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At least 145 records · Page 8

Thixotropy, antithixotropy, and viscoelasticity in hysteresis

Thixotropy, antithixotropy, and viscoelasticity are three types of time-dependent dynamics that involve fundamentally different underlying physical processes. Here, we show that the three dynamics exhibit different signatures in hysteresis by examining the fingerprints of the simplest thixotropic kinetic model, a new antithixotropic model that we introduce here, and the Giesekus model. We start by showing that a consistent protocol to generate hysteresis loops is a discrete shear-rate controlled ramp that begins and ends at high shear rates, rather than at low shear rates. Using this protocol, we identify two distinguishing features in the resulting stress versus shear rate loops. The first is the direction of the hysteresis loops: clockwise for thixotropy, but counterclockwise for viscoelasticity and antithixotropy. A second feature is achieved at high ramping rates where all responses lose hysteresis: the viscoelastic response shows a stress plateau at low shear rates due to lack of stress relaxation, whereas the thixotropic and antithixotropic responses are purely viscous with minimal shear thinning or thickening. We establish further evidence for these signatures by experimentally measuring the hysteresis of Laponite suspensions, carbon black suspensions, and poly(ethylene oxide) solutions, each representing a historically accepted example of each class of material behavior. The signatures measured in experiments are consistent with those predicted by the three models. This study reveals different fingerprints in hysteresis loops associated with thixotropy, antithixotropy, and viscoelasticity, which may be helpful in distinguishing the three time-dependent responses.

Mechanics↗

Well-designed Crosslinked Polymer Electrolyte Enables High Ionic Conductivity and Enhanced Salt Solvation

A new facile single-step method to fabricate crosslinked polymer electrolyte membranes consisting of branched poly(ethyleneimine), (PEI) and poly(ethylene oxide), (PEO) is demonstrated. The membranes exhibit excellent ionic conductivity (1.2 × 10 –3 S cm –1 at 80 °C) with minimal addition of plasticizer (20 wt%). The amine functional group in the PEI-PEO crosslinked matrix provides Lewis basic and hydrogen bonding characteristics that facilitate the dissolution of lithium salt and enables a higher cation transport number than a PEO crosslinked matrix. The glass transition temperature, degree of crystallinity, and room temperature storage modulus increases with decreasing crosslink density and increasing ratio of free amines. The resultant ionic conductivity and mechanical strength can be flexibly tailored by varying the molar ratio of free amine moieties in the crosslinked PEI-PEO matrix. This study provides an improved synthesis method, in-depth characterization, and fundamental insights on the effect of free amine moieties on the transport properties of a highly conductive gel polymer electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuum Description of the Role of Negative Transference Numbers on Ion Motion in Polymer Electrolytes

New experimental techniques such as electrophoretic NMR (eNMR) are emerging as powerful methods for directly measuring ion velocities in electrolytes under applied electric fields. The aim of this theoretical study is to predict the spatial- and temporal-dependence of these velocities of ions as a function of the magnitude of the applied field and salt concentration. It has recently been shown that mixtures of poly(ethylene oxide)-based (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) electrolytes exhibit negative cation transference numbers in a certain salt concentration range. In this range, the cation motion at early times is directed to the positive electrode at all locations in the cell; ion migration dominates in this regime. As time progresses, the cation velocity in finite zones near both the electrodes changes sign. These zones grow rapidly with time, reflecting the increasing importance of diffusion, and a point in time is reached beyond which the cation velocity in the entire cell is directed toward the negative electrode. Overall, our work reveals the limited time window over which the results of eNMR can be used to determine the transference number. More importantly, it shows how to account for the effect of diffusional flux in such experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Status and Targets for Polymer-Based Solid-State Batteries for Electric Vehicle Applications

There is growing interest in the development of Li-metal-based solid state batteries, driven by their promise in improving the energy density to satisfy electric vehicle requirements. In this work, we examine the status of Solid polymer electrolytes (SPEs) based solid state batteries for electric vehicle applications using a continuum scale mathematical model. We examine LiFePO4(LFP) cathode/lithium metal anode batteries containing three different electrolytes, namely (1) a liquid electrolyte, (2) the polystyrene-b-poly(ethylene oxide) (SEO) block copolymer electrolyte, and (3) a single-ion conducting (SIC) block copolymer electrolyte, with the liquid electrolyte serving as the baseline for the comparison. By using an optimization procedure, we assemble "virtual" batteries to identify the optimal design that maximizes energy density while allowing the power requirements of electric vehicles (EVs) to be satisfied. Results show the present status of different SPEs are still below what is considered acceptable and further improvements are needed to achieve electric vehicle targets. The optimization studies conducted here show that for low transference number electrolytes (similar to 0.2) the conductivity target is 5 x 10(-3)S cm(-1), while for a unity transference number electrolyte this target decreases to 4 x 10(-4)S cm(-1). These targets provide guidance for polymer synthesis researchers to develop better polymers for use in EVs.

25 ENERGY STORAGE↗

Effects of Plasticizer Content and Ceramic Addition on Electrochemical Properties of Cross-Linked Polymer Electrolyte

The development of a safe electrolyte is the key to improving energy density for next generation lithium batteries. In this work, UV-crosslinked poly(ethylene oxide) (PEO) -based polymer and composite electrolytes are systematically investigated on their ionic conductivity, mechanical and electrochemical properties. The polymer electrolytes are plasticized with non-flammable linear short-chain PEO. In the composite electrolytes, a doped lithium aluminum titanium phosphate (LATP) ceramic, LICGC™, is used as the ceramic filler. It is found that the addition of the plasticizer leads to a tradeoff between ion transport and mechanical properties. In contrast, the addition of ceramic fillers improves both the ionic conductivity and mechanical properties. The sample with 20 wt% of LICGC™ shows a conductivity of ~0.6 mS cm –1 at 50 °C. This sample also demonstrates much longer cycle life than the neat polymer electrolyte in Li platting/stripping test with a capacity of 1 mAh cm –2 . Further, a full cell made with this composite electrolyte against Li metal anode and high voltage LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode shows 94% capacity retention after 30 cycles, compared to 58% capacity retention with the neat polymer electrolyte. These results demonstrate that a hybrid of polymer/ceramic/non-flammable plasticizer is a promising path to high energy density, high voltage lithium batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining CO 2 as an Additive for Solid Electrolyte Interphase Formation on Silicon Anodes

In this study, we demonstrate that the addition of CO 2 to a standard 1.0 M LiPF 6 3:7 wt% ethylene carbonate:ethyl methyl carbonate electrolyte results in the formation of a thinner insoluble solid electrolyte interphase (SEI) that is dominated by the presence of LiF. In contrast, cells without CO 2 result in a thicker insoluble SEI layer containing more organic constituents. The CO 2 is incorporated in the dimethyl carbonate soluble part of the SEI composed primarily of polymeric poly(ethylene oxide) (PEO) on the surface of a thin inorganic layer. This combination of properties from CO 2 addition provides an improved cycling performance through the reduction of irreversible side reactions, leading to higher coulombic efficiency. The results indicate that CO 2 incorporates into the SEI and plays a role similar to additives like fluorinated ethylene carbonate and vinylene carbonate with respect to polymeric components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Solvent Motion on Ion Transport in Electrolytes

We use concentrated solution theory to derive an equation governing solvent velocity in a binary electrolyte when a current passes through it. This equation, in combination with the material balance equation, enables the prediction of electrolyte concentration profiles and species velocities as a function of space and time. This framework is used to predict ion velocities in Li-Li symmetric cells containing a mixture of lithium bis(trifluoromethanesulfonyl)imide and poly(ethylene oxide) (LiTFSI/PEO), for which the cation transference number relative to the solvent velocity, ${t}_{+}^{0},$ can be either positive or negative, depending on salt concentration. Accounting for the solvent motion is increasingly important at higher concentrations. Especially for negative ${t}_{+}^{0},$ if solvent velocity is set to zero, the cation velocity, based on the electrode-electrolyte interface reference frame, is pointed opposite to the current flow. However, when solvent motion is taken into account, the cation velocity, based on the same reference frame, is in the same direction as the current. This analysis demonstrates the importance of accounting for solvent velocity rigorously in seemingly simple systems such as symmetric cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparing Experimentally-Measured Sand’s Times with Concentrated Solution Theory Predictions in a Polymer Electrolyte

We compare the electrochemically measured Sand’s time, the time required for the cell potential to diverge when the applied current density exceeds the limiting current, with theoretical predictions for a 0.47 M poly(ethylene oxide) (5 kg mol −1 )/LiTFSI electrolyte. The theoretical predictions are made using concentrated solution theory which accounts for both concentration polarization and polymer motion, using independently measured parameters that depend on concentration, c : conductivity ( κ ), salt diffusion coefficient ( D ), cationic transference number with respect to the solvent velocity ( t + 0 ), thermodynamic factor 1 + dln f ± dln c , and partial molar volume of the salt ( V ̅ ); f ± is the mean molar activity coefficient of the salt. We find quantitative agreement between experimental data and theoretical predictions. We derive a generalized analytical expression for Sand’s time for electrolytes based on dilute solution theory. This expression correctly predicts the divergence of the Sand’s time at the limiting current, in agreement with experimental data and concentrated solution theory predictions. When the applied current is large compared to the limiting current, the analytical expression approaches the standard expression for Sand’s time used in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Transport in Concentrated Crosslinked Solid Polymer Electrolytes

Crosslinking polymers is a common approach to create mechanically stable solid materials such as polymer electrolytes for lithium batteries. In conventional liquid electrolytes, the solvent molecules move freely to accommodate the field-induced motion of ions. However, in crosslinked polymer electrolytes, the rearrangement of polymer segments is constrained by the deformation limits of the network. Herein, we develop a new transport model that accounts for both the formation of concentration gradients and the elasticity of the electrolyte. The elasticity is incorporated by adding an additional term related to the entropy of crosslinked strands to the electrochemical potential of the salt. The resulting Crosslink Model contains two adjustable parameters: $\mathcal{N}$, the average number of monomers in a strand, and λ crit , the maximum strain the network can sustain. These solid-like constraints produce singularities in the governing transport equations, fundamentally altering the concentration profiles. Plateaus in salt concentrations emerge near the electrodes, and network elasticity introduces a strain overpotential. When compared to a Baseline Model ($\mathcal{N}$ → ∞, equivalent to concentrated solution theory), which predicts steepest gradients near the electrodes, both models yield similar current–voltage relationships. Model predictions are compared to electrochemical data for a poly(ethylene oxide)-based crosslinked polymer electrolyte.

Patel, Vivaan [University of California, Berkeley,↗

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗

Study of the Segmental Dynamics and Ion Transport of Solid Polymer Electrolytes in the Semi-crystalline State

Solid polymer electrolytes are promising in fulfilling the requirements for a stable lithium metal anode toward higher energy and power densities. In this work, we investigate the segmental dynamics, ionic conductivity, and crystallinity of a polymer electrolyte consisting of poly(ethylene oxide) (PEO) and lithium triflate salt, in the semi-crystalline state. Using quasi-elastic neutron scattering, the segmental dynamics of PEO chains confined between the crystalline lamellae is quantified, using Cole–Cole analysis. We show that the structural relaxation time, τ 0 , of PEO equilibrated near room temperature is six-fold longer than the same sample that had just cooled down to room temperature. This corresponds to a three-fold smaller ionic conductivity in the equilibrated condition. This work reveals that the segmental dynamics of semi-crystalline polymer electrolytes is very sensitive to thermal history. We demonstrate that quasi-elastic neutron scattering can be used to characterize the ion transport and segmental dynamics in the semi-crystalline state.

36 MATERIALS SCIENCE↗

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes

Ion conducting capability is often imparted to polymeric materials through short polyether side-chains, and yet the impact of this graft polymer architecture on ion solvation and conduction has not been fully explored. Here, we use a combination of impedance spectroscopy, vibrational spectroscopy, and atomistic molecular dynamics (MD) to compare the conductivity, ionic interactions, and polymer dynamics in a series of graft polyether electrolytes. We find that in poly[(oligo ethylene oxide)methyl ether methacrylate] (POEM), a widely used graft polymer electrolyte, the ionic conductivity drops more than an order of magnitude as the side-chain length is decreased from nine ethylene oxide (EO) units to three. This difference in conductivity is unexplained by differences in the calorimetric glass transition temperature (T g ), which varies only slightly with side-chain length. Furthermore, through vibrational spectroscopy and MD simulations we demonstrate that both linear and graft polyethers solvate Li⁺ ions effectively and dissociate them from large counterions, irrespective of side-chain length. Li⁺ ions do, however, show preferential solvation by EO units far from the methacrylate backbone. Similarly, EO units far from the backbone show enhanced segmental dynamics, while those near the immobile methacrylate group move substantially more slowly, as quantified by bond vector autocorrelation relaxation times. This heterogeneity in both ion solvation and local segmental relaxation explains variation in ion conductivity where material-averaged properties such as T g and number of free ions fail to do so. Importantly, the ionic conductivity is dictated primarily by the segmental mobility of the EO units which form effective solvation sites, rather than system-wide dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Not Cutting Corners: Bioderived Triggers Driving Oxidative Main Chain Scission of Poly(ethylene terephthalate)

About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. Furthermore, this model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbonic Anhydrase Enhanced UV-Crosslinked PEG-DA/PEO Extruded Hydrogel Flexible Filaments and Durable Grids for CO 2 Capture

In this study, poly (ethylene glycol) diacrylate/poly (ethylene oxide) (PEG-DA/PEO) interpenetrating polymer network hydrogels (IPNH) were extruded into 1D filaments and 2D grids. The suitability of this system for enzyme immobilization and CO 2 capture application was validated. IPNH chemical composition was verified spectroscopically using FTIR. The extruded filament had an average tensile strength of 6.5 MPa and elongation at break of 80%. IPNH filament can be twisted and bent and therefore is suitable for further processing using conventional textile fabrication methods. Initial activity recovery of the entrapped carbonic anhydrase (CA) calculated from esterase activity, showed a decrease with an increase in enzyme dose, while activity retention of high enzyme dose samples was over 87% after 150 days of repeated washing and testing. IPNH 2D grids that were assembled into spiral roll structured packings exhibited increased CO 2 capture efficiency with increasing enzyme dose. Long-term CO 2 capture performance of the CA immobilized IPNH structured packing was tested in a continuous solvent recirculation experiment for 1032 h, where 52% of the initial CO 2 capture performance and 34% of the enzyme contribution were retained. These results demonstrate the feasibility of using rapid UV-crosslinking to form enzyme-immobilized hydrogels by a geometrically-controllable extrusion process that uses analogous linear polymers for both viscosity enhancement and chain entanglement purposes, and achieves high activity retention and performance stability of the immobilized CA. Potential uses for this system extend to 3D printing inks and enzyme immobilization matrices for such diverse applications as biocatalytic reactors and biosensor fabrication.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microfluidic synthesis of multilayered lipid–polymer hybrid nanoparticles for the formulation of low solubility drugs

Hybrid phospholipid/block copolymer membranes where polymers and lipids are molecularly mixed or phase-separated into polymer-rich and lipid-rich domains are promising drug delivery materials. Harnessing the chemical diversity of polymers and the biocompatability of lipids is a compelling approach to design the next generation of drug carriers. Here, we report on the development of a microfluidics-based strategy analogous to produce lipid nanoparticles (LNPs) for the nanomanufacturing of multilayered hybrid nanoparticles (HNPs). In conclusion, using X-ray scattering, Cryo-electron, and polarized microscopy we show that phosphatidylcholine (PC) and PBD-b-PEO (poly(butadiene-block-ethylene oxide)) hybrid membranes can be nanomanufactured by microfluidics into HNPs with dense and multilayered cores which are ideal carriers of low-solubility drugs of the Biopharmaceutical Classification System (BCS) II and IV such as antimalarial DSM265 and Paclitaxel, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗