A Lab-based Multi-length Scale Approach To Characterize Lithium-ion Cathode Materials

X-ray computed tomography has emerged as a valuable tool to analyze battery materials. This paper explores the possibilities and limitations offered by a multi-length scale lab-based approach to study a lithium nickel manganese cobalt oxide electrode for lithium ion battery applications. The porosity, tortuosity and particle size distribution are extracted from micro- and nano-CT datasets and discussed in terms of the resolution available for the measurement. This work sets the basis for a range of studies to understand how different manufacturing routes affect the microstructure of the electrode and how this in turn affects battery performance

Influence of Flow Field Design on Zinc Deposition and Performance in a Zinc-Iodide Flow Battery

Among the aqueous redox flow battery systems, redox chemistries using a zinc negative electrode have a relatively high energy density, but the potential of achieving high power density and long cycle life is hindered by dendrite growth at the anode. In this study, a new cell design with a narrow gap between electrode and membrane was applied in a zinc-iodide flow battery. In this design, some of the electrolyte flows over the electrode surface and a fraction of the flow passes through the porous felt electrode in the direction of current flow. The flow battery was tested under constant current density over 40 cycles, and the efficiency, discharge energy density, and power density of the battery were significantly improved compared to conventional flow field designs. The power density obtained in this study is one of the highest power densities reported for the zinc-iodide battery. The morphology of the zinc deposition was studied using scanning electron microscopy and optical profilometry. It was found that the flow through the electrode led to a thinner zinc deposit with lower roughness on the surface of the electrode, in comparison to the case where there was no flow through the electrode. In addition, inhibition of dendrite formation enabled operation at a higher range of current density. Ex situ tomographic measurements were used to image the zinc deposited on the surface and inside the porous felt. Volume rendering of graphite felt from X-ray computed tomography images showed that in the presence of flow through the electrode, more zinc deposition occurred inside the porous felt, resulting in a compact and thinner surface deposit, which may enable higher battery capacity and improved performance

Investigating the Three-Dimensional Microstructural Characteristics of Lithium-Sulfur Electrodes with X-Ray Micro-Tomography

The Li-S battery has the potential to replace Li-ion batteries in high capacity and high gravimetric energy density applications, but certain technical challenges result in diminished cycle life and have hindered its commercialization. Lab-scale X-ray micro-tomography was performed on an elemental sulfur electrode and a miniaturized in-situ tomography Li-S cell, and the 3D visualization achieved with this technique provides a wealth of information, improving understanding of the evolution of morphological and microstructural parameters of the different phases. As X-ray imaging is inherently non-destructive, it enables these parameters to be observed in-situ as a function of cycle life and state of charge. The inherently anisotropic nature of active material dissolution, recrystallization and other degradation processes within the electrode necessitates a three-dimensional approach to enable their visualization and quantification, and X-ray tomography is a useful tool in informing the development of more optimal electrode designs

Three-dimensional image based modelling of transport parameters in lithium-sulfur batteries

An elemental sulfur electrode was imaged with X-ray micro and nano computed tomography and segmented into its constituent phases. Morphological parameters including phase fractions and pore and particle size distributions were calculated directly from labelled image data, and flux based simulations were performed to determine the effective molecular diffusivity of the pore phase and electrical conductivity of the conductive carbon and binder phase, Deff and σeff, that can be used as an input for Li-S battery modelling. In addition to its crucial role in providing electrical conductivity within the sulfur electrode, the intrinsic porosity of the carbon binder domain was found to significantly influence Li-ion transport within the electrode. Neglecting this intrinsic porosity results in an overestimation of the electrical conductivity within the sulfur electrode, and an underestimation of the tortuosity of the Li-ion conducting phase by ca. 56%. The derivation of effective transport parameters directly from image data may aid in the development of more realistic models of Li-S battery systems by reducing the reliance on empirical correlations, and the uncertainties arising from assumptions made in these correlations

The Detection of Monoclinic Zirconia and Non-Uniform 3D Crystallographic Strain in a Re-Oxidized Ni-YSZ Solid Oxide Fuel Cell Anode

The solid oxide fuel cell (SOFC) anode is often composed of nickel (Ni) and yttria-stabilized zirconia (YSZ). The yttria is added in small quantities (e.g., 8 mol %) to maintain the crystallographic structure throughout the operating temperatures (e.g., room-temperature to >800 °C). The YSZ skeleton provides a constraining structural support that inhibits degradation mechanisms such as Ni agglomeration and thermal expansion miss-match between the anode and electrolyte layers. Within this structure, the Ni is deposited in the oxide form and then reduced during start-up; however, exposure to oxygen (e.g., during gasket failure) readily re-oxidizes the Ni back to NiO, impeding electrochemical performance and introducing complex structural stresses. In this work, we correlate lab-based X-ray computed tomography using zone plate focusing optics, with X-ray synchrotron diffraction computed tomography to explore the crystal structure of a partially re-oxidized Ni/NiO-YSZ electrode. These state-of-the-art techniques expose several novel findings: non-isotropic YSZ lattice distributions; the presence of monoclinic zirconia around the oxidation boundary; and metallic strain complications in the presence of variable yttria content. This work provides evidence that the reduction–oxidation processes may destabilize the YSZ structure, producing monoclinic zirconia and microscopic YSZ strain, which has implications upon the electrode’s mechanical integrity and thus lifetime of the SOFC

Evolution of Electrochemical Cell Designs for In-Situ and Operando 3D Characterization

Lithium-based rechargeable batteries such as lithium-ion (Li-ion), lithium-sulfur (Li-S), and lithium-air (Li-air) cells typically consist of heterogenous porous electrodes. In recent years, there has been growing interest in the use of in-situ and operando micro-CT to capture their physical and chemical states in 3D. The development of in-situ electrochemical cells along with recent improvements in radiation sources have expanded the capabilities of micro-CT as a technique for longitudinal studies on operating mechanisms and degradation. In this paper, we present an overview of the capabilities of the current state of technology and demonstrate novel tomography cell designs we have developed to push the envelope of spatial and temporal resolution while maintaining good electrochemical performance. A bespoke PEEK in-situ cell was developed, which enabled imaging at a voxel resolution of ca. 230 nm and permitted the identification of sub-micron features within battery electrodes. To further improve the temporal resolution, future work will explore the use of iterative reconstruction algorithms, which require fewer angular projections for a comparable reconstruction

Microstructural Evolution of Battery Electrodes During Calendering

Calendering is a crucial manufacturing process in the optimization of battery performance and lifetime due to its significant effect on the 3D electrode microstructure. By conducting an in situ calendering experiment on lithium-ion battery cathodes using X-ray nano-computed tomography, here we show that the electrodes composed of large particles with a broad size distribution experience heterogeneous microstructural self-arrangement. At high C-rates, the performance is predominantly restricted by sluggish solid-state diffusion, which is exacerbated by calendering due to the increased microstructural and lithiation heterogeneity, leading to active material underutilization. In contrast, electrodes consisting of small particles are structurally stable with more homogeneous deformation and a lower tortuosity, showing a much higher rated capacity that is less sensitive to calendering densification. Finally, the dependence of performance on the dual variation of both porosity and electrode thickness is investigated to provide new insights into the microstructural optimization for different applications in electrode manufacturing

Crack detection in lithium-ion cells using machine learning

It is an open question how the particle microstructure of a lithium-ion electrode influences a potential thermal runaway. In order to investigate this, information on the structural changes, in particular cracked particles, caused by the failure are desirable. For a reliable analysis of these changes a reasonably large amount of data is necessary, which necessitates automatic extraction of particle cracks from tomographic 3D image data. In this paper, a classification model is proposed which is able to decide whether a pair of particles is the result of breakage, of the image segmentation, or neither. The classifier is developed using simulated data based on a 3D stochastic particle model. Its validity is tested by applying the methodology to hand-labelled data from a real electrode. For this dataset, an overall accuracy of 73% is achieved

Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes

The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell’s performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded Li_{x}Mn_{2)O_{4} electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO_{2} within the first cycle. Other particles contain monoclinic Li_{2}MnO_{3}near the surface and almost pure spinel Li_{x}Mn_{2}O_{4} near the core. Following 150 cycles, concentrations of LiMnO_{2} and Li_{2}MnO_{3} significantly increase and widely vary between particles

Exploring cycling induced crystallographic change in NMC with X-ray diffraction computed tomography

This study presents the application of X-ray diffraction computed tomography for the first time to analyze the crystal dimensions of LiNi0.33Mn0.33Co0.33O2 electrodes cycled to 4.2 and 4.7 V in full cells with graphite as negative electrodes at 1 μm spatial resolution to determine the change in unit cell dimensions as a result of electrochemical cycling. The nature of the technique permits the spatial localization of the diffraction information in 3D and mapping of heterogeneities from the electrode to the particle level. An overall decrease of 0.4% and 0.6% was observed for the unit cell volume after 100 cycles for the electrodes cycled to 4.2 and 4.7 V. Additionally, focused ion beam-scanning electron microscope cross-sections indicate extensive particle cracking as a function of upper cut-off voltage, further confirming that severe cycling stresses exacerbate degradation. Finally, the technique facilitates the detection of parts of the electrode that have inhomogeneous lattice parameters that deviate from the bulk of the sample, further highlighting the effectiveness of the technique as a diagnostic tool, bridging the gap between crystal structure and electrochemical performance