Guidelines for Safe, High Performing Li-Ion Battery Designs for Manned Vehicles

New design features and test methods are in development at NASA to take advantage of the newest high power and energy dense commercial Li-ion cell designs and to achieve passively thermal runaway (TR) propagation resistant (PPR) designs for manned missions requiring high power/voltage. The goal is to minimize the parasitic mass and volume of the battery components; thus reaching a balance between high battery specific power (W/kg) and energy (Wh/kg) as well as power (W/L) and energy density (Wh/L). Current 18650 cell designs achieve greater than 275 Wh/kg, greater than 725 Wh/L, but present high risks of side wall breaching during TR which can defeat many other safety features resulting in nearly immediate TR propagation. This work seeks to better understand the phenomena of cell side wall breaches and to determine the effectiveness of promising battery design features for achieving safe, high performing battery designs for high voltage/power applications

Quantitative Relationships Between Pore Tortuosity, Pore Topology, and Solid Particle Morphology Using a Novel Discrete Particle Size Algorithm

To sustain the continuous high-rate charge current required for fast charging of electric vehicle batteries, the ionic effective diffusion coefficient of the electrodes must be high enough to avoid the electrode being transport limited. Tortuosity factor and porosity are the two microstructure parameters that control this effective diffusion coefficient. While different methods exist to experimentally measure or calculate the tortuosity factor, no generic relationship between tortuosity and microstructure presently exists that is applicable across a large variety of electrode microstructures and porosities. Indeed, most relationships are microstructure specific. In this work, generic relationships are established using only geometrically defined metrics that can thus be used to design thick electrodes suitable for fast charging. To achieve this objective, an original, discrete particle-size algorithm is introduced and used to identify and segment particles across a set of 19 various electrode microstructures (nickel-manganese-cobalt [NMC] and graphite) obtained from X-ray computed tomography (CT) to quantify parameters such as porosity, particle elongation, sinuosity, and constriction, which influence the effective diffusion coefficient. Compared to the widely used watershed method, the new algorithm shows less over-segmentation. Particle size obtained with different numerical methods is also compared. Lastly, microstructure-tortuosity relationship and particle size and morphology analysis methods are reviewed

Nitrogen Blanketing and Hydrogen Starvation in Dead-Ended-Anode Polymer Electrolyte Fuel Cells Revealed by Hydro-Electro-Thermal Analysis

Dead-ended anode operation has a number of practical advantages that simplify system complexity and lower cost for polymer electrolyte fuel cells. However, dead-ended mode leads to performance loss over time which can only be reversed by performing intermittent purge events. This work applies a combined hydro-electro-thermal analysis to an air-cooled open-cathode fuel cell, presenting experimental functional maps of water distribution, current density and temperature. This approach has allowed the identification of a 'nitrogen blanketing' effect due to nitrogen cross-over from the cathode and a 'bypass' effect where a peripheral gap between the gasket and the GDL offers a hydrogen flow 'short circuit' to the border of the electrode. A consequence of high local current density at the margin of the electrode, and resulting high temperatures, may impact the lifetime of the cell in dead-end mode

The Hydro-electro-thermal Performance of Air-cooled, Open-cathode Polymer Electrolyte Fuel Cells: Combined Localised Current Density, Temperature and Water Mapping

In situ diagnostic techniques provide a means of understanding the internal workings of fuel cells so that improved designs and operating regimes can be identified. Here, a novel metrology approach is reported that combines current and temperature mapping with water visualisation using neutron radiography. The approach enables a hydro-electro-thermal performance map to be generated that is applied to an air-cooled, open-cathode polymer electrolyte fuel cell. This type of fuel cell exhibits a particularly interesting coupled relationship between water, current and heat, as the air supply has the due role of cooling the stack as well as providing the cathode reactant feed via a single source. It is found that water predominantly accumulates under the cooling channels (thickness of 70-100 μm under the cooling channels and 5-25 μm in the active channels at 0.5 A cm−2), in a similar fashion to the lands in a closed-cathode design, but contrary to passive open-cathode systems. The relationship between current, temperature and water accumulation is complex and highly dependent on location within the cell. However, there is a general trend that higher currents and cooling limitations, especially above 0.7 A cm−2 and below 3.9 × 10−3 m3 s−1, leads to temperatures above 60 °C, which dehydrate the membrane (water thickness of 10-25 um) and the cell operates below 0.5 V

Investigation of cycling-induced microstructural degradation in silicon-based electrodes in lithium-ion batteries using X-ray nanotomography

The microstructural degradation of a composite silicon electrode at different stages in its cycle life was investigated in 3D using X-ray nano-computed tomography. A reconstructed volume of 36 μm × 27 μm × 26 μm from the composite electrode was imaged in its pristine state and after 1, 10 and 100 cycles. Particle fracturing and phase transformation was observed within the electrode with increased cycling. In addition, a distinct, lower X-ray attenuating phase was clearly resolved, which can be associated with surface film formation resulting from electrolyte breakdown and with silicon particle phase transformation. Changes in quantified microstructural properties such as phase volume fraction and particle specific surface area were tracked. Electrode performance loss is associated with loss of active silicon. These imaging results further highlight the capability of high resolution X-ray tomography to investigate the role of electrode microstructure in battery degradation and failure

Quantitative spatiotemporal mapping of thermal runaway propagation rates in lithium-ion cells using cross-correlated Gabor filtering

Abuse testing of lithium-ion batteries is widely performed in order to develop new safety standards and strategies. However, testing methodologies are not standardised across the research community, especially with failure mechanisms being inherently difficult to reproduce. High-speed X-ray radiography is proven to be a valuable tool to capture events occurring during cell failure, but the observations made remain largely qualitative. We have therefore developed a robust image processing toolbox that can quantify, for the first time, the rate of propagation of battery failure mechanisms revealed by high-speed X-ray radiography. Using Gabor filter, the toolbox selectively tracks the electrode structure at the onset of failure. This facilitated the estimation of the displacement of electrodes undergoing abuse via nail penetration, and also the tracking of objects, such as the nail, as it propagates through a cell. Further, by cross-correlating the Gabor signals, we have produced practical, illustrative spatiotemporal maps of the failure events. From these, we can quantify the propagation rates of electrode displacement prior to the onset of thermal runaway. The highest recorded acceleration (≈514 mm s−2) was when a nail penetrated a cell radially (perpendicular to the electrodes) as opposed to axially (parallel to the electrodes). The initiation of thermal runaway was also resolved in combination with electrode displacement, which occurred at a lower acceleration (≈108 mm s−2). Our assistive toolbox can also be used to study other types of failure mechanisms, extracting otherwise unattainable kinetic data. Ultimately, this tool can be used to not only validate existing theoretical mechanical models, but also standardise battery failure testing procedures

Effect of gas diffusion layer properties on water distribution across air-cooled, open-cathode polymer electrolyte fuel cells: A combined ex-situ X-ray tomography and in-operando neutron imaging study

In-operando diagnostic techniques provide a means of understanding the internal workings of fuel cells under normal operating conditions so that improved designs and operating regimes can be identified. Here, an approach is used which combines ex‐situ characterisation of two anode gas diffusion/microporous layers (GDL-A and GDL-B) with X-ray computed tomography (CT) and in-operando analysis using neutron imaging of operating fuel cells. The combination of TGA, SEM and X-ray CT reveals that GDL-A has a thin microporous layer with ∼26% PTFE covering a thick diffusion layer composed of ‘spaghetti’-shaped fibres. GDL-B is covered by two microporous media (29% and 6.6% PTFE) penetrating deep within the linear fibre network. The neutron imaging reveals two pathways for water transport underneath the cooling channel, either diffusing through the cathode GDL to the active channels, or diffusing through the membrane and towards the anode. The behaviour of water in the GDL is directly affected by the anode gas diffusion, PTFE content and porosity

Multiscale dynamics of charging and plating in graphite electrodes coupling operando microscopy and phase-field modelling

The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined with non-equilibrium thermodynamics implemented in a multi-dimensional (1D+1D to 3D) phase-field modeling framework to reveal the rate-dependent spatial dynamics of phase separation and plating in graphite electrodes. Here we visualize and provide mechanistic understanding of the multistage phase separation, plating, inter/intra-particle lithium exchange and plated lithium back-intercalation phenomena. A strong dependence of intra-particle lithiation heterogeneity on the particle size, shape, orientation, surface condition and C-rate at the particle level is observed, which leads to early onset of plating spatially resolved by a 3D image-based phase-field model. Moreover, we highlight the distinct relaxation processes at different state-of-charges (SOCs), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs. These physics-based insights into the distinct SOC-dependent relaxation efficiency provide new perspective towards developing advanced fast charge protocols to suppress plating and shorten the constant voltage regime