf Latz

Multiscale modeling of lithium ion batteries: thermal aspects

Summary The thermal behavior of lithium ion batteries has a huge impact on their lifetime and the initiation of degradation processes. The development of hot spots or large local overpotentials leading, e.g., to lithium metal deposition depends on material properties as well as on the nano- und microstructure of the electrodes. In recent years a theoretical structure emerges, which opens the possibility to establish a systematic modeling strategy from atomistic to continuum scale to capture and couple the relevant phenomena on each scale. We outline the building blocks for such a systematic approach and discuss in detail a rigorous approach for the continuum scale based on rational thermodynamics and homogenization theories. Our focus is on the development of a systematic thermodynamically consistent theory for thermal phenomena in batteries at the microstructure scale and at the cell scale. We discuss the importance of carefully defining the continuum fields for being able to compare seemingly different phenomenological theories and for obtaining rules to determine unknown parameters of the theory by experiments or lower-scale theories. The resulting continuum models for the microscopic and the cell scale are numerically solved in full 3D resolution. The complex very localized distributions of heat sources in a microstructure of a battery and the problems of mapping these localized sources on an averaged porous electrode model are discussed by comparing the detailed 3D microstructure-resolved simulations of the heat distribution with the result of the upscaled porous electrode model. It is shown, that not all heat sources that exist on the microstructure scale are represented in the averaged theory due to subtle cancellation effects of interface and bulk heat sources. Nevertheless, we find that in special cases the averaged thermal behavior can be captured very well by porous electrode theory.

Modeling nucleation and growth of zinc oxide during discharge of primary zinc-air batteries

Metal-air batteries are among the most promising next-generation energy storage devices. Relying on abundant materials and offering high energy densities, potential applications lie in the fields of electro-mobility, portable electronics, and stationary grid applications. Now, research on secondary zinc-air batteries is revived, which are commercialized as primary hearing aid batteries. One of the main obstacles for making zinc-air batteries rechargeable is their poor lifetime due to the degradation of alkaline electrolyte in contact with atmospheric carbon dioxide. In this article, we present a continuum theory of a commercial Varta PowerOne button cell. Our model contains dissolution of zinc and nucleation and growth of zinc oxide in the anode, thermodynamically consistent electrolyte transport in porous media, and multi-phase coexistance in the gas diffusion electrode. We perform electrochemical measurements and validate our model. Excellent agreement between theory and experiment is found and novel insights into the role of zinc oxide nucleation and growth and carbon dioxide dissolution for discharge and lifetime is presented. We demonstrate the implications of our work for the development of rechargeable zinc-air batteries.

Characterization of gas diffusion electrodes for metal-air batteries

Gas diffusion electrodes are commonly used in high energy density metal-air batteries for the supply of oxygen. Hydrophobic binder materials ensure the coexistence of gas and liquid phase in the pore network. The phase distribution has a strong influence on transport processes and electrochemical reactions. In this article we present 2D and 3D Rothman-Keller type multiphase Lattice-Boltzmann models which take into account the heterogeneous wetting behavior of gas diffusion electrodes. The simulations are performed on FIB-SEM 3D reconstructions of an Ag model electrode for predefined saturation of the pore space with the liquid phase. The resulting pressure-saturation characteristics and transport correlations are important input parameters for modeling approaches on the continuum scale and allow for an efficient development of improved gas diffusion electrodes.

Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries

Abstract Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc–air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders‐of‐magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell‐level performance of pH‐buffered aqueous electrolytes. We apply our model to conduct the first continuum‐scale simulation of secondary ZABs using aqueous ZnCl2–NH4Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine‐containing solids may precipitate in addition to ZnO.

Fundamental principles of battery design

Abstract With an increasing diversity of electrical energy sources, in particular with respect to the pool of renewable energies, and a growing complexity of electrical energy usage, the need for storage solutions to counterbalance the discrepancy of demand and offer is inevitable. In principle, a battery seems to be a simple device since it just requires three basic components – two electrodes and an electrolyte – in contact with each other. However, only the control of the interplay of these components as well as their dynamics, in particular the chemical reactions, can yield a high-performance system. Moreover, specific aspects such as production costs, weight, material composition and morphology, material criticality, and production conditions, among many others, need to be fulfilled at the same time. They present some of the countless challenges, which make battery design a long-lasting, effortful task. This chapter gives an introduction to the fundamental concepts of batteries. The principles are exemplified for the basic Daniell cell followed by a review of Nernst equation, electrified interface reactions, and ionic transport. The focus is addressed to crystalline materials. A comprehensive discussion of crystal chemical and crystal physical peculiarities reflects favourable and unfavourable local structural aspects from a crystallographic view as well as considerations with respect to electronic structure and bonding. A brief classification of battery types concludes the chapter.

MULTIBAT: Unified workflow for fast electrochemical 3D simulations of lithium-ion cells combining virtual stochastic microstructures, electrochemical degradation models and model order reduction

We present a simulation workflow for efficient investigations of the interplay between 3D lithium-ion electrode microstructures and electrochemical performance, with emphasis on lithium plating. Our approach addresses several challenges. First, the 3D microstructures of porous electrodes are generated by a parametric stochastic model, in order to significantly reduce the necessity of tomographic imaging. Secondly, we integrate a consistent microscopic, 3D spatially-resolved physical model for the electrochemical behavior of the lithium-ion cells taking lithium plating and stripping into account. This highly non-linear mathematical model is solved numerically on the complex 3D microstructures to compute the transient cell behavior. Due to the complexity of the model and the considerable size of realistic microstructures even a single charging cycle of the battery requires several hours computing time. This renders large scale parameter studies extremely time consuming. Hence, we develop a mathematical model order reduction scheme. We demonstrate how these aspects are integrated into one unified workflow, which is a step towards computer aided engineering for the development of more efficient lithium-ion cells.

Identifying the Mechanism of Continued SEI Growth

Continued growth of the solid-electrolyte interphase (SEI) is the major reason for capacity fade in modern lithium-ion batteries. This growth is made possible by a yet unidentified transport mechanism that limits the passivating ability of the SEI towards electrolyte reduction. We, for the first time, differentiate the proposed mechanisms by analyzing their dependence on the electrode potential. Our calculations are compared to recent experimental capacity-fade data. We show that the potential dependence of SEI growth facilitated by solvent diffusion, electron conduction, or electron tunneling qualitatively disagrees with the experimental observations. Only diffusion of Li interstitials results in a potential dependence matching the experiments. Therefore, we identify the diffusion of neutral radicals, such as Li interstitials, as the cause of long-term SEI growth.