Search Results (27)

The integration of microstructured current collectors offers a potential pathway to enhance interface properties in solid-state battery architectures. In this work, we investigate the influence of surface morphology on the electrochemical performance of Zn/Na_2.99Ba_0.005OCl/Cu electrodeless pouch cells by fabricating copper thin films on microstructured parylene-C substrates using a combination of colloidal lithography and reactive ion etching. O₂ plasma etching times ranging from 0 to 15 min were used to tune the surface topography, resulting in a systematic increase in root-mean-square roughness and a surface area enhancement of up to ~30% for the longest etching duration, measured via AFM. Kelvin probe force microscopy-analyzed surface potential showed maximum differences of 270 mV between non-etched and 12-minute-etched Cu collectors. The results revealed that the chemical potential is the property that relates the surface of the Cu current collector/electrode with the cell’s ionic transport performance, including the bulk ionic conductivity, while four-point sheet resistance measurements confirmed that the copper layers’ resistivity maintained values close to those of bulk copper (1.96–4.5 µΩ.cm), which are in agreement with electronic mobilities (−6 and −18 cm²V⁻¹s⁻¹). Conversely, the charge carrier concentrations (−1.6 to −2.6 × 10²³ cm⁻³) are indirectly correlated with the performance of the cell, with the samples with lower CCC_bulk (fewer free electrons) performing better and showing higher maximum discharge currents, interfacial capacitance, and first-cycle discharge plateau voltage and capacity. The data were further consolidated with Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy analyses. These results highlight that the correlation between the surface morphology and the cell is not straightforward, with the microstructured current collectors’ surface chemical potential and the charge carriers’ concentration being determinant in the performance of all-solid-state electrodeless sodium battery systems. Full article

Thin films of manganese–nickel–cobalt oxide with graphene (G@MNCO) were deposited on copper foam using electrochemical deposition. NiCo₂O₄ is the main phase in these films. As the proportion of graphene in the precursor solution increases, the oxygen vacancies in the samples also increase. The microstructure of these samples evolves into hierarchical vertical flake structures. Cyclic voltammetry measurements conducted within the potential range of 0–1.2 V reveal that the electrode with the highest graphene content achieves the highest specific capacitance, approximately 475 F/g. Furthermore, it exhibits excellent cycling durability, maintaining 95.0% of its initial capacitance after 10,000 cycles. The superior electrochemical performance of the graphene-enhanced, manganese-doped nickel–cobalt oxide electrode is attributed to the synergistic contributions of the hierarchical G@MNCO structure, the three-dimensional Cu foam current collector, and the binder-free fabrication process. These features promote quicker electrolyte ion diffusion into the electrode material and ensure robust adhesion of the active materials to the current collector. Full article

Composite copper foil, a novel negative electrode current collector developed in recent years, can significantly enhance battery safety and energy density while also conserving metallic resources. It is found that after 9 months of long-term storage, the tensile strength of the composite copper foil decreases by 9.76%, and the elongation rate drops by 26.32%. The internal texture of the composite copper foil shifts from a highly oriented (111) plane to a more random crystal plane orientation and the bonding strength is significantly improved. The study reveals that the residual stress within the copper layer provides the driving force for the changes in the microstructure; the intermediate PET layer plays a buffering and absorbing role in the stress-release process. It regulates the redistribution of stress, promoting the alteration of the copper layer’s texture and the refinement of grains. Full article

Silicon-based materials are considered the most promising next-generation anode materials for lithium-ion batteries due to their high theoretical specific capacity, rich reserves, and advantages of low discharge potential. However, the significant volume expansion of silicon during the cycling process leads to the detachment of active substances and the loss of electrical contact between the active substances and the current collector, ultimately resulting in a decline in battery performance. Nanostructured anodes have advantages of high specific surface area, short diffusion path, and the ability to effectively alleviate the volume expansion of electrode material during circulation. Therefore, how to rationally design the nanostructured silicon-based anodes is currently one of the research hotspots. This article first reviews and evaluates the advantages and disadvantages of microstructured and nano-structured silicon anodes in rate performance, discusses cycle stability and volumetric energy density, and discusses and summarizes the lithium storage mechanism of silicon-based materials, with a focus on the influence of some nanostructured silicon anodes and silicon/carbon composites and conductive polymers and silicon/metal composites on the electrochemical properties of materials. Finally, some suggestions and prospects for the future development of silicon-based materials are proposed. Full article

Fast electrochemical phenomena occurring in supercapacitors are hard to analyze by ex situ or in situ techniques because many of them are meta-stable (the supercapacitor relaxes once it is not further polarized). In a steady state, one observes the effect of charge storage but not necessarily the mechanism. This is a problem for Raman spectroscopy, too, even though Raman spectra of the electrodes of supercapacitors are commonly recorded ex situ or in a steady state in situ. Raman operando is desired, but it represents a technological challenge since the electrochemical events in a supercapacitor are very fast (occurring within seconds), and in contrast, Raman requires from seconds to minutes to collect enough photons for reliable spectra. This work presents the development of electrodes made of thin layers of iron oxide grown solvothermally on Si wafers, with a porosified surface and resistivity of 0.005 Ωcm, to study their performance as electrodes in supercapacitors and analyze their energy storage mechanisms by cyclic voltammetry and Raman operando. Being flat and containing just iron oxide and silicon, these electrodes allow for studying interfacial phenomena with minor interferents. Full article

As the demand for lithium-ion batteries increases, higher quality requirements are being placed on pure aluminum ultra-thin strips, one of the main materials used in lithium-ion battery current collectors. Roller vibration during the rolling process of pure aluminum ultra-thin strips is unavoidable and significantly affects the quality of the strips. This paper uses 1A99 pure aluminum ultra-thin strips as raw materials and employs a controlled vibration method during the rolling process to obtain products under two conditions: stable rolling and vibrational rolling. The surface and cross-section of the aluminum strips were characterized using scanning electron microscopy (SEM), and the microstructure of the surface and cross-section was studied using electron backscatter diffraction (EBSD) technology. The results show that, during stable rolling, the surface quality of the aluminum strip is good without defects. Under vibration, obvious vibration marks appear on the surface of the aluminum strip, showing characteristics of peaks and troughs. With the increase in strain at the trough position, there is a transition from low-angle grain boundaries to high-angle grain boundaries, and the grain size is uneven at the peak and trough positions, with noticeable grain refinement at the troughs. At the same time, under the influence of vibration, the aluminum strip induces a different texture morphology from conventional rolling. Due to the different plastic strains at the peak and trough positions, a texture alternation phenomenon occurs at these positions. The tensile test results indicate that aluminum strips exhibit poor mechanical properties under roller vibration, with the reduction in mechanical performance primarily attributed to the uneven microstructure distribution caused by roller vibration. Full article

Currently, the process of creating industrial installations is associated with digital technologies and must involve the stage of developing digital models. It is also necessary to combine installations with different properties, functions, and operational principles into a single system. Some tasks require the use of predictive modeling and the creation of “digital twins”. The main processes during the fuel cell modeling involve electrochemical transformations as well as the movement of heat and mass flows, including monitoring and control processes. Numerical methods are utilized in addressing various challenges related to fuel cells, such as electrochemical modeling, collector design, performance evaluation, electrode microstructure impact, thermal stress analysis, and the innovation of structural components and materials. A digital model of the membrane-electrode unit for a solid oxide fuel cell (SOFC) is presented in the article, incorporating factors like fluid dynamics, mass transfer, and electrochemical and thermal effects within the cell structure. The mathematical model encompasses equations for momentum, mass, mode, heat and charge transfer, and electrochemical and reforming reactions. Experimental data validates the model, with a computational mesh of 55 million cells ensuring numerical stability and simulation capability. Detailed insights on chemical flow distribution, temperature, current density, and more are unveiled. Through a numerical model, the influence of various fuel types on SOFC efficiency was explored, highlighting the promising performance of petrochemical production waste as a high-efficiency, low-reagent consumption fuel with a superior fuel utilization factor. The recommended voltage range is 0.6–0.7 V, with operating temperatures of 900–1300 K to reduce temperature stresses on the cell when using synthesis gas from petrochemical waste. The molar ratio of supplied air to fuel is 6.74 when operating on synthesis gas. With these parameters, the utilization rate of methane is 0.36, carbon monoxide CO is 0.4, and hydrogen is 0.43, respectively. The molar ratio of water to synthesis gas is 2.0. These results provide an opportunity to achieve electrical efficiency of the fuel cell of 49.8% and a thermal power of 54.6 W when using synthesis gas as fuel. It was demonstrated that a high-temperature fuel cell can provide consumers with heat and electricity using fuel from waste from petrochemical production. Full article

The mixing process is the basis of the electrode microstructure, which defines key cell performance indicators. This work investigated the effects of varying the energy input within the mixing procedure on slurry rheology, coating behavior, mechanical and electrical properties of dry electrodes and electrochemical performance of cells fabricated from these negative electrodes. Energy input differences were achieved by varying the solids content within the mixing procedure; however, the final total solids content of the slurries was always the same. The slurries, produced with graphite and silicon oxide as active materials and carboxymethylcellulose (CMC) and styrene-butadiene rubber as binders, showed large differences in flow behavior which were explained by changes in CMC adsorption and mechanical degradation because of increasing energy input. Low shear viscosity and the degree of shear thinning decreased with increasing energy input, resulting in a narrower stability window for slot-die coating. The resistance between the electrode and current collector decreased as more CMC was adsorbed on the active material. Electrode adhesion drastically dropped at the highest energy input, presumably due to a change in SBR distribution. Despite these variations, all fabricated pouch cells demonstrated excellent electrochemical performance and a slight trend of increased charge capability was observed in cells prepared with higher energy input. Full article

Si is a highly promising anode material due to its superior theoretical capacity of up to 3579 mAh/g. However, it is worth noting that Si anodes experience significant volume expansion (>300%) during charging and discharging. Due to the weak adhesion between the anode coating and the smooth Cu foil current collector, the volume-expanded Si anode easily peels off, thus damaging anode cycling performance. In the present study, a femtosecond laser with a wavelength of 515 nm is used to texture Cu foils with a hierarchical microstructure and nanostructure. The peeling and cracking phenomenon in the Si anode are successfully reduced, demonstrating that volume expansion is effectively mitigated, which is attributed to the high specific surface area of the nanostructure and the protection of the deep-ablated microgrooves. Moreover, the hierarchical structure reduces interfacial resistance to promote electron transfer. The Si anode achieves improved cycling stability and rate capability, and the influence of structural features on the aforementioned performance is studied. The Si anode on the 20 μm-thick Cu current collector with a groove density of 75% and a depth of 15 μm exhibits a capacity of 1182 mAh/g after 300 cycles at 1 C and shows a high-rate capacity of 684 mAh/g at 3 C. Full article

Using three-dimensional (3D) metal foams as current collectors is considered to be a promising approach to improve the areal specific capacity and meet the demand for increased energy density of lithium-ion batteries. Electrodes with an open-porous metal foam as current collector exhibit a 3D connected electronic network within the active mass, shortening the electron transport pathways and lowering the electrodes’ intrinsic electronic resistance. In this study, NMC622 cathodes using an aluminium foam as current collector with a measured areal capacity of up to 7.6 mAh cm⁻² were investigated. To this end, the infiltrated foams were densified to various thicknesses between 200 µm and 400 µm corresponding to an electrode porosity between 65% and 30%. The microstructural analysis reveals (i) the elimination of shrinking cavities and a decrease in the porosity of the infiltrated active mass, (ii) an improved contact of active mass to the current collector structure and (iii) a pronounced clogging of the surface pores. The electrochemical properties such as capacity and rate capability are correlated to the electrode’s microstructure, demonstrating that densification is necessary to improve active material utilization and volumetric capacity. However, strong densification impairs the rate capability caused by increased pore resistance and hindered electrolyte accessibility. Full article

Microstructure engineering of electrodes is one of the efficient routes to improve rate performance of lithium-ion batteries (LIBs). Currently, there is a lack of descriptors to rationally guide the regional electrode design. Here, we propose two descriptors, the time differential of the average state of lithium (SoL) and the span of SoL in individual particles, to identify the rate performance constraints across the electrode depth. 3D microstructure-based electrochemical simulations are performed on a homogeneous electrode, and the predictability of the microstructure-based model is verified with the experimental measurement on a LiNi_1/3Mn_1/3Co_1/3O₂ electrode. At electrode level, the descriptors divide the electrode into four regions, namely, a solid-state transport (SST)-controlled region, two mixed SST and liquid-state transport (LST)-controlled regions (SST-dominant and LST-dominant, respectively), and an LST-controlled region. Based on these insights, dual-gradient electrodes are designed with smaller particles in the SST-controlled region and graded porosity increasing from current collector to the separator. Results show that the optimized dual-gradient electrode has significantly more excellent LST capability compared to the homogeneous electrode, thus improving the utilization of particles near the collector. As a result, the capacity performance of the optimized dual-gradient electrode increases by 39% at 5C without sacrificing the gravimetric energy density. Full article

We study the capability of nanosecond laser-induced breakdown spectroscopy (ns-LIBS) for depth-resolved concentration measurements of Li-Ion battery cathodes. With our system, which is optimized for quality control applications in the production line, we pursue the goal to unveil manufacturing faults and irregularities during the production process of cathodes as early as possible. Femtosecond laser-induced breakdown spectroscopy (fs-LIBS) is widely considered to be better suited for depth-resolved element analysis. Nevertheless, the small size and intensity of the plasma plume, non-thermal energy distribution in the plasma and high investment costs of fs-LIBS make ns-LIBS more attractive for inline application in the industrial surrounding. The system, presented here for the first time, is able to record quasi-depth-resolved relative concentration profiles for carbon, nickel, manganese, cobalt, lithium and aluminum which are the typical elements used in the binder/conductive additive, the active cathode material and the current collector. LIBS often causes high variations in signal intensity from pulse to pulse, so concentration determination is, in general, conducted on the average of many pulses. We show that the spot-to-spot variations we measure are governed by the microstructure of the cathode foil and are not an expression of the limited precision of the LIBS setup. Full article

Large variations in the polarization resistance of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathodes are reported in the literature, which are usually related to different preparation methods, sintering temperatures, and resulting microstructures. However, the influence of the electrolyte on the electrochemical activity and the rate-limiting steps of LSCF remains unclear. In this work, LSCF nanostructured electrodes with identical microstructure are prepared by spray-pyrolysis deposition onto different electrolytes: Zr_0.84Y_0.16O_1.92 (YSZ), Ce_0.9Gd_0.1O_1.95 (CGO), La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 (LSGM), and Bi_1.5Y_0.5O_3-δ (BYO). The ionic conductivity of the electrolyte has a great influence on the electrochemical performance of LSCF due to the improved oxide ion transport at the electrode/electrolyte interface, as well as the extended ionic conduction paths for the electrochemical reactions on the electrode surface. In this way, the polarization resistance of LSCF decreases as the ionic conductivity of the electrolyte increases in the following order: YSZ > LSGM > CGO > BYO, with values ranging from 0.21 Ω cm² for YSZ to 0.058 Ω cm² for BYO at 700 °C. In addition, we demonstrate by distribution of relaxation times and equivalent circuit models that the same rate-limiting steps for the ORR occur regardless of the electrolyte. Furthermore, the influence of the current collector material on the electrochemical performance of LSCF electrodes is also analyzed. Full article

Sodium–metal chloride batteries are suitable alternatives in battery energy storage systems (BESSs), since they are widely known as a type of high-safety battery. To accurately analyze the cathode microstructure of sodium–metal chloride batteries, in this study, we demonstrate the improved tubular-type simple test cell. This improved tubular-type simple test cell was supplemented from the setbacks of our previous test cell, such as a leak, Ni current collector wavering, and sodium wicking. Through testing of the improved test cells, we focus on cathode microstructure analysis, owing to the elimination of the external failure factors mentioned above. The group of improved test cells have a lower capacity gap of 9.5% in the 1st cycle than the capacity gap of previous test cells (37.2%). This result indicates the advancement of reproducibility. Moreover, the improved test cell has a long life of approximately 7200 h by changing the previous test cell structure. In particular, it is expected that this improved tubular simple test cell can advance the research of tubular-type sodium–metal chloride batteries in a small and academic laboratory. Full article

The drying process of electrodes might seem to be a simple operation, but it has profound effects on the microstructure. Some unexpected changes can happen depending on the drying conditions. In prior work, we developed the multiphase-smoothed-particle (MPSP) model, which predicted a relative increase in the carbon additive and binder adjacent to the current collector during drying. This motivated us to undertake the present experimental investigation of the relationship between the drying rate and microstructure and transport properties for a typical anode and cathode. Specifically, the drying rate was controlled by means of temperature for both an NMC532 cathode and graphite anode. The material distribution was analyzed using a combination of cross-section SEM images and the energy-dispersive X-ray spectroscopy elemental maps. The binder concentration gradients were developed in both the in- and through-plane directions. The through-plane gradient is evident at a temperature higher than 150 °C, whereas the in-plane variations resulted at all drying temperatures. The measurements identified an optimum temperature (80 °C) that results in high electronic conductivity and low ionic resistivity due to a more uniform binder distribution. Trends in transport properties are not significantly altered by calendering, which highlights the importance of the drying rate itself on the assembled cell properties. Full article