Unraveling the Role of Solvation and Ion Valency on Redox-Mediated Electrosorption through In Situ Neutron Reflectometry and Ab Initio Molecular Dynamics.

Solvation and ion valency effects on selectivity of metal oxyanions at redox-polymer interfaces are explored through in situ spatial-temporally resolved neutron reflectometry combined with large scale ab initio molecular dynamics. The selectivity of ReO4- vs MoO42- for two redox-metallopolymers, poly(vinyl ferrocene) (PVFc) and poly(3-ferrocenylpropyl methacrylamide) (PFPMAm) is evaluated. PVFc has a higher Re/Mo separation factor compared to PFPMAm at 0.6 V vs Ag/AgCl. In situ techniques show that both PVFc and PFPMAm swell in the presence of ReO4- (having higher solvation with PFPMAm), but do not swell in contact with MoO42-. Ab initio molecular simulations suggest that MoO42- maintains a well-defined double solvation shell compared to ReO4-. The more loosely solvated anion (ReO4-) is preferably adsorbed by the more hydrophobic redox polymer (PVFc), and electrostatic cross-linking driven by divalent anionic interactions could impair film swelling. Thus, the in-depth understanding of selectivity mechanisms can accelerate the design of ion-selective redox-mediated separation systems for transition metal recovery and recycling.

Studying Transient Phenomena in Thin Films with Reinforcement Learning.

Neutron reflectometry has long been a powerful tool to study the interfacial properties of energy materials. Recently, time-resolved neutron reflectometry has been used to better understand transient phenomena in electrochemical systems. Those measurements often comprise a large number of reflectivity curves acquired over a narrow q range, with each individual curve having lower information content compared to a typical steady-state measurement. In this work, we present an approach that leverages existing reinforcement learning tools to model time-resolved data to extract the time evolution of structure parameters. By mapping the reflectivity curves taken at different times as individual states, we use the Soft Actor-Critic algorithm to optimize the time series of structure parameters that best represent the evolution of an electrochemical system. We show that this approach constitutes an elegant solution to the modeling of time-resolved neutron reflectometry data.

Charged Biological Membranes Repel Large Neutral Molecules by Surface Dielectrophoresis and Counterion Pressure.

Macromolecular crowding is the usual condition of cells. The implications of the crowded cellular environment for protein stability and folding, protein-protein interactions, and intracellular transport drive a growing interest in quantifying the effects of crowding. While the properties of crowded solutions have been extensively studied, less attention has been paid to the interaction of crowders with the cellular boundaries, i.e., membranes. However, membranes are key components of cells and most subcellular organelles, playing a central role in regulating protein channel and receptor functions by recruiting and binding charged and neutral solutes. While membrane interactions with charged solutes are dominated by electrostatic forces, here we show that significant charge-induced forces also exist between membranes and neutral solutes. Using neutron reflectometry measurements and molecular dynamics simulations of poly(ethylene glycol) (PEG) polymers of different molecular weights near charged and neutral membranes, we demonstrate the roles of surface dielectrophoresis and counterion pressure in repelling PEG from charged membrane surfaces. The resulting depletion zone is expected to have consequences for drug design and delivery, the activity of proteins near membrane surfaces, and the transport of small molecules along the membrane surface.

Janus bottlebrush compatibilizers.

Bottlebrush random copolymers (BRCPs), consisting of a random distribution of two homopolymer chains along a backbone, can segregate to the interface between two immiscible homopolymers. BRCPs undergo a reconfiguration, where each block segregates to one of the homopolymer phases, adopting a Janus-type structure, reducing the interfacial tension and promoting adhesion between the two homopolymers, thereby serving as a Janus bottlebrush copolymer (JBCP) compatibilizer. We synthesized a series of JBCPs by copolymerizing deuterated or hydrogenated polystyrene (DPS/PS) and poly(tert-butyl acrylate) (PtBA) macromonomers using ruthenium benzylidene-initiated ring-opening metathesis polymerization (ROMP). Subsequent acid-catalyzed hydrolysis converted the PtBA brushes to poly(acrylic acid) (PAA). The JBCPs were then placed at the interface between DPS/PS homopolymers and poly(2-vinyl pyridine) (P2VP) homopolymers, where the degree of polymerization of the backbone (NBB) and the grafting density (GD) of the JBCPs were varied. Neutron reflectivity (NR) was used to determine the interfacial width and segmental density distributions (including PS homopolymer, PS block, PAA block and P2VP homopolymer) across the polymer-polymer interface. Our findings indicate that the star-like JBCP with NBB = 6 produces the largest interfacial broadening. Increasing NBB to 100 (rod-like shape) and 250 (worm-like shape) reduced the interfacial broadening due to a decrease in the interactions between blocks and homopolymers by stretching of blocks. Decreasing the GD from 100% to 80% at NBB = 100 caused an increase the interfacial width, yet further decreasing the GD to 50% and 20% reduced the interfacial width, as 80% of GD may efficiently increase the flexibility of blocks and promote interactions between homopolymers, while maintaining relatively high number of blocks attached to one molecule. The interfacial conformation of JBCPs was further translated into compatibilization efficiency. Thin film morphology studies showed that only the lower NBB values (NBB = 6 and NBB = 24) and the 80% GD of NBB = 100 had bicontinuous morphologies, due to a sufficient binding energy that arrested phase separation, supported by mechanical testing using asymmetric double cantilever beam (ADCB) tests. These provide fundamental insights into the assembly behavior of JBCPs compatibilizers at homopolymer interfaces, opening strategies for the design of new BCP compatibilizers.

Thermo-Electro-Responsive Redox-Copolymers for Amplified Solvation, Morphological Control, and Tunable Ion Interactions.

Electro-responsive metallopolymers can possess highly specific and tunable ion interactions, and have been explored extensively as electrode materials for ion-selective separations. However, there remains a limited understanding of the role of solvation and polymer-solvent interactions in ion binding and selectivity. The elucidation of ion-solvent-polymer interactions, in combination with the rational design of tailored copolymers, can lead to new pathways for modulating ion selectivity and morphology. Here, we present thermo-electrochemical-responsive copolymer electrodes of N-isopropylacrylamide (NIPAM) and ferrocenylpropyl methacrylamide (FPMAm) with tunable polymer-solvent interactions through copolymer ratio, temperature, and electrochemical potential. As compared to the homopolymer PFPMAm, the P(NIPAM0.9-co-FPMAm0.1) copolymer ingressed 2 orders of magnitude more water molecules per doping ion when electrochemically oxidized, as measured by electrochemical quartz crystal microbalance. P(NIPAM0.9-co-FPMAm0.1) exhibited a unique thermo-electrochemically reversible response and swelled up to 83% after electrochemical oxidation, then deswelled below its original size upon raising the temperature from 20 to 40 °C, as measured through spectroscopic ellipsometry. Reduced P(NIPAM0.9-co-FPMAm0.1) had an inhomogeneous depth profile, with layers of low solvation. In contrast, oxidized P(NIPAM0.9-co-FPMAm0.1) displayed a more uniform and highly solvated depth profile, as measured through neutron reflectometry. P(NIPAM0.9-co-FPMAm0.1) and PFPMAm showed almost a fivefold difference in selectivity for target ions, evidence that polymer hydrophilicity plays a key role in determining ion partitioning between solvent and the polymer interface. Our work points to new macromolecular engineering strategies for tuning ion selectivity in stimuli-responsive materials.

Extraction of interaction parameters from specular neutron reflectivity in thin films of diblock copolymers: an "inverse problem".

Diblock copolymers have been shown to undergo microphase separation due to an interplay of repulsive interactions between dissimilar monomers, which leads to the stretching of chains and entropic loss due to the stretching. In thin films, additional effects due to confinement and monomer-surface interactions make microphase separation much more complicated than in that in bulks (i.e., without substrates). Previously, physics-based models have been used to interpret and extract various interaction parameters from the specular neutron reflectivities of annealed thin films containing diblock copolymers (J. P. Mahalik, J. W. Dugger, S. W. Sides, B. G. Sumpter, V. Lauter and R. Kumar, Interpreting neutron reflectivity profiles of diblock copolymer nanocomposite thin films using hybrid particle-field simulations, Macromolecules, 2018, 51(8), 3116; J. P. Mahalik, W. Li, A. T. Savici, S. Hahn, H. Lauter, H. Ambaye, B. G. Sumpter, V. Lauter and R. Kumar, Dispersity-driven stabilization of coexisting morphologies in asymmetric diblock copolymer thin films, Macromolecules, 2021, 54(1), 450). However, extracting Flory-Huggins χ parameters characterizing monomer-monomer, monomer-substrate, and monomer-air interactions has been labor-intensive and prone to errors, requiring the use of alternative methods for practical purposes. In this work, we have developed such an alternative method by employing a multi-layer perceptron, an autoencoder, and a variational autoencoder. These neural networks are used to extract interaction parameters not only from neutron scattering length density profiles constructed using self-consistent field theory-based simulations, but also from a noisy ad hoc model constructed previously. In particular, the variational autoencoder is shown to be the most promising tool when it comes to the reconstruction and extraction of parameters from an ad hoc neutron scattering length density profile of a thin film containing a symmetric di-block copolymer (poly(deuterated styrene-b-n-butyl methacrylate)). This work paves the way for automated analysis of specular neutron reflectivities from thin films of copolymers using machine learning tools.

Neutron Reflectometry and Molecular Simulations Demonstrate HIV-1 Nef Homodimer Formation on Model Lipid Bilayers.

The HIV-1 Nef protein plays a critical role in viral infectivity, high-titer replication in vivo, and immune escape of HIV-infected cells. Nef lacks intrinsic biochemical activity, functioning instead through interactions with diverse host cell signaling proteins and intracellular trafficking pathways. Previous studies have established an essential role for Nef homodimer formation at the plasma membrane for most if not all its functions. Here we combined neutron reflectometry of full-length myristoylated Nef bound to model lipid bilayers with molecular simulations based on previous X-ray crystal structures of Nef homodimers. This integrated approach provides direct evidence that Nef associates with the membrane as a homodimer with its structured core region displaced from the membrane for partner protein engagement. Parallel studies of a dimerization-defective mutant, Nef-L112D, demonstrate that the helical dimerization interface present in previous crystal structures stabilizes the membrane-bound dimer. X-ray crystallography of the Nef-L112D mutant in complex with the SH3 domain of the Nef-associated host cell kinase Hck revealed a monomeric 1:1 complex instead of the 2:2 dimer complex formed with wild-type Nef. Importantly, the crystal structure of the Nef-L112D core and SH3 interface are virtually identical to the wild-type complex, indicating that this mutation does not affect the overall Nef fold. These findings support the intrinsic capacity of Nef to homodimerize at lipid bilayers using structural features present in X-ray crystal structures of dimeric complexes.

Understanding the Solution Dynamics and Binding of a PVDF Binder with Silicon, Graphite, and NMC Materials and the Influence on Cycling Performance.

The impact of the binding, solution structure, and solution dynamics of poly(vinylidene fluoride) (PVDF) with silicon on its performance as compared to traditional graphite and Li1.05Ni0.33Mn0.33Co0.33O2 (NMC) electrode materials was explored. Through refractive index (RI) measurements, the concentration of the binder adsorbed on the surface of electrode materials during electrode processing was determined to be less than half of the potentially available material resulting in excessive free binder in solution. Using ultrasmall-angle neutron scattering (USANS) and small-angle neutron scattering (SANS), it was found that PVDF forms a conformal coating over the entirety of the silicon particle. This is in direct contrast to graphite-PVDF and NMC-PVDF slurries, where PVDF only covers part of the graphite surface, and the PVDF chains make a network-like graphite-PVDF structure. Conversely, a thick layer of PVDF covers NMC particles, but the coating is porous, allowing for ion and electronic transport. The homogeneous coating of silicon breaks up percolation pathways, resulting in poor cycling performance of silicon materials as widely reported. These results indicate that the Si-PVDF interactions could be modified from a binder to a dispersant.

Additively Manufactured NdFeB Polyphenylene Sulfide Halbach Magnets to Generate Variable Magnetic Fields for Neutron Reflectometry.

Halbach arrays are the most efficient closed structures for generating directed magnetic fields and gradients, and are widely used in various electric machines. We utilized fused deposition modeling-based Big Area Additive Manufacturing technology to print customized, compensated concentric Halbach array rings, using polyphenylene sulfide-bonded NdFeB permanent magnets for polarized neutron reflectometry. The Halbach rings could generate a 0 ≤ B ≤ 0.30 T field, while preserving 90% polarization of an axial neutron beam. Polarized neutron beams are used to study a wide range of structural and magnetic phenomena spanning physics, chemistry, and biology. In this study, we demonstrate the effectiveness of additive manufacturing for producing prototype Halbach arrays, characterize their magnetic properties, and generated magnetic fields, and discuss the conservation of neutron beam polarization as a function of magnetic field.

Structure and dynamics of small polyimide oligomers with silicon as a function of aging.

The effect of UV curing and shearing on the structure and behavior of a polyimide (PI) binder as it disperses silicon particles in a battery electrode slurry was investigated. PI dispersant effectiveness increases with UV curing time, which controls the overall binder molecular weight. The shear force during electrode casting causes higher molecular weight PI to agglomerate, resulting in battery anodes with poorly dispersed Si particles that do not cycle well. It is hypothesized that when PI binder is added above a critical amount, it conformally coats the silicon particles and greatly impedes Li ion transport. There is an "interzonal region" for binder loading where it disperses silicon well and provides a coverage that facilitates Li transport through the anode material and into the silicon particles. These results have implications in ensuring reproducible electrode manufacturing and increasing cell performance by optimizing the PI structure and coordination with the silicon precursor.

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting.

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.

A high temperature cell for investigating interfacial structure on the molecular scale in molten salt/alloy systems.

In this work, we describe the design and development of an in situ neutron reflectometry cell for high temperature investigations of structural changes occurring at the interface between inorganic salts, in their molten state up to 800 °C, and corrosion resistant alloys or other surfaces. In the cell, a molten salt is confined by an annular ring of single crystal sapphire constrained between the sample substrate and a sapphire plate using two gold O-rings, enclosing a liquid salt volume of 20 ml, along with a dynamic cell volume to accommodate expansion of the liquid with heating. As a test case for the cell, we report on an in situ neutron reflectometry measurement of the interface between a eutectic salt mixture of MgCl2-KCl (32:68 molar ratio) and a single crystal sapphire substrate at 450 °C, resulting in the formation of a 60 Å layer having a scattering length density of 1.72 × 10-6 Å-2. While the origin of this layer is uncertain, it is likely to have resulted from the salt reacting with an existing impurity layer on the sapphire substrate.

Probing clustering dynamics between silicon and PAA or LiPAA slurries under processing conditions.

This work explores the complex interplay between slurry aggregation, agglomeration, and conformation (i.e. shape) of poly(acrylic acid) (PAA) and lithiated poly(acrylic acid) (LiPAA) based silicon slurries as a function of shear rate, and the resulting slurry homogeneity. These values were measured by small angle neutron scattering (SANS) and rheology coupled ultra-small angle neutron scattering (rheo-USANS) at conditions relevant to battery electrode casting. Different binder solution preparation methods, either a ball mill (BM) process or a planetary centrifugal mixing (PCM) process, dramatically modify the resulting polymer dynamics and organization around a silicon material. This is due to the different energy profiles of mixing where the more violent and higher energy PCM causes extensive breakdown and reformation of the binder, which is now likely in a branched conformation, while the lower energy BM results in simply lower molecular weight linear polymers. The break down and reorganization of the polymer structure affects silicon slurry homogeneity, which affects subsequent electrode architecture.

The Study of the Binder Poly(acrylic acid) and Its Role in Concomitant Solid-Electrolyte Interphase Formation on Si Anodes.

We use neutron reflectometry to study how the polymeric binder, poly(acrylic acid) (PAA), affects the in situ formation and chemical composition of the solid-electrolyte interphase (SEI) formation on a silicon anode at various states of charge. The reflectivity is correlated with electrochemical quartz crystal microbalance to better understand the viscoelastic effects of the polymer during cycling. The use of model thin films allows for a well-controlled interface between the amorphous Si surface and the PAA layer. If the PAA perfectly coats the Si surface and standard processing conditions are used, the binder will prevent the lithiation of the anode. The PAA suppresses the growth of a new layer formed at early states of discharge (open circuit voltage to 0.8 V vs Li/Li+), protecting the surface of the anode. At 0.15 V, the SEI layer underneath the PAA changes in chemical composition as indicated by an increase in the scattering length density and thickness as the layer incorporates components from the electrolyte, most likely the salt. At lithiated and delithiated states, the SEI layer changes in chemical composition and grows in thickness with delithiation and shrinks during lithiation.

Quantifying the Extent of Hydration of a Surface-Bound Peptide Using Neutron Reflectometry.

Establishing how water, or the absence of water, affects the structure, dynamics, and function of proteins in contact with inorganic surfaces is critical to developing successful protein immobilization strategies. In the present article, the quantity of water hydrating a monolayer of helical peptides covalently attached to self-assembled monolayers (SAMs) of alkyl thiols on Au was measured using neutron reflectometry (NR). The peptide sequence was composed of repeating LLKK units in which the leucines were aligned to face the SAM. When immersed in water, NR measured 2.7 ± 0.9 water molecules per thiol in the SAM layer and between 75 ± 13 and 111 ± 13 waters around each peptide. The quantity of water in the SAM was nearly twice that measured prior to peptide functionalization, suggesting that the peptide disrupted the structure of the SAM. To identify the location of water molecules around the peptide, we compared our NR data to previously published molecular dynamics simulations of the same peptide on a hydrophobic SAM in water, revealing that 49 ± 5 of 95 ± 8 total nearby water molecules were directly hydrogen-bound to the peptide. Finally, we show that immersing the peptide in water compressed its structure into the SAM surface. Together, these results demonstrate that there is sufficient water to fully hydrate a surface-bound peptide even at hydrophobic interfaces. Given the critical role that water plays in biomolecular structure and function, these results are expected to be informative for a broad array of applications involving proteins at the bio/abio interface.

Role of conductive binder to direct solid-electrolyte interphase formation over silicon anodes.

With the use of in situ neutron reflectometry (NR) we show how the addition of an electronically conductive polymeric binder, PEFM, mediates the solid-electrolyte interphase (SEI) formation and composition on an amorphous Si (a-Si) electrode as a function of the state-of-charge. Upon initial contact with the electrolyte a Li rich, 41 Å thick, layer forms on the surface of the anode below the polymer layer. At 0.8 V (vs. Li/Li+), a distinct SEI layer forms from the incorporation of electrolyte decomposition products in the reaction layer that is organic in nature. In addition, solvent uptake in the PEFM layer occurs resulting in the layer swelling to ∼200 Å. Upon further polarization to 0.4 and 0.15 V (vs. Li/Li+) a thick layer (800 Å) on the surface of the Si is evident where a diffuse interface between the PEFM and SEI occurs resulting in a matrix between the two layers, as the binder has taken up a large amount of electrolyte. The two layers appear to be interchanging solvent molecules from the PEFM to the SEI to the Si surface preventing the lithiation of the a-Si. By 0.05 V (vs. Li/Li+) a Li rich, 72 Å thick, SEI layer condenses on the surface of the anode, and a 121 Å intermixed layer on top of the SEI with LiF and Li-C-O species is present with the rest blended into the electrolyte.

Direct Measurement of Water Permeation in Submerged Alkyl Thiol Self-Assembled Monolayers on Gold Surfaces Revealed by Neutron Reflectometry.

Self-assembled monolayers (SAMs) of alkyl thiols are frequently used to chemically functionalize gold surfaces for applications throughout materials chemistry, electrochemistry, and biotechnology. Despite this, a detailed understanding of the structure of the SAM-water interface generated from both formation and use of the SAM in an aqueous environment is elusive, and analytical measurements of the structure and chemistry of the SAM-water interface are an ongoing experimental challenge. To address this, we used neutron reflectometry (NR) to measure water association with both hydrophobic and hydrophilic SAMs under both wet and dry conditions. SAMs used for this study were made from hydrophobic decanethiol mixed with hydrophilic 11-azido-1-undecanethiol with compositions of 0-100% of the azide-terminated thiol. All SAMs were formed by conventional solution incubation of a Au substrate immersed in ethanol. Each SAM was characterized by grazing incidence angle reflection-absorption Fourier transfer infrared spectroscopy, contact angle goniometry, and electrochemical methods to confirm it was a completely formed monolayer with evidence of extensive crystalline-like domains. NR measured significant absorption of water into each SAM, ranging from 1.6 to 5.7 water molecules per alkyl thiol, when SAMs were immersed in water. Water infiltration was independent of SAM composition and terminal group hydrophilicity. These results demonstrate that water accesses defects, fluid regions, and heterogeneous domains inherent to even well-formed SAMs.

Shear Thickening Electrolyte Built from Sterically Stabilized Colloidal Particles.

We present a method to prepare shear thickening electrolytes consisting of silica nanoparticles in conventional liquid electrolytes with limited flocculation. These electrolytes rapidly and reversibly stiffen to solidlike behaviors in the presence of external shear or high impact, which is promising for improved lithium ion battery safety, especially in electric vehicles. However, in initial chemistries the silica nanoparticles aggregate and/or sediment in solution over time. Here, we demonstrate steric stabilization of silica colloids in conventional liquid electrolyte via surface-tethered PMMA brushes, synthesized via surface-initiated atom transfer radical polymerization. The PMMA increases the magnitude of the shear thickening response, compared to the uncoated particles, from 0.311 to 2.25 Pa s. Ultrasmall-angle neutron scattering revealed a reduction in aggregation of PMMA-coated silica nanoparticles compared to bare silica nanoparticles in solution under shear and at rest, suggesting good stabilization. Conductivity tests of shear thickening electrolytes (30 wt % solids in electrolyte) at rest were performed with interdigitated electrodes positioned near the meniscus of electrolytes over the course of 24 h to track supernatant formation. Conductivity of electrolytes with bare silica increased from 10.1 to 11.6 mS cm-1 over 24 h due to flocculation. In contrast, conductivity of electrolytes with PMMA-coated silica remained stable at 6.1 mS cm-1 over the same time period, suggesting good colloid stability.

Determination of the Solid Electrolyte Interphase Structure Grown on a Silicon Electrode Using a Fluoroethylene Carbonate Additive.

In this work we explore how an electrolyte additive (fluorinated ethylene carbonate - FEC) mediates the thickness and composition of the solid electrolyte interphase formed over a silicon anode in situ as a function of state-of-charge and cycle. We show the FEC condenses on the surface at open circuit voltage then is reduced to C-O containing polymeric species around 0.9 V (vs. Li/Li+). The resulting film is about 50 Å thick. Upon lithiation the SEI thickens to 70 Å and becomes more organic-like. With delithiation the SEI thins by 13 Å and becomes more inorganic in nature, consistent with the formation of LiF. This thickening/thinning is reversible with cycling and shows the SEI is a dynamic structure. We compare the SEI chemistry and thickness to 280 Å thick SEI layers produced without FEC and provide a mechanism for SEI formation using FEC additives.