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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Efficient Synthesis of High-Performance Anion Exchange Membranes by Applying Clickable Tetrakis(dialkylamino)phosphonium Cations

Tetrakis(dialkylamino)phosphonium (TKDAAP) compounds exhibit extraordinary base resistance, a prerequisite feature for high-performance anion exchange membranes (AEMs). It is, however, challenging to synthesize a TKDAAP compound with reactive functionality that can be used to link the cation to a polymer backbone. In this study, two TKDAAP compounds with alkyne functionality were synthesized and incorporated into an azide-modified SBS triblock copolymer backbone via Cu(I)-catalyzed alkyne–azide cycloaddition (CuAAC) “click” chemistry. The properties of the resulting AEMs were characterized. It was found that (1) the triazole linker between the cation and the polymer backbone was stable under alkaline conditions; (2) varying the substituents of TKDAAP compounds could dramatically alter the stability; and (3) increasing the hydrophilicity of the AEM was an efficient way to enhance its ionic conductivity. Using clickable TKDAAP compounds makes it easy to combine various cations into polymer backbones with adjustable cation content, thus potentially leading to an efficient way to screen a wide variety of polyelectrolyte structures to identify the most promising candidates for high-performance AEMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Microstructural refinement of cement paste internally cured by polyacrylamide composite hydrogel particles containing silica fume and nanosilica

Supplementary cementitious materials were incorporated into hydrogel-based internal curing agents to improve the hydration, microstructure, and ultimately strength of internally cured high-performance cement paste. Polyacrylamide composite hydrogel particles containing amorphous silica – either silica fume or nanosilica – and two different polymer network crosslink densities were synthesized and incorporated into cement paste. The presence of silica and low crosslink density increased the absorption capacity of the particles in pore solution. Micrographs of internally cured paste indicated a significant improvement in hydrogel-related void-filling ability and an increase in void size for low crosslink density particles containing silica. Compressive strength and electrical resistivity increased at later ages for paste samples containing particles with higher silica dosage. The relationship between extent of hydration, void size, and void-filling activity was found to strongly influence the paste's long-term strength and is thus an important structure-property relationship to consider when selecting hydrogels for internal curing purposes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Impact of Ion–Ion Correlated Motion on Salt Transport in Solvated Ion Exchange Membranes

The influence of dynamical ion-ion correlations and ion pairing on salt transport in ion exchange membranes remain poorly understood. In this study, we use the framework of Onsager transport coefficients within atomistic molecular dynamics sim- ulations to study the impact of ion-ion correlated motion on salt transport in hydrated polystyrene sulfonate membranes and compare with the results from aqueous salt so- lutions. At sufficiently high salt concentrations, cation-anion dynamical correlations exert a significant influence on both salt diffusivities and conductivities. Anion-anion distinct correlations, arising from the imbalance between the concentration of free (mo- bile) cations and anions, and the retarding effect of the fixed charge groups on cations, proves to be an additional important feature for polymer membranes. Furthermore, our results demonstrate that dynamical correlations should become an important consideration in experimental measurements of salt diffusivities and conductivities for non-dilute salt solutions in polymer membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at intermediate temperatures

High temperature proton exchange membrane fuel cells are being lately investigated because of their high energy efficiency, their superior heat/water management, CO tolerance, and electrode reaction kinetics. To further advance this technology, the polymer membrane portfolio and performance should be improved for intermediate or high temperature operation (>100 °C). In this work we present new poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at 120 °C. First, new protic ionic liquids, hereafter called DAMAH + X - , were synthesized leading to diallylmethylammonium monomers with different counter-anions. By radical cyclopolymerization through thermal and photoinitiation mechanisms, self-standing protic polymeric membranes of poly(diallylmethylammonium X - ) were obtained. Membranes showed good thermal stability (>250 °C) and mechanical properties without the need of additives such as (protic) ionic liquids, solvents or inorganic charges. Great attention was paid to understand the effect of the different counter-anions on the membrane properties. As a general trend, fluorinated anions coming from strong acids confer high ionic conductivity and allow to reduce the hygroscopic properties on the protic polymeric membranes. Proton structural and dynamical stability at different temperatures and humidification conditions were investigated by Neutron Scattering (QENS and NR). The optimized poly(diallylmethylammonium X - ) shows similar ionic conductivity values than Nafion 212 under varying relative humidity conditions at 80 °C. Furthermore, it shows a high ionic conductivity value of 1.9 × 10 -3 Scm -1 at 120 °C under dry conditions.

08 HYDROGEN↗
DOE OSTI2024

Reversible two-way tuning of thermal conductivity in an end-linked star-shaped thermoset

Polymeric thermal switches that can reversibly tune and significantly enhance their thermal conductivities are desirable for diverse applications in electronics, aerospace, automotives, and medicine; however, they are rarely achieved. Here, we report a polymer-based thermal switch consisting of an end-linked star-shaped thermoset with two independent thermal conductivity tuning mechanisms—strain and temperature modulation—that rapidly, reversibly, and cyclically modulate thermal conductivity. The end-linked star-shaped thermoset exhibits a strain-modulated thermal conductivity enhancement up to 11.5 at a fixed temperature of 60 °C (increasing from 0.15 to 2.1 W m –1 K –1 ). Additionally, it demonstrates a temperature-modulated thermal conductivity tuning ratio up to 2.3 at a fixed stretch of 2.5 (increasing from 0.17 to 0.39 W m –1 K –1 ). When combined, these two effects collectively enable the end-linked star-shaped thermoset to achieve a thermal conductivity tuning ratio up to 14.2. Moreover, the end-linked star-shaped thermoset demonstrates reversible tuning for over 1000 cycles. The reversible two-way tuning of thermal conductivity is attributed to the synergy of aligned amorphous chains, oriented crystalline domains, and increased crystallinity by elastically deforming the end-linked star-shaped thermoset.

42 ENGINEERING↗
DOE OSTI2021

A Polymer-in-Salt Electrolyte with Enhanced Oxidative Stability for Lithium Metal Polymer Batteries

Lithium (Li) metal polymer batteries (LMPBs) are a promising candidate of solid-state batteries with high safety. However, rare progress has been demonstrated so far in high voltage stability of polyethylene oxide (PEO) based polymer electrolytes for LMPBs. Herein, we revived the polymer-in-salt electrolyte (PISE) strategy based on the PEO-LiFSI system with EO/Li = 8 through a dry process to avoid the contamination of the residual solvent. The obtained PISEs exhibit quite different morphologies and coordination structures which greatly enhance the oxidative stability of polymer electrolytes. P(EO)1LiFSI has a low melting temperature, a high ionic conductivity at 60 ?C and an oxidative stability of ~4.5 V vs. Li/Li+ (overcoming the inherent low oxidative stability of PEO). With an effective interphase rich in inorganic species, in combination with good stability of the hybrid polymer electrolyte towards Li metal, the cycling stability of Li||LiNi1/3Co1/3Mn1/3O2 is greatly improved. The LMPB can retain 74.4% of capacity after 186 cycles at 60 ?C under the charge cutoff voltage of 4.3 V. The findings point out a promising strategy to develop high-voltage stable polymer electrolytes for high energy-density and safe LMPBs.

Polymer-in-salt electrolyte, lithium metal battery↗
DOE OSTI2025

Intrachain Electron Transport in a Naphthalene Diimide–Bithiophene Copolymer: A Mixed-Valence Approach

The mechanism of electron transport in the polymer P(NDI2OD-T2) (poly(N,N'-bis-2-octyldodecylnaphthalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-2,2'-bithiophene-5,5'-diyl), N2200) is investigated. Here, we use spectroelectrochemical measurements on P(NDI2OD-T2), spectroscopic studies of a chemically reduced model compound, 2,2'-(2,2'-bithiophene-5,5'-diyl)-bis(N,N'-di-n-hexylnaphthalene-1,8:4,5-bis(dicarboximide)) (NDI-T2-NDI), and electronic structure calculations to evaluate the microscopic charge-transport parameters. Experimental and computational data suggest that NDI-T2-NDI•– is a class-II mixed-valence compound, strongly supporting the small-polaron hopping model as a charge-transport mechanism for electrons along polymer chains in P(NDI2OD-T2). The electronic coupling between the NDI redox units is at least 21 meV, while the reorganization energy is between 0.45 and 0.56 eV. Using a hopping model, we estimated the mobility and activation energy for electron transport along P(NDI2OD-T2) polymer chains to be 0.15 cm 2 V –1 s –1 and 60 meV, respectively. Our study elucidates a long-standing issue of explaining the coexistence in P(NDI2OD-T2) of localized redox sites with relatively large electron mobilities more usually achieved only in highly conjugated polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2020

First Ever Polymer Flood Field Pilot To Enhance The Recovery Of Heavy Oils On Alaska’s North Slope - Pushing Ahead One Year Later

In June 2018 the team embarked on an ambitious project to address the slow development pace of Alaska’s 20+ billion barrels heavy oil resource via the first ever polymer flood pilot. Following the successful commencement of the pilot in August 2018, the field demonstration, supporting laboratory experiments and numerical simulation have steadily progressed. A significant amount of valuable data and lessons learned have been collected, and are reported in this paper. The ongoing pilot and the research activities is making headway toward the primary objective of validating the use of polymer flooding for extracting heavy oil in Alaska’s challenging environment. The pilot is conducted in two pre-existing pairs of horizontal injectors and producers in an isolated fault block of the Schrader Bluff heavy oil reservoir at the Milne Point Field. A customized polymer blending and pumping unit injects HPAM polymer at a concentration of 1,750 ppm to achieve a target viscosity of 45 cP. Supporting coreflood laboratory experiments have focused on quantification of polymer retention in the rock, and effect of injection water salinity, polymer, and their combinations on oil recovery. The injection and production response of the pilot flood pattern is utilized to develop a history matched reservoir simulation model for forecasting oil recovery beyond the pilot. Finally, specially designed laboratory experiments address anticipated operating concerns regarding post-polymer breakthrough such as oil-water separation efficiency and polymer induced fouling of heater tubes. Polymer has been injected continuously since startup except for two short equipment modification shutdowns, and more recently a prolonged disruption due to polymer hydration issues at the J-pad field site. Cumulatively, over 600,000 lbs. of polymer has been injected, corresponding to ~7%PV. The two producers show significant decrease in the water cut, gradually increasing oil rate, and no polymer breakthrough. Two main observations from the coreflood are a significant uncertainty in polymer retention values, and positive oil recovery response to low salinity water (2,600 mg/liter TDS). The heterogeneity in the flood pattern presents some challenges in obtaining a robust history matched simulation model. Experimental results on produced fluids treatment indicate the formation of a dense polymer deposit, at certain conditions, on heating tubes that can negatively impact the heat transfer efficiency. The scientific knowledge, including the lessons learned during unanticipated shutdowns, quality control, logistics and field data that is being acquired from this effort has referential value for other planned EOR projects. Finally, by all indications, the polymer field pilot is steadily progressing toward achieving the ultimate goal of unlocking the massive heavy oil resources on Alaska North Slope (ANS).

Dandekar, Abhijit↗
DOE OSTI2021

Damage detection through Förster Resonance Energy Transfer in mechanoresponsive polymer nanocomposites

Polymer nanocomposites offer design solutions to control and tune optical, conductive, topological, and thermomechanical properties of advanced and multifunctional materials. Because of their ubiquitous nature, methodologies to diagnose failure or structural changes in the nanocomposites are of significant interest. Herein, we report a nanocomposite system loaded with quantum dots and coumarin-modified carbon nanotubes that transduce mechanical force into fluorescence at a strain, for the first time, as low as 7.5%. Our comprehensive studies detail the optical, morphological, and thermomechanical properties of these nanocomposites to establish the fundamental reason behind the activation of fluorescence. Here our results indicate that bare carbon nanotubes can irreversibly quench the fluorescence from quantum dots and that the coumarin-modified carbon nanotubes mitigate the quenching through Förster Resonance Energy Transfer. Next, the application of force to the sample changes the quantum dot-carbon nanotube spacing as well as the carbon nanotube morphology to activate fluorescence in the nanocomposite. Overall, this force activation of fluorescence can serve as a general strategy for the development of a new class of mechano-responsive nanocomposites that impart polymeric materials with desirable functionalities including damage sensing and mechanical strength.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

Designing polymers with controlled nanoscale morphologies and scalable synthesis is of great interest in the development of fluorine-free materials for proton-exchange membranes in fuel cells. This study focuses on a precision polyethylene with phenylsulfonic acid branches at every fifth carbon, p5PhSA, with a high ion-exchange capacity (4.2 mmol/g). The polymers self-assemble into hydrophilic and hydrophobic co-continuous nanoscale domains. In the hydrated state, the hydrophilic domain, composed of polar sulfonic acid moieties and water, serves as a pathway for efficient mesoscopic proton conductivity. The morphology and proton transport of p5PhSA are evaluated under hydrated conditions using in situ X-ray scattering and electrochemical impedance spectroscopy techniques. Additionally, at 40 °C and 95% relative humidity, the proton conductivity of p5PhSA is 0.28 S/cm, which is four times greater than Nafion 117 under the same conditions. Atomistic molecular dynamics (MD) simulations are also used to elucidate the interplay between the structure and the water dynamics. The MD simulations show strong nanophase separation between the percolated hydrophilic and hydrophobic domains over a wide range of water contents. The percolated hydrophilic nanoscale domain facilitates the rapid proton transport in p5PhSA and demonstrates the potential of precise hydrocarbon-based polymers as processible and effective proton-exchange membranes.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Data Mining of Polymer Phase Transitions upon Temperature Changes by Small and Wide-Angle X-ray Scattering Combined with Raman Spectroscopy

The complex physical transformations of polymers upon external thermodynamic changes are related to the molecular length of the polymer and its associated multifaceted energetic balance. The understanding of subtle transitions or multistep phase transformation requires real-time phenomenological studies using a multi-technique approach that covers several length-scales and chemical states. A combination of X-ray scattering techniques with Raman spectroscopy and Differential Scanning Calorimetry was conducted to correlate the structural changes from the conformational chain to the polymer crystal and mesoscale organization. Current research applications and the experimental combination of Raman spectroscopy with simultaneous SAXS/WAXS measurements coupled to a DSC is discussed. In particular, we show that in order to obtain the maximum benefit from simultaneously obtained high-quality data sets from different techniques, one should look beyond traditional analysis techniques and instead apply multivariate analysis. Data mining strategies can be applied to develop methods to control polymer processing in an industrial context. Crystallization studies of a PVDF blend with a fluoroelastomer, known to feature complex phase transitions, were used to validate the combined approach and further analyzed by MVA.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Using Preformed Meisenheimer Complexes as Dopants for n-Type Organic Thermoelectrics with High Seebeck Coefficients and Power Factors

A pre-formed Meisenheimer complex of a naphthalenediimide (NDI) with tetrabutylammonium fluoride (TBAF) is obtained in a simple way by mixing dibrominated 4,9-dibromo-2,7-bis(2-octyldodecyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone and TBAF in solution and used as a dopant for n-type organic thermoelectrics. Additionally, two n-type polymers PNDIClTVT and PBDOPVTT are synthesized, n-doped, and characterized as conductive and thermoelectric materials. PNDIClTVT doped with NDI-TBAF presents a high σ value of 0.20 S cm –1 , a Seebeck coefficient (S) of -1854 µV K –1 , and a power factor (PF) of 67 µW m –1 K –2 , among the highest reported PF in solution-processed conjugated n-type polymer thermoelectrics. Using 4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl)dimethylamine and NDI-TBAF as co-dopants, PNDIClTVT has a PF > 35 µW m –1 K –2 ; while for PBDOPVTT σ = 0.75 S cm –1 and PF = 58 µW m –1 K –2 . In this study it is found that an ionic adduct together with a neutral dopant improves the performance of n-type organic thermoelectrics leading to an enhanced power factor, and more generally, the role of such an adduct in polymer doping is also elucidated.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Impact of Polymer Rheology on Gel Treatment Performance of Horizontal Wells with Severe Channeling

Summary Gel treatment has been a cost-effective method to control the conformance of a reservoir with severe heterogeneity problems. The water channels in such reservoirs can be classified as open fractures or high permeability porous media with pore-throat network. Many simulation studies have been conducted to discuss gel treatment performance for conformance control. However, nobody considered the polymer rheology difference in open fractures and porous media in simulation. Previous simulation studies also ignored the residual resistance factor as a function of rock permeability rather than a constant parameter. In this study, a conceptual simulation model was established to simulate the linear flow system for the reservoir with horizontal wells considering the two factors mentioned above. The results demonstrate that the gel treatment always provides the better placement results in the open fracture type channel than pore-throat network type channel. Moreover, it is very necessary to consider residual resistance factor as a function of permeability, which is based on the experimental results and can provide much greater plugging efficiency in the higher permeable channels than constant residual resistance factor. Sensitivity analysis studies and multifactor analysis indicate that increasing oil viscosity and permeability ratio has a strong positive influence on conformance control results, which indicate in-situ gel treatment can be better applied in heavy or viscous oil reservoirs with fracture-like channels. Besides, the results also indicate that in reservoirs with severe channeling problem where channel velocity was high, the differences of gelant placement and profile improvement in models with two different types of channels could be enlarged greatly.

Engineering↗
DOE OSTI2022

DFT simulation of conductivity of the p-type doped and charge-injected cis-polyacetylene

Semiconducting conjugated polymers (CPs) have shown great potential in organic solar cells and organic field-effect transistors (OFETs), due to their tunable electronic and optical properties. In this study, we compare computational predictions of electronic and optical properties of ensembles of cis-polyacetylene (cis-PA) multiple oligomers in two different forms (a) undoped cis-PA and (b) cis-PA doped by phosphorous fluoride (PF¯ 6 ) via density functional theory (DFT) with hybrid functionals. The comparison of undoped cis-PA under the constraint of injected charge carrier and cis-PA doped by PF¯ 6 shows that either doping or injection provides very similar features in electronic structure and optical properties. Doped and injected are similar to each other and different from the pristine, undoped PA. Computed results also indicate that the injection of charge carriers and adding p-type doping into the semiconducting CP model both greatly affect the conductivity. Furthermore, these observations provide a better understanding and practical use of the properties of polyacetylene films for flexible electronic applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Retrospective on Recent DOE-Funded Studies Concerning the Extraction of Rare Earth Elements & Lithium from Geothermal Brines (Final Report)

Rare earth elements (REE) and lithium are non-toxic metals that are considered critical materials due to their use in electronics, magnets, batteries, and a wide variety of industrial processes important for the economy and military preparedness. Demand for REE and lithium is increasing and these critical materials are imported, so identifying and exploiting domestic sources of REE and lithium is a national priority. The U.S. Department of Energy (DOE) Geothermal Technologies Office (GTO) has been in the forefront of sponsoring research investigating the potential recovery of REE, lithium, and other critical minerals from geothermal brines. It has been proposed that the future of geothermal energy should include “hybrid systems” that combine electricity generation with other revenue-generating activities, such as recovery of valuable and critical minerals, including REE and lithium. Two recent GTO funding opportunities have focused on the recovery of REE and other valuable minerals from geothermal brines. The research supported by the GTO’s mineral recovery program is focused on three areas: resource characterization, technology for the extraction of REE, and technology for the extraction of lithium (Tables 1 and 2). This report is a retrospective study examining the outcome of GTO’s two recent mineral recovery programs (DE-FOA-0001016 in FY 2014 and DE-FOA-0001376 in FY 2016). In this report, the knowledge, technology, and techniques that were developed by researchers funded by GTO are summarized and discussed. Four projects were funded to assess the concentrations and amounts of REE found in geothermal brines and oil field produced waters. The GTO-funded studies compiled publically available data on REE concentrations from brines and produced water from all over the USA. In addition, new samples were collected and characterized from major geothermal and hydrocarbon basins in the Western USA. The studies examined the relationship between lithology and REE concentrations and developed models examining the influence of geology on REE concentrations in produced brines. It was determined that REE are frequently found at higher concentrations in oil field produced water than geothermal brines, but that some geothermal areas had significant REE resources. Significant reservoirs of REE were identified in the Western USA. In some cases, concentrations of REE were more than 1000 times the concentrations found in seawater. Collectively, these studies represent a comprehensive picture of REE resources associated with geothermal and hydrocarbon systems in the USA. The studies did not examine lithium resources, but in some cases, lithium concentration data was collected. Data from these studies are housed in the Geothermal Data Repository (GDR) and represent a significant information resource and it is recommended that these data be further analyzed in a future study. Eight projects were funded to develop new technology for REE extraction from geothermal fluids. These projects investigated sorption as an approach for removal and recovery of REE from geothermal brines. The projects investigated cutting-edge technology for selective sorption of ions from complex solutions, including the application of metal-organic frameworks and biosorbent proteins. The REE sorption studies tested different combinations of metal-binding ligands and solid supports. The most promising metal-binding ligands for REE included phosphonic acid, thiol, and carboxylic acid functional groups. Ligands were attached or incorporated into a wide variety of solid supports. In most cases, attachment was via covalent bonding to organic resins, polymers, or silica-based supports. Most of the REE projects were conducted at a low technology readiness level (TRL) and showed promise, but direct comparison between technologies was not possible based on the available information. It is recommended that testing and reporting be standardized to the extent possible to facilitate comparisons between technologies. Two projects were directed at novel lithium extraction technology. Both projects investigated the use of inorganic sorbents, including manganese oxides. One study also examined the use of metal- ion imprinted polymers as selective ion-exchange resins for the separation of lithium and manganese from brines. Both approaches showed promise for the selective extraction of lithium from brines, including potentially geothermal brines. Results from these GTO studies indicated that selective REE and lithium extraction is possible, but interference from co-occurring solutes, such as calcium, magnesium, or heavy metals, will interfere with process efficiency and negatively impact process economics. Techno-economic analysis conducted as part of the resource and technology studies suggest extraction of REE from geothermal brines is unlikely to be economically viable, especially since non-geothermal produced waters frequently have higher REE concentrations. It is recommended that benchmarks for techno-economic analysis be established to the extent possible for future studies, to facilitate direct comparison of various technologies. Based on the collective results of this program, it appears that hybrid geothermal power would benefit more from recovery of lithium and other metals, rather than REE. It is recommended that future studies be conducted at a higher- TRL and that sorbents be tested against actual geothermal fluid samples. Prior higher-TRL efforts to extract metals from geothermal brines should be further evaluated for lessons learned.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal stability of filler‐based ethylene/vinyl acetate/vinyl alcohol terpolymer in nitroplasticizer oxidative environment

Abstract To study the thermal stability of ethylene/vinyl acetate/vinyl alcohol (EVA‐OH) composite with filler particles, systematic thermogravimetric analysis (TGA) investigation was conducted in both nonisothermal and isothermal modes. The effect of polymer concentration on the aging behavior of EVA‐OH was investigated in the nitroplasticizer (NP) environment. Fourier transform infrared spectroscopy was used to probe chemical structural changes in the EVA‐OH polymer before and after thermal aging. The results suggest that filler addition accelerates the rate of NP exudation out of the EVA‐OH composites and deteriorates the thermal stability of NP at moderate temperatures (up to 70°C). The degradation of NP, in turn, accelerates the degradation of EVA‐OH polymer in its composite form through oxidation and hydrolysis indicating the importance of antioxidants in such phase blends.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Entropic Penalty Switches Li + Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes

Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li + ) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li + solvation and transport in poly(oligo ethylene methacrylate) (POEM) and its copolymers with poly(glycerol carbonate methacrylate) (PGCMA). We find that Li + is solvated by ether oxygens instead of the highly polar PGCMA, due to lower entropic penalties. The presence of PGCMA promotes single-chain solvation, thereby suppressing interchain Li + hopping. The conductivity difference between random copolymer PGCMA-r-POEM and block copolymer PGCMA-b-POEM is explained in terms of a hybrid solvation site mechanism. With diffuse microscopic interfaces between domains, PGCMA near the POEM contributes to Li + transport by forming hybrid solvation sites. The formation of such sites is hindered when PGCMA is locally concentrated. These findings help explain how thermodynamic driving forces govern Li + solvation and transport in mixed SPEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Intrinsic Ion Transport Properties of Block Copolymer Electrolytes

Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10 -3 S/cm at 90 degrees C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10 -4 S/cm at 90 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗