Antioxidative Lithium Reservoir Based on Interstitial Channels of Carbon Nanotube Bundles.

Lithium (Li) metal has garnered considerable attention in next-generation battery anodes. However, its environmental vulnerability, along with the electrochemical instability and safety failures, poses a formidable challenge to commercial use. Here, we describe a new class of antioxidative Li reservoir based on interstitial channels of single-walled carbon nanotube (SWCNT) bundles. The Li preferentially confined in the interstitial channels exhibits unusual thermodynamic stability and exceptional capacity even after exposure to harsh environmental conditions, thereby enabling us to propose a new lithiation/delithiation mechanism in carbon nanotubes. To explore practical application of this approach, the Li confined in the SWCNT bundles is electrochemically extracted and subsequently plated on a copper foil. The resulting Li-plated copper foil shows reliable charge/discharge behavior comparable to those of pristine Li foils. Benefiting from the confinement effect of the interstitial channels, the SWCNT bundles hold great promise as an environmentally tolerant, high-capacity Li reservoir.

COF-Net on CNT-Net as a Molecularly Designed, Hierarchical Porous Chemical Trap for Polysulfides in Lithium-Sulfur Batteries.

The hierarchical porous structure has garnered considerable attention as a multiscale engineering strategy to bring unforeseen synergistic effects in a vast variety of functional materials. Here, we demonstrate a "microporous covalent organic framework (COF) net on mesoporous carbon nanotube (CNT) net" hybrid architecture as a new class of molecularly designed, hierarchical porous chemical trap for lithium polysulfides (Li2Sx) in Li-S batteries. As a proof of concept for the hybrid architecture, self-standing COF-net on CNT-net interlayers (called "NN interlayers") are fabricated through CNT-templated in situ COF synthesis and then inserted between sulfur cathodes and separators. Two COFs with different micropore sizes (COF-1 (0.7 nm) and COF-5 (2.7 nm)) are chosen as model systems. The effects of the pore size and (boron-mediated) chemical affinity of microporous COF nets on Li2Sx adsorption phenomena are theoretically investigated through density functional theory calculations. Benefiting from the chemical/structural uniqueness, the NN interlayers effectively capture Li2Sx without impairing their ion/electron conduction. Notably, the COF-1 NN interlayer, driven by the well-designed microporous structure, allows for the selective deposition/dissolution (i.e., facile solid-liquid conversion) of electrically inert Li2S. As a consequence, the COF-1 NN interlayer provides a significant improvement in the electrochemical performance of Li-S cells (capacity retention after 300 cycles (at charge/discharge rate = 2.0 C/2.0 C) = 84% versus 15% for a control cell with no interlayer) that lies far beyond those accessible with conventional Li-S technologies.

Printable Solid-State Lithium-Ion Batteries: A New Route toward Shape-Conformable Power Sources with Aesthetic Versatility for Flexible Electronics.

Forthcoming flexible/wearable electronic devices with shape diversity and mobile usability garner a great deal of attention as an innovative technology to bring unprecedented changes in our daily lives. From the power source point of view, conventional rechargeable batteries (one representative example is a lithium-ion battery) with fixed shapes and sizes have intrinsic limitations in fulfilling design/performance requirements for the flexible/wearable electronics. Here, as a facile and efficient strategy to address this formidable challenge, we demonstrate a new class of printable solid-state batteries (referred to as "PRISS batteries"). Through simple stencil printing process (followed by ultraviolet (UV) cross-linking), solid-state composite electrolyte (SCE) layer and SCE matrix-embedded electrodes are consecutively printed on arbitrary objects of complex geometries, eventually leading to fully integrated, multilayer-structured PRISS batteries with various form factors far beyond those achievable by conventional battery technologies. Tuning rheological properties of SCE paste and electrode slurry toward thixotropic fluid characteristics, along with well-tailored core elements including UV-cured triacrylate polymer and high boiling point electrolyte, is a key-enabling technology for the realization of PRISS batteries. This process/material uniqueness allows us to remove extra processing steps (related to solvent drying and liquid-electrolyte injection) and also conventional microporous separator membranes, thereupon enabling the seamless integration of shape-conformable PRISS batteries (including letters-shaped ones) into complex-shaped objects. Electrochemical behavior of PRISS batteries is elucidated via an in-depth analysis of cell impedance, which provides a theoretical basis to enable sustainable improvement of cell performance. We envision that PRISS batteries hold great promise as a reliable and scalable platform technology to open a new concept of cell architecture and fabrication route toward flexible power sources with exceptional shape conformability and aesthetic versatility.

Heterolayered, one-dimensional nanobuilding block mat batteries.

The rapidly approaching smart/wearable energy era necessitates advanced rechargeable power sources with reliable electrochemical properties and versatile form factors. Here, as a unique and promising energy storage system to address this issue, we demonstrate a new class of heterolayered, one-dimensional (1D) nanobuilding block mat (h-nanomat) battery based on unitized separator/electrode assembly (SEA) architecture. The unitized SEAs consist of wood cellulose nanofibril (CNF) separator membranes and metallic current collector-/polymeric binder-free electrodes comprising solely single-walled carbon nanotube (SWNT)-netted electrode active materials (LiFePO4 (cathode) and Li4Ti5O12 (anode) powders are chosen as model systems to explore the proof of concept for h-nanomat batteries). The nanoporous CNF separator plays a critical role in securing the tightly interlocked electrode-separator interface. The SWNTs in the SEAs exhibit multifunctional roles as electron conductive additives, binders, current collectors and also non-Faradaic active materials. This structural/physicochemical uniqueness of the SEAs allows significant improvements in the mass loading of electrode active materials, electron transport pathways, electrolyte accessibility and misalignment-proof of separator/electrode interface. As a result, the h-nanomat batteries, which are easily fabricated by stacking anode SEA and cathode SEA, provide unprecedented advances in the electrochemical performance, shape flexibility and safety tolerance far beyond those achievable with conventional battery technologies. We anticipate that the h-nanomat batteries will open 1D nanobuilding block-driven new architectural design/opportunity for development of next-generation energy storage systems.

Inverse opal-inspired, nanoscaffold battery separators: a new membrane opportunity for high-performance energy storage systems.

The facilitation of ion/electron transport, along with ever-increasing demand for high-energy density, is a key to boosting the development of energy storage systems such as lithium-ion batteries. Among major battery components, separator membranes have not been the center of attention compared to other electrochemically active materials, despite their important roles in allowing ionic flow and preventing electrical contact between electrodes. Here, we present a new class of battery separator based on inverse opal-inspired, seamless nanoscaffold structure ("IO separator"), as an unprecedented membrane opportunity to enable remarkable advances in cell performance far beyond those accessible with conventional battery separators. The IO separator is easily fabricated through one-pot, evaporation-induced self-assembly of colloidal silica nanoparticles in the presence of ultraviolet (UV)-curable triacrylate monomer inside a nonwoven substrate, followed by UV-cross-linking and selective removal of the silica nanoparticle superlattices. The precisely ordered/well-reticulated nanoporous structure of IO separator allows significant improvement in ion transfer toward electrodes. The IO separator-driven facilitation of the ion transport phenomena is expected to play a critical role in the realization of high-performance batteries (in particular, under harsh conditions such as high-mass-loading electrodes, fast charging/discharging, and highly polar liquid electrolyte). Moreover, the IO separator enables the movement of the Ragone plot curves to a more desirable position representing high-energy/high-power density, without tailoring other battery materials and configurations. This study provides a new perspective on battery separators: a paradigm shift from plain porous films to pseudoelectrochemically active nanomembranes that can influence the charge/discharge reaction.

Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries.

A class of imprintable, bendable, and shape-conformable polymer electrolyte with excellent electrochemical performance in a lithium battery system is reported. The material consists of a UV-cured polymer matrix, high-boiling point liquid electrolyte, and Al2 O3 nanoparticles, formulated for use in lithium-ion batteries with 3D-structured electrodes or flexible characteristics. The unique structural design and well-tuned rheological characteristics of the UV-curable electrolyte mixture, in combination with direct UV-assisted nanoimprint lithography, allow the successful fabrication of polymer electrolytes in geometries not accessible with conventional materials.