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At least 235 records · Page 13

Co-intercalation-free ether electrolytes for graphitic anodes in lithium-ion batteries

Carbonate-based electrolytes are widely used in Li-ion batteries but are limited by a small operating temperature window and poor cycling with silicon-containing graphitic anodes. The lack of non-carbonate electrolyte alternatives such as ether-based electrolytes is due to undesired solvent co-intercalation that occurs with graphitic anodes. Here, we show that fluoroethers are the first class of ether solvents to intrinsically support reversible lithium-ion intercalation into graphite without solvent co-intercalation at conventional salt concentrations. In full cells using a graphite anode, they enable 10-fold higher energy densities compared to conventional ethers, and better thermal stability over carbonate electrolytes (operation up to 60 °C) by producing a robust solvent-derived solid electrolyte interphase (SEI). As single-solvent–single-salt electrolytes, they remarkably outperform carbonate electrolytes with fluoroethylene carbonate (FEC) and vinylene carbonate (VC) additives when cycled with graphite–silicon composite anodes. In conclusion, our molecular design strategy opens a new class of electrolytes that can enable next generation Li-ion batteries with higher energy density and a wider working temperature window.

25 ENERGY STORAGE↗

Elucidating the degradation mechanisms of Pt-free anode anion-exchange membrane fuel cells after durability testing

The development of anion-exchange membrane fuel cells (AEMFCs) has recently accelerated due to synergistic improvements yielding highly conductive membranes, stable ionomers, and enhanced alkaline electrocatalysts. However, cell durability, especially under realistic conditions, still poses a major challenge. Herein, we employ low-loadings of Pt-free Pd-based catalysts in the anode of AEMFCs and elucidate potential degradation mechanisms impacting long-term performance under conditions analogous to the real-world (high current density, H 2 –air (albeit CO 2 -free), and intermittent operation). Our high-performing AEMFCs achieve impressive performance with power densities approaching 1 W cm —2 and current densities up to 3.5 A cm —2 . Over a 200 h period of continuous operation in H 2 –air at a current density of 600 mA cm —2 , our model Pd/C–CeO 2 anode cell exhibits record stability (~30 μV h —1 degradation) compared to the literature and up to 6× better stability than our Pd/C and commercial Pt/C anode cells. Following an 8 h shutdown, the Pd/C–CeO 2 anode cell was restarted and continued for an additional 300 h with a higher degradation rate of ~600 μV h —1 . Thorough in situ evaluations and post-stability analyses provide insights into potential degradation mechanisms to be expected during extended operation under more realistic conditions and provide mitigation strategies to enable the widespread development of highly durable AEMFCs.

08 HYDROGEN↗

Controlled lithium stripping enables a stable interface for long-cycling anode-free solid-state batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, the entire Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenge, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi0.82Mn0.07Co0.11O2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades the interfacial contact between the current collector and the solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge-cutoff-voltage strategy that intentionally retains a thin residual Li layer after stripping. This preserved Li-containing interfacial reservoir not only improves interfacial contact but also serves as an in situ formed seed layer that enables more homogeneous subsequent Li plating. As a result, the optimized anode-free cell with limited stripping depth exhibits excellent long-term cycling stability, maintaining a discharge capacity of 112.1 mAh g−1 with a capacity retention of 80.6% and an average coulombic efficiency of approximately 99.9% after 500 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g−1 after 50 cycles with a capacity retention of 40.7%. This work demonstrates that limiting deep stripping to preserve a thin Li-containing interfacial layer can effectively improve the cycling stability of sulfide-based AFSSBs.

Wang, Jiwei [Northeastern University, Boston]↗

Effects of cathode loadings and anode protection on the performance of lithium metal batteries

Abstract While lithium-ion batteries (LIBs) are approaching their energy limits, lithium metal batteries (LMBs) are undergoing intensive investigation for higher energy density. Coupling LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode with lithium (Li) metal anode, the resultant Li||NMC811 LMBs are among the most promising technologies for future transportation electrification, which have the potential to realize an energy density two times higher than that of state-of-the-art LIBs. To maximize their energy density, the Li||NMC811 LMBs are preferred to have their cathode loading as high as possible while their Li anode as thin as possible. To this end, we investigated the effects of different cathode active material loadings (2–14 mg cm −2 ) on the performance of the Li||NMC811 LMBs. Our study revealed that the cathode loadings have remarkably affected the cell performance, in terms of capacity retention and sustainable capacity. Cells with high cathode loadings are more liable to fade in capacity, due to more severe formation of the CEI and more sluggish ion transport. In this study, we also verified that the protection of the Li anode is significant for achieving better cell performance. In this regard, our newly developed Li-containing glycerol (LiGL) via molecular layer deposition (MLD) is promising to help boost the cell performance, which was controllably deposited on the Li anode.

Materials Science↗

Anode sensitivity calibration of photomultiplier tubes used as a readout of the ELOSS detector

We present and discuss the methodology and results for an anode sensitivity calibration of Photomultiplier Tubes (PMTs) that serve as the optical readout of the Energy Loss Optical Scintillation System (ELOSS). The ELOSS detector, under development at the Facility for Rare Isotope Beams (FRIB), is a gaseous Xe scintillation-based detector designed to identify the atomic number (Z) of nuclear reaction fragments by energy-loss measurement. Variation in the anode sensitivity from tube to tube of commercially available PMTs limits ELOSS from reaching its ultimate Z resolution. A methodical approach to calibrating PMT anode sensitivities to a single target value by systematic PMT gain corrections is presented. Although the calibration process is discussed in terms of its impact on ELOSS performance, the presented method is applicable to any optical detector system composed of a large number of PMTs needing anode sensitivity calibration.

Instrumentation for heavy-ion accelerators↗

Advancing Temperature Monitoring of the Bottom Anode in a Direct Current Electric Arc Furnace Operations with Distributed Optical Fiber Sensors.

The bottom anode in the Direct Current Electric Arc Furnace (DC EAF) is critical for completing the electrical circuit necessary for sustaining the arc within the furnace. For pin-type bottom anodes, monitoring of the temperature of select pins instrumented with thermocouples is performed to track bottom wear in the EAF and inform the operator when the furnace should be removed from service. Furthermore, this work presents the results from a plant trial using distributed temperature monitoring of bottom anode pins in a 165-ton DC EAF over a two-month service period utilizing two optical fiber sensing techniques: fiber Bragg grating (FBG) and Rayleigh backscattering (RBS). The early detection of temperature anomalies along the length of the anode pin through distributed sensing enhances operational safety, providing a robust alternative to traditional thermocouples.

42 ENGINEERING↗

Fabrication of anodic aluminum oxide on silica optical fiber with nanopore channels oriented off surface normal

Abstract Aluminum coating on silica optical fiber was anodized by applying an electric field off‐axis to surface normal of the fiber coating with simulation of the electric field lines between angularly positioned anode and cathode as a guide. The nanostructure features, including nanopore orientation, of the resultant anodized aluminum oxide (AAO) were characterized using scanning electron microscopy. This unique off‐axis electric field arrangement enabled the formation of AAO with uniformly tilted nanopore channel arrays. Nanopore channels with tilting angles around 10°–20° relative to surface normal of AAO were obtained. These results are in general agreement with the simulated electric field lines between the anode and cathode.

Materials Science↗

Improving SOFC Anode Electrocatalytic Activity Using Nanoparticle Infiltration into MIEC Compositions

Mitigating activation polarization in the anode is one of the major challenges in intermediate-temperature operation of solid oxide fuel cells (SOFCs). Liquid phase infiltration of nanoscale electrocatalysts has been shown to result in significant reductions in activation polarization in SOFC anodes. In this study, we explore liquid-phase infiltration of nickel, gadolinium doped ceria (GDC), and Ni/GDC electrocatalysts into two different types of cermet anodes: one with a conventional Ni-YSZ composition, and the other with a Ni-MIEC cermet anode where the YSZ has been doped with 3 mol% TiO 2 to impart electronic conductivity. The principal goal of this study is to explore the role of electronic transport in the MIEC phase in effective utilization of the infiltrated nanoscale electrocatalysts. The role of temperature, infiltration cycles and the type of electrocatalysts have been experimentally studied in symmetric cells using electrochemical impedance spectroscopy (EIS). Distribution of relaxation times (DRT) modeling has been used to elucidate the contributions of various charge transfer processes.

25 ENERGY STORAGE↗

Resolving Anodic Current and Temperature Distributions in a Polymer Electrolyte Membrane Water Electrolysis Cell Using a Pseudo-Two-Phase Computational Fluid Dynamics Model

Expanding upon our prior experimental work, we constructed a three-dimensional model of a polymer electrolyte membrane water electrolyzer using computational fluid dynamics. We applied the assumption of pseudo-two-phase flow, the flow of two phases with equal velocity. Experimental data were used to obtain parameters and to determine the conditions under which this model was valid. Anodic distributions of current density, temperature, liquid saturation, and relative humidity were obtained at various flow rates. The overall current density and temperature difference from inlet to outlet at the anode agreed strongly with experimental measurements under most circumstances. This verification allowed us to further examine the apparent gas coverage calculated from experimental and model temperature data. Results suggested a low liquid saturation and low relative humidity at the anode due to the consumption of liquid water and water vapor. However, we questioned the accuracy of the pseudo-two-phase assumption at low water feed rates. We concluded that the model was applicable to systems with liquid water feed rates greater than 0.6 ml min -1 cm -2 . Therefore, it is a fair screening method that can advise which operating conditions lead to excessive temperatures or drying at the anode, thereby promoting the longevity of the membrane and catalyst.

25 ENERGY STORAGE↗

The Role of Oxygen in Lithiation and Solid Electrolyte Interphase Formation Processes in Silicon-Based Anodes

Silicon oxides (SiO x ) have been considered as promising alternatives to pure Si in high energy anodes in lithium-ion batteries (LIBs) due to their improved cycling stability. However, their fundamental lithiation mechanism has not yet been systematically investigated, and potential collateral downsides remain unclear. In this work, we report on the role of oxygen in lithiation/delithiation and solid electrolyte interphase (SEI) formation processes in SiO x thin film model electrodes with different oxygen contents. Here, we show that the SiO x anodes with higher oxygen content experience smaller volume change and form a thinner and more stable SEI, both of which are beneficial for cycling stability. However, these SiO x anodes also show an irreversible lithiation at around 0.7 V attributed to the reduction of Si oxides, leading to lower first cycle coulombic efficiency that is undesirable for practical applications. Overall, these results offer a balanced perspective on the advantages and disadvantages that oxygen brings to Si-based anodes in LIBs.

25 ENERGY STORAGE↗

Anodic Dissolution Rates Accelerate with Decreasing MoS 2 Nanoflake Thickness

Electrochemical gating of 2D transition metal dichalcogenide (TMD) electrodes is an emerging frontier in the field of semiconductor electrochemistry. In this approach, an applied bias modifies the charge carrier concentration of the 2D TMD, causing band edge shifts and drastic changes in charge transfer rates. However, leveraging this effect for (photo)electrocatalysis is practically limited by the stability of the TMD material under gating conditions. Gerischer showed anodic dissolution of bulk TMD electrodes can occur in the dark and hypothesized that the reaction proceeds via an electron tunneling mechanism from surface states to the TMD conduction band [H. Gerischer, D. Ross, and M. Lubke, Z. Physickalische Chem., 139, 1 (1984)]. Here we investigate this possibility in single MoS 2 nanoflakes using in situ optical microscopy and explore whether Gerischer’s electron tunneling mechanism can explain anodic dissolution rates of thin 2D semiconductors. Here, spatially resolved measurements show anodic dissolution initiates at perimeter edge sites and accelerates exponentially with decreasing layer thickness, consistent with Gerischer’s tunneling mechanism. Interestingly, single layer MoS 2 is impervious to anodic dissolution at applied potentials >200 mV more positive than those required to drive dissolution in bulk and multilayer-thick nanoflakes.

2D semiconductor↗

Computational Analysis of Anode and Cathode Structuring Effects on Charge and Discharge in Graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 Batteries

Structured electrodes (SEs) improve the rate capability of Lithium-ion batteries by engineering micrometer-scale electrolyte regions into the electrode, promoting rapid ionic transport. Prior research has focused on structuring one electrode (anode or cathode) with an analysis on either the charge or discharge performance. We present a holistic study using three-dimensional models to investigate the isolated effects of structuring either electrode and the combined effects of structuring both electrodes on the charge and discharge capacity of single-layer cells at 4 C and 6 C. Volumetric and gravimetric discharge energy density (Wh/L stack and Wh/kg stack ) and charge capacity (Ah/kg stack and Ah/L stack ) are evaluated for multi-layer pouch cell stacks. Pairing SE anodes with SE cathodes demonstrated improvements up to 15% in discharge Wh/kg stack and up to 33% in charge Ah/kg stack over a conventional cell; Energy required to charge per Ah/kg stack was improved by 13%–14%. SE cathodes paired with a conventional anode exhibited improvements of 0.3%–22% across all performance metrics evaluated. Conversely, pairing a SE anode with a conventional cathode demonstrated improved charge capacity up to 13% but showed a 2%–23% lower discharge energy density. The importance of aligning SEs in a cell from a performance and manufacturing perspective is also analyzed.

25 ENERGY STORAGE↗

Graphene coating on silicon anodes enabled by thermal surface modification for high-energy lithium-ion batteries

Silicon is a high-energy density anode material for lithium-ion batteries, but it possesses shortcomings such as poor electronic conductivity, interfacial instability and mechanical fracturing that hinder its battery cycling. Carbon coating has been an important strategy for stabilizing silicon anodes, but the effects of the silicon surface properties on carbon coating morphology and the consequent silicon cycling stability have not been clearly elucidated. Herein, we find that thermal oxidation of the silicon anodes followed by chemical vapor deposition of carbonaceous precursors leads to a well-ordered graphene coating, whereas disordered graphite coating is formed on the native silicon surface. Graphene-coated silicon exhibits superior cycling performance, retaining a discharge capacity of ~1300 mAh g -1 after 300 cycles, whereas the disordered graphite-coated silicon suffers continuous degradation, retaining only~600 mAh g -1 after 300 cycles. Cryogenic electron microscopy reveals the mechanism behind the difference in cycling stabilities; graphene coated silicon is able to withstand the large mechanical strains induced during extended cycling, whereas disordered graphite coating is ruptured, exposing silicon surfaces to the electrolyte, leading to extensive buildup of SEI and poor cycling performance. Characterization of the silicon surface reveals that thermal treatment yields an oxygen-rich surface layer, which is hypothesized to play a decisive role in dictating the carbon coating. This work highlights the effect of silicon surface properties on carbon coating microstructure, and presents thermal treatment as a facile avenue to attain graphene coating on silicon anodes.

25 ENERGY STORAGE↗

Development of a Chlorine Cathode and Anode Basket Assembly for Production of Uranium Chloride

A chlorine cathode has been developed for in situ chlorination of metals, oxides, and oxychlorides in molten chloride electrolytes that could be used to support synthesis of chloride fuel salts for molten salt reactors. The chlorine cathode is designed to electrochemically reduce chlorine gas to generate chloride ions that, when paired with a metal anode, chlorinate that metal as it is oxidized into the salt. The designed porous carbon electrode effectively distributes Cl 2 to the electrode surface and efficiently generates Clions in the molten chloride electrolyte. This report highlights recent improvements made to the electrode assembly, with a focus on operational control of the anode basket stability. Synthesis tests demonstrated the successful chlorination of uranium metal, resulting in 3.6 wt% uranium generated in the LiCl-KCl base salt in 45 minutes, performed in a bench-scale chlorination apparatus. Higher concentrations could be achieved by applying longer chlorination times or increasing the amount of uranium loaded in the anode basket. Overall, the chlorine cathode can be used with an appropriately designed anode to chlorinate uranium in situ for synthesis of molten salt reactor fuel salts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Morphological Modulation of TiO 2 Nanotube via Optimal Anodization Condition for Solar Water Oxidation

With the depletion of fossil fuels and the rising global demand for energy, photoelectrochemical (PEC) water splitting presents a promising solution to avert an energy crisis. Titanium dioxide (TiO 2 ), an n -type semiconductor, has gained popularity as a photoanode due to its remarkable PEC properties. Nevertheless, inherent challenges such as a wide band gap (~3.2 eV), charge recombination, and slow oxygen evolution reaction (OER) rates at the surface limit its practical application by constraining light absorption. To overcome these limitations, we have developed TiO 2 nanotubes (NTs) using a facile anodization method. This study examines the impact of anodization growth parameters on solar water oxidation performance. Specifically, TiO 2 NTs with modified anodization time (referred to as TiO 2 -6) showed a 3.5-fold increase in photocurrent density compared to the as-grown TiO 2 NTs. Furthermore, electrochemical analyses, such as electrochemical impedance spectroscopy (EIS), indicated a significant decrease in charge transfer resistance following the adjustment of on-off anodization time. Additionally, the TiO 2 -6 photoanode demonstrated a higher electrochemically active surface area (ECSA) than other samples. Therefore, optimal nanostructuring parameters are crucial for enhancing the PEC properties of TiO 2 NTs. Overall, our findings offer valuable insights for fabricating high-quality TiO 2 NTs photoanodes, contributing to developing efficient PEC systems for sustainable energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid anodes for energy storage devices

Energy storage devices having hybrid anodes can address at least the problems of active material consumption and anode passivation that can be characteristic of traditional batteries. The energy storage devices each have a cathode separated from the hybrid anode by a separator. The hybrid anode includes a carbon electrode connected to a metal electrode, thereby resulting in an equipotential between the carbon and metal electrodes.

25 ENERGY STORAGE↗

Protection layers for metal anodes

A protection layer is formed on a highly-reactive substantially-pure metal anode to a thickness of between 1 nm and 200 nm, inclusive, using atomic layer deposition (ALD). The ALD protection layer allows the conduction of ions of the metal of the anode therethrough but suppresses electron transport therethrough. The ALD protection layer may also be effective to inhibit passage of air and/or water therethrough. The ALD protection layer can allow more relaxed purity requirements for subsequent battery assembly, electrolyte specifications, and/or cathode gas purity. Fabrication methods for the protection layers, protected metal anodes, and systems and devices incorporating such protected metal anodes are also disclosed herein.

Kozen, Alexander C.↗

Bismuth composite nanoparticle anodes, methods of making same, and uses thereof

Provided are bismuth composite anodes and methods of making same. The bismuth composite anodes comprise nanomaterials comprising bismuth domains (e.g., bismuth nanoparticles) disposed in a lithium phosphate material. The bismuth domains (e.g., bismuth nanoparticles) may be formed in situ. The nanomaterials may be at least partially or completely covered in a layer of a conducting material. The bismuth composite anodes also comprise a bulk conducting material. The nanomaterials and bulk conducting materials are present as a mixture. Also, provided are batteries comprising one or more bismuth composite anodes.

Wang, YuHuang↗