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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 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Dynamic Structure and Phase Behavior of a Block Copolymer Electrolyte under dc Polarization

There is an important consideration when designing lithium battery electrolytes for advanced applications is how the electrolyte facilitates ion transport at fast charge and discharge rates. Large current densities are accompanied by large salt concentration gradients across the electrolyte. Nanostructured composite electrolytes have been proposed to enable the use of high energy density lithium metal anodes, but many questions about the interplay between the electrolyte morphology and the salt concentration gradient that forms under dc polarization remain unanswered. To address these questions, we use an in situ small-angle X-ray scattering technique to examine the nanostructure of a polystyrene- block -poly(ethylene oxide) copolymer electrolyte under dc polarization with spatial and temporal resolution. In the quiescent state, the electrolyte exhibits a lamellar morphology. The passage of ionic current in a lithium symmetric cell leads to the formation of concurrent phases: a disordered morphology near the negative electrode, lamellae in the center of the cell, and coexisting lamellae and gyroid near the positive electrode. The most surprising result of this study was obtained after the applied electric field was turned off: a current-induced gyroid phase grows in volume for 6 h in spite of the absence of an obvious driving force. We show that this reflects the formation of localized pockets of salt-dense electrolyte, termed concentration hotspots, under dc polarization. Our methods may be applied to understand the dynamic structure of composite electrolytes at appreciable current densities.

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

Understanding kinetics of defect annihilation in chemoepitaxy-directed self-assembly.

Directed self-assembly (DSA) of block copolymers (BCP) has attracted considerable interest from the semiconductor industry because it can achieve semiconductor-relevant structures with a relatively simple process and low cost. However, the self-assembling structures can become kinetically trapped into defective states, which greatly impedes the implementation of DSA in high-volume manufacturing. Understanding the kinetics of defect annihilation is crucial to optimizing the process and eventually eliminating defects in DSA. Such kinetic experiments, however, are not commonly available in academic laboratories. To address this challenge, we perform a kinetic study of chemoepitaxy DSA in a 300 mm wafer fab, where the complete defectivity information at various annealing conditions can be readily captured. Through extensive statistical analysis, we reveal the statistical model of defect annihilation in DSA for the first time. The annihilation kinetics can be well described by a power law model, indicating that all dislocations can be removed by sufficiently long annealing time. We further develop image analysis algorithms to analyze the distribution of dislocation size and configurations and discover that the distribution stays relatively constant over time. The defect distribution is determined by the role of the guiding stripe, which is found to stabilize the defects. Although this study is based on polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA), we anticipate that these findings can be readily applied to other BCP platforms as well.

block copolymer↗
DOE OSTI2021

Evolution of Protrusions on Lithium Metal Anodes Stabilized by a Solid Block Copolymer Electrolyte Studied Using Time-Resolved X-ray Tomography

The growing demand for rechargeable batteries with higher energy densities has motivated research focused on enabling the lithium metal anode. A prominent failure mechanism in such batteries is short circuiting due to the uncontrolled propagation of lithium protrusions that often have a dendritic morphology. In this paper, the electrodeposition of metallic lithium through a rigid polystyrene- b -poly(ethylene oxide) (PS- b -PEO or SEO) block copolymer electrolyte was studied using hard X-ray microtomography. In this system, protrusions were approximately ellipsoidal globules: we take advantage of this simple geometry to quantify their growth as a function of polarization time and electrolyte salt concentration. The growth of 47 different globules was tracked with time to obtain average velocities of globule growth into the electrolyte. The globule diameter was a linear function of globule height in the electrolyte with a slope of about 6, independent of time and electrolyte salt concentration.

25 ENERGY STORAGE↗
DOE OSTI2021

Swelling-Assisted Sequential Infiltration Synthesis of Nanoporous ZnO Films with Highly Accessible Pores and Their Sensing Potential for Ethanol

Here, we report a swelling-assisted sequential infiltration synthesis (SIS) approach for the design of highly porous zinc oxide (ZnO) films by infiltration of block copolymer templates such as polystyrene-block- polyvinyl pyridine with inorganic precursors followed by UV ozone-assisted removal of the polymer template. We show that porous ZnO coatings with the thickness in the range between 140 and 420 nm can be obtained using only five cycles of SIS. The pores in ZnO fabricated via swelling-assisted SIS are highly accessible, and up to 98% of pores are available for solvent penetration. The XPS data indicate that the surface of nanoporous ZnO films is terminated with -OH groups. Density functional theory calculations show a lower energy barrier for ethanol-induced release of the oxygen restricted depletion layer in the case of the presence of -OH groups at the ZnO surface, and hence, it can lead to higher sensitivity in sensing of ethanol. We monitored the response of ZnO porous coatings with different thicknesses and porosities to ethanol vapors using combined mass-based and chemiresistive approaches at room temperature and 90 °C. The porous ZnO conformal coatings reveal a promising sensitivity toward detection of ethanol at low temperatures. In conclusion our results suggest the excellent potential of the SIS approach for the design of conformal ZnO coatings with controlled porosity, thickness, and composition that can be adapted for sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns

Here, nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported that overcomes the limitation of fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative crosslinking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA) with PS and PMMA homopolymer, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce hole diameter by as much as 50% or increase PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step towards fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Structure-Based Design of Dual Bactericidal and Bacteria-Releasing Nanosurfaces

Here, we report synergistic nanostructured surfaces combining bactericidal and bacteria-releasing properties. A polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer is used to fabricate vertically oriented cylindrical PS structures (“PS nanopillars”) on silicon substrates. The results demonstrate that the PS nanopillars (with a height of about 10 nm, size of about 50 nm, and spacing of about 70 nm) exhibit highly effective bactericidal and bacteria-releasing properties (“dual properties”) against Escherichia coli for at least 36 h of immersion in an E. coli solution. Interestingly, the PS nanopillars coated with a thin layer (≈3 nm thick) of titanium oxide (TiO 2 ) (“TiO 2 nanopillars”) show much improved dual properties against E. coli (a Gram-negative bacterium) compared to the PS nanopillars. Moreover, the dual properties emerge against Listeria monocytogenes (a Gram-positive bacterium). To understand the mechanisms underlying the multifaceted property of the nanopillars, coarse-grained molecular dynamics (MD) simulations of a lipid bilayer (as a simplified model for E. coli) in contact with a substrate containing hexagonally packed hydrophilic nanopillars were performed. The MD results demonstrate that when the bacterium–substrate interaction is strong, the lipid heads adsorb onto the nanopillar surfaces, conforming the shape of a lipid bilayer to the structure/curvature of nanopillars and generating high stress concentrations within the membrane (i.e., the driving force for rupture) at the edge of the nanopillars. Membrane rupture begins with the formation of pores between nanopillars (i.e., bactericidal activity) and ultimately leads to the membrane withdrawal from the nanopillar surface (i.e., bacteria-releasing activity). In the case of Gram-positive bacteria, the adhesion area to the pillar surface is limited due to the inherent stiffness of the bacteria, creating higher stress concentrations within a bacterial cell wall. In conclusion, the present study provides insight into the mechanism underlying the “adhesion-mediated” multifaceted property of nanosurfaces, which is crucial for the development of next-generation antibacterial surface coatings for relevant medical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. Here, to understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV–vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Cocontinuous Nanostructures by Microphase Separation of Statistically Cross-Linked Polystyrene/Poly(2-vinylpyridine) Networks

Cocontinuous polymeric nanostructures have drawn considerable attention due to their ability to combine distinct, percolation-dependent properties of two different polymer domains. Randomly end-linked copolymer networks (RECNs) have previously been shown to support the formation of disordered cocontinuous nanostructures across wide composition windows in a robust way. However, achieving highly efficient linking of telechelic polymers with excellent end-group fidelity often requires complex synthetic routes. As an alternative, we study here statistically cross-linked copolymer networks (SCCNs) composed of polystyrene and poly(2-vinylpyridine) (PS and P2VP) with cross-linkable allyl pendent groups that are conveniently synthesized by controlled radical copolymerization. Via selective extraction of P2VP, coupled with gravimetry, small-angle X-ray scattering, and electron microscopy, we find disordered cocontinuous phases across wide composition ranges (up to ≈ 35 wt %), approaching values previously determined for RECNs. Remarkably, even for samples that appear to exhibit full percolation, a substantial fraction of P2VP (≈ 20–30 wt %) cannot be removed, which we ascribe to short strands between nearby cross-linkers that are physically embedded within PS domains. Here, the resulting PS porous monoliths with residual surface P2VP layers enable facile surface modification to resist protein adsorption and templating of porous gold nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interconnected Nanoporous Polysulfone by the Self-Assembly of Randomly Linked Copolymer Networks and Linear Multiblocks

Porous materials have attracted considerable attention due to their versatile applications, especially in water purification. Interconnected nanoporous structures are distinguished by their high degree of porosity and resistance to clogging, as well as their insensitivity to nanostructural orientation. Previous works on randomly linked copolymer systems have shown that they can effectively produce disordered cocontinuous nanostructures, which upon removal of one component yield interconnected nanoporous materials. However, the cocontinuous nanomaterials previously developed using polystyrene (PS) and poly(d,l-lactic acid) (PLA) strands, and the resulting interconnected nanoporous PS monoliths, were far too brittle to enable practical use as membranes. Here, we study the self-assembly of randomly linked copolymer networks prepared using blocks of the engineering polymer polysulfone (PSU). A wide cocontinuous regime (spanning 40 wt %) was found for randomly end-linked copolymer networks (RECNs) constructed from PSU and PLA strands, via a combination of mechanical testing, gravimetry, small-angle X-ray scattering, and scanning electron microscopy. The PSU/PLA cocontinuous nanomaterial with symmetric composition showed 2.4 times higher Young’s modulus and ~100 times greater toughness than the corresponding PS/PLA sample. The interconnected nanoporous PSU fabricated after etching of PLA even exhibited 1.6 times greater toughness than PS/PLA prior to PLA removal. To facilitate the production of thin films of cocontinuous nanomaterials, we applied solution-processable randomly linked linear PSU/PLA multiblock polymers onto ultrafiltration membranes. Here, the interconnected nanoporous PSU thin film generated by etching PLA was found to effectively reject 50 nm diameter particles without significantly compromising permeability. This discovery presents a valuable addition to the existing techniques used to fabricate PSU membranes. In contrast to traditional methods, which are sensitive to processing conditions, produce a wide range of pore sizes, and offer limited adjustability of pore size, the current technique is anticipated to enable interconnected PSU membranes with more uniform and tailorable porosity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers

Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.

Cellulose↗
DOE OSTI2015

Direct Immersion Annealing of Thin Block Copolymer Films

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene–poly(methyl methacrylate) (PS–PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the “optimal long-range order” processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Three-Tone Chemical Patterns for Block Copolymer Directed Self-Assembly

Chemical patterns for directed self-assembly (DSA) of lamellaeforming block copolymers (BCP) with density multiplication can be fabricated by patterning resist on a cross-linked polystyrene layer, etching to create guide stripes, and depositing end-grafted brushes in between the stripes as background. To date, two-tone chemical patterns have been targeted with the guide stripes preferentially wet by one block of the copolymer and the background chemistry weakly preferentially wet by the other block. In the course of fabricating chemical patterns in an all-track process using 300 mm wafers, it was discovered that the etching process followed by brush grafting could produce a three-tone pattern. We characterized the three regions of the chemical patterns with a combination of SEM, grazing-incidence small-angle X-ray scattering (GISAXS), and assessment of BCP-wetting behavior, and evaluated the DSA behavior on patterns over a range of guide stripe widths. In its best form, the three-tone pattern consists of guide stripes preferentially wet by one block of the copolymer, each flanked by two additional stripes that wet the other block of the copolymer, with a third chemistry as the background. Three-tone patterns guide three times as many BCP domains as two-tone patterns and thus have the potential to provide a larger driving force for the system to assemble into the desired architecture with fewer defects in shorter time and over a larger process window.

block copolymer↗
DOE OSTI2017

Electrochemical Characterization and Catalytic Application of Gold-Supported Ferrocene-Containing Diblock Copolymer Thin Films in Ethanol Solution

This study reports the electrochemical behavior and catalytic property of electrode-supported thin films of polystyrene- block -poly(2-(acryloyloxy)ethyl ferrocenecarboxylate) (PS- b -PAEFc) in an ethanol (EtOH) solution. The electrochemical properties of PS- b -PAEFc films with different PAEFc volume fractions (f PAEFc = 0.47, 0.30, and 0.17) in 0.1 M ethanolic sodium hexafluorophosphate were compared with those in an acetonitrile (MeCN) solution of 0.1 M tetrabutylammonium hexafluorophosphate. Pristine PS- b -PAEFc films did not afford significant faradaic currents in the EtOH solution because EtOH is a nonsolvent for both PS and PAEFc. However, the films could be rendered redox-active in the EtOH solution by applying potentials in the MeCN solution to induce the redox-associated incorporation of the supporting electrolytes into the films. Atomic force microscopy images verified the stability of PAEFc microdomains upon electrochemical measurements in these solutions. Cyclic voltammograms measured in the EtOH solution for PS- b -PAEFc with the larger f PAEFc were diffusion-controlled regardless of ellipsometric film thickness (23 – 152 nm) at relatively slow scan rates, in contrast to those in the MeCN solution that were controlled by surface-confined redox species. The electron propagation efficiency in the EtOH solution was significantly lower than that in the MeCN solution due to the poorer swelling of the films, which limited the migration of counter ions and the collisional motions of the ferrocene moieties. PS- b -PAEFc films were applied as electrochemically-responsive heterogeneous catalysts based on the ferrocenium moieties for Michael addition reaction between methyl vinyl ketone and ethyl 2-oxocyclopentanecarboxylate (E2OC) in 0.1 M NaPF 6 /EtOH. The catalytic activities of thin films were similar regardless of f PAEFc , suggesting that the catalytic reaction took place for the reactants that could penetrate through the film and reach PAEFc microdomains communicable with the underlying electrode. Interestingly, the permeability of PS-b-PAEFc films provided a means to control the reaction selectivity, as suggested by negligible reaction of E2OC with trans -4-phenyl-3-buten-2-one.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Synthesis of nanostructured/macroscopic low-density copper foams based on metal-coated polymer core–shell particles [Templated synthesis of nanowalled low-density copper foams]

A robust, millimeter-sized low-density Cu foam with ~90% (v/v) porosity, ~30 nm thick walls, and ~1 μm diameter spherical pores is prepared by the slip-casting of metal-coated polymer core–shell particles followed by a thermal removal of the polymer. In this paper, we report our key findings that enable the development of the low-density Cu foams. First, we need to synthesize polystyrene (PS) particles coated with a very thin Cu layer (in the range of tens of nanometers). A simple reduction in the amount of Cu deposited onto the PS was not sufficient to form such a low-density Cu foams due to issues related to foam collapse and densification upon the subsequent polymer removal step. Precise control over the morphology of the Cu coating on the particles is essential for the synthesis of a lower density of foams. Second, improving the dispersion of PS–Cu particles in a suspension used for the casting as well as careful optimization of a baking condition minimize the formation of irregular large voids, leading to Cu foams with a more uniform packing and a better connectivity of neighboring Cu hollow shells. Finally, we analyzed mechanical properties of the Cu foams with a depth-sensing indentation test. The uniform Cu foams show a significant improvement in mechanical properties (~1.5× modulus and ~3× hardness) compared to those of uncontrolled foam samples with a similar foam density but irregular large voids. As a result, higher surface areas and a good electric conductivity of the Cu foams present a great potential to future applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mitigating electrochemical degradation in CsPbBr{sub 3} gamma detectors by organic and inorganic encapsulation.

CsPbBr3 perovskite semiconductors have emerged as a leading candidate for nextgeneration radiation detectors because of their exceptional charge transport properties, defect tolerance, and record-breaking sensitivity and energy resolution. Their long-term stability, however, is hindered by electrode-driven electrochemical decomposition, which is accelerated by moisture- and oxygen-assisted ion migration during operation. Here, we investigated organic and inorganic encapsulation strategies as both environmental barriers and means to suppress interfacial degradation pathways. Atomic layer deposition (ALD) of Al2O3 provided a conformal passivation layer that blocked environmental ingress, suppressed ionic diffusion, reduced leakage current, enhanced energy resolution and expanded the operational electric-field window beyond 5 kV∙cm1 . By contrast, organic encapsulants such as paraffin wax and polystyrene slowed moisture diffusion but did not suppress interfacial reactions, with wax extending stability to over 90 days. These results show that ALD-Al2O3 suppresses dominant interfacial degradation pathways, enabling stable, high-field operation and advancing the practical deployment of CsPbBr3 γ-ray detectors.

Unal, Mustafa↗
DOE OSTI2017

Polymer Chromophore-Catalyst Assembly for Solar Fuel Generation

A polystyrene-based chromophore-catalyst assembly (poly- 2 ) has been synthesized and assembled at a mesoporous metal oxide photoanode. The assembly contains water oxidation catalyst centers based on [Ru(trpy) (phenq)] 2+ (Ru-Cat) and [Ru(bpy) 3 ] 2+ derivatives (Ru-C) as chromophores (trpy= 2,2';6,2"- terpyridine, phenq = 2-(quinol-8'-yl)-1,10-phenanthroline and bpy = 2,2'-bipyridine). The photophysical and electrochemical properties of the polychromophore-oxidation catalyst assembly were investigated in solution and at the surface of mesoporous metal oxide films. The layer-by-layer (LbL) method was utilized to construct multilayer films with cationic poly- 2 and anionic poly(acrylic acid) (PAA) for light-driven photochemical oxidations. We report photocurrent measurements of (PAA/poly- 2 ) 10 LbL films on mesoporous TiO 2 demonstrate light-driven oxidation of phenol and benzyl alcohol in aqueous solution. Interestingly, illumination of (PAA/poly- 2 ) 5 LbL films on a fluorine doped SnO 2 /TiO 2 core/shell photoanode in aqueous solution gives rise to an initial photocurrent (~18.5 μA·cm –2 ) that is in part ascribed to light driven water oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Carboxylated Fullerene at the Oil/Water Interface

The self-assembly of carboxylated fullerene with poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) with different molecular weights, poly-2-vinylpyridine, and amine-terminated polystyrene, at the interface between toluene and water was investigated. For all values of the pH, the functionalized fullerene interacted with the polymers at the water/toluene interface, forming a nanoparticle network, reducing the interfacial tension. At pH values of 4.84 and 7.8, robust, elastic films were formed at the interface, such that hollow tubules could be formed in situ when an aqueous solution of the functionalized fullerene was jetted into a toluene solution of PS-b-P2VP at a pH of 4.84. Lastly, with variation of the pH, the mechanical properties of the fullerene/polymer assemblies can be varied by tuning the strength of the interactions between the functionalized fullerenes and the PS-b-P2VP.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Impact of Salt Concentration on Nonuniform Lithium Electrodeposition through Rigid Block Copolymer Electrolytes

There is a growing demand for higher energy density lithium batteries. One approach for addressing this demand is enabling lithium metal anodes. However, nucleation and growth of electronically conductive protrusions, which cause short circuits, prevent the use of this technology with liquid electrolytes. The use of rigid solid electrolytes such as polystyrene-b-poly(ethylene oxide) electrolytes is one solution. An additional requirement for practical cells is needed to use electrolytes with high salt concentration to maximize the flux of lithium ions in the cell. The first systematic study of the effect of salt concentration on the morphology of electrodeposited lithium through a rigid block copolymer electrolyte is presented. The nature, areal density, and morphologies of defective lithium deposits created during galvanostatic cycling of lithium-lithium symmetric cells were determined using hard X-ray microtomography. Cycle life decreases rapidly with increasing salt concentration. X-ray microtomography reveals the presence of multiglobular protrusions, which are nucleated at impurity particles at low salt concentrations; here, the areal density of defective lithium deposits was independent of salt concentration. Finally, at the highest salt concentration, this density increases abruptly by a factor of about 10, and defects were also nucleated at locations where no impurities were visible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗