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At least 37 records · Page 2

Fast and Simple Ag/Cu Ion Exchange on Cu Foil for Anode-Free Lithium-Metal Batteries

Lithium-metal batteries with zero excess lithium on the anode side paired with a fully lithiated cathode are regarded as a form of the highest energy-density configuration. Unfortunately, the continuous lithium loss over cycling from a limited amount of lithium reservoir significantly degrades the overall cell performance in the anode-free system. To mitigate the deterioration, modifying the current collector for enhanced lithium cycling is an indispensable route. Here, we apply a Ag/Cu ion exchange to precipitate micro-sized Ag particles on the Cu current collector to enhance the lithium reversibility via (de)alloying process. Further, we show a smoother morphology of lithium upon alloying, which leads to a lowered nucleation potential as well as increased average Coulombic efficiency in Li||Cu cells regardless of electrolyte formulation. The preferred lithium adsorption on Ag and AgLi over Cu is demonstrated with density functional theory calculations, which supports that Li is forming a gamma-phase alloy in the last stage rather than being deposited beneath the alloy. Lastly, this simple Cu foil modification enhances lithium reversibility and reduces its nucleation barrier, thus mitigating the capacity fade of a Cu||LiFePO 4 with reduced polarization.

25 ENERGY STORAGE↗

Activation behavior for ion permeation in ion-exchange membranes: Role of ion dehydration in selective transport

Here we explored the mechanisms governing the selectivity of anion- and cation-exchange membranes for the transport of four monovalent anions (i.e., fluoride, chloride, bromide, and nitrate) and four monovalent cations (i.e., sodium, potassium, cesium, and ammonium), respectively. Our ion adsorption and transport tests with mixed ion solutions reveal that an ion with larger ionic radius and lower hydration energy is more favorably adsorbed onto the ion-exchange membrane but diffuses more slowly through the polymer matrix compared to an ion with smaller ionic radius and higher hydration energy. Individual anion (as sodium salt) or cation (as chloride salt) permeation tests at different temperatures were performed to evaluate the activation behavior of ion transport through the ion-exchange membranes by calculating the energy barrier and pre-exponential factor (i.e., the ion flux when the energy barrier is negligible) for ion transport from an Arrhenius-type equation. Our results show that an ion with smaller ionic radius and higher hydration energy experiences higher energy barrier (e.g., fluoride, 10.3 kcal mol -1 ) and possesses higher pre-exponential factor compared to an ion with larger ionic radius and lower hydration energy (e.g., bromide, 4.6 kcal mol -1 ). This correlation corroborates our main hypothesis that the activation behavior observed for ion transport is a result of ion dehydration at the water-membrane interface. Our proposed ion selectivity mechanism elucidates how ion dehydration governs the extent of ion permeation into the membrane and the subsequent transport through the charged polymer matrix. Future membrane design that promotes dehydration of target ions is challenging but can result in unprecedented ion selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MODELING RESULTS FROM CESIUM ION EXCHANGE PROCESSING WITH SPHERICAL RESINS

Ion exchange modeling was conducted at the Savannah River National Laboratory to compare the performance of two organic resins in support of Small Column Ion Exchange (SCIX). In-tank ion exchange (IX) columns are being considered for cesium removal at Hanford and the Savannah River Site (SRS). The spherical forms of resorcinol formaldehyde ion exchange resin (sRF) as well as a hypothetical spherical SuperLig{reg_sign} 644 (SL644) are evaluated for decontamination of dissolved saltcake wastes (supernates). Both SuperLig{reg_sign} and resorcinol formaldehyde resin beds can exhibit hydraulic problems in their granular (nonspherical) forms. SRS waste is generally lower in potassium and organic components than Hanford waste. Using VERSE-LC Version 7.8 along with the cesium Freundlich/Langmuir isotherms to simulate the waste decontamination in ion exchange columns, spherical SL644 was found to reduce column cycling by 50% for high-potassium supernates, but sRF performed equally well for the lowest-potassium feeds. Reduced cycling results in reduction of nitric acid (resin elution) and sodium addition (resin regeneration), therefore, significantly reducing life-cycle operational costs. These findings motivate the development of a spherical form of SL644. This work demonstrates the versatility of the ion exchange modeling to study the effects of resin characteristics on processing cycles, rates, and cold chemical consumption. The value of a resin with increased selectivity for cesium over potassium can be assessed for further development.

36 MATERIALS SCIENCE↗

Manning condensation in ion exchange membranes: A review on ion partitioning and diffusion models

Here, the rational design of ion exchange membranes (IEMs) is becoming more pertinent as their usage becomes broader and as their staple applications (i.e., electrodialysis, flow batteries, and fuel cells) improve in commercial viability. Such efforts would be catalyzed by an improved fundamental understanding of ion transport in IEMs. This review discusses recent progress in modeling ion partitioning and diffusion in IEMs in an effort to relate IEM performance metrics to fundamental membrane properties over which researchers and membrane manufacturers possess direct and sometimes precise control. Central focus is given to the Donnan-Manning model for ion partitioning and the Manning-Meares model for ion diffusion in IEMs. These two frameworks, which are derived from Manning's counter-ion condensation theory for polyelectrolyte solutions, have been widely used within the IEM literature since their recent introduction. To explore this topic, the mathematical derivation of both models is revisited, followed by a survey of experimental and computational discussions of counter-ion condensation in IEMs. Alternative models which fulfill similar roles in predicting IEM transport properties are compared. This review concludes by highlighting the uniquely favorable positions of the Donnan-Manning and Manning-Meares models and discussing their prospects as leading predictors of IEM partitioning and diffusive properties.

25 ENERGY STORAGE↗

THREE-DIMENSIONAL THERMAL MODELING ANALYSIS OF CST MEDIA FOR THE SMALL ION EXCHANGE PROJECT

The Small Column Ion Exchange (SCIX) project is designed to accelerate closure of High Level Waste (HLW) tanks at the Savannah River Site (SRS). The SRS tanks store HLW in three forms: sludge, saltcake, and supernate. An in-tank ion exchange process is being designed to treat supernate and dissolved saltcake waste. Through this process, radioactive cesium from the salt solution is adsorbed into Crystalline Silicotitanate (CST) ion exchange media packed within a flow-through column. A packed column loaded with radioactive cesium generates significant heat from radiolytic decay. The waste supernate solution within the ion exchange bed will boil around 120 C. Solution superheating above the boiling point within the column could lead to violent hazardous energy releases. System heating from loaded CST is also of concern in other process modules, such as the waste tank. Due to tank structural integrity concerns, the wall temperature limit for the SRS waste tanks is 100 C. The transfer of cesium-loaded CST to the tank could result in localized hot spots on the tank floor and walls which may exceed this limit. As a result, thermal modeling calculations have been conducted to predict the maximum temperatures achievable both in the column and in the waste tank. As specified in the associated Technical Task Plan, one objective of the present work was to compute temperature distributions within the ion exchange column module under accident scenarios including loss of salt solution flow through the bed and loss of coolant system flow. The column modeling domain and the scope of the calculations in this case were broadened relative to previous two-dimensional calculations to include vertical temperature distributions within the packed bed of ion exchange media as well as the upper column plenum region containing only fluid. The baseline design conditions and in-column modeling domain for the ion-exchange column module are shown in Figure 1. These evaluations assumed the maximum bounding cesium loading considered possible based on current knowledge regarding CST media and the anticipated feed compositions. Since this cesium loading was considerably higher than the nominal loading conditions in SRS waste, cases with lower loading were also evaluated. Modeling parameters were the same as those used previously unless otherwise indicated. The current model does not capture multi-phase cooling mechanisms operative when solution boiling occurs. This feature is conservative in the sense that it does not account for the large cooling effects associated with phase transfer. However, the potential transfer of heat to the plenum region associated with vertical bubble ascension through the column during boiling is also neglected. Thermal modeling calculations were also performed for the entire waste storage tank for the case where loaded and ground CST was transferred to the tank. The modeling domain used for the in-tank calculations is provided in Figure 2. The in-tank domain is based on SRS Tank 41, which is a Type-IIIA tank. Temperature distributions were evaluated for cylindrical, ground CST mounds located on the tank floor. Media grinding is required prior to vitrification processing of the CST in the SRS Defense Waste Processing Facility (DWPF). The location of the heat source region on the tank floor due to the accumulation of CST material was assumed to be just under the grinder. The shape of the CST mound was assumed to be cylindrical. This shape is believed to be most representative of the actual mound shape formed in the tank, given that submersible mixing pumps will be available for media dispersion. Alternative configurations involving other geometrical shapes for the CST mound were evaluated in the previous work. Sensitivity analysis for the in-tank region was performed for different amounts of CST media. As was the case for the in-column model, the in-tank model does not include multi-phase cooling mechanisms operative when solution boiling occurs. The in-column and the in-tank evaluations incorporated recently updated maximum cesium loading levels calculated using the current SCIX feed compositions, which resulted in significantly higher cesium loading than previously calculated. The calculations were conducted to ensure conservative predictions for the maximum temperatures achievable using the current baseline design. The degree of conservatism was reduced for in-column calculations relative to the previous work by using a three-dimensional modeling approach and selecting parameters which were nearer to expected conditions. The degree of conservatism for the in-tank calculations was also reduced by lowering the soil penetration depth below the tank from 150 to 20 feet. The primary goals of the extended thermal modeling effort were to determine whether fluid boiling or superheating are possible within the column module and to determine the maximum floor temperatures within the tank loaded with spent CST.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

WaterTAP Technical Brief: Ion Exchange Model Demonstration and Optimization

Ion exchange is an important water treatment process for removal of targeted contaminants, including those associated with hardness. In this report, we introduce the ion exchange model developed for WaterTAP and present some example analysis of Ca 2+ removal for 0.1 MGD and 10 MGD systems. The model is a single-component, steady-state implementation that enables process optimization based on the influent ion concentration, resin capacity, and resin selectivity. Based on a survey of costing references for ion exchange, the WaterTAP ion exchange model returns reasonable estimates for the levelized cost of water (LCOW) of an ion exchange process, and performs as expected when critical design parameters, such as the resin capacity and selectivity, are varied.

54 ENVIRONMENTAL SCIENCES↗

Standard Operating Protocol for Ion-Exchange Capacity of Anion Exchange Membranes

Ion-exchange capacity (IEC) is the measure of a material’s capability to displace ions formerly incorporated within its structure. IEC is a key feature of anion-exchange membranes (AEM), as it determines the AEM’s ability to conduct the ions required to sustain the electrochemical reactions where they are utilized. As an intrinsic property, measuring the IEC accurately is essential to study AEMs and understand their performance within devices. In this method article, a facile and accurate standard operating procedure (SOP) to measure the IEC of AEMs is proposed. When compared to conventional acid-base back-titration or Mohr titration, the proposed method combines the fast reaction between silver and halide ions and the accuracy of the potentiometric titration, providing a convenient and precise protocol for researchers in the field.

42 ENGINEERING↗

Studies on Oxidation Treatment of Spent Ion-Exchange Resins (2) - 17330

Ion-exchange resins used in nuclear power plants adsorb radioactive nuclides, like Co-60, Ni-63 and so on. The large amounts of spent ion-exchange resins must be stored. In Japan, the volume reduction of spent ion-exchange resins, which have been categorized as low-level radioactive waste with relatively high radioactivity (hereinafter called 'Level 1'), are required by methods other than incineration. In this study, to reduce the amount of Level 1, a method for the removal of radioactive nuclides involving oxidation with O{sub 3}, H{sub 2}O{sub 2}, and Fe{sup 2+} ions (hereinafter called 'radical oxidation') was investigated. Radicals generated with O{sub 3}, H{sub 2}O{sub 2}, and Fe{sup 2+} ions oxidized and dissolved resins and radioactive nuclides in the liquid phase at ordinary pressures and temperatures less than 100 deg. C. Then the dissolved radioactive nuclides were separated by coprecipitation with iron ions. In this study, using radical oxidation and coprecipitation with iron ions, Level 1 spent ion-exchange resins were separated into a small amount of Level 1 and other comparatively low radioactive wastes. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Method of stripping genetically tagged biomolecules from porous solid ion exchange wafer

A porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer. Also disclosed is a porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer containing a biomolecule with a tag. A separate bioreactor is also disclosed incorporating the wafer described above.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion-exchange hollow fibers

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, crosslinked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Rembaum, A.↗

Ion-exchange hollow fibers

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Rembaum, Alan↗

Ion-exchange hollow fibers

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Rembaum, Alan↗

Improved polyelectrolyte for ion exchange fibers

Technique increases ion exchange capacity of hollow-fiber-substrate ion exchange resins. Procedure increases number of quaternary sites on polyquaternary copolymer by 15 to 35 percent.

Rembaum, A.↗

Studies on Oxidation Treatment of Spent Ion-Exchange Resin - 16083

Organic ion-exchange resins used at nuclear power plants of light water reactor adsorb radioactive nuclides, {sup 60}Co, {sup 63}Ni and so on, and the large amounts of spent ion-exchange resins are generated. In this study, to reduce the amount of spent ion-exchange resin, removal of radioactive nuclides through oxidation with O{sub 3}, H{sub 2}O{sub 2}, and Fe{sup 2+} was investigated. Radicals generated with O{sub 3}, H{sub 2}O{sub 2}, and Fe{sup 2+} oxidized and dissolved the resin. The radioactive nuclides and decomposition products (organic acids and some other decomposition products) were dissolved in the liquid phase. More than 99% of simulated adsorbed radioactive nuclide (non-radioactive cobalt) was removed by selected conditions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Gadolinium-hydrogen ion exchange of zirconium phosphate

The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

Liu, D. C.↗