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At least 145 records · Page 8

Microwave-Based Synthesis of Functional Morphological Variants and Carbon Nanotube-Based Composites of VS 4 for Electrochemical Applications

A novel facile, fast, and efficient microwave-assisted method was developed to synthesize a number of diverse nanostructured motifs (ranging from nanorods to nanoflowers) of VS 4 along with its associated composite heterostructures, VS 4 /multi-walled carbon nanotube (MWNT; i.e., multi-walled carbon nanotubes). Specifically, we have probed and correlated the effects of a number of specific experimental variables, including primarily precursor, solvent, temperature, and time. We noted that nanorods formed more readily with VO(acac) 2 as the vanadium precursor and n-methyl-2-pyrrolidone (NMP) as a polar reaction solvent. By contrast, we determined that hierarchical three-dimensional (3D) nanoflower-like assemblies, ranging in size from 100 to 200 nm in average diameter, could be controllably synthesized by using Na 3 VO 4 as the vanadium precursor and an aqueous water: polar solvent mixture as the reaction medium. We also observed that VS 4 disintegrates, when in the presence of either air, solution, or a combination of these environments, and established that the extent of VS4 nanorod decomposition could be almost fully prevented by storage under nitrogen. From an application’s perspective, our VS 4 is electrochemically active and shows behavior, consistent with the literature. In particular, as compared with pristine VS 4 nanorods alone, we observed enhanced electrochemical activity with (i) 3D hierarchical flower-like motifs, (ii) unique necklace-like VS 4 nanorod–MWNT composites, and (iii) samples in which as-prepared VS4 nanorods had been annealed. Moreover, we found that the rational application of specific physical and chemical processing treatments, such as (i) thermal annealing to improve crystallinity, (ii) the addition of MWNTs to form conductive composites, and (iii) the evolution of morphology from one-dimensional (1D) nanorods to more complex 3D nanoflowers, was favorable to the resulting electrochemical performance with respect to increasing stability and reversibility.

25 ENERGY STORAGE↗

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

36 MATERIALS SCIENCE↗

Evaporative Assembly: Dual-Scale Nanostructures via Evaporative Assembly (Adv. Mater. Interfaces 7/2020)

In article number 1901954, Sunita Srivastava, Surita R. Bhatia, and co-workers demonstrate that evaporative assembly of functionalized nanoparticles can yield striking dual-scale hierarchical structures. Regular microscale stripes of nanoparticle monolayers with hexagonal nanoscale order are obtained on physically and chemically homogeneous substrates through evaporation of a suspension of DNAfunctionalized nanoparticles with a charged shell. The stripe width, spacing and nanoparticle ordering can be controlled by varying nanoparticle concentration and can be described by a simple analytical model. The results indicate that the interplay between “stick-slip” motion of the droplet contact line and Coulombic and steric nanoparticle interactions control the formation of the observed structures. Finally, this work demonstrates a simple cost-effective mask-free method for fabricating nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Exploiting Chemistry and Molecular Systems for Quantum Information Science

The power of chemistry to prepare new compositions of matter has driven the quest for new approaches to solve problems having global societal impact, such as renewable energy, healthcare, and information science. In the latter case, the intrinsic quantum nature of molecules offers intriguing new possibilities to advance the emerging field of Quantum Information Science (QIS). In this Perspective, we discuss how chemical systems and reactions can impact quantum computing, communication, and sensing. Hierarchical molecular design and synthesis, from small molecules to supramolecular assemblies, combined with new spectroscopic probes of quantum coherence and theoretical modeling of complex systems, offer a broad range of possibilities to realize practical QIS applications.

quantum computing, Spectrocopy, computational chem↗

Diversifying Composition Leads to Hierarchical Composites with Design Flexibility and Structural Fidelity

Although significant progress has been made in the self-assembly of nanostructures, present successes heavily rely on precision in building block design, composition, and pair interactions. These requirements fundamentally limit our ability to synthesize macroscopic materials where the likelihood of impurity inclusion escalates and, more importantly, to access molecular-to-nanoscopic-to-microscopic-to-macroscopic hierarchies, since the types and compositions of building blocks vary at each stage. Inspired by biological blends and high-entropy alloys, we hypothesize that diversifying the blend’s composition can overcome these limitations. Increasing the number of components increases mixing entropy, leading to the dispersion of different components and, as a result, enhances interphase miscibility, weakens the dependence on specific pair interactions, and enables long-range cooperativity. This hypothesis is validated in complex blends containing small molecules, block copolymer-based supramolecules, and nanoparticles/colloidal particles. Hierarchically structured composites can be obtained with formulation flexibility in the filler selection and blend composition. It is worth noting that, by adding small molecules, we can solve the size constraint that plagues traditional block copolymer/nanoparticle blends. Detailed characterization and simulation further confirm that each component is distributed to locally mediate unfavorable interactions, cooperatively mitigate composition fluctuations, and retain structural fidelity. Furthermore, the blends have sufficient mobility to access tunable microstructures without compromising the order of the nanostructure. Besides establishing a kinetically viable pathway to release current constraints in the composite design and to navigate uncertainties during structure formation over multiple length scales, the present study demonstrates that entropy-driven behaviors can be realized in systems beyond high-entropy alloys despite inherent differences between metal alloys and organic/inorganic hybrids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assembly of short amphiphilic peptoids into nanohelices with controllable supramolecular chirality

Abstract A long-standing challenge in bioinspired materials is to design and synthesize synthetic materials that mimic the sophisticated structures and functions of natural biomaterials, such as helical protein assemblies that are important in biological systems. Herein, we report the formation of a series of nanohelices from a type of well-developed protein-mimetics called peptoids. We demonstrate that nanohelix structures and supramolecular chirality can be well-controlled through the side-chain chemistry. Specifically, the ionic effects on peptoids from varying the polar side-chain groups result in the formation of either single helical fiber or hierarchically stacked helical bundles. We also demonstrate that the supramolecular chirality of assembled peptoid helices can be controlled by modifying assembling peptoids with a single chiral amino acid side chain. Computational simulations and theoretical modeling predict that minimizing exposure of hydrophobic domains within a twisted helical form presents the most thermodynamically favorable packing of these amphiphilic peptoids and suggests a key role for both polar and hydrophobic domains on nanohelix formation. Our findings establish a platform to design and synthesize chiral functional materials using sequence-defined synthetic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. Furthermore, we demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro‐ and Thermo‐Chemical Pathways

Abstract Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero‐emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low‐carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro‐ and thermo‐ chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt‐group metal (PGM) and non‐PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high‐level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Deng, Chenxin↗

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗

Creating self-assembled arrays of mono-oxo (MoO 3 ) 1 species on TiO 2 (101) via deposition and decomposition of (MoO 3 ) n oligomers

Significance The design and synthesis of hierarchically ordered oxides remains a critical challenge in material science and catalysis. Here, we demonstrate that well-ordered homotopic arrays of mono-oxo (MoO 3 ) 1 can be easily prepared on anatase TiO 2 (101) via the deposition of (MoO 3 ) n oligomers. As revealed by our combined experiential and theoretical studies, the oligomers spontaneously decompose and self-assemble into chemically identical and thermally stable monomers. The oligomer decomposition is permitted at room temperature due to the dynamic coupling of decomposition steps to the lattice phonons of TiO 2 . We identify transient mobility of the oligomers as key to the self-assembly of the complete overlayer. The ease of preparation and thermal stability of this atomically precise system makes it highly suitable for a broad range of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-similar mesocrystals form via interface-driven nucleation and assembly

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.

36 MATERIALS SCIENCE↗

Hierarchically ordered porous transition metal compounds from one-pot type 3D printing approaches

Solution-based soft matter self-assembly (SA) promises unique material structures and properties from approaches including additive manufacturing/three-dimensional (3D) printing. The 3D printing of periodically ordered porous functional inorganic materials through SA unfolding during printing remains a major challenge, however, due to the often vastly different ordering kinetics of separate processes at different length scales. Here, we report a “one-pot” direct ink writing process to produce hierarchically porous transition metal nitrides and precursor oxides from block copolymer (BCP) SA. Heat treatment protocols identified in various environments enable mesostructure retention in the final crystalline materials with periodic lattices on three distinct length scales. Moreover, embedded printing enables the first BCP directed mesoporous non-self-supporting helical oxides and nitrides. Resulting nitrides are superconducting, with record nanoconfinement-induced upper critical fields correlated with BCP molar mass and record surface areas for compound superconductors. Results suggest scalable porous functional inorganic material formation approaches for applications including catalysis, sensing, and microelectronics.

36 MATERIALS SCIENCE↗

Activation and Assembly of Plasmonic-Magnetic Nanosurfactants for Encapsulation and Triggered Release

Multifunctional surfactants hold great potentials in catalysis, separation, and biomedicine. Highly active plasmonic-magnetic nanosurfactants are developed through a novel acid activation treatment of Au–Fe 3 O 4 dumbbell nanocrystals. The activation step significantly boosts nanosurfactant surface energy and enables the strong adsorption at interfaces, which reduces the interfacial energy one order of magnitude. Mediated through the adsorption at the emulsion interfaces, the nanosurfactants are further constructed into free-standing hierarchical structures, including capsules, inverse capsules, and two-dimensional sheets. The nanosurfactant orientation and assembly structures follow the same packing parameter principles of surfactant molecules. Furthermore, nanosurfactants demonstrate the capability to disperse and encapsulate homogeneous nanoparticles and small molecules without adding any molecular surfactants. The assembled structures are responsive to external magnetic field, and triggered release is achieved using an infrared laser by taking advantage of the enhanced surface plasmon resonance of nanosurfactant assemblies. Finally, solvent and pH changes are also utilized to achieve the cargo release.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Hierarchically Templated Synthesis of 3D‐Printed Crosslinked Cyclodextrins for Lycopene Harvesting

Abstract Plants produce a wide range of bioactive phytochemicals, such as antioxidants and vitamins, which play crucial roles in aging prevention, inflammation reduction, and reducing the risk of cancer. Selectively harvesting these phytochemicals, such as lycopene, from tomatoes through the adsorption method is cost‐effective and energy efficient. In this work, a templated synthesis of 3D‐printed crosslinked cyclodextrin polymers featuring nanotubular structures for highly selective lycopene harvesting is reported. Polypseudorotaxanes formed by triethoxysilane‐based telechelic polyethylene glycols and α‐cyclodextrins (α‐CDs) are designed as the template to (1) synthetically access urethane‐based nanotubular structures at the molecular level, and (2) construct 3D‐printed architectures with designed macroscale voids. The polypseudorotaxane hydrogels showed good rheological properties for direct ink writing, and the 3D‐printed hydrogels were converted to the desired α‐CD polymer network through a three‐step postprinting transformation. The obtained urethane‐crosslinked α‐CD monoliths possess nanotubular structures and 3D‐printed voids. They selectively adsorb lycopene from raw tomato juice, protecting lycopene from photo‐ or thermo‐degradations. This work highlights the hierarchically templated synthesis approach in developing functional 3D‐printing materials by connecting the bottom‐up molecular assembly and synthesis with the top‐down 3D architecture control and fabrication.

Chemistry↗

Multiquanta flux jumps in superconducting fractal

We study the magnetic field response of millimeter scale fractal Sierpinski gaskets (SG) assembled of superconducting equilateral triangular patches. Directly imaged quantitative induction maps reveal hierarchical periodic filling of enclosed void areas with multiquanta magnetic flux, which jumps inside the voids in repeating bundles of individual flux quanta Φ 0 . The number N s of entering flux quanta in different triangular voids of the SG is proportional to the linear size s of the void, while the field periodicity of flux jumps varies as 1/s. We explain this behavior by modeling the triangular voids in the SG with effective superconducting rings and by calculating their response following the London analysis of persistent currents, J s , induced by the applied field H a and by the entering flux. With changing H a , J s reaches a critical value in the vertex joints that connect the triangular superconducting patches and allows the giant flux jumps into the SG voids through phase slips or multiple Abrikosov vortex transfer across the vertices. The unique flux behavior in superconducting SG patterns, may be used to design tunable low-loss resonators with multi-line high-frequency spectrum for microwave technologies.

36 MATERIALS SCIENCE↗

Strong polaronic effect in a superatomic two-dimensional semiconductor

Crystalline solids assembled from superatomic building blocks are attractive functional materials due to their hierarchical structure, multifunctionality, and tunability. An interesting example is Re 6 Se 8 Cl 2 , in which the Re 6 Se 8 building blocks are covalently linked into two-dimensional (2D) sheets that are stacked into a layered van der Waals solid. It is an indirect gap semiconductor that, when heavily doped, becomes a superconductor at low temperatures. Given the finite electronic bandwidths (300–400 meV), carrier properties in this material are expected to be strongly influenced by coupling to phonons. Here, we apply angle-resolved photoemission spectroscopy to probe the valence band edge (VBE) of Re 6 Se 8 Cl 2 . We find that dispersion of the VBE is a strong function of temperature. The bandwidth is W = 120 ± 30 meV at 70 K and decreases by one order of magnitude to W ~ 10 ± 20 meV as temperature is increased to 300 K. This observation reveals the dominant polaronic effects in Re 6 Se 8 Cl 2 , consistent with the Holstein polaron model commonly used to describe molecular solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

VTO_2021_APR_LLNL_Ye

Traditional batteries are composed of two-dimensional films that are stacked and/or rolled. Thin film batteries display high power density while their thick film counterparts show good energy density, but it has proven difficult to concurrently achieve both within these planar form factors. In addition, conventional Li-ion batteries based on liquid organic electrolytes or gel polymer electrolytes have raised severe safety concerns due to the intrinsic flammable properties of the organic electrolytes. They are also not ideal for the use of high energy density metallic lithium (Li) anodes due to Li dendrite growth, or sulfur cathodes due to shuttling effects that result in fast capacity fade. There is an urgent need to develop safe, high-performance solid-state batteries (SSBs) with advanced electrolyte and separator technologies. Although in recent years a series of superionic conductors have been developed for electrolytes and separators, their performance does not satisfy demanding criteria due to large impedance from poor solid electrolyte-electrode contact and questionable electrochemical and mechanical stability. Unlike the well-established roll-to-roll fabrication of conventional Li-ion batteries, the processing of SSBs is unique due to the brittleness of solid-state electrolytes (SSEs). The commercially available or lab-developed SSE discs are usually very thick (hundreds of micrometers to millimeters) to overcome their brittle nature, which unfortunately increases the cell impedance and accounts for the majority of the overall cell weight and volume, leading to dramatically decreased power and energy densities. In this project, we will investigate 3D printing techniques to overcome safety, fabrication, mechanical, and electrochemical issues in SSBs. 3D printing builds complex structures in a layer-by-layer fashion, which allows rapid production of hierarchical architectures, gradient and multi-material structures, and multi-component assemblies. 3D printing is an emerging area that could fundamentally transform energy storage devices. For example, 3D printing can produce batteries with arbitrary form factors to fit a product’s specific volume requirements and can create interwoven electrode arrangements over a wide range of length scales to improve transport and increase power density for a given energy density. For SSBs, 3D printing may dramatically reduce the separator thickness from ~1 mm (by hydraulic pressing) to tens of micrometers or less. In addition, the interfacial contact area between the electrolyte and the electrode may be increased via 3D interdigitated designs. Hence, we expect a significant reduction of the overall cell impedance and enhancement of both energy and power densities of SSBs by harnessing an array of 3D printing technologies being developed at Lawrence Livermore National Laboratory (LLNL).

25 ENERGY STORAGE↗