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At least 181 records · Page 10

Electrochemical Ammonia Compression

An electrochemical (EC) compressor is a solid-state compression device. For decades, researchers have been studying EC compressors for applications for a variety of energy systems. As the world transitions away from fossil fuel energy sources, EC compression emerges as a promising technique for energy storage, specifically energy stored in the form of pressurized ammonia. Ammonia is also a commonly used refrigerant. The present studies examine the viability of EC compression for ammonia storage and refrigeration. EC ammonia compression increases the concentration of an ammonia-hydrogen mixture via the input of electrical energy and a series of chemical reactions. A polymer electrolyte membrane separates the low-concentration side from the high-concentration side of the device. On the low-pressure (anode) side hydrogen atoms oxidize and react with ammonia molecules, forming positively charge ammonium ions. The ions traverse the membrane electrolytically. The ammonium ions are reduced and revert back to hydrogen and ammonia upon reaching the high-pressure (cathode). An external circuit provides the current needed to sustain the reactions. In this project, we studied the performance of the ammonia EC compressor under a variety of different conditions. We replicated preliminary data and using a small cell with 5 cm2 of active area. We demonstrated the operation of larger cells with 100 cm2 of active area. Further, we used a commercially available hydrogen EC compressor stack to analyze the scaled-up compressor performance. While previous experiments examined only the transient EC compressor performance, we developed test facilities that allowed the compressor to reach steady state. We analyzed the effects of pressure and current on the EC compressor performance. We measured the flow rates of gas leaving the compressors and analyzed the composition using gas chromatography. We tested methods of separating ammonia from the effluent vapor, which contained hydrogen and water vapor. We found that back diffusion adversely affected the performance, especially when we maintained high pressure lifts.

25 ENERGY STORAGE↗

HPC4Mfg with Sepion

We employed ab-initio simulations and quantum chemical calculations to develop a computational framework for simulating the microscopic structure and mechanical properties of novel polymer membranes used in lithium sulfur batteries. To meet industry targets, next generation batteries with high specific energy (Wh/kg) are essential. Efforts to commercialize light-weight, energy-dense lithium-sulfur secondary batteries (2510 Wh/kg) have been stalled by ongoing problems with the battery’s separator membrane, which should prevent cross-over of active material from cathode to anode that, if unchecked, limits cycle-life. However, Sepion Technologies’ polymer membranes yield long-lasting lithium-sulfur cells. Advancing to 10 Ah battery prototypes, Sepion faces challenges in membrane manufacturing related to polymer processing and the molecular basis for membrane performance and durability. High performance computing offers critical new insight into these phenomena, which in turn will accelerate product entry into the market.

25 ENERGY STORAGE↗

Investigating intermolecular interactions among CO 2 , water and PEEK-ionene membrane using cryo ToF-SIMS and isotopic labeling

Cryogenic time-of-flight secondary ion mass spectrometry (cryo ToF-SIMS) has emerged as a powerful tool for investigating molecular interactions, speciation, and dynamics in materials for CO 2 capture. In this study, we apply cryo ToF-SIMS to probe interactions between CO 2 , water, and PEEK-ionene membranes—a promising material for direct CO 2 capture due to its selectivity, durability, and efficiency. Despite this potential, the mechanisms governing CO 2 diffusion and the influence of water vapor on CO 2 behavior remain unclear. To address this, we loaded PEEK-ionene membranes with 13 CO 2 and D 2 O and employed cryo ToF-SIMS to visualize the 3D distribution of CO 2 and water within the membrane. While prior studies suggest that 13 CO 2 is absorbed under ambient conditions, our cryo ToF-SIMS analysis revealed no enhancement of the 13 C/ 12 C ratio, suggesting weak CO 2 -membrane interactions. As a result, CO 2 vaporizes even at low temperatures (−140°C) under vacuum conditions. In contrast, D 2 O displayed a relatively homogeneous distribution in the membrane, suggesting stronger water-membrane interactions via hydrogen bonding (18–20 kJ/mol). Interestingly, CO 2 was not detected in D 2 O-loaded membranes, indicating minimal interference from water vapor on CO 2 diffusion. As a comparison, the cryo ToF-SIMS data show that 13 CO 2 can readily react with a basic Na 2 CO 3 aqueous solution to form NaH 13 CO 3 . These findings demonstrate cryo ToF-SIMS as a critical technique for understanding gas-water-membrane interactions, offering insights for membrane functionalization to improve CO 2 capture efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Abstract Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

25 ENERGY STORAGE↗

Generalized optimization-based synthesis of membrane systems for multicomponent gas mixture separation

Synthesizing a membrane system to separate multicomponent gas mixture is challenging due to the combinatorial number of feasible configurations and the difficulties in describing the multicomponent permeators. Here we present a mixed-integer nonlinear programming (MINLP) model for synthesizing membrane systems for multicomponent gas mixture separation. The approach employs a richly connected superstructure to represent numerous potential system configurations, and different physics-based surrogate permeator models, such as countercurrent flow or crossflow, to be used in each stage. Moreover, to describe realistic systems, pressure drop equations can be included. We also present solution methods to accelerate the solution process. Through a case study of natural gas sweetening, we demonstrate that the proposed approach is able to obtain good solutions using an off-the-shelf global optimization solver. Finally, we expand the conventional membrane system synthesis problem by introducing feed variability in our model through a case study of an integrated reactor-separation system.

42 ENGINEERING↗

Elastic Single-Ion Conducting Polymer Electrolytes: Toward a Versatile Approach for Intrinsically Stretchable Functional Polymers

Fabrication of stretchable functional polymeric materials usually relies on the physical adhesion between functional components and elastic polymers, while the interfacial resistance is a potential problem. Herein, a versatile approach on the molecular-level intrinsically stretchable polymer materials with defined functionality is reported. The single-ion conducting polymer electrolytes (SICPEs) were employed to demonstrate the proposed concept along with its potential application in stretchable batteries/electronics with improved energy efficiency and prolonged cell lifetime. The obtained membranes exhibit 88–252% elongation before breaking, and the mechanical properties are well adjustable. The galvanostatic test of the assembled cells using the obtained SICPE membrane exhibited a good cycling performance with a capacity retention of 81.5% after 100 cycles. The applicability of a proposed molecular-level design for intrinsically stretchable polymer materials is further demonstrated in other types of stretchable functional materials, including poly(vinylcarbazole)-based semiconducting polymers and poly(ethylene glycol)-based gas separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An All-Soluble Fe/Mn-Based Alkaline Redox Flow Battery System

Redox flow batteries (RFBs) are membrane-separated rechargeable flow cells with redox electrolytes, offering the potential for large-scale energy storage and supporting renewable energy grids. Yet, creating a cost-effective, high-performance RFB system is challenging. In this work, we investigate an Fe/Mn RFB alkaline system based on the [(TEA)Fe–O–Fe(TEA)] 3– / 4– and MnO 4 – / 2– redox couples with a theoretical cell voltage of ~1.43 V. This combination has not been systematically studied previously, but it can lead to a very low-cost and sustainable materials for high energy storage. Constant current cycling tests were performed at ±41 mA cm –2 between 20% and 80% SOC over 800 h (400 cycles) with an apparent Coulombic efficiency (CE) approaching 100%, while the voltage efficiency (VE) gradually decreased from ~75.3% to ~61.4% due to increasing internal resistances. Finally, the voltage efficiency loss can be mitigated through a periodic acid treatment to remove MnO 2 deposits from the separator.

25 ENERGY STORAGE↗

Engineering In Situ Catalytic Cleaning Membrane Via Prebiotic-Chemistry-Inspired Mineralization

Pressure-driven membrane separation promises a sustainable energy-water nexus but is hindered by ubiquitous fouling. Natural systems evolved from prebiotic chemistry offer a glimpse of creative solutions. Herein, a prebiotic-chemistry-inspired aminomalononitrile (AMN)/Mn 2+ -mediated mineralization method is reported for universally engineering a superhydrophilic hierarchical MnO 2 nanocoating to endow hydrophobic polymeric membranes with exceptional catalytic cleaning ability. Green hydrogen peroxide catalytically triggered in-situ cleaning of the mineralized membrane and enabled operando flux recovery to reach 99.8%. The mineralized membrane exhibited a 9-fold higher recovery compared to the unmineralized membrane, which is attributed to active catalytic antifouling coupled with passive hydration antifouling. Electron density differences derived from the precursor interaction during mediated mineralization unveiled an electron-rich bell-like structure with an inner electron-deficient Mn core. This work paves the way to construct multifunctional engineered materials for energy-efficient water treatment as well as for diverse promising applications in catalysis, solar steam generation, biomedicine, and beyond.

36 MATERIALS SCIENCE↗

3D Printed Microfluidic Supported Liquid Membrane Module for Radionuclide Separations

Microfluidic supported liquid membrane extraction is a promising technique for microliter-scale radionuclide separations because it requires very small reagent volumes and combines extraction and stripping in a single unit operation. Flat sheet supported liquid membrane (FS-SLM) modules with 100, 200, 300, and 400 μm deep channels were fabricated at a cost of less than 5 USD in material using a commercially available resin three-dimensional (3D) printer. The performance of these modules was characterized by quantifying uranium transport across a 15 v/v% tributyl phosphate (TBP) liquid membrane at flow rates between 5 and 60 μL min –1 and developing a two-dimensional (2D) numerical transport model for the system. The extent of uranium extraction was found to increase with increasing residence time and decreasing channel depth, with quantitative extraction occurring at the slowest flow rates and shallowest channel depths. The numerical model agreed well with the experimental extraction results. Time-dependent calculations showed that the modules reach steady state in fewer than 9 min and that there is a considerable buildup of uranium in the membrane during that time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Is Pt dissolution a concern from the counter electrode in electrochemical oxygen evolution reaction?

The Pt metal and its oxides dissolution from the counter electrode (CE, in hydrogen evolution reaction (HER)) has been suspected to affect the non-noble metal catalysts toward oxygen evolution reaction (OER). However, little effort has been devoted to this concern, and this work aims to determine the effect. The influence of electrolytes (H 2 SO 4 and NaOH) and Pt CE (acid-treated and pristine) on the Pt dissolution and membrane separations (Nafion and PiperION) on preventing Pt species migration were evaluated. Here, the results indicate only 11.2 ppb Pt from the cathodic electrolyte with Nafion 211 and 5 M NaOH electrolyte is observed, and no Pt is found from all other samples with acid-treated Pt CE. Regarding pristine Pt CE, 0.4 and 4.4 ppb Pt are observed from 0.5 M H 2 SO 4 and 5 M NaOH electrolytes, respectively. The findings in this work include: (1) Nafion membrane can effectively prevent the migration of Pt species from the cathode to the anode side; (2) a simple acid treatment of Pt could minimize the Pt dissolution into the acid electrolyte while showing an opposite role in the alkaline electrolyte; (3) the Pt dissolution from all experiments is minor, indicating Pt is a suitable CE for OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2019 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, a means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations, though the ink processing, coating and drying processes, to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product.

42 ENGINEERING↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2020 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product. To solve the problems associated with these challenges, the R2R Collaboration is executing a research program with outcomes that will ultimately link modeling, processing, metrology and defect detection tools, thereby directly relating the properties of constituent particles and processing conditions to the performance of final devices. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy materials development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this project leverages the capabilities and expertise at each of five National Laboratories to further the development of multilayer technologies that will enable high-volume, cost-competitive platforms. A typical R2R process has three steps: (1) mixing of particles and various constituents in a slurry, (2) coating of the ink/slurry mixture on a substrate, and (3) drying/curing and processing of the coating. Final performance of devices made via R2R processes is dependent on the active materials (e.g., electrochemical particles in battery or fuel cell electrodes) and the device structure that stems from the governing component interactions within the various steps. However, a fundamental understanding of the underlying mechanisms and phenomena is still lacking, which is why industrial-scale R2R process development and manufacturing is still largely empirical in nature. The FY 2019 through FY 2021 program addresses aspects of the following two targets from the AMO Multi-Year Program Plan: (1) Target 8.1 Develop technologies to reduce the cost per manufactured throughput of continuous R2R manufacturing processes. (A) Increasing throughput of R2R processes by 5 times for batteries (to 50 square feet per minute (50 ft 2 /min)) and capacitors and 10 times for printed electronics and the manufacture of other substrates and MEs used in support of these products. (B) Developing resolution capabilities to enable registration and alignment that will detect, align, and co-deposit multiple layers of coatings and print < 1-micron (1 µm) features using continuous process scalable for commercial production. (C) Developing scalable and reliable R2R processes for solution deposition of ultra-thin (<10 nm) films for active and passive materials. (D) Develop in-line multilayer coating technology on thin films with yields greater than 95%. (2) Target 8.2 Develop in-line instrumentation tools that will evaluate the quality of single and multilayer materials in-process. (A) Developing in-line QC technologies and methodologies for real-time identification of defects and expected product properties “in-use/application” during continuous processing at all size-scales with a focus on the “micro” and “nano” scale traces, lines, and devices, i.e., <1 μm at 300 ft./min for R2R processing in air and <10 nm at 20 ft./min for vacuum (B) Developing technologies to increase the measurement frequency of surface rheology without significant cost increases with a goal of a 10-nanometer in-line profilometry at a production rate of 100,000 square millimeters per minute (100,000 mm 2 /min).

42 ENGINEERING↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration - Early Stage R&D: Phase 2 and FY21 (Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto substrates or membranes that are on moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final product. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes and electrolytes for energy storage, and barrier and membrane materials for decarbonization and air and water filtration. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and heated drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product.

36 MATERIALS SCIENCE↗

Porin-Inspired Ionomers with sub-nm Gated Ion Channels for High Ion Conductivity and Selectivity (Final Project Report (2026))

The physiological functions of living systems heavily rely on biological ion channels, whose malfunction can lead to disease. These channels enable selective and regulated transport of water, ions, or small molecules across membranes. Analogously, ionomers used in energy conversion and storage technologies govern ion transport within membrane separators and catalyst binder layers. This DOE Office of Science Early CAREER project aimed to achieve molecular-level control over ionic conductivity and ion permselectivity by translating the functionalities of biological, gated ion channels into a novel class of ion-conducting polymers (ionomers) incorporating macrocyclic calix[4]arene-based repeat units. The overarching goal was to establish fundamental design principles and elucidate proton conduction mechanisms through strategic design of macrocyclic calix[4]arene-containing ionomers, with close relevance to energy conversion and storage devices, including proton exchange membrane fuel cells (PEMFCs). The project leveraged sub-nm-sized macrocyclic pores to facilitate exceptionally fast ion transport (beneficial to addressing sluggish ORR kinetics of PEMFC electrodes) and achieve functionalities of ionic diodes under applied electrochemical fields, beneficial for selective transport/separation.

59 BASIC BIOLOGICAL SCIENCES↗

In-house synthesized poly(ether ether ketone) ionenes. I. ToF-SIMS spectra in the positive ion mode

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf 2 N]- counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO 2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO 2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A 3D nm-thin biomimetic membrane for ultimate molecular separation

Multi-functional membranes with high permeance and selectivity that can mimic nature's designs have tremendous industrial and bio-medical applications. In this paper, we report a novel concept of a 3D nanometer (nm)-thin membrane that can overcome the shortcomings of conventional membrane structures. Our 3D membrane is composed of two three-dimensionally interwoven channels that are separated by a continuous nm-thin amorphous TiO 2 layer. This 3D architecture dramatically increases the surface area by 6000 times, coupled with an ultra-short diffusion distance through the 2–4 nm-thin selective layer that allows for ultrafast gas and water transport, ~900 l m –2 h –1 bar –1 . The 3D membrane also exhibits a very high ion rejection (R ~ 100% for potassium ferricyanide) due to the combined size- and charge-based exclusion mechanisms. The combination of high ion rejection and ultrafast permeation makes our 3DM superior to the state-of-the-art high-flux membranes whose performances are limited by the flux-rejection tradeoff. Furthermore, its ultimate Li+ selectivity over polysulfide or gas can potentially solve major technical challenges in energy storage applications, such as lithium–sulfur or lithium–O 2 batteries.

36 MATERIALS SCIENCE↗