Helical peptide structure improves conductivity and stability of solid electrolytes.

Ion transport is essential to energy storage, cellular signalling and desalination. Polymers have been explored for decades as solid-state electrolytes by either adding salt to polar polymers or tethering ions to the backbone to create less flammable and more robust systems. New design paradigms are needed to advance the performance of solid polymer electrolytes beyond conventional systems.

Ionic Peltier effect in Li-ion electrolytes.

The coupled transport of charge and heat provide fundamental insights into the microscopic thermodynamics and kinetics of materials. We describe a sensitive ac differential resistance bridge that enables measurements of the temperature difference on two sides of a coin cell with a resolution of better than 10 μK. We use this temperature difference metrology to determine the ionic Peltier coefficients of symmetric Li-ion electrochemical cells as a function of Li salt concentration, solvent composition, electrode material, and temperature.

Highly Ordered Eutectic Mesostructures via Template-Directed Solidification within Thermally Engineered Templates.

Template-directed self-assembly of solidifying eutectics results in emergence of unique microstructures due to diffusion constraints and thermal gradients imposed by the template. Here, the importance of selecting the template material based on its conductivity to control heat transfer between the template and the solidifying eutectic, and thus the thermal gradients near the solidification front, is demonstrated. Simulations elucidate the relationship between the thermal properties of the eutectic and template and the resultant microstructure.

A Self-Healing System for Polydicyclopentadiene Thermosets.

Self-healing offers promise for addressing structural failures, increasing lifespan, and improving durability in polymeric materials. Implementing self-healing in thermoset polymers faces significant manufacturing challenges, especially due to the elevated temperature requirements of thermoset processing. To introduce self-healing into structural thermosets, the self-healing system must be thermally stable and compatible with the thermoset chemistry.

Enabling High Precision Gradient Index Control in Subsurface Multiphoton Lithography.

Multiphoton lithography inside a mesoporous host can create optical components with continuously tunable refractive indices in three-dimensional (3D) space. However, the process is very sensitive at exposure doses near the photoresist threshold, leading previous work to reliably achieve only a fraction of the available refractive index range for a given material system. Here, we present a method for greatly enhancing the uniformity of the subsurface micro-optics, increasing the reliable index range from 0.

Reversible Reactions, Mesh Size, and Segmental Dynamics Control Penetrant Diffusion in Ethylene Vitrimers.

The diffusion of two aromatic dyes with nearly identical sizes was measured in ethylene vitrimers with precise linker lengths and borate ester cross-links using fluorescence recovery after photobleaching (FRAP). One dye possessed a reactive hydroxyl group, while the second was inert. The reaction of the hydroxyl group with the network is slow relative to the hopping times of the dye, resulting in a large slowdown by a factor of 50 for a reactive probe molecule.

Hybrid achromatic microlenses with high numerical apertures and focusing efficiencies across the visible.

Compact visible wavelength achromats are essential for miniaturized and lightweight optics. However, fabrication of such achromats has proved to be exceptionally challenging. Here, using subsurface 3D printing inside mesoporous hosts we densely integrate aligned refractive and diffractive elements, forming thin high performance hybrid achromatic imaging micro-optics.

Electrically switchable metallic polymer metasurface device with gel polymer electrolyte.

We present an electrically switchable, compact metasurface device based on the metallic polymer PEDOT:PSS in combination with a gel polymer electrolyte. Applying square-wave voltages, we can reversibly switch the PEDOT:PSS from dielectric to metallic. Using this concept, we demonstrate a compact, standalone, and CMOS compatible metadevice.

Visualizing ion transport in polymers via ion-chromic indicators.

There is growing interest in polymers with high ionic conductivity for applications including batteries, fuel cells, and separation membranes. However, measuring ion diffusion in polymers can be challenging, requiring complex procedures and instrumentation. Here, a simple strategy to study ion diffusion in polymers is presented that utilizes ion-chromic spiropyan as an indicator to measure the diffusion of LiTFSI, KTFSI, and NaTFSI within poly(ethylene oxide)-based polymer networks.

Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes.

Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics.

Designing Multicomponent Polymer Colloids for Self-Stratifying Films.

Aqueous polymer colloids known as latexes are widely used in coating applications. Multicomponent latexes comprised of two incompatible polymeric species organized into a core-shell particle morphology are a promising system for self-stratifying coatings that spontaneously partition into multiple layers, thereby yielding complex structured coatings requiring only a single application step. Developing new materials for self-stratifying coatings requires a clear understanding of the thermodynamic and kinetic properties governing phase separation and polymeric species transport.

Static and Dynamic Gradient Based Directional Transportation of Neutral Molecules in Swollen Polymer Films.

Materials which selectively transport molecules offer powerful opportunities for concentrating and separating chemical agents. Here, utilizing static and dynamic chemical gradients, transport of molecules within swollen crosslinked polymers is demonstrated. Using an ≈200 μm static hydroxyl to hexyl gradient, the neutral ambipolar nerve agent surrogate diethyl (cyanomethyl)phosphonate (DECP) is directionally transported and concentrated 60-fold within 4 hours.

A Lipid-Inspired Highly Adhesive Interface for Durable Superhydrophobicity in Wet Environments and Stable Jumping Droplet Condensation.

Creating thin (<100 nm) hydrophobic coatings that are durable in wet conditions remains challenging. Although the dropwise condensation of steam on thin hydrophobic coatings can enhance condensation heat transfer by 1000%, these coatings easily delaminate. Designing interfaces with high adhesion while maintaining a nanoscale coating thickness is key to overcoming this challenge.

Biomimetic and Biologically Compliant Soft Architectures via 3D and 4D Assembly Methods: A Perspective.

Recent progress in soft material chemistry and enabling methods of 3D and 4D fabrication-emerging programmable material designs and associated assembly methods for the construction of complex functional structures-is highlighted. The underlying advances in this science allow the creation of soft material architectures with properties and shapes that programmably vary with time. The ability to control composition from the molecular to the macroscale is highlighted-most notably through examples that focus on biomimetic and biologically compliant soft materials.

A Lamellar Yolk-Shell Lithium-Sulfur Battery Cathode Displaying Ultralong Cycling Life, High Rate Performance, and Temperature Tolerance.

The shuttling behavior and slow conversion kinetics of the intermediate lithium polysulfides are the severe obstacles for the application of lithium-sulfur (Li-S) batteries over a wide temperature range. Here, an engineered lamellar yolk-shell structure of In O @void@carbon for the Li-S battery cathode is developed for the first time to construct a powerful barrier that effectively inhibits the shuttling of polysulfides. On the basis of the unique nanochannel-containing morphology, the continuous kinetic transformation of sulfur and polysulfides is confined in a stable framework, which is demonstrated by using X-ray nanotomography.

A Nearly Packaging-Free Design Paradigm for Light, Powerful, and Energy-Dense Primary Microbatteries.

Billions of internet connected devices used for medicine, wearables, and robotics require microbattery power sources, but the conflicting scaling laws between electronics and energy storage have led to inadequate power sources that severely limit the performance of these physically small devices. Reported here is a new design paradigm for primary microbatteries that drastically improves energy and power density by eliminating the vast majority of the packaging and through the use of high-energy-density anode and cathode materials. These light (50-80 mg) and small (20-40 µL) microbatteries are enabled though the electroplating of 130 µm-thick 94% dense additive-free and crystallographically oriented LiCoO onto thin metal foils, which also act as the encapsulation layer.

Linear and nonlinear viscoelasticity of concentrated thermoresponsive microgel suspensions.

We present an integrated experimental and theoretical study of the dynamics and rheology of self-crosslinked, slightly charged, temperature responsive soft poly(N-isopropylacrylamide) (pNIPAM) microgels over a wide range of concentration and temperature spanning the sharp change in particle size and intermolecular interactions across the lower critical solution temperature (LCST). Dramatic, non-monotonic changes in viscoelasticity are observed as a function of temperature, with distinct concentration dependence in the dense fluid, glassy, and soft-jammed regimes. Motivated by our experimental observations, we formulate a minimalistic model for the size dependence of a single microgel particle and the change of the interparticle interaction from purely repulsive to attractive upon heating.

Good Solid-State Electrolytes Have Low, Glass-Like Thermal Conductivity.

Thermal management in Li-ion batteries is critical for their safety, reliability, and performance. Understanding the thermal conductivity of the battery materials is crucial for controlling the temperature and temperature distribution in batteries. This work provides systemic quantitative measurements of the thermal conductivity of three important classes of solid electrolytes (SEs) over the temperature range 150 < T < 350 K.

Electrodeposition of atmosphere-sensitive ternary sodium transition metal oxide films for sodium-based electrochemical energy storage.

We introduce an intermediate-temperature (350 °C) dry molten sodium hydroxide-mediated binder-free electrodeposition process to grow the previously electrochemically inaccessible air- and moisture-sensitive layered sodium transition metal oxides, NaMO (M = Co, Mn, Ni, Fe), in both thin and thick film form, compounds which are conventionally synthesized in powder form by solid-state reactions at temperatures ≥700 °C. As a key motivation for this work, several of these oxides are of interest as cathode materials for emerging sodium-ion-based electrochemical energy storage systems. Despite the low synthesis temperature and short reaction times, our electrodeposited oxides retain the key structural and electrochemical performance observed in high-temperature bulk synthesized materials.

Revealing the role of the cathode-electrolyte interface on solid-state batteries.

Interfaces have crucial, but still poorly understood, roles in the performance of secondary solid-state batteries. Here, using crystallographically oriented and highly faceted thick cathodes, we directly assess the impact of cathode crystallography and morphology on the long-term performance of solid-state batteries. The controlled interface crystallography, area and microstructure of these cathodes enables an understanding of interface instabilities unknown (hidden) in conventional thin-film and composite solid-state electrodes.

Measuring Molecular Diffusion Through Thin Polymer Films with Dual-Band Plasmonic Antennas.

A general and quantitative method to characterize molecular transport in polymers with good temporal and high spatial resolution, in complex environments, is an important need of the pharmaceutical, textile, and food and beverage packaging industries, and of general interest to the polymer science community. Here we show how the amplified infrared (IR) absorbance sensitivity provided by plasmonic nanoantenna-based surface enhanced infrared absorption (SEIRA) provides such a method. SEIRA enhances infrared (IR) absorbances primarily within 50 nm of the nanoantennas, enabling localized quantitative detection of even trace quantities of analytes and diffusion measurements in even thin polymer films.

Direct and Divergent Solid-Phase Synthesis of Azobenzene and Spiropyran Derivatives.

Here, we report a solid-phase approach to synthesize azobenzene and spiropyran derivatives. The divergent synthesis process requires no purification steps to obtain the desired product with a 28-55% yield, depending on the specific compound. For the spiropyran compounds, solid-phase resin cleavage is performed under mild conditions to minimize spiropyran ring opening.

Improved synthesis of TiCT MXenes resulting in exceptional electrical conductivity, high synthesis yield, and enhanced capacitance.

For the first time, an "Evaporated-Nitrogen" Minimally Intensive Layer Delamination (EN-MILD) synthesis approach is reported to synthesize exceptionally high quality MXene sheets. In the EN-MILD method, the concentrations of acids and Li-ions are continuously increased during the etching process. By implementing the EN-MILD approach, the electrical conductivity increases up to 2.

MRS Communications.

, Istituto Italiano di Tecnologia, and Università degli Studi di Napoli Federico II, Italy; , Istituto Italiano di Tecnologia, Italy; , Istituto Italiano di Tecnologia, Italy, and Stanford University, USA; , Stanford University, USA; , Forschungszentrum Jülich GmbH, Germany; , , Stanford University, USA; , Istituto Italiano di Tecnologia, Italy.