In-Situ Li-Ion Pouch Cell Diagnostics Utilising Plasmonic Based Optical Fibre Sensors

As the drive to improve the cost, performance characteristics and safety of lithium-ion batteries increases with adoption, one area where significant value could be added is that of battery diagnostics. This paper documents an investigation into the use of plasmonic-based optical fibre sensors, inserted internally into 1.4 Ah lithium-ion pouch cells, as a real time and in-situ diagnostic technique. The successful implementation of the fibres inside pouch cells is detailed and promising correlation with battery state is reported, while having negligible impact on cell performance in terms of capacity and columbic efficiency. The testing carried out includes standard cycling and galvanostatic intermittent titration technique (GITT) tests, and the use of a reference electrode to correlate with the anode and cathode readings separately. Further observations are made around the sensor and analyte interaction mechanisms, robustness of sensors and suggested further developments. These finding show that a plasmonic-based optical fibre sensor may have potential as an opto-electrochemical diagnostic technique for lithium-ion batteries, offering an unprecedented view into internal cell phenomena

Electrochemical recovery of lithium-ion battery materials from molten salts by microstructural characterization using X-ray imaging

Recycling spent lithium-ion batteries (LiBs) guarantees the conservation of important metal resources by reducing demands on raw supply and offsetting the energy and environmental costs associated with its manufacture. Employing a molten salt as a solvent for extraction affords a much greener and simpler route to metal recovery by electrochemical means. The current mechanistic understanding of the electrochemical recovery of metals in molten salts needs to be improved for the process to be optimized. X-ray computed tomography offers a non-destructive approach for 3D microstructure visualization and subsequent quantification. Here, we study the electrochemical deposition of recovered cobalt metal from lithium cobalt oxide, LiCoO2 in LiCl-KCl eutectic (LKE). This diagnostic approach has been applied to LiCoO2-LKE samples before and after electrolysis at 450°C, yielding key insights into the morphological evolution of product formation

Nonuniform compensation of current density distribution in polymer electrolyte fuel cells by local heating

A homogeneous current density distribution improves a fuel cell’s performance and prolongs its service life. Effective cell structure designs and uniform compression during assembly could support this goal by ensuring a homogeneous reaction rate across the activation area. Due to the coupling of hydro-electro-thermal relationships, for instance, the concentration of reactants along the flow field decreases continuously as the electrochemical reaction proceeds, and the subsequent accumulation of liquid water leads to a low current density at the outlet. The effect of operating conditions, such as local heating, on the current density distribution requires further investigation. This paper studies the impact of local heating on polymer electrolyte fuel cell (PEFC) performance and analyses the effects on voltage by mapping the current density distribution across the active area. Local heating was supplied to the three regions of the electrode, namely, fuel inlet, central and outlet regions, with the latter exhibiting the best performance (in the activation, Ohmic and mass transport controlled region, the output voltage increases compared to no local heating corresponding to 1.28%, 2.17% and 2.46%, respectively). Here, we show that in all local heating cases, outlet heating can compensate for the lowest current density region with the largest current density increased by 91.10 mA cm−2 and achieves a more homogeneous current distribution, while inlet heating aggravates heterogeneity. This study provides practical guidance for optimal thermal management system development whereby the cooling channel design should be locally optimised for more uniform distributions of current density and temperature compared to heating the cell uniformly

Observation of Zn Dendrite Growth via Operando Digital Microscopy and Time-Lapse Tomography

The zinc-ion battery is one of the promising candidates for next-generation energy storage devices beyond lithium technology due to the earth’s abundance of Zn materials and their high volumetric energy density (5855 mA h cm–3). To date, the formation of Zn dendrites during charge–discharge cycling still hinders the practical application of zinc-ion batteries. It is, therefore, crucial to understand the formation mechanism of the zinc dendritic structure before effectively suppressing its growth. Here, the application of operando digital optical microscopy and in situ lab-based X-ray computed tomography (X-ray CT) is demonstrated to probe and quantify the morphologies of zinc electrodeposition/dissolution under multiple galvanostatic plating/stripping conditions in symmetric Zn||Zn cells. With the combined microscopy approaches, we directly observed the dynamic nucleation and subsequent growth of Zn deposits, the heterogeneous transportation of charged clusters/particles, and the evolution of ‘dead’ Zn particles via partial dissolution. Zn electrodeposition at the early stage is mainly attributed to activation, while the subsequent dendrite growth is driven by diffusion. The high current not only facilitates the formation of sharp dendrites with a larger mean curvature at their tips but also leads to dendritic tip splitting and the creation of a hyper-branching morphology. This approach offers a direct opportunity to characterize dendrite formation in batteries with a metal anode in the laboratory

Nonuniform compensation of current density distribution in polymer electrolyte fuel cells by local heating

A homogeneous current density distribution improves a fuel cell's performance and prolongs its service life. Effective cell structure designs and uniform compression during assembly could support this goal by ensuring a homogeneous reaction rate across the activation area. Due to the coupling of hydro-electro-thermal relationships, for instance, the concentration of reactants along the flow field decreases continuously as the electrochemical reaction proceeds, and the subsequent accumulation of liquid water leads to a low current density at the outlet. The effect of operating conditions, such as local heating, on the current density distribution requires further investigation. This paper studies the impact of local heating on polymer electrolyte fuel cell (PEFC) performance and analyses the effects on voltage by mapping the current density distribution across the active area. Local heating was supplied to the three regions of the electrode, namely, fuel inlet, central and outlet regions, with the latter exhibiting the best performance (in the activation, Ohmic and mass transport controlled region, the output voltage increases compared to no local heating corresponding to 1.28%, 2.17% and 2.46%, respectively). Here, we show that in all local heating cases, outlet heating can compensate for the lowest current density region with the largest current density increased by 91.10 mA cm−2 and achieves a more homogeneous current distribution, while inlet heating aggravates heterogeneity. This study provides practical guidance for optimal thermal management system development whereby the cooling channel design should be locally optimised for more uniform distributions of current density and temperature compared to heating the cell uniformly

Effects of an easy-to-implement water management strategy on performance and degradation of polymer electrolyte fuel cells

Intermittent switching between wet and dry reactant gases during operation in a polymer electrolyte fuel cell (PEFC) can improve performance stability, alleviating the effects of flooding by controlling the water content within the system. However, lifetime durability may be affected due to membrane electrode assembly (MEA) boundary delamination and membrane damage. Two relative humidity (RH) control strategies were investigated, using electrochemical performance and MEA degradation as critical indicators. It was found that intermittent switching between wet and dry gases does not accelerate fuel cell degradation if the duration of the dry gas period is set reasonably (dry gases stops before the voltage reaches the apex of the hump). Additionally, current and temperature distribution mapping was utilised to capture the dynamic response between these transitional stages. The switching of dry gases first makes the current density distribution homogeneous, and the maximum current density is reduced subsequently. Then, the current density near the inlet keeps decreasing. Intermittent switching between wet and dry reactant gases is easy to implement and overcomes limitations in mass transfer at medium and high current densities

PEMFC Electrochemical Degradation Analysis of a Fuel Cell Range-Extender (FCREx) Heavy Goods Vehicle after a Break-In Period

With the increasing focus on decarbonisation of the transport sector, it is imperative to consider routes to electrify vehicles beyond those achievable using lithium-ion battery technology. These include heavy goods vehicles and aerospace applications that require propulsion systems that can provide gravimetric energy densities, which are more likely to be delivered by fuel cell systems. While the discussion of light-duty vehicles is abundant in the literature, heavy goods vehicles are under-represented. This paper presents an overview of the electrochemical degradation of a proton exchange membrane fuel cell integrated into a simulated Class 8 heavy goods range-extender fuel cell hybrid electric vehicle operating in urban driving conditions. Electrochemical degradation data such as polarisation curves, cyclic voltammetry values, linear sweep voltammetry values, and electrochemical impedance spectroscopy values were collected and analysed to understand the expected degradation modes in this application. In this application, the proton exchange membrane fuel cell stack power was designed to remain constant to fulfil the mission requirements, with dynamic and peak power demands managed by lithium-ion batteries, which were incorporated into the hybridised powertrain. A single fuel cell or battery cell can either be operated at maximum or nominal power demand, allowing four operational scenarios: maximum fuel cell maximum battery, maximum fuel cell nominal battery, nominal fuel cell maximum battery, and nominal fuel cell nominal battery. Operating scenarios with maximum fuel cell operating power experienced more severe degradation after endurance testing than nominal operating power. A comparison of electrochemical degradation between these operating scenarios was analysed and discussed. By exploring the degradation effects in proton exchange membrane fuel cells, this paper offers insights that will be useful in improving the long-term performance and durability of proton exchange membrane fuel cells in heavy-duty vehicle applications and the design of hybridised powertrains

Investigation of the effect of temperature on lithium-sulfur cell cycle life performance using system identification and x-ray tomography

In this study, cycle life performance of a prototype lithium-sulfur (Li−S) pouch cell is investigated using system identification and X-ray tomography methods. Li−S cells are subjected to characterization and ageing tests while kept inside a controlled-temperature chamber. After completing the experimental tests, two analytical approaches are used: i) The parameter variations of an equivalent-circuit model due to ageing are determined using a system identification technique. ii) Physical changes of the aged Li−S cells are analyzed using X-ray tomography. The results demonstrate that Li−S cell's degradation is significantly affected by temperature. Comparing to 10 °C, Li−S cell capacity fade happens 1.4 times faster at 20 °C whereas this number increases to 3.3 at 30 °C. In addition, X-ray results show a significant swelling when temperature rises from 10 to 20 °C, correspondingly the gas volume increases from 13 to 62 mm3.Innovate UK: TS/R013780/1. European Union funding: 814471. Engineering and Physical Sciences Research Council (EPSRC): EP/S003053/1, FIRG014, FIRG027

Thermal Runaway of Li-Ion Cells: How Internal Dynamics, Mass Ejection, and Heat Vary with Cell Geometry and Abuse Type

Thermal runaway of lithium-ion batteries can involve various types of failure mechanisms each with their own unique characteristics. Using fractional thermal runaway calorimetry and high-speed radiography, the response of three different geometries of cylindrical cell (18650, 21700, and D-cell) to different abuse mechanisms (thermal, internal short circuiting, and nail penetration) are quantified and statistically examined. Correlations between the geometry of cells and their thermal behavior are identified, such as increasing heat output per amp-hour (kJ Ah-1) of cells with increasing cell diameter during nail penetration. High-speed radiography reveals that the rate of thermal runaway propagation within cells is generally highest for nail penetration where there is a relative increase in rate of propagation with increasing diameter, compared to thermal or internal short-circuiting abuse. For a given cell model tested under the same conditions, a distribution of heat output is observed with a trend of increasing heat output with increased mass ejection. Finally, internal temperature measurements using thermocouples embedded in the penetrating nail are shown to be unreliable thus demonstrating the need for care when using thermocouples where the temperature is rapidly changing. All data used in this manuscript are open access through the NREL and NASA Battery Failure Databank