Control of Two Solid Electrolyte Interphases at the Negative Electrode of an Anode-Free All Solid-State Battery based on Argyrodite Electrolyte.

Anode-free all solid-state batteries (AF-ASSBs) employ "empty" current collector with three active interfaces that determine electrochemical stability; lithium metal - Solid electrolyte (SE) interphase (SEI-1), lithium - current collector interface, and collector - SE interphase (SEI-2). Argyrodite LiPSCl (LPSCl) solid electrolyte (SE) displays SEI-2 containing copper sulfides, formed even at open circuit. Bilayer of 140 nm magnesium/30 nm tungsten (Mg/W-Cu) controls the three interfaces and allows for state-of-the-art electrochemical performance in half-cells and fullcells.

Visible-Light-Fueled Polymerizations for 3D Printing.

ConspectusLight-driven polymerizations and their application in 3D printing have revolutionized manufacturing across diverse sectors, from healthcare to fine arts. Despite the popularized notion that with 3D printing "imagination is the only limit", we and others in the scientific community have identified fundamental hurdles that restrict our capabilities in this space. Herein, we describe the group's efforts in developing photochemical systems that respond to nontraditional colors of light to elicit the rapid, spatiotemporally controlled formation of plastics.

Multimaterial Thermoset Synthesis: Switching Polymerization Mechanism with Light Dosage.

The synthesis of polymeric thermoset materials with spatially controlled physical properties using readily available resins is a grand challenge. To address this challenge, we developed a photoinitiated polymerization method that enables the spatial switching of radical and cationic polymerizations by controlling the dosage of monochromatic light. This method, which we call Switching Polymerizations by Light Titration (SPLiT), leverages the use of substoichiometric amounts of a photobuffer in combination with traditional photoacid generators.

Simultaneous Color- and Dose-Controlled Thiol-Ene Resins for Multimodulus 3D Printing with Programmable Interfacial Gradients.

Drawing inspiration from nature's own intricate designs, synthetic multimaterial structures have the potential to offer properties and functionality that exceed those of the individual components. However, several contemporary hurdles, from a lack of efficient chemistries to processing constraints, preclude the rapid and precise manufacturing of such materials. Herein, the development of a photocurable resin comprising color-selective initiators is reported, triggering disparate polymerization mechanisms between acrylate and thiol functionality.

Onium Photocages for Visible-Light-Activated Poly(thiourethane) Synthesis and 3D Printing.

The lack of chemical diversity in light-driven reactions for 3D printing poses challenges in the production of structures with long-term ambient stability, recyclability, and breadth in properties (mechanical, optical, etc.). Herein we expand the scope of photochemistries compatible with 3D printing by introducing onium photocages for the rapid formation of poly(thiourethanes) (PTUs).

Silicon-photonics-enabled chip-based 3D printer.

Imagine if it were possible to create 3D objects in the palm of your hand within seconds using only a single photonic chip. Although 3D printing has revolutionized the way we create in nearly every aspect of modern society, current 3D printers rely on large and complex mechanical systems to enable layer-by-layer addition of material. This limits print speed, resolution, portability, form factor, and material complexity.

Supersoft Norbornene-Based Thermoplastic Elastomers with High Strength and Upper Service Temperature.

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.

Triplet Upconversion under Ambient Conditions Enables Digital Light Processing 3D Printing.

The rapid photochemical conversion of materials from liquid to solid (i.e., curing) has enabled the fabrication of modern plastics used in microelectronics, dentistry, and medicine.

3D-Printed Porous Supramolecular Sorbents for Cobalt Recycling.

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated.

Record release of tetramethylguanidine using a green light activated photocage for rapid synthesis of soft materials.

Photocages have enabled spatiotemporally governed organic materials synthesis with applications ranging from tissue engineering to soft robotics. However, the reliance on high energy UV light to drive an often inefficient uncaging process limits their utility. These hurdles are particularly evident for more reactive cargo, such as strong organobases, despite their attractive potential to catalyze a range of chemical transformations.

Boron-Methylated Dipyrromethene as a Green Light Activated Type I Photoinitiator for Rapid Radical Polymerizations.

Unimolecular (Type I) radical photoinitiators (PIs) have transformed the chemical manufacturing industry by enabling (stereo)lithography for microelectronics and emergent 3D printing technologies. However, the reliance on high energy UV-violet light (≤420 nm) restricts the end-use applications. Herein, boron-methylated dipyrromethene (methylated-BODIPY) is shown to act as a highly efficient Type I radical PI upon irradiation with low energy green light.

Rapid hydrogel formation via tandem visible light photouncaging and bioorthogonal ligation.

The formation of benign polymer scaffolds in water using green-light-reactive photocages is described. These efforts pave an avenue toward the fabrication of synthetic scaffolds that can facilitate the study of cellular events for disease diagnosis and treatment. First, a series of boron dipyrromethene (BODIPY) photocages with nitrogen-containing nucleophiles were examined to determine structure-reactivity relationships, which resulted in a >1,000× increase in uncaging yield.

Digital Light Processing 3D Printing of Soft Semicrystalline Acrylates with Localized Shape Memory and Stiffness Control.

Multimaterial three-dimensional (3D) printing of objects with spatially tunable thermomechanical properties and shape-memory behavior provides an attractive approach toward programmable "smart" plastics with applications in soft robotics and electronics. To date, digital light processing 3D printing has emerged as one of the fastest manufacturing methods that maintains high precision and resolution. Despite the common utility of semicrystalline polymers in stimuli-responsive materials, few reports exist whereby such polymers have been produced via digital light processing (DLP) 3D printing.

Fluorescent copolymer aggregate sensor for lithium chloride.

We report a copolymeric fluorescent sensor that is selective for lithium chloride. The two constituent polymers comprise pendent triphenylethylene (TPE) moieties for aggregate induced emission (AIE) along with either strapped-calix[4]pyrrole or secondary ammonium groups that drive aggregation self-assembly upon polymer mixing. Addition of LiCl in acetonitrile disrupts the strapped-calix[4]pyrrole/secondary ammonium chloride salt host-guest crosslinks leading to disaggregation of the polymer chains and a decrease in TPE emission.

Do The Twist: Efficient Heavy-Atom-Free Visible Light Polymerization Facilitated by Spin-Orbit Charge Transfer Inter-system Crossing.

The use of visible light to drive polymerizations with spatiotemporal control offers a mild alternative to contemporary UV-light-based production of soft materials. In this spectral region, photoredox catalysis represents the most efficient polymerization method, yet it relies on the use of heavy-atoms, such as precious metals or toxic halogens. Herein, spin-orbit charge transfer intersystem crossing from boron dipyrromethene (BODIPY) dyads bearing twisted aromatic groups is shown to enable efficient visible light polymerizations in the absence of heavy-atoms.

Multimorphic Materials: Spatially Tailoring Mechanical Properties via Selective Initiation of Interpenetrating Polymer Networks.

Access to multimaterial polymers with spatially localized properties and robust interfaces is anticipated to enable new capabilities in soft robotics, such as smooth actuation for advanced medical and manufacturing technologies. Here, orthogonal initiation is used to create interpenetrating polymer networks (IPNs) with spatial control over morphology and mechanical properties. Base catalyzes the formation of a stiff and strong polyurethane, while blue LEDs initiate the formation of a soft and elastic polyacrylate.

Polymeric multimaterials by photochemical patterning of crystallinity.

An organized combination of stiff and elastic domains within a single material can synergistically tailor bulk mechanical properties. However, synthetic methods to achieve such sophisticated architectures remain elusive. We report a rapid, facile, and environmentally benign method to pattern strong and stiff semicrystalline phases within soft and elastic matrices using stereo-controlled ring-opening metathesis polymerization of an industrial monomer, -cyclooctene.

Camphene-Assisted Fabrication of Free-Standing Lithium-Ion Battery Electrode Composites.

Free-standing electrode (FSE) architectures hold the potential to dramatically increase the gravimetric and volumetric energy density of lithium-ion batteries (LIBs) by eliminating the parasitic dead weight and volume associated with traditional metal foil current collectors. However, current FSE fabrication methods suffer from insufficient mechanical stability, electrochemical performance, or industrial adoptability. Here, we demonstrate a scalable camphene-assisted fabrication method that allows simultaneous casting and templating of FSEs comprising common LIB materials with a performance superior to their foil-cast counterparts.

Visible Light Chemical Micropatterning Using a Digital Light Processing Fluorescence Microscope.

Patterning chemical reactivity with a high spatiotemporal resolution and chemical versatility is critically important for advancing revolutionary emergent technologies, including nanorobotics, bioprinting, and photopharmacology. Current methods are complex and costly, necessitating novel techniques that are easy to use and compatible with a wide range of chemical functionalities. This study reports the development of a digital light processing (DLP) fluorescence microscope that enables the structuring of visible light (465-625 nm) for high-resolution photochemical patterning and simultaneous fluorescence imaging of patterned samples.

"Invisible" Digital Light Processing 3D Printing with Near Infrared Light.

The ability to 3D print structures with low-intensity, long-wavelength light will broaden the materials scope to facilitate inclusion of biological components and nanoparticles. Current materials limitations arise from the pervasive absorption, scattering, and/or degradation that occurs upon exposure to high-intensity, short-wavelength (ultraviolet) light, which is the present-day standard used in light-based 3D printers. State-of-the-art techniques have recently extended printability to orange/red light.

Selective Separation of Lithium Chloride by Organogels Containing Strapped Calix[4]pyrroles.

Reported herein are two functionalized crown ether strapped calix[4]pyrroles, and . As inferred from competitive salt binding experiments carried out in nitrobenzene- and acetonitrile-, these hosts capture LiCl selectively over four other test salts, . NaCl, KCl, MgCl, and CaCl.

Paper without a Trail: Time-Dependent Encryption using Pillar[5]arene-Based Host-Guest Invisible Ink.

A stimuli-responsive invisible ink for time-dependent encryption of information is reported. Consisting of a pillar[5]arene-based supramolecular network grafted with spiropyran moieties, these materials display time-dependent photochromic behavior with tailorable fading rates. Ultraviolet (UV) light results in isomerization of the colorless spiropyran to the corresponding colored merocyanine, while visible light or heat causes the reverse isomerization with a rate that is dependent on the density of host-guest crosslinks.

Additives for Ambient 3D Printing with Visible Light.

With 3D printing, the desire is to be "limited only by imagination," and although remarkable advancements have been made in recent years, the scope of printable materials remains narrow compared to other forms of manufacturing. Light-driven polymerization methods for 3D printing are particularly attractive due to unparalleled speed and resolution, yet the reliance on high-energy UV/violet light in contemporary processes limits the number of compatible materials due to pervasive absorption, scattering, and degradation at these short wavelengths. Such issues can be addressed with visible-light photopolymerizations.

Tough Multimaterial Interfaces through Wavelength-Selective 3D Printing.

Strong and well-engineered interfaces between dissimilar materials are a hallmark of natural systems but have proven difficult to emulate in synthetic materials, where interfaces often act as points of failure. In this work, curing reactions that are triggered by exposure to different wavelengths of visible light are used to produce multimaterial objects with tough, well-defined interfaces between chemically distinct domains. Longer-wavelength (green) light selectively initiates acrylate-based radical polymerization, while shorter-wavelength (blue) light results in the simultaneous formation of epoxy and acrylate networks through orthogonal cationic and radical processes.