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At least 289 records · Page 16

Impacts of PTL coating gaps on cell performance for PEM water electrolyzer

The anode porous transport layer (PTL) is a critical component of polymer electrolyte membrane (PEM) water electrolyzers, providing electrical conduction and water/oxygen transport to the anode catalyst layer. Platinum group metal (PGM) coatings are applied to titanium PTLs to prevent oxidation and preserve conductivity. To implement PEM water electrolysis on a large scale, it is essential to minimize the cost of mass-manufactured cell components while ensuring that defects in materials and components do not adversely affect the performance of the cell. In this study, we created gaps in the Pt coatings that are typically applied to PTLs to understand their effects on cell performance and inform on fabrication tolerances. The PTL coatings were fabricated by sputter deposition of Pt, intentionally leaving uncoated regions in either large patches or thin strips. For either geometry, the cell performance decreased with the increasing fraction of the uncoated regions. However, PTLs containing multiple thin uncoated strips caused a less severe performance effect than PTLs with continuous uncoated regions of the same relative total area. Through analysis of cell performance, impedance, and 3D charge transport modelling, here we demonstrate that both the anode catalyst layer and membrane play a role in distributing current to mitigate the impact of coating defects at a short length scale. These results allow to draw conclusions about the tolerance requirements with regards to PTL coating uniformity in terms of both the size and total area of defects.

08 HYDROGEN↗

Coupling gas purging with inorganic carbon supply to enhance biohydrogen production with Clostridium thermocellum

Clostridium thermocellum is a desirable biocatalyst for biohydrogen production, with a native ability to simultaneously saccharify cellulose and to metabolize released cellodextrins for hydrogen production. During fermentation with C. thermocellum , partial pressures of two gases - CO 2 and H 2 - are critical drivers of overall reaction kinetics. Biohydrogen production is enhanced by maintaining a low hydrogen partial pressure, while high concentrations of dissolved CO 2 promote microbial biomass synthesis. Our study evaluates the inherent trade-offs between hydrogen stripping and inorganic carbon supply for optimized biohydrogen synthesis. Here, we find that nitrogen sparging at low flow rates increases hydrogen production when compared with an equivalent nitrogen overlay, but that high rates of nitrogen sparging inhibit cell growth and hydrogen production. Decreasing dissolved hydrogen partial pressure via nitrogen sparging also lowers the production of reduced metabolites, including lactate and ethanol. To address potential stripping of inorganic carbon from the production medium, we supplemented CO 2 to the sparging gas and co-optimized for gas flow rate and for the CO 2 fraction of the sparging gas. Total hydrogen production increased from 50 mmol∙L -1 in the base condition, when the bioreactor was sparged with 0.1 LPM of pure nitrogen, to 181.3 mmol∙L -1 when sparged with 1.3 LPM of 33 % CO 2 , demonstrating that biohydrogen production is highly sensitive to both parameters. Fine sensitivity of biohydrogen production to sparging conditions highlights the critical importance of bioreactor design and operation to achieve maximum H 2 removal without compromising inorganic carbon supply to bacterial central metabolism.

09 BIOMASS FUELS↗

Removable coatings: Thermal stability and decontamination of steel surfaces from 241 Am

This study presents a comparative analysis of several strippable materials for decontamination of steel surfaces from 241 Am. The strippable coatings were chosen to have a history of application, to be commercially available, easily handled and have different composition and formulation. Carbon steel and stainless steel surfaces (coupons) were utilized as the most representative industrial materials, and the experimental series were expanded to include the rusting treatment of these surfaces as it is common for decommissioned old nuclear facilities. The experiments followed the path of pre-screening of the strippable materials (easiness of application, peeling etc.), their characterization with Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), decontamination factors (DF) or removal efficiencies for different types of steel surfaces, and enhancement of the removal efficiencies of the select strippable coatings via amendment with EDTA. As a result, DF and removal efficiencies for stainless steel (both pristine and with rusting treatment) are higher than for pristine carbon steel, and decontamination factors and removal efficiencies are higher for pristine than for rusted carbon steel across all the coatings. It is also shown that EDTA amendment can improve DF and removal efficiency for a strippable coating (i.e., CC Strip), however other factors should also be considered. Thus, the coating CC Strip exhibited easiness in handling and high DF (up to 97% when EDTA-amended), but its drying period was the longest among the rest of the materials and its thermal decomposition indicates on a risk of intense release of heat in case of a fire event.

36 MATERIALS SCIENCE↗

Lithium plating induced degradation during fast charging of batteries subjected to compressive loading

Here we report the lithium plating associated capacity loss during fast charging of compressively loaded lithium-ion batteries (LIBs). The charging and discharging of LIB under compressive loading during service may affect the cell performance or initiate localized defects in the electrodes. Pouch cells of capacity 20 mAh were compressively loaded to nominal pressures of 0–440 kPa and subjected to 10 cycles of fast charging at 1 C and 4 C. Experimental results show that cells charged at 4 C-rate experienced significant capacity fade, and applying compressive loads exacerbated the capacity loss. The coulombic efficiency study shows that active lithium loss was higher for the initial cycles before gradually reducing to a minimal capacity loss for the tenth charging cycle. The cell voltage relaxation immediately after charging was monitored to identify the stripping of plated lithium after fast charging cycles and showed that the duration of lithium stripping was higher for cells under mechanical compressive loading. Scanning electron microscopy (SEM) and electron paramagnetic resonance spectroscopy (EPR) characterization of the anode showed significantly higher lithium deposits on the anodes charged at a 4 C rate under compressive loads. These results indicate that applied mechanical compression causes increased lithium plating during fast charging of batteries.

25 ENERGY STORAGE↗

Process design of the piperazine advanced stripper for a 460 MW NGCC

The Texas Carbon Management Program is conducting a Front-End Engineering Design (FEED) for Piperazine with the Advanced Stripper™ (PZAS™) at a natural gas combined cycle power plant in west Texas. Here, this paper presents the design of the advanced stripper system with an emphasis on the selection of packing type, packing height, column diameter, and heat exchanger size, demonstrates the effect of ambient temperature swing on the regeneration energy requirement, and investigates two alternate process configurations that provide better energy performance than PZAS™. The design uses 2 stripper trains, and each train uses two cold cross exchangers, one hot cross exchanger, a stripper column, a CO 2 exchanger, and a condenser. Each column consists of two sections of random packing with RSR 2 packing at the top and RSR 3 packing at the bottom, with a total packed height of 7.5 m. The cold exchanger was designed with an NTU of 6, the hot exchanger with an NTU of 2, and the CO 2 exchanger with an NTU of 5. At 0.4 rich loading and 0.2 lean loading, this design resulted in a heat duty of 2.85 GJ/tonne CO 2 . The heat duty can vary up to 3.1 GJ/tonne CO 2 due to lower rich loading at higher summer temperature, but the absolute steam requirement is 8–15% lower in the summer. An alternate design, PZAS with hot rich bypass, is proposed, which can reduce the equivalent work of stripping by 1.5–3.5% compared to PZAS at low heat exchanger size, due to a reduction in stripper driving force. Using a hot rich bypass increases the vapor fraction of the total rich bypass stream from 0.3 to 1 mol% compared to using the warm rich bypass, which also contributes to a reduction in lost work in the column. PZAS with hot rich bypass outperforms PZAS in energy requirement below a packing height of 15 m, but fails to do so above 15 m of packing due to a column pinch that results in little change in LMTD of the column. PZAS with hot rich bypass has the potential to minimize capital cost in addition to reducing energy requirement as it requires less packing to strip CO 2 than PZAS and requires only one cross exchanger with 8 heat transfer units.

03 NATURAL GAS↗

Overview and technology opportunities for thermochemically-produced bio-blendstocks

Global demand for transportation fuels is projected to increase 40% by 2040, and biomass-derived fuels (biofuels) play a crucial role in substituting fossil fuels and mitigating greenhouse gas emissions. Currently, biofuels are mainly consumed as blendstocks combined with petroleum-based fuels, and effective conversion technologies can address the quality challenges for offering standalone biofuels. Thermochemical conversion process is one of the most promising pathways among existing technologies for biofuel production. However, the major barriers are unwanted characteristics (e.g., thermal instability) of intermediate products, such as bio-oil, and required upgrading treatments for producing compatible fuels. Here, this study highlights the merits and critical challenges of thermochemical conversion and physicochemical upgrading technologies for bio-blendstock production from lignocellulosic biomass. The novelty of this study lies in potential directions for future research through both critical and systematic literature reviews, and the proposed intensified process for lignocellulosic-based fuel blendstocks production. It is concluded that recovery and fractionation strategies (e.g., quenching and stripping) can maximize process yields and add values in the efficient conversion pathways. Effective quenching can stop secondary free radical reactions and improve liquid yields over gas and solid yields. Stripping process can improve process yield, catalyst lifespan, and thermal stability. It is further concluded that physicochemical treatments are not as effective as thermochemical treatments, but have advantages of mild operating conditions and potential for integrated solutions in conjunction with other treatments.

09 BIOMASS FUELS↗

Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries

“Anode-free” solid-state batteries feature high energy density since there is no anode active material. Although the beneficial effects of interfacial layers at the anode-solid electrolyte interface have been demonstrated, the mechanisms through which they influence lithium plating/stripping are unclear. Here, in this study, we reveal the evolution of 100-nm silver and gold interfacial layers during lithium plating/stripping using electrochemical methods, electron microscopy, X-ray microcomputed tomography, and modeling. The alloy layers improve Coulombic efficiency and resistance to short circuiting, even though the alloys form solute regions or particulates that detach from the current collector during plating. In situ electrochemical impedance spectroscopy shows that the alloys return to the interface and mitigate contact loss at the end of stripping, avoiding a critical vulnerability of anode-free cells. Contact retention is driven by even Li thickness that promotes spatially uniform stripping, as well as local alloy delithiation in response to current concentrations that homogenizes current and diminishes voiding.

25 ENERGY STORAGE↗

Investigation of signal characteristics and charge sharing in AC-LGADs with laser and test beam measurements

AC-LGADs, also referred to as resistive silicon detectors, are a recent development of low-gain avalanche detectors (LGADs), based on a sensor design where the multiplication layer and n + contact are continuous, and only the metal layer is patterned. In AC-LGADs, the signal is capacitively coupled from the continuous, resistive n + layer over a dielectric to the metal electrodes. Therefore, the spatial resolution is not only influenced by the electrode pitch, but also the relative size of the metal electrodes. Signal propagation between the metallized areas and charge sharing between electrodes plays a larger role in these detectors than in conventional silicon sensors read out in DC mode. AC-LGADs from two manufacturers were studied in beam tests and with infrared laser scans. The impact of n + layer resistivity and metal electrode pitch on the charge sharing and achievable position resolution is shown. For strips with 100 μm pitch, a resolution of ¡ 5 μm can be reached. Additionally, the charge sharing between neighboring strips is investigated in more detail, indicating the induction of signal charge and subsequent re-sharing over the n + layer. Furthermore, an approach to identify signal sharing over large distances is presented.

47 OTHER INSTRUMENTATION↗

Correcting beam space charge effects in Active-Target Time Projection Chamber

By providing a large gaseous volume for nuclear interactions while simultaneously recording the tracks of resulting reaction products, an active target serves as both a thick target and a detector. Once a reaction occurs, the emitted charged fragments strip electrons from the target gas along their path as they transverse the detector. Collection of these stripped electrons allow for detection of the product tracks. As beam intensity increases, the resulting ionization in the active target can significantly distort this collection of electrons. If left uncorrected, the resulting measurements could be wrong. In this paper, we investigate the impact of the space charge produced by heavy radioactive beams within the Active Target - Time Projection Chamber at Michigan State University. The beams are injected parallel to the electric field of the time projection chamber which is operated without a magnetic field for this experiment. Furthermore, we analyze the rate dependence of the space charge effects and demonstrate that they can be modeled and effectively corrected.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Comparative study on the overall energy performance between photovoltaic and Low-E insulated glass units

In this report a novel semi-transparent building integrated photovoltaic (BIPV) laminate was developed and introduced in this paper. It was produced by cutting standard mono-crystalline silicon solar cells into small strips and then making electrical connections between each strip before laminating the cells between two layers of glass. The overall energy performance and energy saving potential of the BIPV insulated glass unit (IGU) under real world conditions were identified through a side by side comparative study. Compared to the reference IGU, the BIPV IGU had lower solar heat gain coefficient (SHGC) but much higher U-factor. The average HVAC electricity saving of the BIPV IGU was about 10% relative to the reference IGU. Daylighting measurement and analysis were carried out to evaluate the trade-offs associated with the BIPV IGU between daylight, glare, and lighting energy use. The results indicated that the BIPV IGU is better than the reference IGU in reducing discomfort glare. However, if the most conservative viewpoint near the window is used for the assessment, a lower transmittance BIPV IGU is required to bring the overall discomfort levels below the perceptible level. Lastly, the net energy saving potential associated with the novel BIPV IGU was identified based on the power, thermal and daylighting performance. On average, the BIPV IGU saved 16.8% of the total electricity use of the room. Further studies and improvement on the energy conversion efficiency of solar cells, the optimal transmittance as well as the thermal properties would make this technology more energy-efficient and affordable.

14 SOLAR ENERGY↗

Bio-Oil Impact on Water Diffusion and Durability of Bitumen: Influence of Aging and Salinity

Bio-oils derived from inexpensive biomass offer environmentally friendly options for modifying bitumen for improved durability or rejuvenating aged material, although their impact on bitumen moisture resistance can be mixed. A better understanding of water diffusion into bitumen and its interactions with bio-oil compounds would aid the development of effective bio-oils. In this study, the effect of water exposure on bio-oil-modified bitumen blends was examined by de-wetting contact angle measurements and differential FTIR spectroscopy. The bio-oils improved the anti-stripping behavior of the bitumen but also increased water absorption which could weaken cohesive strength. Short-term thermal aging increased water diffusion for all bitumen blends including the control, probably due to the presence of more oxidized compounds. Negative peaks of alkanes and polar groups in the differential FTIR data suggest the co-diffusion of surfactant molecules towards the bitumen-water interface. Basic pH increased de-wetting of some bitumen blends from silica, possibly by attacking the silica surface itself. The presence of salt in solution altered the bitumen surface composition through the formation of salt complexes with bitumen or bio-oil compounds. In particular, the formation of calcium-carboxylate complexes appeared to greatly improve anti-stripping effects of bio-oils. Water diffusion into most of the bitumen blends was insensitive to pH or salt concentration except for a few notable outliers. Identifying the compounds responsible for increasing or decreasing water diffusion in these outlier cases would be valuable developing future bio-oil formations that avoid or promote those compounds.

Hung, Albert M.↗

Rapid Quantification of 237 U Specific Activity for Nuclear Forensics

In the event of an unattributed nuclear explosion, rapid assessment of the short-lived uranium isotope activity and mass can provide valuable information for subsequent forensic analysis. Rapid analysis in the field is enabled by using microfluidic chemistry and deployable instrumentation. Here, this work presents a flow chemistry system, controlled in LabVIEW, that integrates three functionalities: (1) selective extraction of uranium from the sample matrix via a 3D-printed supported liquid membrane module; (2) UV–visible absorbance spectrophotometry to measure the total uranium concentration in the strip flow; and (3) a portable CdTe γ-ray spectrometer coupled to a 3D-printed flow cell to measure 237 U activity concentration in the strip solution. The system was calibrated using standard solutions, and its functionality was demonstrated using a solution of depleted uranium spiked with 237 U. Uranium concentrations of 40–5000 μg/mL were directly quantified online using a 100 mm optical flow cell, while concentrations of 0.5–10 μg/mL were quantified online using a colorimetric reagent. The mass concentration measurement takes approximately 60 min while the activity concentration via γ-ray spectrometry varies depending on the activity of 237 U, with 1 kBq/mL requiring about 30 min of acquisition time to obtain <10% uncertainty at 1σ. This platform provides a fieldable approach for quantifying uranium mass and radioactivity relevant to postdetonation nuclear debris.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Analysis of X-ray Fluorescence Measurements of the Interfacial Density of Eu Ions at Liquid–Liquid Interfaces for Solvent Back-Extraction

X-ray fluorescence near total reflection (XFNTR) is the primary technique used to measure the element-specific interfacial density of ions at liquid−liquid interfaces. Fluorescence from ions in the bulk liquids can complicate the determination of the interfacial density; consequently, measurements have been previously limited to samples without ions in the upper phase and with concentrations on the order of 10 μM or less in the lower phase. We modify the analysis of XFNTR data to account for ions in both bulk phases, then demonstrate its use in the context of rare-earth separations processes. In a model of ion stripping (i.e., back-extraction), dodecane solutions of di(2-ethylhexyl)- phosphoric acid (HDEHP) loaded with Eu(III) at the 1 mM level are placed in contact with either pure water or aqueous solutions of nitric or citric acid at pH 3. XFNTR measurements of equilibrated, quiescent samples reveal that citric acid solutions produce a disproportionately large depletion of ions from the interface compared to that from the bulk organic solution, whereas stripping by pure water or nitric acid solutions is negligible. As a result, this advance in the methodology of XFNTR may have broad applicability to the investigation of metal ions in chemical and biological processes at liquid−liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Li Morphology Evolution during Initial Cycles in a Gel Composite Polymer Electrolyte

Understanding and controlling lithium morphology evolution and lithium dendrite formation and growth during cycling is one of the key challenges for high-energy lithium metal batteries. This challenge applies to liquid electrolyte batteries as well as solid-state and semi-solid-state batteries. Our current knowledge about the evolution of the Li morphology is mostly obtained from liquid electrolyte-based studies in a Li–Li symmetrical cell configuration. The knowledge obtained in such conditions may not readily transfer into solid-state or semi-solid-state batteries. In this work, Li morphology evolution during initial cycling in a full cell configuration with the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC 622) cathode and a semi-solid-state gel composite electrolyte is monitored via post-mortem photographs and scanning electron microscopy at multiple length scales. The gel composite electrolyte contains a cross-linked poly(ethylene oxide)-based polymer electrolyte, ceramic fillers, and a liquid plasticizer. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution during the stripping process are the main cause of the Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and ceramic solid electrolytes, the dendrite growth mechanism observed in this model electrolyte resembles that of the liquid electrolyte the most. This study suggests that strategies to control Li morphology and prevent dendrite growth in a gel composite electrolyte should be similar to strategies applicable to liquid electrolytes.

25 ENERGY STORAGE↗

Solubility-Dependent Protective Effects of Binary Alloys for Lithium Anode

Recently, alloys have been widely utilized as protection layers for homogenized Li growth. However, the protective mechanisms for different alloys are not clearly understood. In this work, guided by the binary phase diagrams, Mg, Au, Zn, Al, Fe, and Cu protective layers have been selected for study of their protective abilities and mechanisms. The selected metals can be classified into three categories according to the nature of their associated alloy protective layers: (1) metals with high solubility in Li while not forming any intermediate line compounds, e.g., Mg, which is good for fast Li stripping; (2) metals with limited solid solubility but forming stable line compounds with Li upon the lithiation, e.g., Au, Zn, and Al, where the formed stable line compounds Li x Au, Li x Zn, and Li x Al will hamper Li kinetics; (3) metals with negligible mutual solubility and no line compound formation with Li, e.g., Fe and Cu, which block the Li stripping path and therefore result in the highest polarization voltage.

25 ENERGY STORAGE↗

Electrochemical Healing of Dendrites in Garnet-Based Solid Electrolytes

Garnet oxides are a promising material family for solid-state batteries (SSBs). Dendrite formation in solid electrolytes critically limits the applicability of SSBs because of limiting Coulombic efficiency and power capability. In this study, the authors report operando electrochemical healing of dendrites in a garnet-based solid electrolyte (SE). Dendrites were deliberately formed at high operational current density (2 mA cm –2 ) beyond the critical current density (0.55 mA cm –2 ) of the used garnet SE. Electrochemical impedance spectroscopy and scanning electron microscopy were used to confirm dendrite growth in the SE. Dendrites were subsequently healed electrochemically via plating and stripping at 20 and 1 μA cm –2 current densities. Removal of dendrites was shown by an increase in bulk and interfacial resistance and a progressive increase in polarization during galvanostatic plating and stripping. High local current density at the dendrite tips was identified as the mechanism for preferentially removing dendrites electrochemically. The dendrite detection and healing methods discussed here are crucial for extending the life of SSBs.

25 ENERGY STORAGE↗

The Crucial Role of Vacancy Concentration in Enabling Superatomic Diffusion in Lithium Intermetallics

Anode-free solid-state Li batteries promise significant increases in energy densities compared to current commercial batteries that rely on liquid electrolytes. Major challenges persist in controlling morphological evolution during the plating and stripping of lithium metal at the anode current collector. Elemental additives that alloy with lithium have been found to modify the plating and stripping behavior of lithium. Many alloying elements form intermetallics with lithium and the mobility of Li through these intermetallics is believed to have an important effect on morphological evolution. This study shows that Li transport coefficients through intermetallics span a wide range in values, with the B32 LiAl intermetallic predicted to have a Li tracer diffusion coefficient as high as 10 –6 cm 2 /s at room temperature, which is 8 orders of magnitude larger than that of isostructural B32 LiZn. This work demonstrates the crucial role of vacancy concentration in controlling the mobility of Li atoms through intermetallics. While the migration barriers for Li-vacancy exchanges in both LiAl and LiZn are remarkably low, the superatomic conductivity in LiAl is shown to arise from the unique electronic structure of the B32 LiAl compound, which favors high concentrations of vacancies.

25 ENERGY STORAGE↗

Determination of Arsenic Content in Water Using a Silver Coordination Polymer

In this report, we describe a practical method for the colorimetric determination of dissolved inorganic arsenic content in water samples, using a silver coordination polymer as the sensing material. We demonstrate that a crystalline polymer framework can be used to stabilize silver(I) ions, greatly reducing both photosensitivity and water solubility, while still affording sufficient reactivity to detect arsenic in water samples at low parts-per-billion (ppb) levels. Test strips fabricated with the silver-based polymer are shown to be effective for field tests of groundwater under real-world operating conditions and display performance that is competitive with commercially available mercury-based test strips. Spectroscopic methods are also used to probe the reaction products formed, in order to better understand the sensing mechanism. Thus, our work provides the foundation for an improved field test that could be deployed to help manage groundwater usage in regions where arsenic contamination is problematic but sophisticated lab testing is not readily available.

36 MATERIALS SCIENCE↗