Most Li ion insertion batteries consist of a porous cathode, a separator filled with electrolyte and an anode, which very often also has some porous structure. The solid part especially in the cathode is usually produced by mixing a powder of the actual active particles, in which Li ions will be intercalated, binder and carbon black to enhance the electronic conductivity of the electrode. As a result the porous structure of the electrodes is very complex, leading to complex potential, ion and temperature distributions within the electrodes. The intercalation and deintercalation of ions cannot be expected to be homogeneously distributed over the electrode due to the different transport properties of electrolyte and active particles in the electrode and the complex three-dimensional pore structure of the electrode. The influence of the final microstructure on the distribution of temperature, electric potential and ions within the electrodes is not known in detail, but may influence strongly the onset of degradation mechanisms. For being able to numerically simulate the transport phenomena, the equations and interface conditions for ion, charge and heat transport within the complex structure of the electrodes and through the electrolyte filled separator are needed. We will present a rigorous derivation of these equations based exclusively on general principles of nonequilibrium thermodynamics. The theory is thermodynamically consistent i.e. it guarantees strictly positive entropy production. The irreversible and reversible sources of heat are derived within the theory. Especially the various contribution to the Peltier heat due to the intercalation of ions are obtained as a result of the theory

Li-ion batteries are commonly used in portable electronic devices due to their outstanding energy and power density. A remaining issue which hinders the breakthrough e.g. in the automotive sector is the high production cost. For low power applications, such as stationary storage, batteries with electrodes thicker than 300 µm were suggested. High energy densities can be attained with only a few electrode layers which reduces production time and cost. However, mass and charge transport limitations can be severe at already small Crates due to long transport pathways. In this article we use a detailed 3D micro-structure resolved model to investigate limiting factors for battery performance. The model is parametrized with data from the literature and dedicated experiments and shows good qualitative agreement with experimental discharge curves of thick NMC-graphite Li-ion batteries. The model is used to assess the effect of inhomogeneities in carbon black distribution and gives answers to the possible occurrence of lithium plating during battery charge. Based on our simulations we can predict optimal operation strategies and improved design concepts for future Li-ion batteries employing thick electrodes.

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Perspective on recent improvements in experiment and theory towards realizing lithium metal electrodes with liquid electrolytes.

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SummaryThe 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.

For hard ellipsoids of revolution we calculate the phase diagram for the idealized glass transition. Our equations cover the glass physics in the full phase space, for all packing fractions and all aspect ratios X0. With increasing aspect ratio we find the idealized glass transition to become primarily driven by orientational degrees of freedom. For needlelike or platelike systems the transition is strongly influenced by a precursor of a nematic instability. We obtain three types of glass transition line. The first one (straight phi((B))(c)) corresponds to the conventional glass transition for spherical particles which is driven by the cage effect. At the second one (straight phi((B'))(c)), which occurs for rather nonspherical particles, a glass phase is formed that consists of domains. Within each domain there is a nematic order where the center of mass motion is quasiergodic, whereas the interdomain orientations build an orientational glass. The third glass transition line (straight phi((A))(c)) occurs for nearly spherical ellipsoids where the orientational degrees of freedom with odd parity, e.g., 180 degrees flips, freeze independently from the positions.

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.