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At least 1,063 records · Page 59

Perovskite Photovoltaic Devices with Carbon-Based Electrodes Withstanding Reverse-Bias Voltages up to –9 V and Surpassing IEC 61215:2016 International Standard

One of the key challenges of perovskite photovoltaics (PV) is the long-term stability. Although efforts are made to improve the lifetime of perovskite PV devices, their degradation under reverse-bias conditions is barely addressed. Herein, perovskite solar cells with carbon-based electrodes are presented which demonstrate superior resilience against reverse-bias-induced degradation. Although their breakdown voltage is identified to be at approximately -3.6 V, cells do not degrade until the applied reverse-bias exceeds -9 V. Two main degradation mechanisms are identified: 1) iodine loss due to hole tunneling into perovskite, which takes place even at low reverse-bias but decomposes the perovskite only after long time durations; and 2) rapid heating at large reverse-bias leading to formation of PbI2, which starts at shunts and then follows the path of the least resistance for the cell current, which is primarily influenced by the electrode sheet resistances. Finally, perovskite solar modules with carbon-based electrodes are demonstrated, which are subjected to a "hotspot" test described in the IEC 61215:2016 international standard at an accredited module testing laboratory. Passing this accelerated test for the first time confirms the superior stability of perovskite PV devices with carbon-based electrodes and highlights their large industrialization potential.

14 SOLAR ENERGY↗

Topology optimization for the full-cell design of porous electrodes in electrochemical energy storage devices

In this paper, we introduce a density-based topology optimization framework to design porous electrodes for maximum energy storage. We simulate the full cell with a model that incorporates electronic potential, ionic potential, and electrolyte concentration. The system consists of three materials, namely pure liquid electrolyte and the porous solids of the anode and cathode, for which we determine the optimal placement. We use separate electronic potentials to model each electrode, which allows interdigitated designs. As a result, a penalization is required to ensure that the anode and cathode do not touch, i.e., causing a short circuit. We compare multiple 2D designs generated for different fixed conditions, e.g. material properties. A 3D design with complex channel and interlocked structure is also created. All optimized designs are far superior to the traditional monolithic electrode design with respect to energy storage metrics. We observe up to a 750% increase in energy storage for cases with slow effective ionic diffusion within the porous electrode.

25 ENERGY STORAGE↗

Ozone Generator Aluminum Electrode Soldering

The creation of an entirely soldered ozone electrode component is proposed and implemented for the first time by the authors. Electrode construction with a ribbed plate insert within it is the most perfect heat exchange device from the point of view of effective heat exchange and uniform distribution of liquid flow through its section. Stages are considered for electrode preparation for soldering and a standard heating cycle is proposed for soldering and electrode with eutectic silumin. It is shown that as a result of the soldering thermal cycle metal structure becomes coarse-grained and favorable for subsequent electrochemical formation of a nanostructured anodic oxide coating 50–60 μm thick.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Role of nanocellulose in tailoring electroanalytical performance of hybrid nanocellulose/multiwalled carbon nanotube electrodes

Abstract Nanocellulose has emerged as a promising green dispersant for carbon nanotubes (CNTs), and there is an increasing trend in developing nanocellulose/CNT hybrid materials for electrochemical detection of various small molecules. However, there have been very few comprehensive studies investigating the role of nanocellulosic material properties upon the electroanalytical performance of the resultant hybrid electrodes. In this work, we demonstrate the influence of both nanocellulose functionalization and geometry, utilizing sulfated cellulose nanocrystals, sulfated cellulose nanofibers, and TEMPO-oxidized cellulose nanofibers. Transmission electron microscopy tomography enables direct visualization of the effect of nanocellulosic materials on the hybrid architectures. High resolution X-ray absorption spectroscopy verifies that the chemical nature of CNTs in the different hybrids is unmodified. Electroanalytical performances of the different nanocellulose/CNT hybrid electrodes are critically evaluated using physiologically relevant biomolecules with different charge such as, dopamine (cationic), paracetamol (neutral), and uric acid (anionic). The hybrid electrode containing fibrillar nanocellulose geometry with a high degree of sulfate group functionalization provides the highest electroanalytical sensitivity and strongest enrichment towards all studied analytes. These results clearly demonstrate for the first time, the extent of tailorability upon the electroanalytical response of nanocellulose/CNT hybrid electrodes towards different biomolecules, offered simply by the choice of nanocellulosic materials.

Durairaj, Vasuki↗

Engineering the surface of LiCoO 2 electrodes using atomic layer deposition for stable high-voltage lithium ion batteries

Here, developing advanced technologies to stabilize positive electrodes of lithium ion batteries under high-voltage operation is becoming increasingly important, owing to the potential to achieve substantially enhanced energy density for applications such as portable electronics and electrical vehicles. Here, we deposited chemically inert and ionically conductive LiAlO 2 interfacial layers on LiCoO 2 electrodes using the atomic layer deposition technique. During prolonged cycling at high-voltage, the LiAlO 2 coating not only prevented interfacial reactions between the LiCoO 2 electrode and electrolyte, as confirmed by electrochemical impedance spectroscopy and Raman characterizations, but also allowed lithium ions to freely diffuse into LiCoO 2 without sacrificing the power density. As a result, a capacity value close to 200 mA·h·g –1 was achieved for the LiCoO 2 electrodes with commercial level loading densities, cycled at the cut-off potential of 4.6 V vs. Li + /Li for 50 stable cycles; this represents a 40% capacity gain, compared with the values obtained for commercial samples cycled at the cut-off potential of 4.2 V vs. Li + /Li.

25 ENERGY STORAGE↗

Multiparticle Simulations of Quadrupolar Ion Detection in an Ion Cyclotron Resonance Cell with Four Narrow Aperture Detection Electrodes

The current paradigm in FT-ICR cell design is to approximate the ideal three-dimensional quadratic trapping potential as closely as possible to maintain ion cloud spatial coherence and achieve long transients, either with hyperbolically shaped electrodes, shimming electrodes, or by dynamic harmonization. In sharp contrast, the FT-ICR analyzer cell with four narrow aperture detection electrodes (NADEL) introduces significant anharmonic terms to the trapping potential. This analyzer cell is capable of quadrupolar detection by which one can measure a signal that is close to the unperturbed cyclotron frequency. This is far less sensitive to trapping potential and space charge shifts than the reduced cyclotron frequency measured in conventional ICR cells. The quadrupolar mode of ion detection in NADEL cells has been examined previously by SIMION simulations of ion clouds with up to 500 ions per simulation. Here, the behavior of the NADEL analyzer cell is examined through particle-in-cell (PIC) simulations, which allows us to examine the behavior of large populations (tens of thousands) of ions with space charge considerations, and to calculate the induced charge on the NADEL detection electrodes, and thus the transient signal. PIC simulations confirm a unique spatial distribution of the ions, with a coherent motion that results in long transient signals. Dependence of the ion cloud and image current signal on cell design, ion energy, and magnetron radius are examined. Coalescence effects are compared with those found in a dynamically harmonized cell. The insensitivity of the measured cyclotron frequency to space-charge is demonstrated both with simulations and experimentally. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Nano-structured platinum group metal-free catalysts and their integration in fuel cell electrode architectures

The novel platinum group metal-free (PGM-free) catalyst for the oxygen reduction reaction (ORR) is synthesized by a modified sacrificial support method (SSM). The catalyst chemical/surface composition is studied by X-ray photoelectron spectroscopy, and the morphology of the material is observed using both HR-SEM and HR-TEM, demonstratingthe open-frame, self-supported catalysts. This new catalyst’s electrochemical performance is evaluated by polarization curves and has behaviour comparable to the state-of-the-art PGM-free catalysts. Meso-structure imaging shows pores on the order of 100 nm, the mean size of the individual silica particles in the sacrificial support. For the first time, PGM-free catalyst layer (CL) morphology in a membrane electrode assembly (MEA) is studied in detail by combined nano- and micro X-ray computed tomography (CT) and interpretational modelling. The highly inhomogeneous, high-tortuosity, through-thickness structure of the CL is observed with micro-CT. The nano-CT method for these thick PGM-free electrodes is not sufficient to capture the full through-thickness morphology of these electrodes. Water retention curves suggest water pooling at the MEA components‘ interfaces and significant dependence of capilary pressure and saturation on through-thickness location. Lastly, this study is the first of its kind to identify morphology-dependent transport losses in the thick PGM-free electrodes using scale-bridging between meso -, micro-, and macro.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable membrane-less microbial electrolysis cell with multiple compact electrode assemblies for high performance hydrogen production

Bioelectrochemical hydrogen production via microbial electrolysis cells (MECs) is a promising method for sustainable energy production and decarbonization of energy systems. However, the application of MECs is limited by the electrochemical performance, scalability, and the cost associated with expensive materials. Here, in this study, a scalable MEC (500 mL) with novel compact electrode assemblies and high electrode surface area to volume ratio (160 m 2 /m 3 ) was designed and constructed. The use of membranes, precious metal catalyst, and current collectors with high costs was avoided. A high current density at the steady state of 49.5 ± 5.3 A/m 2 was achieved using acetate as the substrate with phosphate buffer under the applied voltage of 1.01 V. The corresponding volumetric current density was 3948 ± 422 A/m 3 . The compact electrode assembly design limited methane production rate to 3.9 ± 0.2 L/L/D, while achieving a hydrogen production rate of 33.7 ± 1.7 L/L/D. With the suppression of microbial hydrogen consumption, the hydrogen production rate was 39.8 ± 1.9 L/L/D, higher by almost one order of magnitude than those of MECs with scaling up attempts. The compact electrode configuration reduced internal resistance to 88.5 ± 4.4 Ω cm 2 . The energy efficiency based on input electricity was 146 ± 7 % to 189 ± 9 % within the applied voltage range of 0.71 to 1.05 V. The results in this study demonstrated successful scaling up of high performance small MECs and offered a new possible approach of scaling up MECs by stacking high-performance subunits, with no trade-offs on electrochemical performance.

08 HYDROGEN↗

Carbon polyaniline capacitive deionization electrodes with stable cycle life

Electrode materials for capacitive deionization (CDI), an energy efficient method for desalination, were developed in this work. Waste-tire derived carbon (TC) coated with polyaniline was used to form a carbon polymer composite (CPC). CPC was used as an electrode in CDI configurations to determine the salt adsorption capability of the material. Chemical treatment of TC with KOH led to an enhancement in surface area to 952 m 2 /g and microporosity in the sub-2-nm range. This unique microstructure is considered to be beneficial for effective ion uptake in CDI applications. The capacitance of the electrodes was further enhanced through surface coating with polyaniline, resulting in a specific capacitance of 168.2 F/g. In batch cell testing with 1.2 V applied potential, the salt adsorption capacity (SAC), measured in mg of salt adsorbed per gram of active material, in a 1500–1700 ppm KCl solution was measured at 14.2 mg/g. Scale-up of the process with ionic-membrane-assisted CDI (MCDI) led to improvement in SAC at 18.9 mg/g. Further, cycling tests revealed that the electrodes had comparable or better longevity compared to other CDI materials, retaining >92.8% charging capacity after 300 cycles. In conclusion, high adsorption capacities for other salts such as LiCl, NaCl, MgCl 2 and CaCl 2 have been found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insight on electrolyte infiltration of lithium ion battery electrodes by means of a new three-dimensional-resolved lattice Boltzmann model

Electrolyte filling takes place between sealing and formation in Lithium Ion Battery (LIB) manufacturing process. This step is crucial as it is directly linked to LIB quality and affects the subsequent time consuming electrolyte wetting process. Although having fast, homogeneous and complete wetting is of paramount importance, this process has not been sufficiently examined and fully understood. For instance, experimentally available data is insufficient to fully capture the complex interplay upon filling between electrolyte and air inside the porous electrode. We report here for the first time a 3D-resolved Lattice Boltzmann Method (LBM) model able to simulate electrolyte filling upon applied pressure of LIB porous electrodes obtained both from experiments (micro X-ray tomography) and computations (stochastic generation, simulation of the manufacturing process using Coarse Grained Molecular Dynamics and Discrete Element Method). The model allows obtaining advanced insights about the impact of the electrode mesostructures on the speed of electrolyte impregnation and wetting, highlighting the importance of porosity, pore size distribution and pores interconnectivity on the filling dynamics. Furthermore, we identify scenarios where volumes with trapped air (dead zones) appear and evaluate the impact of those on the electrochemical behavior of the electrodes.

25 ENERGY STORAGE↗

An ultrathin solid-state electrolyte film coated on LiNi 0.8 Co 0.1 Mn 0.1 O 2 electrode surface for enhanced performance of lithium-ion batteries

We report layered Ni-rich oxide is a promising cathode material for lithium-ion batteries (LIBs) of high energy density, yet its poor electrochemical stability induced by electrode-electrolyte interfacial degradation has still needed to be addressed. Surface coating is one of the powerful techniques to tackle this issue, nevertheless, it has been extensively used on particle but not electrode regarding a larger area of protection. Herein, we have covered a nano-scaled layer of lithium phosphorus oxynitride (LiPON) on the electrode level of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM) surface and found lower impedance, longer cycle life, and better safety for treated battery. Most notably, such an NCM-LiPON based 1.3 Ah pouch cell delivers an energy density of 364.4 Wh kg -1 (based on positive and negative materials), along with the retention of 80.0% over 745 cycles at 0.5 C-rate, which is 1.3 times longer than the bare one. This results from modification of both superficial cathode-electrolyte interphase (CEI) and structure stabilization of general particle surface, therefore, role of conformal coating upon electrode surface should be highlighted.

36 MATERIALS SCIENCE↗

Design and processing for high performance Li ion battery electrodes with double-layer structure

A two-layer LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode has been designed and fabricated containing a “power layer” and “energy layer”, with corresponding porosity and particle size prescribed to each layer to achieve best utilization of electrode material (maximum integrated depth of discharge across the electrode thickness) at high applied current. The cathode showed a 17% improvement in capacity when tested in symmetric cells. When applying the design to a full cell, where both positive and negative electrodes contain power and energy layers, a 74% increase in discharge capacity at 2C was achieved compared to the cell with conventional electrodes. Furthermore, this demonstrates an avenue to increase energy and power density of lithium–ion batteries and enable fast charging capability.

25 ENERGY STORAGE↗

Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

In order to investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO 2 ) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO 2 , polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were then quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO 2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO 2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm 3 packing density and 4 C rate.

25 ENERGY STORAGE↗

The electrochemical behavior of poly 1-pyrenemethyl methacrylate binder and its effect on the interfacial chemistry of a silicon electrode

The physico-chemical properties of poly (1-pyrenemethyl methacrylate) (PPy) are presented with respect to its use as a binder in a Si composite anode for Li-ion batteries. PPy thin-films on Si(100) wafer and Cu model electrodes are shown to exhibit superior adhesion as compared to conventional polyvinylidene difluoride (PVdF) binder. Electrochemical testing of the model bi-layer PPy/Si(100) electrodes in a standard organic carbonate electrolyte reveal higher electrolyte reduction current and an overall irreversible cathodic charge consumption during initial cycling versus the uncoated Si electrode. The PPy thin-film is also shown to impede lithiation of the underlying Si. XAS, AFM, TGA and ATR-FTIR analysis indicated that PPy binder is both chemically and electrochemically stable in the cycling potential range however significant swelling is observed due to a selective uptake of diethyl carbonate (DEC) from the electrolyte. The increased concentration of DEC and depletion of ethylene carbonate (EC) at the Si/PPy interface leads to continuous decomposition of the electrolyte and results in non-passivating behavior of the Si(100)/PPy electrode as compared to pristine silicon. Consequently, PPy binder improves the mechanical integrity of composite Si anodes but it influences mass transport at the Si(100)/PPy interface and alters electrochemical response of silicon during cycling in an adverse manner.

25 ENERGY STORAGE↗

Quantifying gas generation from slurries used in fabrication of Si-containing electrodes for lithium-ion cells

The high capacity of silicon motivates its use as anode material for Li-ion batteries. While such Si-based electrodes are typically processed from aqueous slurries, elemental silicon is highly susceptible to hydrolysis, yielding flammable hydrogen gas as a byproduct. This gassing can present numerous safety and quality concerns for scaling up of the production. In this study we describe a method to quantify the volume of gases generated using the Archimedes principle. We show that the gas volumes are affected by various factors, which include the characteristics of the electrode slurry and attributes (particle size, surface coatings) of the silicon powders. A catalytic effect on gas evolution is observed when a lithiated polycarboxylate binder is present in the solution. On the other hand, negligible gas generation is observed in electrode slurries containing the N -methyl-2-pyrrolidone (NMP) solvent, which could be considered as an alternative to the water-based processes presently under consideration. Lastly, our study can be used as a guide for the development of slurry mixtures that can mitigate the safety concerns associated with the silicon-electrode fabrication process.

25 ENERGY STORAGE↗

Direct reuse of graphite and lithium nickel manganese cobalt oxide (NMC) recovered from ultrafast-laser ablation debris in Li-ion battery electrodes

Here we demonstrate that debris collected from the ultrafast-laser ablation of graphite anodes can be directly reused in a lithium-ion battery with little to no negative effects on electrochemical performance. Further, we show that while post-ablation NMC (LiNi 0.33 Mn 0.33 Co 0.33 O) cathode debris will require additional processing before being incorporated into an electrode, its critical materials (nickel, manganese, and cobalt) are not lost during ablation and can be recovered for recycling. Pre- and post-ablation materials are characterized with a suite of diagnostics, including SEM, TEM, X-ray CT, EDS, and XRD, to study changes in material morphology, composition and crystal structure. Graphite exhibited little to no morphological or compositional changes and a slight annealing of its crystal structure. NMC underwent profound morphological and crystallographic changes, but retained its elemental composition. Finally, post-ablation materials were re-manufactured into electrodes and cycled vs lithium metal. Graphite showed equal or better capacity and Coulombic efficiency compared to pre-ablation electrodes, while the post-ablation NMC exhibited severely reduced electrochemical performance. Furthermore, we discuss the outlook for application of this work to advanced manufacturing lines that produce next-generation, laser-patterned electrodes.

25 ENERGY STORAGE↗

Surface modification of cathode material enhances electrochemical performance in dry-processed Li-ion battery electrodes

The transition to electric vehicles (EVs) is pivotal for achieving energy security and integrating grid stability, with lithium-ion batteries (LIBs) playing a central role in this transformation. However, the conventional wet electrode manufacturing relying on N-methyl-2-pyrrolidone (NMP) solvent is energy intensive and costly. Dry processing (DP) has emerged as a promising alternative, eliminating solvents and using polytetrafluoroethylene (PTFE) binder for electrode fabrications. Despite its advantages, DP faces a critical challenge: poor interfacial adhesion between the hydrophobic PTFE binder and the hydrophilic cathode active material (CAM), particularly LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), which undermines electrode performance. Here, to address this, we introduced a novel vapor-phase trimethoxymethylsilane (TMMS) coating to hydrophobize the CAM surface, enhancing compatibility with PTFE. This surface modification significantly enhances binder – CAM interactions, enabling uniform mixing and robust electrode integrity without damaging the CAM particles. Our findings advance the feasibility of environmentally sustainable and cost-effective dry processing, representing a significant step toward sustainable battery manufacturing.

Choi, Junbin [Oak Ridge National Laboratory (ORNL)↗

Combustion synthesis of MgFe{sub 2}O{sub 4}/graphene nanocomposite as a high-performance negative electrode for lithium ion batteries

We present a facile and cost-effective urea-assisted auto-combustion method for synthesizing pure MgFe{sub 2}O{sub 4} nanoparticle and MgFe{sub 2}O{sub 4}/graphene nanocomposite samples followed by annealing at 600 °C for 5 h under N{sub 2} atmosphere. The X-ray diffraction pattern confirmed the single phase formation for both samples. The obtained morphology of the nanocomposite sample shows that the MgFe{sub 2}O{sub 4} nanoparticles are highly dispersed on conductive graphene nanosheets with particle size in the range of 50–100 nm. When applied as an anode material, MgFe{sub 2}O{sub 4}/graphene nanocomposite electrode shows a high reversible charge capacity of 764.4 mAh g{sup −1} at 0.04 C over 60 charge/discharge cycles and in spite of that it also retained a capacity of 219.9 mAh g{sup −1} at high current rate of 4.2 C. The obtained result is much better than the synthesized pure MgFe{sub 2}O{sub 4} nanoparticle electrode. The excellent electrochemical performance of the MgFe{sub 2}O{sub 4}/graphene nanocomposite electrode can be attributed to the strong favorable synergistic interaction between MgFe{sub 2}O{sub 4} and reduced graphene nanosheets, which supplied a large number of accessible active sites for Li{sup +}-ion insertion and short diffusion length for both Li{sup +} ions and electrons. In addition, the graphene nanosheets in the nanocomposite electrode provide high conductivity and accommodate the large volume expansion/contraction during cycling, resulting in high capacity and long cycling stability. - Highlights: • MgFe{sub 2}O{sub 4}/graphene nanocomposite was synthesized by facile urea-assisted method. • Such well-designed structure results in fine and strong interfacial interaction. • Nanocomposite anode shows high rate capability and long cycling stability. • Better performance is due to synergistic effect between MgFe{sub 2}O{sub 4} and graphene. • Simple, low cost and fast synthesis is attractive for large scale applications.

36 MATERIALS SCIENCE↗