Global energy and climate-change concerns have accelerated the electrifi cation of vehicles, aided by advances in battery technology. It is now recognized that low-cost, scalable energy storage will also be key to continued growth of renewable energy technologies (wind and solar) and improved effi ciency of the electric grid. While electrochemical energy storage remains attractive for its high energy density, simplicity, and reliability, existing battery technologies remain limited in their ability to meet many future storage needs. Here we propose and demonstrate a new storage concept, the semi-solid fl ow cell (SSFC), which combines the high energy density of rechargeable batteries with the fl exible and scalable architecture of fuel cells and fl ow batteries. In contrast to previous fl ow batteries, energy is stored in suspensions of solid storage compounds to and from which charge transfer is accomplished via dilute yet percolating networks of nanoscale conductors. These novel electrochemical composites constitute fl owable semi-solid 'fuels' that are here charged and discharged in prototype fl ow cells. Potential advantages of the SSFC approach include projected system-level energy densities that are more than ten times those of aqueous fl ow batteries, and the simplifi ed low-cost manufacturing of large-scale storage systems compared to conventional lithiumion batteries.Demand for batteries of higher energy and power has driven several decades of research in electrochemical storage materials, resulting recently in signifi cant improvements in the stored energy of cathodes and anodes. [ 1 , 2 ] However, most batteries have designs that have not departed substantially from Volta's galvanic cell of 1800, and which accept an inherently poor utilization of the active materials. [ 3 ] Even the highest energy density lithium ion cells currently available, e.g., 2.8-2.9 Ah 18650 cells having > 600 Wh L − 1 , have less than 50 vol% active material. The reduced energy density, along with higher cost, result because the high-energy-storage compounds are diluted by inactive and costly components necessary to extract power (e.g., currentcollector foils, tabs, separator fi lm, liquid electrolyte, electrode binders and conductive additives, and external packaging). Further dilution of energy density, by about a factor of two, occurs between the cell and system level. [ 4 ] Electrode designs that minimize inactive material, bio-and self-assembly, and 3D architectures are new approaches that promise improved design efficiency but have yet to be fully realized. [ 5 -9 ] Decoupling power components from energy-storage components so that stored energy can be scaled independently of power is a strategy for improving system-level energy density. Redox fl ow batteries have such a design, in which active materials are stored within external reservoirs and pumped into an ion-exchange/electron-extraction power stack. [ 10 ] As the system increases in capacity, its energy density may asymptotically approach that of the redox acti...

As LiCoO 2 cathodes are charged, delithiation of the LiCoO 2 active material leads to an increase in the lattice spacing, causing swelling of the particles. When these particles are packed into a bicontinuous, percolated network, as is the case in a battery electrode, this swelling leads to the generation of significant mechanical stress. In this study we performed coupled electrochemical-mechanical simulations of the charging of a LiCoO 2 cathode in order to elucidate the mechanisms of stress generation and the effect of charge rate and microstructure on these stresses. Energy dispersive spectroscopy combined with scanning electron microscopy imaging was used to create 3D reconstructions of a LiCoO 2 cathode, and the Conformal Decomposition Finite Element Method is used to automatically generate computational meshes on this reconstructed microstructure. Replacement of the ideal solution Fickian diffusion model, typically used in battery simulations, with a more general non-ideal solution model shows substantially smaller gradients of lithium within particles than is typically observed in the literature. Using this more general model, lithium gradients only appear at states of charge where the open-circuit voltage is relatively constant. While lithium gradients do affect the mechanical stress state in the particles, the maximum stresses are always found in the fully-charged state and are strongly affected by the local details of the microstructure and particle-to-particle contacts. These coupled electrochemical-mechanical simulations begin to yield insight into the partitioning of volume change between reducing pore space and macroscopically swelling the electrode. Finally, preliminary studies that include the presence of the polymeric binder suggest that it can greatly impact stress generation and that it is

Lithium-ion battery electrodes rely on a percolated network of solid particles and binder that must maintain a high electronic conductivity in order to function. Coupled mechanical and electrochemical simulations may be able to elucidate the mechanisms for capacity fade. We present a framework for coupled simulations of electrode mechanics that includes swelling, deformation, and stress generation driven by lithium intercalation. These simulations are performed at the mesoscale, which requires 3D reconstruction of the electrode microstructure from experimental imaging or particle size distributions. We present a novel approach for utilizing these complex reconstructions within a finite element code. A mechanical model that involves anisotropic swelling in response to lithium intercalation drives the deformation. Stresses arise from small-scale particle features and lithium concentration gradients. However, we demonstrate, for the first time, that the largest stresses arise from particle-to-particle contacts, making it important to accurately represent the electrode microstructure on the multi-particle scale. Including anisotropy in the swelling mechanics adds considerably more complexity to the stresses and can significantly enhance peak particle stresses. Shear forces arise at contacts due to the misorientation of the lattice structure. These simulations will be used to study mechanical degradation of the electrode structure through charge/discharge cycles. Capacity fade in lithium-ion batteries (LIB) is potentially influenced by a large number of mechanisms, 1 one of which is mechanical degradation of the electrode microstructure. Both electrodes experience mechanical deformation, and in this paper, we focus on the cathode of the lithium-cobalt-oxide (LiCoO 2 , or LCO) system.2 Cathodes are made up of a three-dimensional (3D), percolating, bicontinuous network consisting of solid, electroactive particles, a polymer binder, and electrolyte. The bicontinuous nature of this network is critical, as Li + ions must be able to transport from the anode, through the separator, to any particle in the cathode via the electrolyte. At the same time, electrons must be able to transport through the solid particle network to the current collector. Any particle that becomes physically isolated from, or poorly connected to, its network or from the electrolyte does not contribute to the electrochemical reactions, resulting in capacity loss.One way in which particles may become disconnected from their network is by the swelling, shrinking, and fracture mechanisms that may occur through many charge-discharge cycles.3-6 As lithium intercalates into the electrode particles, the crystal lattice spacing may change either isotropically or anisotropically. For LiCoO 2 cathodes in particular, the crystal lattice shrinks anisotropically upon lithium intercalation 7,8 As was measured by Reimers and Dahn, 7 and later in more detail by Amatucci et al., 8 the lattice shrinkage upon lithiation can be quite significant and is anisotropic in n...

Lithium-ion battery electrodes are composed of active material particles, binder, and conductive additives that form an electrolytefilled porous particle composite. The mesoscale (particle-scale) interplay of electrochemistry, mechanical deformation, and transport through this tortuous multi-component network dictates the performance of a battery at the cell-level. Effective electrode properties connect mesoscale phenomena with computationally feasible battery-scale simulations. We utilize published tomography data to reconstruct a large subsection (1000+ particles) of an NMC333 cathode into a computational mesh and extract electrode-scale effective properties from finite element continuum-scale simulations. We present a novel method to preferentially place a composite binder phase throughout the mesostructure, a necessary approach due difficulty distinguishing between non-active phases in tomographic data. We compare stress generation and effective thermal, electrical, and ionic conductivities across several binder placement approaches. Isotropic lithiation-dependent mechanical swelling of the NMC particles and the consideration of strain-dependent composite binder conductivity significantly impact the resulting effective property trends and stresses generated. Our results suggest that composite binder location significantly affects mesoscale behavior, indicating that a binder coating on active particles is not sufficient and that more accurate approaches should be used when calculating effective properties that will inform battery-scale models in this inherently multi-scale battery simulation challenge.

Battery electrodes are composed of polydisperse particles and a porous, composite binder domain. These materials are arranged into a complex mesostructure whose morphology impacts both electrochemical performance and mechanical response. We present image-based, particle-resolved, mesoscale finite element model simulations of coupled electrochemical-mechanical performance on a representative NMC electrode domain. Beyond predicting macroscale quantities such as half-cell voltage and evolving electrical conductivity, studying behaviors on a per-particle and per-surface basis enables performance and material design insights previously unachievable. Voltage losses are primarily attributable to a complex interplay between interfacial charge transfer kinetics, lithium diffusion, and, locally, electrical conductivity. Mesoscale heterogeneities arise from particle polydispersity and lead to material underutilization at high current densities. Particle-particle contacts, however, reduce heterogeneities by enabling lithium diffusion between connected particle groups. While the porous composite binder domain (CBD) may have slower ionic transport and less available area for electrochemical reactions, its high electrical conductivity makes it the preferred reaction site late in electrode discharge. Mesoscale results are favorably compared to both experimental data and macrohomogeneous models. This work enables improvements in materials design by providing a tool for optimization of particle sizes, CBD morphology, and manufacturing conditions.