Adaptive Ion Channels Formed in Ultrathin and Semicrystalline Polymer Interphases for Stable Aqueous Batteries.

Aqueous Zn batteries have recently emerged as promising candidates for large-scale energy storage, driven by the need for a safe and cost-effective technology with sufficient energy density and readily accessible electrode materials. However, the energy density and cycle life of Zn batteries have been limited by inherent chemical, morphological, and mechanical instabilities at the electrode-electrolyte interface where uncontrolled reactions occur. To suppress the uncontrolled reactions, we designed a crystalline polymer interphase for both electrodes, which simultaneously promotes electrode reversibility via fast and selective Zn transport through the adaptive formation of ion channels. The interphase comprises an ultrathin layer of crystalline poly(1H,1H,2H,2H-perfluorodecyl acrylate), synthesized and applied as a conformal coating in a single step using initiated chemical vapor deposition (iCVD). Crystallinity is optimized to improve interphase stability and Zn-ion transport. The optimized interphase enables a cycle life of 9500 for Zn symmetric cells and over 11,000 for Zn-MnO2 full-cell batteries. We further demonstrate the generalizability of this interphase design using Cu and Li as examples, improving their stability and achieving reversible cycling in both. The iCVD method and molecular design unlock the potential of highly reversible and cost-effective aqueous batteries using earth-abundant Zn anode materials, pointing to grid-scale energy storage.

Self-sufficient metal-air battery systems enabled by solid-ion conductive interphases.

Metal-air batteries including Li-air, Na-air, Al-air, and Zn-air, have received significant scientific and technological interest for at least the last three decades. The interest stems primarily from the fact that the electrochemically active material (O2) in the cathode can in principle be harvested from the surroundings. In practice, however, parasitic reactions with reactive components other than oxygen in dry air passivate the anode, limit cycling stability of air-sensitive (e.g., Li, Na, Al) and electrolyte-sensitive (e.g., Zn) anodes, in most cases obviating the energy-density benefits of harvesting O2 from ambient air. As a compromise, so-called metal-oxygen batteries in which pure O2 is used as the active cathode material have been extensively studied but are understood to be of little practical relevance because of the large infrastructure required to produce the pure O2 stream. Here, we report on the design of solid-ion conductive chemically inert metal interphases that simultaneously protect a metal anode from parasitic reactions with electrolyte components and which facilitate rapid interfacial ion transport. Interphases composed of indium (In) are reported to be of particular interest for protecting Li and Na anodes from passivation in air whereas interphases composed of Sn are shown to prevent chemical and electrochemical corrosion of Zn anodes in alkaline electrolytes. We report further that these protections enable so-called self-sufficient metal-air batteries capable of extended cycling stability in ambient air environments.

Thermoresponsive Conductivity of Graphene-Based Fibers.

Smart materials are versatile material systems which exhibit a measurable response to external stimuli. Recently, smart material systems have been developed which incorporate graphene in order to share on its various advantageous properties, such as mechanical strength, electrical conductivity, and thermal conductivity as well as to achieve unique stimuli-dependent responses. Here, a graphene fiber-based smart material that exhibits reversible electrical conductivity switching at a relatively low temperature (60 °C), is reported. Using molecular dynamics (MD) simulation and density functional theory-based non-equilibrium Green's function (DFT-NEGF) approach, it is revealed that this thermo-response behavior is due to the change in configuration of amphiphilic triblock dispersant molecules occurring in the graphene fiber during heating or cooling. These conformational changes alter the total number of graphene-graphene contacts within the composite material system, and thus the electrical conductivity as well. Additionally, this graphene fiber fabrication approach uses a scalable, facile, water-based method, that makes it easy to modify material composition ratios. In all, this work represents an important step forward to enable complete functional tuning of graphene-based smart materials at the nanoscale while increasing commercialization viability.

Zwitterionic Polymer Gradient Interphases for Reversible Zinc Electrochemistry in Aqueous Alkaline Electrolytes.

Aqueous alkaline zinc batteries are of scientific and technological interest because of the potential they offer for cost-effective and safe storage of electrical energy. Poor electrochemical reversibility and shape change of the Zn anode, propensity of Zn to become passivated by surface oxides and hydroxide films upon prolonged exposure to the electrolyte, and electroreduction of water are well-studied but remain unsolved challenges. Here, we create and study electrochemical and transport properties of precise, spatially tunable zwitterionic polymer interphases grown directly on Zn using an initiated-chemical vapor deposition polymerization methodology. In aqueous alkaline media, spatial gradients in composition─from the polymer-electrolyte interface to the solid-polymer interface─promote highly reversible redox reactions at high current density (20 mA cm-2) and high areal capacity (10 mAh cm-2). Via molecular dynamics and experimental analyses, we conclude that the interphases function by regulating the distribution and activity of interfacial water molecules, which simultaneously enables fast ion transport and suppression of surface passivation and the hydrogen evolution reaction. To illustrate the practical relevance of our findings, we study aqueous Zn||NiOOH and Zn||air batteries and observe that zwitterionic polymer interphases produce extended life at high currents and high areal capacity.

A prospect of cost-effective handling and transportation of graphene oxides: folding and redispersion of graphene oxide microsheets.

Controlling the assembly of 2D materials such as graphene oxides (GO) has a significant impact on their properties and performance. One of the critical issues on the processing and handling of GO is that they need to be in dilution solution (0.5 to 2.5 wt%) to maintain their high degree of exfoliation and dispersion. As a result, the shipment of GO in large quantity involves a huge volume of solvent (water) and thus the transportation costs for large sales volume would become extremely high. Through cross-sectional scanning electron microscopy and polarized optical microscopy together with x-ray diffraction and small-angle x-ray scattering studies, we demonstrated that the assembly and structure of GO microsheets can be preserved without restacking, when assembled GO via water-based wet spinning are re-dispersed into solution. A couple of alkyl ammonium bromides, CTAB and TBAB, as well as NaOH, were examined as coagulants and the resulting fibers were redispersed in an aqueous solution. The redispersed solution of fibers that were wet-spun into the commonly used CTAB and TBAB coagulation baths, maintained their physico-chemical properties (similar to the original GO dispersion) however, did not reveal preservation of liquid crystallinity. Meanwhile, the redispersed fibers that were initially spun into NaOH coagulation bath were able to maintain their liquid crystallinity if the lateral size of the GO sheets was large. Based on these findings, a cost-effective solid handling approach is devised which involves (i) processing GO microsheets in solution into folded layers in solid-state, (ii) transporting assembled GO to the customers, and (iii) redispersion of folded GO into a solution for their use. The proposed solid handling of GO followed by redispersion into solution can greatly reduce the transportation costs of graphene oxide materials by reducing the transportation volume by more than 90%.

Three-dimensional line edge roughness in pre- and post-dry etch line and space patterns of block copolymer lithography.

In this work, we employ large-scale coarse-grained molecular dynamics (CGMD) simulations to study the three-dimensional line edge roughness associated with line and space patterns of chemo-epitaxially directed symmetric block copolymers (BCPs) on a flat substrate. The di-block copolymer chain length and interaction parameters are validated with the experimental BCP period, L0 and corresponding molecular weight. Defect-free lamellae are formed, after which the system is quenched below the glass transition temperature before selectively dry-etching off one of the BCP phases. The effect of varying etch-selectivity on post-etch resist domain morphology was studied. The roughness of the polymer domain was evaluated over three process stages: annealing, pre-etching, and post-etching. Power spectral density plots were then generated to elucidate the contributions of low and high frequency roughness for the three process stages. The roughness results obtained from simulations are shown to be in close agreement with the roughness result obtained from analyzing experimental SEM images. Parameters like the Hurtz roughness exponent and correlation length inherent to the process and the BCP were also revealed from the experimental study.

Control of formation of viscoelastic droplets and distribution of nano-inclusions in functional deposition for lithium-sulfur batteries.

The electrospray process produces micro/nanodroplets for various applications such as thin and uniform coatings, drug carriers and mass spectrometry. In this paper, we study the spray processes of viscoelastic jets using simulations and experiments. In discretized modeling, the jet is perturbed with axisymmetric instability and the growth of this instability causes the jet to break into droplets. For the experiments, a solution of polyvinyl alcohol in water is sprayed and is visualized using a high-speed camera. The droplet size distribution is studied from simulations with experiments for three spray cases: electrospray, air spray, and air-controlled electrospray. Our simulations and experiments reveal that the electric field is effective in reducing the droplet size, while air flow offers more jet break-ups and thus a larger number of droplets. As a result, air-controlled electrospray where these two driving forces are synergistically combined leads to a larger number of smaller droplets than electrospray or air spray. Finally, we applied three spray processes to obtain a deposition of sulfur/mesoporous carbon/graphene/polymer binder composites as a lithium sulfur battery cathode and demonstrated that air-controlled electrospray leads to a higher capacity and rate capability than other processes, exhibiting 800 mA h g-1 at 0.5C and 600 mA h g-1 at 2C.

Simultaneous uniaxial extensional deformation and cylindrical confinement of block copolymers using non-equilibrium molecular dynamics.

Using coarse-grained nonequilibrium molecular dynamics, symmetric block copolymers are simulated under the combined effects of cylindrical confinement and uniaxial extensional deformation. For a given confinement diameter, a block copolymer (BCP) will self-assemble into a fixed number of concentric cylinder lamellae at equilibrium. The changing diameter during uniaxial extensional deformation therefore is expected to affect the morphology of the BCPs. The aim of this study is to investigate the interplay of deformation and confinement on BCP morphology by varying the simulation strain rate and diameter. Two different simulation approaches are conducted: constant time simulations with varying initial diameter and constant strain simulations with varying simulation time. A comparison of self-assembly at different strain rates shows that for low strain rates, near-equilibrium morphology can form despite the deformation, while for progressively higher strain rates, extra lamellae and disordered morphologies appear. By defining a Weissenberg number based on the deformation and polymer self-assembly time-scales, the morphologies at different strain rates and diameters are explained. Using the time scale analysis, ordered morphologies appear for Wi < 1, while extra lamellae and disordered morphologies occur at Wi > 1. For the latter case, the cylinder diameter shrinks too quickly for polymers to form the equilibrium morphology, which results in a mixture of lamellar structures along the cylinder length.

Designing an ordered template of cylindrical arrays based on a simple flat plate confinement of block copolymers: a coarse-grained molecular dynamics study.

In this paper we study the morphology formed by asymmetric di-block copolymers (di-BCPs) under various confinements using a large-scale coarse-grained molecular dynamics (CGMD) framework. We start with a simple flat plate confinement with the bottom and the top substrate attractive to the minor phase. Studies at a lower confinement length of 17σ have shown that there exists a critical chain length above which a transition from a three-domain morphology to a two-domain morphology is observed. Increasing the confinement length to 42σ, where the chains experience considerably lower confinement effects, also revealed the existence of a critical chain length - a transition from a multi-domain morphology (>3) to a three-domain morphology. The results obtained from the flat plate study with two confinement dimensions were used to design a topography of silica pillars with and without a bottom substrate to form ordered cylindrical BCP arrays. The least and highest radial separation lengths between adjacent pillars are kept at 17σ and 42σ, respectively. A direct correlation was observed in the number of continuous micro-domains of the maximum and minimum confinement dimensions with the 17σ and 42σ flat plate trials. With the optimum chain length employed, the surfaces with affinity to the minor phase can direct the BCP self-assembly to form ordered arrays of minor phase cylinders. The current study thus elucidates a useful tool to predict the morphology formed in an intricate nano-lithographic template by using simple length scale arguments derived from a flat plate confinement study.

Controlling the Placement of Spherical Nanoparticles in Electrically Driven Polymer Jets and its Application to Li-Ion Battery Anodes.

Employing circumferentially uniform air flow through the sheath layer of the concentric coaxial nozzle, the gas-assisted electrospinning (GAES) utilizes both high electric field and controlled air flow to produce nanofibers. The ability to tailor the distribution of various nanofillers (1.85-12.92 vol% of spherical SiO2 and Si nanoparticles) in a polyvinyl alcohol jet is demonstrated by varying airflow rates in GAES. The distribution of nanofillers is measured from transmission electron microscopy and is analyzed using an image processing technique to perform the dispersion area analysis and obtain the most probable separation between nanoparticles using fast Fourier transform (FFT). The analysis in this study indicates an additional 350% improvement in dispersion area with the application of high but controlled airflow, and a 75 percent decrease in separation between nanoparticles from the FFT. The experiments in this study are in good agreement with a coarse-grained MD simulation prediction for a polymer nanocomposite system subjected to extensional deformation. Lastly, utilizing the sheath layer air flow in production of Li-battery anode material, a 680 mAh g-1 improvement is observed in capacity for nanofibers spun via GAES compared to ES at the same Si NP loading, which is associated with better dispersion of the electrochemically active nanoparticles.

Enhanced Dispersion and Stability of Petroleum Coke Water Slurries via Triblock Copolymer and Xanthan Gum: Rheological and Adsorption Studies.

The rheology of petroleum coke (petcoke) water slurries was investigated with a variety of nonionic and anionic dispersants including poly(ethylene oxide) (PEO)-b-poly(propylene oxide) (PPO)-b-PEO triblock copolymers (trade name: Pluronic, BASF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), poly(ethylene oxide) (PEO), poly(carboxylate acid) (PCA), sodium lignosulfonate (SLS), and poly(acrylic acid) (PAA). Each effective dispersant system shared very similar rheological behavior to the others when examined at the same volume fraction from its maximum petcoke loading. Triblock copolymer, Pluronic F127 (F127), was found to be the best dispersant by comparing the maximum petcoke loading for each dispersant. The yield stress was measured as a function of petcoke loading and dispersant concentration for F127, and a minimum dispersant concentration was observed. An adsorption isotherm and atomic force microscopy (AFM) images reveal that this effective dispersion of petcoke particles by F127 is due to the formation of a uniform monolayer of brushes where hydrophobic PPO domains of F127 adhere to the petcoke surface, while hydrophilic PEO tails fill the gap between petcoke particles. F127 was then compared to other Pluronics with various PEO and PPO chain lengths, and the effects of surface and dispersant hydrophilicity were examined. Finally, xanthan gum (XG) was tested as a stabilizer in combination with F127 for potential industrial application, and F127 appears to break the XG aggregates into smaller aggregates through competitive adsorption, leading to an excellent degree of dispersion but the reduced stability of petcoke slurries.

Tailoring nanorod alignment in a polymer matrix by elongational flow under confinement: simulation, experiments, and surface enhanced Raman scattering application.

Mesoscale simulation, electrospinning and Raman scattering experiments have been carried out to demonstrate that examination and control of nanorod configuration in a polymer matrix under elongational flow and confinement can lead to enhanced sensing. First, coarse-grained molecular dynamics (CGMD) was employed to probe the diffusivity, orientation, and dispersion of nanorods in a model polymer melt under planar elongational flow. Compared to shear flow, elongational flow gives rise to enhanced dispersion and orientation of nanorods, which are predicted to be improved with increasing the aspect ratio of nanorods and polymer chain length. As comparative experiments, we have electrospun gold (Au) nanorods with polyvinyl alcohol (PVA), and the resulting Au nanorod configuration in PVA nanofibers is in good agreement with the predicted simulation. Furthermore, coaxial electrospinning of Au nanorod/PVA-PVA (shell-core) was applied to selectively place Au nanorods in the cylindrical sheath layer, and the alignment of Au nanorods near the fiber surface was confirmed by TEM analysis and CGMD simulation under uniaxial elongation. Finally, the Au nanorod-PVA fibers were tested for surface-enhanced Raman spectroscopy for sensing applications. The coaxially electrospun fibers have demonstrated much greater signal peak strength when compared with monoaxially electrospun fibers with the same Au nanorod loading. This comprehensive study demonstrates how extensional flow and multi-layered fluids can direct the orientation and dispersion of nanorod in a polymer matrix, leading to enhanced sensing performance.

Formation of interconnected morphologies via nanorod inclusion in the confined assembly of symmetric block copolymers.

We have investigated the effect of nanorods on the symmetry breaking of a model diblock copolymer under cylindrical confinement using coarse-grained molecular dynamics. Unlike nanoparticles, nanorods can readily be interconnected with each other and also induce connection across self-assembly domains at much lower loading than nanoparticles. Such interconnecting nanorods, when incorporated within the nanofiber confined assembled block copolymer, have great potential for providing highly conductive pathways for energy applications, such as battery electrodes and separators. Symmetric block copolymers (BCP) under cylindrical confinement with a nanorod aspect ratio (N) of 1, 5, and 10 are examined with three different types of nanorod-BCP attractions: (a) neutral nanorods, (b) A (wall-attractive phase)-attractive nanorods, and (c) B (wall-repulsive phase)-attractive nanorods. The system was studied with both selective and neutral walls, which affect the orientation of the interconnected nanorod network. Upon close examination of the BCP-nanorod self-assembly, we discovered that the ratio of the interphase distance to the nanorod aspect ratio (I/N) can be correlated to the onset of nanorod interconnectivity and formation of asymmetrical interconnected BCP morphology. By developing a phase diagram with respect to I/N, one can predict the formation of desired BCP morphology and the critical loading of nanorods for connected morphologies in cylindrical confinement.

Controlling the dispersion and orientation of nanorods in polymer melt under shear: coarse-grained molecular dynamics simulation study.

Incorporation of nanorods (NRs) into a polymer matrix can greatly enhance the material properties, but the aggregation of NRs prevents the full realization of their potential. Using coarse-grained molecular dynamics simulation with the dissipative particle dynamics thermostat, we have systematically examined how key material and processing parameters, such as aspect ratio, particle diameter, rigidity and concentration of NR, polymer chain length, and shear rate can influence the placement and orientation of the self-aggregating NRs in a model polymer melt under shear. When compared with nanoparticles (NPs), the NRs tend to aggregate more severely even under strong shear flow. To improve the dispersion of NRs within the polymer matrix under a given flow condition, we incorporated additional NPs with selective interactions into polymer/NR composites, demonstrating that the current mesoscale simulation study offers insights on how to control the dispersion and orientation of NRs in polymer under shear flow.

Facile Adaptation of a Fused Deposition Modeling 3D Printer to Motionless Printing through Programmable Electric Relay: Discretized Modeling and Experiments.

In this study, a fused deposition modeling 3D printer is modified into a motionless printer, which has the potential to print patterns in a noiseless manner possibly with improved resolution and in less delay time by eliminating the movement of nozzle or collector. In this motionless 3D printer, both nozzle and collector are fixed, whereas the extruded polymer melt is driven by high-voltage switching points on the collector. By this approach, simple 3D patterns such as multilayer circles, squares, and walls have been printed using two polymer melts with different rheological properties, high-temperature polylactic acid and acrylonitrile butadiene styrene. Furthermore, a discretized, nonisothermal bead and spring model is developed to probe printing patterns. The effect of parameters, such as number of conducting points, switching time, voltage and material properties on the accuracy of the printed simple 3D patterns, are thoroughly studied, and we demonstrated that various fiber collection patterns obtained from the experiments are favorably compared with the simulation results.

Analysis of the Structure, Thermal, and Molecular Dynamics of Organic-Inorganic Hybrid Crystal at Phases IV, III, II, and I: [NH2(CH3)2]2CdBr4.

A comprehensive understanding of the physicochemical properties of organic-inorganic hybrids is essential for their solid-state lighting applications. Therefore, a single crystal of [NH2(CH3)2]2CdBr4 was grown; the crystal structure was monoclinic, and the phase transition temperatures for the four phases IV, III, II, and I were 383 K (TC1), 417 K (TC2), and 427 K (TC3). Furthermore, the chemical shifts caused by the local field around 1H, 13C, 14N, and 113Cd changed continuously with temperature, especially near TC1, indicating that the local environment changes with temperature. Owing to the large change in 113Cd chemical shifts, the coordination geometry of Br around Cd in the CdBr4 tetrahedra changes near TC1. Therefore, it is proposed that Br plays a significant role in the N-H···Br hydrogen bond. Finally, the spin-lattice relaxation time T1ρ, representing the energy transfer around the 1H and 13C atoms of the cation, changed significantly with temperature. The activation energies obtained from the T1ρ results were two times larger at high temperatures than at low temperatures. This study provides an understanding of the fundamental properties of organic-inorganic hybrid compounds to broaden their applications.

Effects of organoclay on colorless and transparent polyimide nanocomposites: thermomechanical properties, morphology, and optical transparency.

Although aromatic polyimide (PI) exhibits excellent mechanical performance and thermal stability, its dark color limits applicability in optical displays. Therefore, it is desirable to manufacture colorless, transparent PI (CPI) nanocomposite films that retain excellent physical properties. In this study, a solution intercalation method was used to disperse organoclay (Cloisite 25A; CS25A) in poly(amic acid), which was prepared using 4,4'-oxydiphthalic dianhydride and 3,4'-oxydianiline as monomers. This dispersion was then subjected to thermal imidization to synthesize CPI hybrid films. The influence of the CS25A content (0-1.00 wt%) on the thermomechanical properties, optical transmittance, and morphology of the prepared films was investigated. The hybrid film with a CS25A content of 0.50 wt% exhibited the best thermomechanical properties. However, upon further increasing the organoclay content to 1.00 wt%, the physical properties deteriorated. At 0.50 wt% CS25A, some agglomeration occurred but most of the clay was well dispersed as nano-sized particles, as revealed by transmission electron microscopy. In contrast, when the CS25A content exceeded a critical content, most of the clay was agglomerated and the physical properties were reduced. All the obtained CPI hybrid films were colorless and transparent, regardless of the organoclay content.

Lithium Iron Phosphate Enhances the Performance of High-Areal-Capacity Sulfur Composite Cathodes.

Lithium iron phosphate (LiFePO4, "LFP") was investigated as an additive in the cathode of lithium-sulfur (Li-S) batteries. LFP addition boosted the sulfur utilization during Li-S cycling, achieving an initial capacity of 1465 mAh/gS and a long cycle life (>300 cycles). Polysulfide adsorption experiments showed that LFP attracted polysulfides, and thus, the presence of LFP should alleviate the shuttle effect, a common failure mode. Postmortem characterization found iron phosphides, iron phosphates, and LiF in the electrode, indicating that LFP underwent dynamic reconstruction during Li-S cycling. We suspect that the formation of these species played a role in the observed performance. From the processing standpoint, adding LFP improved slurry rheology, making the preparation of a high-loading electrode more consistent. Benefiting from the high sulfur utilization and the ability to prepare electrodes with high mass loading, the S-LFP hybrid cell showed an excellent areal capacity of 2.65 mAh/cm2 and could be stably cycled at 2 mAh/cm2 for 250 cycles. Our results demonstrated the LFP addition as a promising strategy for realizing Li-S batteries with high sulfur loading and areal capacity.

Metal nanofibers with highly tunable electrical and magnetic properties via highly loaded water-based electrospinning.

Nanofibers are synthesized by electrospinning highly loaded water-based precursor-polymer hybrid solutions followed by thermal treatment to control crystal structure. Electrical conductivity and magnetic coercivity, as shown, are tested displaying independent magnetic and electrical property control from coercive to superparamagnetic and resistive to near-bulk conductivity at room temperature.

Preparation and characterization of amphiphilic triblock terpolymer-based nanofibers as antifouling biomaterials.

Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers.