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At least 145 records · Page 8

Effect of isotropic and anisotropic porous microstructure on electrochemical performance of Li ion battery cathodes: An experimental and computational study

Liquid electrolyte mass transport is a major limitation affecting high-power Li ion batteries. Fast discharging causes Li salt depletion in the current collector region of the cathode which produces overpotential in the electrolyte and consequently a drop of cell voltage to below the cut-off voltage, especially at higher electrode thickness and discharge rate. In this study, through experiment and simulation, we have investigated the effect of electrode thickness, mass loading, discharge rate and tortuosity on electrolyte mass transport and final derived areal capacity and specific energy for electrodes having isotropic (normal tape casting) and anisotropic (freeze tape casting) porous microstructure. Furthermore, the macroporous channels in freeze tape cast electrodes facilitate Li salt transport and reduce the Li salt mass transport limitations even at high electrode thickness and discharge rates, and high electrode tortuosity. In our results, computer simulations show that freeze tape cast electrodes may be fully discharged up to 750 μm thickness at 1 C rate compared to 300 μm for normal tape cast electrodes with the same mass loading. Freeze tape cast electrodes also show stable maximum areal capacity for C rates about double the maximum C rates of their normal tape cast electrode counterparts with the same mass loading.

25 ENERGY STORAGE↗

Metal hydrides: a historical perspective

Metal hydrides are known for their outstanding performance as materials for hydrogen storage and processing. These materials find applications for short- and long-term energy storage, compression and supply of hydrogen gas, thermal energy storage, as electrodes and electrolytes in rechargeable batteries, for the microstructural optimisation of functional materials, in thin film technologies, as catalysts, getters and in many other uses. After the discovery of the first binary metal hydrides back in the 19th century, their studies covered all possible binary M-H systems and expanded rapidly into the field of ternary hydrides following the recognition of the excellent hydrogen storage performance of LaNi 5 - and TiFe-based materials, which operate efficiently at room temperature and at near-ambient H 2 pressures. This review aims to provide an overview of the early works, as well as selected recent results on various classes of metal hydrides. It also covers the recent activities from the major contributing countries and continents, including USA, Europe, Japan, China and Australia. These studies relate to achieving the hydrogen storage systems goals set by the Department of Energy in the United States which inspired the research activities at the national and international level, through execution of the tasks on hydrogen-based energy storage managed by the International Energy Agency. The review is prepared by international experts in the field and covers the most important past developments and also presents the recent achievements in the field.

08 HYDROGEN↗

Understanding and Strategies for Controlled Interfacial Phenomena in Lithium-Ion Batteries and Beyond

Electrolyte chemistry and properties and electrode structure and chemical properties particularly at the interfaces are crucial for the development of advanced battery components. This project focused on elucidating the roles of the electrolyte and electrode on the formation and evolution of the SEI layer and cell electrochemical performance on silicon and on Li metal anodes. For Si nano/microstructures we evaluated lithiation, volume changes, reactivity, and chemo-mechanical transformations as functions of nanoparticle size, shape, presence of coatings, electrolyte composition, electron leakage to the electrolyte, and cycling. For Li metal anodes we provided detailed analyses of the electrode and electrolyte effects on interfacial reactivity and as a function of microstructural evolution and underlying stochasticity as dendrites nucleate and grow. We thoroughly investigated and simulated how the chemistry of the various components of the electrolyte and the electrode architecture may affect the electrochemical reactions as well as cell degradation. A multiscale modeling approach was utilized, where atomistic simulations informed about the microscopic behavior of the system, and intermediate time and length scales were investigated with mesoscopic models. Results were also tested against selected experiments from our collaborators. The combined theoretical-experimental strategy saves costs by utilizing predictions from computational analyses to guide experimentation.

25 ENERGY STORAGE↗

Silica–Derived Nanostructured Electrode Materials for ORR, OER, HER, CO 2 RR Electrocatalysis, and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO 2 RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO 2 RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

25 ENERGY STORAGE↗

Red-Ox Robust SOFC Stacks for Affordable, Reliable Distributed Generation Power Systems

While SOFC systems are expected to operate reliably and with limited degradation in steady state or transient performance, SOFC stacks may ultimately fail due to the loss of structural integrity of one or several of the cells as a result of the weakening of the materials and interfaces due to physico-chemical changes that occur during continuous operation as a result of plastic and creep deformations, modification of the temperature profile, and/or degradation of the electrochemical performance of the cells. Degradation mechanisms originating from the cell components include coarsening of the microstructure over time; decomposition of materials; chemical reaction of electrode materials with electrolyte at the interface; delamination from each other; and for the anode, coking and sulfur poisoning. Of all the reliability issues that may occur for SOFCs, the main limitation for Ni-based cermet anodes (e.g., NiO-YSZ) is the poor stability during reduction-oxidation (red-ox) cycling. This project was aimed at the development of ceramic anode SOFCs based on SFCM (SrFe0.2Co0.4Mo0.4O3), which is a conductive perovskite that is red-ox stable. Additionally, the project involved the development of a red-ox robust stack. Scale up of SFCM-based cells to a large format (10 cm by 10 cm) cell size was achieved as well as a maximum power density of 0.9 W/cm 2 at 600 °C (>0.6 W/cm 2 at 0.6 V). Up to a 10-cell stack was successfully assembled and demonstrated, and cells showed similar performance in reformed, pipeline natural gas as in hydrogen. Finally, a 3-cell stack was red-ox cycled without degradation for 40 cycles at ~600 °C.

03 NATURAL GAS↗

Cycling-Induced Microstructural Changes in Alloy Anodes for Lithium-Ion Batteries

Abstract High-capacity electrochemical alloying materials, such as tin and tin-based alloys, present an opportunity for the advancement of lithium-ion batteries. However, the destructive effects of volumetric expansion must be mitigated in order to sustain this high capacity during extended cycling. One way to mitigate these effects is by alloying Sn with more malleable metals to accommodate the strain related to severe volumetric expansion. Ex situ X-ray microtomography data of cycled Cu6Sn5 pellets were used to quantify the microstructural changes that occur during lithiation and delithiation. The microtomography data were segmented into three distinct phases to evaluate phase size distributions, specific surface area, and tortuosity. Electrodes lithiated and then delithiated showed the most substantial reduction in overall phase sizes. This suggests that full lithiation of the Sn followed by partial delithiation of the Li4.4Sn to Li2CuSn can cause substantial microstructural changes related to volume expansion on lithiation and structural collapse upon delithiation. When considering other microstructural characteristics, this subset of the electrodes analyzed showed the highest tortuosity values. These results show that in addition to the mechanical degradation of the electrodes, excessive volume expansion can also influence transport networks in the active material and supporting phases of the electrode. While based on studies of the active–inactive alloy Cu6Sn5 for lithium-ion battery applications, the insights obtained are expected to be applicable to other alloy electrodes and battery chemistries.

Electrochemistry↗

Rheological and microstructural characterization of aqueous suspensions of carbon black and reduced graphene oxide

Carbon black is often used as a conductivity enhancer in battery electrodes. Reduced graphene oxide is another conducting material, with a high aspect ratio sheet-like morphology, and offers the possibility of generating a conducting network at loadings that are small compared to carbon black. Suspensions of conducting carbon, active materials and binders are typically coated on current collectors during the formation of electrodes. The rheology of these suspensions is an important indicator of the connectivity of particles in the suspension and impacts the electrical conductivity as well as the thickness of the coated layer. In this work, the rheology and microstructures of aqueous suspensions of para-aminobenzoic acid terminated carbon black (CB) with and without reduced graphene oxide (RGO) were investigated. The CB loading varied between 0.05 wt.% -10 wt.%, while the samples containing RGO had an RGO loading of 0.05 wt.%. The pH of the suspension was varied from 7.5 to 3. The carboxyl groups on the CB surface are deprotonated at pH 7.5, making the particles hydrophilic. Protonation of the carboxylate groups at pH 3 makes the particles partially hydrophobic. Suspensions of CB showed Newtonian behavior at all loadings for pH 7.5, and at loadings below 1.5 wt.% for pH 3. They are shear thinning at loadings between 1.5–10 wt.%. Interestingly, the low shear viscosity is non-monotonic with CB loading, rising up to a CB loading of 7.5 wt.%, and then dropping at 10 wt.%. Cryogenic scanning electron microscopy (SEM) showed CB particles forming aggregates at pH 3 for CB loadings greater than 1.5 wt.%. At pH 3, addition of 0.05 wt.% RGO resulted in a viscosity increase for suspensions containing 0.5 wt.% CB, as the RGO formed connections with CB particles that enhanced network formation. Adding RGO had little effect on suspensions that had 1.5 wt.% CB. The combination of SEM imaging and suspension rheology provides insight into the particle connectivity for the carbon-based materials studied here. These insights will be useful in determining coating conditions for slurries used in rechargeable battery electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

Effects of processing conditions on flash sintering of commercial ZrN

Flash sintering (FS) is a potentially rapid and low-cost manufacturing technique for advanced ceramics. There are still many unknowns about ceramic FS, especially for highly conductive high-temperature ceramics (HTC), which often display decreased bulk conductivity with increasing temperature. This study qualitatively characterizes the flash behavior of highly conductive HTC materials using zirconium nitride (ZrN) as an example. The effects of processing parameters (e.g., DC voltage/electrical field strength, voltage ramp rate, post-flash holding time, mechanical pressure, sample milling, and choice of electrode materials) on ZrN flash behavior are also qualitatively studied and linked to samples microstructure and hardness. It is observed that best densification was achieved using 5 min Spex-milled ZrN powder under 25 MPa of applied pressure and constant 8 V DC. The potential mechanism for ZrN FS and the similarity and difference from FS of conventional oxides like YSZ have been proposed based on experimental observations, and the directions for future research are also pointed out.

Flash Sintering↗

Distinct Melt Infusion Architectures of Antiperovskite Solid Electrolytes

Antiperovskite solid electrolytes are an emerging class of lithium‐ion conductors distinguished by their unusually low melting points, enabling scalable, low‐temperature processing routes not accessible to most solid electrolytes. In this work, we synthesize phase‐pure chloride (Cl), bromide (Br), and mixed halide (ClBr) variants of antiperovskites and investigate their ionic conductivities in both powder and hot‐pressed forms. Hot pressing significantly enhances conductivity across all compositions, while energy‐dispersive X‐ray spectroscopy (EDS) of the mixed halide system reveals halide surface migration during densification. We further investigate the melt‐infiltration behavior of these electrolytes into substrates relevant to solid‐state battery architectures, including Al and Cu current collectors, conventional NMC and LFP cathodes, and a foamed NMC cathode with a highly porous architecture. The foamed cathode enables deep and uniform electrolyte penetration, highlighting the role of electrode architecture in facilitating melt infiltration. Across all substrates, electrolyte halide chemistry strongly influences wetting behavior, penetration depth, and resulting microstructural morphology. Together, these results establish clear processing–structure relationships for melt‐infiltrated antiperovskite solid electrolytes and demonstrate how electrolyte chemistry and electrode architecture govern interfacial morphology during integration, providing practical guidelines for processing and structural design in solid‐state battery systems.

antiperovskite↗

Gas-mediated defect engineering in earth-abundant Mn-rich layered oxides for non-aqueous sodium-based batteries

Gases are often by-products of battery materials during cell formation and degradation, affecting the cycle life and safety of rechargeable batteries. However, understanding gas-mediated (electro)-chemical reactions and nanoscale structural transformations during the synthesis of battery electrode materials remains challenging because of the lack of suitable characterization routes and the complexity of the interplay between thermodynamics and kinetics. Here, in this study, we use operando synchrotron X-ray diffraction, in situ transmission X-ray microscopy and multiscale modelling to elucidate the reaction pathways and microstructural defect development of earth-abundant Mn-rich layered oxides as positive electrode materials for sodium-based batteries. In particular, we demonstrate the dominant role of CO 2 over O 2 and H 2 O (g) in modulating the competition between entropy and enthalpy during solid-state synthesis. Using Ni 0.25 Mn 0.75 CO 3 as a model precursor, we reveal that CO 2 generation favours the formation of entropy-driven metastable intermediates, suppresses closed pore/nanovoids formation and decreases chemical heterogeneity and residual lattice strain of Mn-rich layered oxides during the synthesis. This result motivates a fast-sintering strategy to promote CO 2 release, which ultimately leads to improved chemo-mechanical and electrochemical stability of the Mn-rich positive electrodes when tested in non-aqueous Na metal coin cells.

36 MATERIALS SCIENCE↗

Multimodal Nanoscale Tomographic Imaging for Battery Electrodes

Accurate representations of the 3D structure within a lithium-ion battery are key to understanding performance limitations. However, obtaining exact reconstructions of electrodes, where the active particles, the carbon black and polymeric binder domain, and the pore space are visualized is challenging. In this work, it is shown that multimodal imaging can be used to overcome this challenge. High-resolution ptychographic X-ray computed tomography are combined with lower resolution but higher contrast transmission X-ray tomographic microscopy to obtain 3D reconstructions of pristine and cycled graphite-silicon composite electrodes. This cross-correlation enables quantitative analysis of the surface of active particles, including the heterogeneity of carbon-black and binder domain and solid-electrolyte interphase coverage. Capturing the active particles as well as the carbon black-binder domain allows using these segmented structures for electrochemical simulations to highlight the influence of the particle embedding on local state of charge heterogeneities.

25 ENERGY STORAGE↗

Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning

High-rate capable, reversible lithium metal anodes are necessary for next generation energy storage systems. In situ tomography of Li/LLZO/Li cells is carried out to track morphological transformations in Li metal electrodes. Machine learning enables tracking the lithium metal morphology during galvanostatic cycling. Nonuniform lithium electrode kinetics are observed at both electrodes during cycling. Hot spots in lithium metal are correlated with microstructural anisotropy in LLZO. Mesoscale modeling reveals that regions with lower effective properties (transport and mechanical) are nuclei for failure. Advanced visualization combined with electrochemistry represents an important pathway toward resolving non-equilibrium effects that limit rate capabilities of solid-state batteries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modeling Oxygen Partial Pressure in Solid Oxide Electrolysis Cells: The Microstructure Effect

Oxygen partial pressure is an important thermodynamic state variable that affects both the performance and degradation of solid oxide electrolysis cells. In this work, a 3D model developed from Virkar’s 1D model has been applied to reconstructed and synthetic microstructures of Ni-YSZ-GDC-LSCF cell. The effect of the microstructures, including the thickness of the YSZ and GDC layer, and the compositions of the hydrogen and oxygen electrode, on the distribution of oxygen partial pressure has been investigated. The results show that the maximum oxygen partial pressure may occur on the interface between oxygen electrode and GDC layer or between GDC layer and YSZ layer depending on the rate of oxygen ion exchange between GDC and YSZ. A thicker GDC layer lowers the maximum oxygen partial pressure in the cell, while a thicker YSZ layer lowers the maximum oxygen partial pressure in the hydrogen electrode. In addition, the Ni:YSZ ratio and porosity also affects the maximum partial pressure. These findings provide insights on mitigating degradation in solid oxide electrolysis cell by tuning the microstructures.

Lei, Yinkai↗

Utilizing Oxygen Redox in Layered Cathode Materials from Multiscale Perspective

We report in high-capacity layered oxide cathode materials, utilization of lattice oxygen as a redox center is considered to be one of the most promising approaches to overcome the capacity limitation set by conventional transition metal redox centers. However, rapid material degradation is often associated with oxygen oxidation, leading to formidable challenges in utilizing oxygen redox. Further mechanistic understanding of the oxygen activities thus becomes critical to better control oxygen redox reactions. This review summarizes recent advances for investigating oxygen redox reactions in cathode materials from a multiscale perspective, i.e., from the atomistic level to the microstructure regime. First the mechanistic aspects of oxygen redox and the consequences of this reaction on various electrode degradation pathways during battery operation (e.g., oxygen loss, transition metal migration, irreversible phase transition), relating structural changes at the crystallographic scale to those at the macro scale, are discussed. Then recent developments based on atomic and microstructure modifications that are promising for improving the reversibility of oxygen redox reaction or mitigating the harmful processes arising from oxidation of the oxygen centers under high operating voltage are recounted. The analysis is concluded with a commentary on further research directions toward optimizing the oxygen activity for high-capacity charge storage.

25 ENERGY STORAGE↗

Oxygen Reduction Reaction Activity of Nanocolumnar Platinum Thin Films by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) were produced by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells. Conventional high-density Pt-TF prepared by low pressure sputtering was also studied for comparison. Pt-TFs were deposited on a microporous layer (MPL)-like surface composed of carbon particles to mimic catalyst-coated gas diffusion electrodes. Electron microscopy imaging revealed that HIPS Pt-TFs developed a cauliflower-like columnar microstructure, which originated from a shadowing effect during HIPS. This shadowing effect is enhanced on the rough surface of the MPL-like carbon that leads to the nano-cauliflower formation. With this approach, we also aimed to relate the catalyst performance obtained by benchtop tests directly to membrane electrode assembly test results. The electrochemically active surface area of Pt-TFs increased from 10 to 19 m 2 /g with increasing sputter pressure. Specific activity of conventional high-density and nanocolumnar films were similar at ~600 μA/cm 2 , which is likely due to their similar crystal grain sizes, >5 nm. On the other hand, mass-specific (MA) activity values increased from ~0.06 A/mgPt for conventional Pt-TF to ~0.13 A/mgPt for HIPS Pt-TFs, which is consistent with the columnar microstructure of HIPS films providing a better catalyst utilization compared to conventional Pt-TF.

08 HYDROGEN↗

Defect formation and microstructure tuning via proton irradiation to control electrochemical and phase reversibility in layered battery materials

The reversibility of phase transformation influences the functionality of electrode materials in batteries. In many battery materials, nanosized grains favor phase reversibility but at the cost of cyclability due to aggravated side reactions with the electrolyte. Here, in this study, we present a novel approach to enhance the phase transformation reversibility of layered oxide cathodes, exemplified by Na 2/3 Fe 1/2 Mn 1/2 O 2 through proton irradiation. In addition to forming defects, proton irradiation at sufficiently high doses can subdivide single grains into multiple nanodomains without physically rupturing them. Hence, the single grains of the material assume a pseudo-secondary particle nature without reducing the overall grain size. Preserving the grain size is advantageous, as it reduces side reactions, which is not possible with conventional grain size reduction methods. While chemical transformations and defect formation induced through proton irradiation can influence the stability of battery materials, it is expected that structural reorganization due to cycling-induced phase transformation will be contained within these nanodomains. Such confinement of phase transformation is potentially responsible for enhancing the reversibility of layered oxide materials in our study. Thus, our study suggests that grain subdivision could become an effective microstructure tuning strategy for managing electrochemical cycling-induced phase changes in battery electrodes.

25 ENERGY STORAGE↗