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Cross-Linked Polyphosphazene Blends as Robust CO2 Separation Membranes

An effective cross-linking technique allows a viscous, highly gas permeable hydrophilic polyphosphazene to be cast as solid membrane films. By judicious blending with other polyphosphazenes to improve mechanical properties, a membrane exhibiting the highest CO2 permeability (610 barrer) combined with good CO2/N2 selectivity (35) among polyphosphazenes is described here. The material demonstrates performance stability after 500 hours of exposure to a coal-fired power plant flue gas, making it attractive for use in carbon capture applications. Its CO2/N2 selectivity under conditions up to full humidity is also stable, and although the gas permeability does decline, the performance is fully recovered upon drying. The high molecular weight of these heteropolymers also allows them to be cast as a thin selective layer on an asymmetric porous membrane, yielding CO2 permeance of 1200 GPU, CO2/N2 pure gas selectivity of 31, which does not decline over 2000 hours due to physical aging. In addition to gas separation membranes, this cross-linked polyphosphazene can potentially be extended to other applications such as drug delivery or proton exchange membranes which take advantage of the polyphosphazene’s versatile chemistry.

Kusuma, Victor↗

Crosslinked polyphosphazene blends for gas separation membranes

The disclosed invention relates to a composition comprising a crosslinked blend of polyphosphazene polymers. The composition comprises a first polyphosphazene and a second polyphosphazene, where the first polyphosphazene and the second polyphosphazene being bound by a thiol bearing crosslinking agent. Such compositions are useful as a membrane material for the separation of gasses in a gaseous mixture.

Hopkinson, David↗

Biocompatible Nanocoatings of Fluorinated Polyphosphazenes through Aqueous Assembly

Nonionic fluorinated polyphosphazenes, such as poly[bis(trifluoroethoxy)phosphazene] (PTFEP), display superb biocompatibility, yet their deposition to surfaces has been limited to solution casting from organic solvents or thermal molding. Here in this paper, hydrophobic coatings of fluorinated polyphosphazenes are demonstrated through controlled deposition of ionic fluorinated polyphosphazenes (iFPs) from aqueous solutions using the layer-by-layer (LbL) technique. Specifically, the assemblies included poly[(carboxylatophenoxy)(trifluoroethoxy)phosphazenes] with varied content of fluorine atoms as iFPs (or poly[bis(carboxyphenoxy)phosphazene] (PCPP) as a control nonfluorinated polyphosphazene) and a variety of polycations. Hydrophobic interactions largely contributed to the formation of LbL films of iFPs with polycations, leading to linear growth and extremely low water uptake. Hydrophobicity-enhanced ionic pairing within iFP/BPEI assemblies gave rise to large-amplitude oscillations in surface wettability as a function of capping layer, which were the largest for the most fluorinated iFP, while control PCPP/polycation systems remained hydrophilic regardless of the film top layer. Neutron reflectometry (NR) studies indicated superior layering and persistence of such layering in salt solution for iFP/BPEI films as compared to control PCPP/polycation systems. Hydrophobicity of iFP-capped LbL coatings could be further enhanced by using a highly porous polyester surgical felt rather than planar substrates for film deposition. Importantly, iFP/polycation coatings displayed biocompatibility which was similar to or superior to that of solution-cast coatings of a clinically validated material (PTFEP), as demonstrated by the hemolysis of the whole blood and protein adsorption studies.

36 MATERIALS SCIENCE↗

Electrodes including a polyphosphazene cyclomatrix, methods of forming the electrodes, and related electrochemical cells

An electrode comprising a polyphosphazene cyclomatrix and particles within pores of the polyphosphazene cyclomatrix. The polyphosphazene cyclomatrix comprises a plurality of phosphazene compounds and a plurality of cross-linkages. Each phosphazene compound of the plurality of phosphazene compounds comprises a plurality of phosphorus-nitrogen units, and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. Each phosphorus-nitrogen unit is bonded to an adjacent phosphorus-nitrogen unit. Each cross-linkage of the plurality of cross-linkages bonds at least one pendant group of one phosphazene compound of the plurality of phosphazene compounds with the at least one pendant group of another phosphazene compound of the plurality of phosphazene compounds. A method of forming a negative electrode and an electrochemical cell are also described.

25 ENERGY STORAGE↗

Polyphosphazene polymer development for mixed matrix membranes using SIFSIX-Cu-2 i as performance enhancement filler particles

Phosphazene-based polymers were synthesized by using different pendant groups such as trifluoroethoxy (TFE), phenoxy (PHO) and octafluoropentoxy (OFP). High performance methoxyethoxyethoxy/cyclohexoxy (MEE/CH) based polyphosphazene was developed for the first time in literature using a mixed-substitution method. The structural, chemical, and thermal properties of these polymers were analyzed using several techniques such as Gel Permeation Chromatography (GPC), Thermal Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Nuclear Magnetic Resonance (NMR). Significant differences in gas transport properties of gases have been observed between these pendant groups because of their differences in glass transition temperature and physical interaction with CO 2 . For the first time, we report on the high performance of TFE polyphophazene based mixed matrix membranes (MMMs) using a SIFSIX-Cu-2i (SIFSIX) metal organic framework (MOF) as the filler particles. These MMMs showed a significant improvement in both CO 2 permeability and CO 2 /N 2 selectivity compared to pure TFE polyphosphazene membranes. As a result, the excellent gas transport properties of these membranes make them very promising material for carbon capture applications.

36 MATERIALS SCIENCE↗

Amphiphilic Polyphosphazene for Fluorocarbon Emulsion Stabilization

High internal phase emulsions (HIPEs) have been of great interest for fabricating fluorinated porous polymers having controlled pore structures and excellent physicochemical properties. However, it remains a challenge to prepare stable fluorocarbon HIPEs, due to the lack of suitable surfactants. By randomly grating hydrophilic and fluorophilic side chains to polyphosphazene (PPZ), a comb-like amphiphilic PPZ surfactant with biodegradability is designed and synthesized for stabilizing water/fluorocarbon oil-based emulsions. The hydrophilic–lipophilic balance of PPZs can be controlled by tuning the grating ratio of the two side chains, leading to the preparation of stable water-in-oil HIPEs and oil-in-water emulsions, and the production of fluorinated porous polymers and particles by polymerizing the oil phase. Finally, these fluorinated porous polymers show excellent thermal stability and, due to the hydrophobicity and porous structure, applications in the field of oil/water separation can be achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO t Bu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2 PO 2 N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph of LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li + . We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2 . The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.

25 ENERGY STORAGE↗

Mechanically robust PIM-1 and polyphosphazene blended polymer for gas separation membranes

Accordingly, it is an object of this disclosure to provide a blend polymeric membrane to provide the separation of CO2 from a gaseous mixture. The blend polymeric membrane comprises a blend of polyphosphazene and polymers of intrinsic microporosity. Further, the present disclosure also provides a method of use for the blend polymeric membrane for the separation of gases in a gaseous mixture.

Sekizkardes, Ali↗

Nanoscale Li, Na, and K ion-conducting polyphosphazenes by atomic layer deposition

A key trailblazer in the development of thin-film solid-state electrolytes has been lithium phosphorous oxynitride (LiPON), the success of which has led to recent progress in thin-film ion conductors. Here we compare the structural, electrochemical, and processing parameters between previously published LiPON and NaPON ALD processes with a novel ALD process for the K analogue potassium phosphorous oxynitride (KPON). In each ALD process, alkali tert-butoxides and diethylphosphoramidate are used as precursors. To understand the ALD surface reactions, this work proposes a reaction mechanism determined by in-operando mass spectrometry for the LiPON process as key to understanding the characteristics of the APON (A = Li, Na, K) family. As expected, NaPON and LiPON share similar reaction mechanisms as their structures are strikingly similar. KPON, however, exhibits similar ALD process parameters but the resulting film composition is quite different, showing little nitrogen incorporation and more closely resembling a phosphate glass. Due to the profound difference in structure, KPON likely undergoes an entirely different reaction mechanism. Furthermore, this paper presents a comprehensive summary of ALD ion conducting APON films as well as a perspective that highlights the versatility of ALD chemistries as a tool for the development of novel thin film ion-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular design and fabrication of PIM-1/polyphosphazene blend membranes with high performance for CO 2 /N 2 separation

New polymeric blend membranes for CO 2 separation were synthesized based on insights from molecular dynamics simulation. A molecular-level structure-property relationship in polymers of intrinsic microporosity (PIM) based blend membranes, was investigated in detail computationally. Calculated local density profiles and energy of interaction of the blend membranes, composed of PIM-1 and various polyphosphazenes, showed that using the polyphosphazene with a higher concentration of ether side chains can improve the compatibility with PIM-1. Furthermore, based on the findings of computational studies, blend membranes were experimentally fabricated from PIM-1 and polyphosphazenes with various polyether side chain concentrations. Polyether concentration in polyphosphazenes was correlated with the film properties and gas transport performance of the blend membranes. Blend membranes showed very high CO 2 permeability (3100-5300 barrer) and improved CO 2 /N 2 selectivity (24-28), outperforming all other PIM-based blend membranes reported to date. Moreover, the CO 2 permeability performance of the blend membranes was tested 566 hours under real post-combustion flue gas from a coal-fired power plant, including CO 2 , N 2 , H 2 O, O 2 , SO x and NO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bench Scale Thin Film Composite Hollow Fiber Membranes for Post-Combustion Carbon Dioxide Capture

GE Global Research, Idaho National Laboratory (INL), Georgia Institute of Technology (Georgia Tech), and Western Research Institute (WRI) proposed to develop high performance thin film polymer composite hollow fiber membranes and advanced processes for economical post-combustion carbon dioxide (CO 2 ) capture from pulverized coal flue gas at temperatures typical of existing flue gas cleanup processes. The project sought to develop and then optimize new gas separations membrane systems at the bench scale, including tuning the properties of a novel polyphosphazene polymer in a coating solution and fabricating highly engineered porous hollow fiber supports. The project also sought to define the processes needed to coat the fiber support to manufacture composite hollow fiber membranes with high performance, ultra-thin separation layers. Physical, chemical, and mechanical stability of the materials (individual and composite) towards coal flue gas components was considered via exposure and performance tests. Preliminary design, technoeconomic, and economic feasibility analyses were conducted to evaluate the overall performance and impact of the process on the cost of electricity (COE) for a coal-fired plant including capture technologies. At the onset of the project, Membranes based on coupling a novel selective material polyphosphazene with an engineered hollow fiber support was found to have the potential to capture greater than 90% of the CO 2 in flue gas with less than 35% increase in COE, which would achieve the DOE-targeted performance criteria. While lab-scale results for the polyphosphazene materials were very promising, and the material was incorporated into hollow-fiber modules, difficulties were encountered relating to the performance of these membrane systems over time. Performance, as measured by both flux of and selectivity for CO 2 over other flue gas constituents was found to deteriorate over time, suggesting a system that was more dynamic than initially hypothesized. These phenomena are believed to be associated with the physical and mechanical properties of the separation material, rather than chemical degradation by flue gas or one of its constituents. Strategies to improve the composite systems via alternate chemistries and processing techniques were only partially successful in creating a more robust system, but the research provided critical insight into the barriers to engineering sophisticated composite systems for gas separation. Promising concepts, including a re-engineering of the separation material with interpenetrating polymer networks were identified which may prove useful to future efforts in this field.

36 MATERIALS SCIENCE↗

Molecular dynamics study of carbon dioxide and nitrogen selectivity through poly[bis((methoxyethoxy)ethoxy)phosphazene] (MEEP) membrane

Here, a molecular dynamics simulation model was developed to comprehensively understand carbon dioxide over nitrogen (CO 2 /N 2 ) selectivity through polyphosphazene-based membrane comprising of poly[bis((methoxyethoxy)ethoxy)phosphazene] (MEEP) selective layer at the molecular level. The effects of temperature, pressure, and initial feed gas composition on the CO 2 transport on a polymer membrane were studied. The computed free energy and density profile of the permeating gas mixture exhibited that CO 2 molecules express higher interactions with the membrane than N 2 molecules, resulting in higher CO 2 /N 2 selectivity. Statistical analysis of gas molecules (CO 2 , water (H 2 O), and N 2 ) transportation suggested that hydro- and CO 2 -philic functional groups in the membrane significantly impact CO 2 permeability and CO 2 /N 2 selectivity. This study suggested that Lewis acid–base and hydrogen bonding combinations contribute to CO 2 permeation and CO 2 /N 2 selectivity. An equal CO 2 /N 2 selectivity was observed with and without water vapor in the feed gas suggesting that water does not hinder CO 2 transport through the membrane.

36 MATERIALS SCIENCE↗

Creation of Polymer Datasets with Targeted Backbones for Screening of High-Performance Membranes for Gas Separation

A simple approach was developed to computationally construct a polymer dataset by combining simplified molecular-input line-entry system (SMILES) strings of a targeted polymer backbone and a variety of molecular fragments. This method was used to create 14 polymer datasets by combining seven polymer backbones and molecules from two large molecular datasets (MOSES and QM9). Polymer backbones that were studied include four polydimethylsiloxane (PDMS) based backbones, poly(ethylene oxide) (PEO), poly(allyl glycidyl ether) (PAGE), and polyphosphazene (PPZ). The generated polymer datasets can be used for various cheminformatics tasks, including high-throughput screening for gas permeability and selectivity. This study utilized machine learning (ML) models to screen the polymers for CO2/CH4 and CO2/N2 gas separation using membranes. Several polymers of interest were identified. Here the results highlight that employing an ML model fitted to polymer selectivities leads to higher accuracy in predicting polymer selectivity compared to using the ratio of predicted permeabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid polymer network cathode-enabled soluble-polysulfide-free lithium–sulfur batteries

Among the emerging 'beyond lithium-ion' technologies for maximized sustainability, lithium-sulfur (Li-S) is a favoured chemistry because of its exceptional energy density from the conversion of sulfur, an element in abundant supply. However, the dissolution of several intermediate polysulfides formed during conversion leads to rapid performance degradation over cycling. Here, in this study, we address this issue by sulfurizing a hybrid polymer network with polyphosphazene and carbon as a cathode for Li-S batteries. With rich sites to re-bond and adsorb dissociative sulfur species, this hybrid polymer network circumvents the formation of soluble polysulfides and enables a unique, reversible inserting conversion reaction. Thus, our cathode delivers both high capacity (~900 mAh g -1 cathode ) and excellent cycling stability in Li-S coin cells, with a pouch cell demonstration of projected energy density of ~300 Wh kg -1 and 84.9% capacity retention after 150 cycles. The strategy can be extended to other cost-effective, recyclable polymers, advancing sulfur-based batteries towards practical energy storage application.

25 ENERGY STORAGE↗

Microporous polymeric composite membranes with advanced film properties: pore intercalation yields excellent CO 2 separation performance

Polymers of intrinsic microporosity (PIMs) are revolutionary gas separation materials because of their ultra-high permeability, but suffer from low gas pair selectivity (for example CO 2 /N 2 ) and poor durability due to brittleness. In this paper, we present a simple solution to these problems by blending PIM-1 with compatible polymer blend composed of PIM-1 and an ether side chain polyphosphazene (MEEP80), which possesses better mechanical flexibility and higher CO 2 /N 2 selectivity than the native PIM-1 while maintaining high CO 2 permeability. Under mixed gas test conditions, a blend of 25 wt% MEEP80 in PIM-1 has a CO 2 permeability of 2440 barrer and a CO 2 /N 2 selectivity of 39 under mixed gas testing conditions, putting it among the best known polymers for CO 2 /N 2 separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Life Cycle Assessment of Innovative Carbon Dioxide Selective Membranes from Low Carbon Emission Sources: A Comparative Study

Carbon capture has been an important topic of the twenty-first century because of the elevating carbon dioxide (CO2) levels in the atmosphere. CO2 in the atmosphere is above 420 parts per million (ppm) as of 2022, 70 ppm higher than 50 years ago. Carbon capture research and development has mostly been centered around higher concentration flue gas streams. For example, flue gas streams from steel and cement industries have been largely ignored due to lower associated CO2 concentrations and higher capture and processing costs. Capture technologies such as solvent-based, adsorption-based, cryogenic distillation, and pressure-swing adsorption are under research, but many suffer from higher costs and life cycle impacts. Membrane-based capture processes are considered cost-effective and environmentally friendly alternatives. Over the past three decades, our research group at Idaho National Laboratory has led the development of several polyphosphazene polymer chemistries and has demonstrated their selectivity for CO2 over nitrogen (N2). Poly[bis((2-methoxyethoxy)ethoxy)phosphazene] (MEEP) has shown the highest selectivity. A comprehensive life cycle assessment (LCA) was performed to determine the life cycle feasibility of the MEEP polymer material compared to other CO2-selective membranes and separation processes. The MEEP-based membrane processes emit at least 42% less equivalent CO2 than Pebax-based membrane processes. Similarly, MEEP-based membrane processes produce 34–72% less CO2 than conventional separation processes. In all studied categories, MEEP-based membranes report lower emissions than Pebax-based membranes and conventional separation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphazenes

Phosphazenes remain an intriguing chemical system

36 MATERIALS SCIENCE↗