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Effective water management is crucial for the optimal operation of low-temperature polymer electrolyte membrane fuel cells (PEMFCs). Excessive liquid water production can cause flooding in the gas diffusion electrodes and flow channels, limiting mass transfer and reducing PEMFC performance. To tackle this issue, a nature-inspired chemical engineering (NICE) approach has been adopted that takes cues from the integument structure of desert-dwelling lizards for passive water transport. By incorporating engraved, capillary microchannels into conventional flow fields, PEMFC performance improves significantly, including a 15% increase in maximum power density for a 25 cm2 cell and 13% for a 100 cm2 cell. Electro-thermal maps of the lizard-inspired flow field demonstrate a more uniform spatial distribution of current density and temperature than the conventional design. Neutron radiography provides evidence that capillary microchannels in the lizard-inspired flow field facilitate the efficient transport and removal of generated liquid water, thereby preventing blockages in the reactant channels. These findings present a universally applicable and highly efficient water management strategy for PEMFCs, with the potential for widespread practical implementation for other electrochemical devices.
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Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.
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The Mo/Fe nitrogenase enzyme is unique in its ability to efficiently reduce dinitrogen to ammonia at atmospheric pressures and room temperature. Should an artificial electrolytic device achieve the same feat, it would revolutionize fertilizer production and even provide an energy-dense, truly carbon-free fuel. This Review provides a coherent comparison of recent progress made in dinitrogen fixation on solid electrodes, homogeneous catalysts and nitrogenases. Specific emphasis is placed on systems for which there is unequivocal evidence that dinitrogen reduction has taken place. By establishing the cross-cutting themes and synergies between these systems, we identify viable avenues for future research.
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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.
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Lithium-ion batteries are the most ubiquitous energy storage devices in our everyday lives. However, their energy storage capacity fades over time due to chemical and structural changes in their components, via different degradation mechanisms. Understanding and mitigating these degradation mechanisms is key to reducing capacity fade, thereby enabling improvement in the performance and lifetime of Li-ion batteries, supporting the energy transition to renewables and electrification. In this endeavor, surface analysis techniques are commonly employed to characterize the chemistry and structure at reactive interfaces, where most changes are observed as batteries age. However, battery electrodes are complex systems containing unstable compounds, with large heterogeneities in material properties. Moreover, different degradation mechanisms can affect multiple material properties and occur simultaneously, meaning that a range of complementary techniques must be utilized to obtain a complete picture of electrode degradation. The combination of these issues and the lack of standard measurement protocols and guidelines for data interpretation can lead to a lack of trust in data. Herein, we discuss measurement challenges that affect several key surface analysis techniques being used for Li-ion battery degradation studies: focused ion beam scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. We provide recommendations for each technique to improve reproducibility and reduce uncertainty in the analysis of NMC/graphite Li-ion battery electrodes. We also highlight some key measurement issues that should be addressed in future investigations.
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X-ray computed tomography (X-ray CT) is a non-destructive characterization technique that in recent years has been adopted to study the microstructure of battery electrodes. However, the often manual and laborious data analysis process hinders the extraction of useful metrics that can ultimately inform the mechanisms behind cycle life degradation. This work presents a novel approach that combines two convolutional neural networks to first locate and segment each particle in a nano-CT LiNiMnCoO2 (NMC) electrode dataset, and successively classifies each particle according to the presence of flaws or cracks within its internal structure. Metrics extracted from the computer vision segmentation are validated with respect to traditional threshold-based segmentation, confirming that flawed particles are correctly identified as single entities. Successively, slices from each particle are analyzed by a pre-trained classifier to detect the presence of flaws or cracks. The models are used to quantify microstructural evolution in uncycled and cycled NMC811 electrodes, as well as the number of flawed particles in a NMC622 electrode. As a proof-of-concept, a 3-phase segmentation is also presented, whereby each individual flaw is segmented as a separate pixel label. It is anticipated that this analysis pipeline will be widely used in the field of battery research and beyond.
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Processamento de Imagem Assistida por Computador , Redes Neurais de Computação , Processamento de Imagem Assistida por Computador/métodos , Tomografia Computadorizada por Raios X/métodos , Computadores , EletrodosRESUMO
Supercapacitors are increasingly used in short-distance electric transportation due to their long lifetime (≈15 years) and fast charging capability (>10 A g-1 ). To improve their market penetration, while minimizing onboard weight and maximizing space-efficiency, materials costs must be reduced (<10 $ kg-1 ) and the volumetric energy-density increased (>8 Wh L-1 ). Carbon nanofibers display good gravimetric capacitance, yet their marketability is hindered by their low density (0.05-0.1 g cm-3 ). Here, the authors increase the packing density of low-cost, free-standing carbon nanofiber mats (from 0.1 to 0.6 g cm-3 ) through uniaxial compression. X-ray computed tomography reveals that densification occurs by reducing the inter-fiber pore size (from 1-5 µm to 0.2-0.5 µm), which are not involved in double-layer capacitance. The improved packing density is directly proportional to the volumetric performances of the device, which reaches a volumetric capacitance of 130 F cm-3 and energy density of 6 Wh L-1 at 0.1 A g-1 using a loading of 3 mg cm-2 . The results outperform most commercial and lab-scale porous carbons synthesized from bioresources (50-100 F cm-3 , 1-3 Wh L-1 using 10 mg cm-2 ) and contribute to the scalable design of sustainable electrodes with minimal 'dead volume' for efficient supercapacitors.
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Accurate modelling of particle shrinkage during biomass pyrolysis is key to the production of biochars with specific morphologies. Such biochars represent sustainable solutions to a variety of adsorption-dependent environmental remediation challenges. Modelling of particle shrinkage during biomass pyrolysis has heretofore been based solely on theory and ex-situ experimental data. Here we present the first in-situ phase-contrast X-ray imaging study of biomass pyrolysis. A novel reactor was developed to enable operando synchrotron radiography of fixed beds of pyrolysing biomass. Almond shell particles experienced more bulk shrinkage and less change in porosity than did walnut shell particles during pyrolysis, despite their similar composition. Alkaline pretreatment was found to reduce this difference in feedstock behaviour. Ex-situ synchrotron X-ray microtomography was performed to study the effects of pyrolysis on pore morphology. Pyrolysis led to a redistribution of pores away from particle surfaces, meaning newly formed surface area may be less accessible to adsorbates.
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Biomassa , Temperatura Alta , Modelos Químicos , Pirólise , Síncrotrons , Microtomografia por Raio-XRESUMO
Due to complex degradation mechanisms, disparities between the theoretical and practical capacities of lithium-ion battery cathode materials persist. Specifically, Ni-rich chemistries such as LiNi0.8Mn0.1Co0.1O2 (or NMC811) are one of the most promising choices for automotive applications; however, they continue to suffer severe degradation during operation that is poorly understood, thus challenging to mitigate. Here we use operando Bragg coherent diffraction imaging for 4D analysis of these mechanisms by inspecting the individual crystals within primary particles at various states of charge (SoC). Although some crystals were relatively homogeneous, we consistently observed non-uniform distributions of inter- and intracrystal strain at all measured SoC. Pristine structures may already possess heterogeneities capable of triggering crystal splitting and subsequently particle cracking. During low-voltage charging (2.7-3.5 V), crystal splitting may still occur even during minimal bulk deintercalation activity; and during discharging, rotational effects within parallel domains appear to be the precursor for the nucleation of screw dislocations at the crystal core. Ultimately, this discovery of the central role of crystal grain splitting in the charge/discharge dynamics may have ramifications across length scales that affect macroscopic performance loss during real-world battery operation.
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Creating effective and stable catalyst nanoparticle-coated electrodes that can withstand extensive cycling is a current roadblock in realising the potential of polymer electrolyte membrane fuel cells. Graphene has been proposed as an ideal electrode support material due to its corrosion resistance, high surface area and high conductivity. However, to date, graphene-based electrodes suffer from high defect concentrations and non-uniform nanoparticle coverage that negatively affects performance; moreover, production methods are difficult to scale. Herein we describe a scalable synthesis for Pt nanoparticle-coated graphene whereby PtCl2 is reduced directly by negatively charged single layer graphene sheets in solution. The resultant nanoparticles are of optimal dimensions and can be uniformly dispersed, yielding high catalytic activity, remarkable stability, and showing a much smaller decrease in electrochemical surface area compared with an optimised commercial catalyst over 30 000 cycles. The stability is rationalised by identical location TEM which shows minimal nanoparticle agglomeration and no nanoparticle detachment.
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Understanding and ultimately controlling the properties of the solid-electrolyte interphase (SEI) layer at the graphite anode/liquid electrolyte boundary are of great significance for maximizing the performance and lifetime of lithium-ion batteries (LIBs). However, comprehensive in situ monitoring of SEI formation and evolution, alongside measurement of the corresponding mechanical properties, is challenging due to the limitations of the characterization techniques commonly used. This work provides a new insight into SEI formation during the first lithiation and delithiation of graphite battery anodes using operando electrochemical atomic force microscopy (EC-AFM). Highly oriented pyrolytic graphite (HOPG) is investigated first as a model system, exhibiting unique morphological and nanomechanical behavior dependent on the various electrolytes and commercially relevant additives used. Then, to validate these findings with respect to real-world battery electrodes, operando EC-AFM of individual graphite particles like those in commercial systems are studied. Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are shown to be effective additives to enhance SEI layer stability in 1 M LiPF6/ethylene carbonate/ethyl methyl carbonate (EC/EMC) electrolytes, attributed to their role in improving its structure, density, and mechanical strength. This work therefore presents an unambiguous picture of SEI formation in a real battery environment, contributes a comprehensive insight into SEI formation of electrode materials, and provides a visible understanding of the influence of electrolyte additives on SEI formation.
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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.
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Vast quantities of powder leave production lines each day, often with strict control measures. For quality checks to provide the most value, they must be capable of screening individual particles in 3D and at high throughput. Conceptually, X-ray computed tomography (CT) is capable of this; however, achieving lab-based reconstructions of individual particles has, until now, relied upon scan-times on the order of tens of hours, or even days, and although synchrotron facilities are potentially capable of faster scanning times, availability is limited, making in-line product analysis impractical. This work describes a preparation method and high-throughput scanning procedure for the 3D characterization of powder samples in minutes using nano-CT by full-filed transmission X-ray microscopy with zone-plate focusing optics. This is demonstrated on various particle morphologies from two next-generation lithium-ion battery cathodes: LiNi0.8Mn0.1Co0.1O2 and LiNi0.6Mn0.2Co0.2O2; namely, NMC811 and NMC622. Internal voids are detected which limit energy density and promote degradation, potentially impacting commercial application such as the drivable range of an electric vehicle.
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We have discovered a very simple method to address the challenge associated with the low volumetric energy density of free-standing carbon nanofiber electrodes for supercapacitors by electrospinning Kraft lignin in the presence of an oxidizing salt (NaNO3) and subsequent carbonization in a reducing atmosphere. The presence of the oxidative salt decreases the diameter of the resulting carbon nanofibers doubling their packing density from 0.51 to 1.03 mg cm-2 and hence doubling the volumetric energy density. At the same time, the oxidative NaNO3 salt eletrospun and carbonized together with lignin dissolved in NaOH acts as a template to increase the microporosity, thus contributing to a good gravimetric energy density. By simply adjusting the process parameters (amount of oxidizing/reducing agent), the gravimetric and volumetric energy density of the resulting lignin free-standing carbon nanofiber electrodes can be carefully tailored to fit specific power to energy demands. The areal capacitance increased from 147 mF cm-2 in the absence of NaNO3 to 350 mF cm-2 with NaNO3 translating into a volumetric energy density increase from 949 µW h cm-3 without NaNO3 to 2245 µW h cm-3 with NaNO3. Meanwhile, the gravimetric capacitance also increased from 151 F g-1 without to 192 F g-1 with NaNO3.
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As the energy density of lithium-ion cells and batteries increases, controlling the outcomes of thermal runaway becomes more challenging. If the high rate of gas generation during thermal runaway is not adequately vented, commercial cell designs can rupture and explode, presenting serious safety concerns. Here, ultra-high-speed synchrotron X-ray imaging is used at >20 000 frames per second to characterize the venting processes of six different 18650 cell designs undergoing thermal runaway. For the first time, the mechanisms that lead to the most catastrophic type of cell failure, rupture, and explosion are identified and elucidated in detail. The practical application of the technique is highlighted by evaluating a novel 18650 cell design with a second vent at the base, which is shown to avoid the critical stages that lead to rupture. The insights yielded in this study shed new light on battery failure and are expected to guide the development of safer commercial cell designs.
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Electrospun custom made flow battery electrodes are imaged in 3D using X-ray computed tomography. A variety of computational methods and simulations are applied to the images to determine properties including the porosity, fiber size, and pore size distributions as well as the material permeability and flow distributions. The simulations are performed on materials before and after carbonization to determine the effect it has in the internal microstructure and material properties. It is found that the deposited fiber size is constantly changing throughout the electrospinning process. The results also show that the surfaces of the fibrous material are the most severely altered during carbonization and that the rest of the material remained intact. Pressure driven flow is modeled using the lattice Boltzmann method and excellent agreement with experimental results is found. The simulations coupled with the material analysis also demonstrate the highly heterogeneous nature of the flow. Most of the flow is concentrated to regions with high porosity while regions with low porosity shield other pores and starve them of flow. The importance of imaging these materials in 3D is highlighted throughout.
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A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO2 to U metal in LiCl-KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl-KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems.
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A new technique combining in situ X-ray diffraction using synchrotron radiation and infrared thermal imaging is reported. The technique enables the application, generation and measurement of significant thermal gradients, and furthermore allows the direct spatial correlation of thermal and crystallographic measurements. The design and implementation of a novel furnace enabling the simultaneous thermal and X-ray measurements is described. The technique is expected to have wide applicability in material science and engineering; here it has been applied to the study of solid oxide fuel cells at high temperature.