Sung-Ju Cho

Mechanically compliant and lithium dendrite growth-suppressing composite polymer electrolytes for flexible lithium-ion batteries

We demonstrate mechanically compliant and lithium dendrite growth-suppressing composite polymer electrolytes for use in flexible lithium-ion batteries. This new composite polymer electrolyte (referred to as “CPE”) is fabricated via an exquisite combination of UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate macromer (serving as a mechanical framework) and Al2O3 nanoparticles (as a functional filler) in the presence of a high boiling point liquid electrolyte. A distinctive structural feature of the CPE is the close-packed Al2O3 nanoparticles in the liquid electrolyte-swollen ETPTA macromer matrix. Owing to this unique morphology, the CPE provides significant improvements in the mechanical bendability and suppression of lithium dendrite growth during charge–discharge cycling.

Bendable and Thin Sulfide Solid Electrolyte Film: A New Electrolyte Opportunity for Free-Standing and Stackable High-Energy All-Solid-State Lithium-Ion Batteries

Bulk-type all-solid-state lithium batteries (ASLBs) are considered a promising candidate to outperform the conventional lithium-ion batteries. Unfortunately, the current technology level of ASLBs is in a stage of infancy in terms of cell-based (not electrode-material-based) energy densities and scalable fabrication. Here, we report on the first ever bendable and thin sulfide solid electrolyte films reinforced with a mechanically compliant poly(paraphenylene terephthalamide) nonwoven (NW) scaffold, which enables the fabrication of free-standing and stackable ASLBs with high energy density and high rate capabilities. The ASLB, using a thin (∼70 μm) NW-reinforced SE film, exhibits a 3-fold increase of the cell-energy-density compared to that of a conventional cell without the NW scaffold.

A shape-deformable and thermally stable solid-state electrolyte based on a plastic crystal composite polymer electrolyte for flexible/safer lithium-ion batteries

A solid-state electrolyte with reliable electrochemical performance, mechanical robustness and safety features is strongly pursued to facilitate the progress of flexible batteries. Here, we demonstrate a shape-deformable and thermally stable plastic crystal composite polymer electrolyte (denoted as “PC-CPE”) as a new class of solid-state electrolyte to achieve this challenging goal. The PC-CPE is composed of UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate (ETPTA) macromer/close-packed Al2O3 nanoparticles (acting as the mechanical framework) and succinonitrile-mediated plastic crystal electrolyte (serving as the ionic transport channel). This chemical/structural uniqueness of the PC-CPE brings remarkable improvement in mechanical flexibility and thermal stability, as compared to conventional carbonate-based liquid electrolytes that are fluidic and volatile. In addition, the PC-CPE precursor mixture (i.e., prior to UV irradiation) with well-adjusted rheological properties, via collaboration with a UV-assisted imprint lithography technique, produces the micropatterned PC-CPE with tunable dimensions. Notably, the cell incorporating the self-standing PC-CPE, which acts as a thermally stable electrolyte and also a separator membrane, maintains stable charge/discharge behavior even after exposure to thermal shock condition (=130 °C/0.5 h), while a control cell assembled with a carbonate-based liquid electrolyte and a polyethylene separator membrane loses electrochemical activity.

Flexible/shape-versatile, bipolar all-solid-state lithium-ion batteries prepared by multistage printing

Bipolar all-solid-state lithium-ion batteries (LIBs) have attracted considerable attention as a promising approach to address the ever-increasing demand for high energy and safety. However, the use of (sulfide- or oxide-based) inorganic solid electrolytes, which have been the most extensively investigated electrolytes in LIBs, causes problems with respect to mechanical flexibility and form factors in addition to their longstanding issues such as chemical/electrochemical instability, interfacial contact resistance and manufacturing processability. Here, we develop a new class of flexible/shape-versatile bipolar all-solid-state LIBs via ultraviolet (UV) curing-assisted multistage printing, which does not require the high-pressure/high-temperature sintering processes adopted for typical inorganic electrolyte-based all-solid-state LIBs. Instead of inorganic electrolytes, a flexible/nonflammable gel electrolyte consisting of a sebaconitrile-based electrolyte and a semi-interpenetrating polymer network skeleton is used as a core element in the printed electrodes and gel composite electrolytes (GCEs, acting as an ion-conducting separator membrane). Rheology tuning (toward thixotropic fluid behavior) of the electrode and GCE pastes, in conjunction with solvent-drying-free multistage printing, enables the monolithic integration of in-series/in-plane bipolar-stacked cells onto complex-shaped objects. Because of the aforementioned material and process novelties, the printed bipolar LIBs show exceptional flexibility, form factors, charge/discharge behavior and abuse tolerance (nonflammability) that far exceed those achievable with inorganic-electrolyte-based conventional bipolar cell technologies.

An effective coupling of nanostructured Si and gel polymer electrolytes for high-performance lithium-ion battery anodes

Nanostructured silicon has garnered considerable attention as a promising lithium-ion battery anode material that can mitigate volume expansion-induced pulverization during electrochemical lithiation–delithiation reaction. However, the advantageous effect of the nanostructured silicon materials is often shadowed by electrochemically-vigorous liquid electrolytes. Herein, a variety of silicon particles featuring well-defined nanostructures were synthesized and then combined with chemically-crosslinked, triacrylate-based gel polymer electrolytes (GPEs), with an aim to pursue unprecedented synergistic coupling and its versatile applicability for high-performance silicon anodes. The silicon anode combined with the GPE showed a specific capacity of over 2000 mA h g−1 after 100 cycles, excellent discharge rate capability (capacity of 80% at 5.0C with respect to 0.2C), and volume change of 53% relative to a control system (silicon anode/liquid electrolyte). Excellent flexibility of the GPE with reliable electrochemical properties is believed to play a viable role as a mechanical cushion that can alleviate the stress and strain of silicon materials inevitably generated during repeated charge/discharge cycling. The nanostructured silicon/GPE-based coupling strategy presented herein opens a new way to enable a significant improvement in the electrochemical performance and long-term durability of high-capacity silicon anodes.

Molecularly designed, dual-doped mesoporous carbon/SWCNT nanoshields for lithium battery electrode materials

Formidable challenges facing lithium-ion rechargeable batteries, which involve performance degradations and safety failures during charge/discharge cycling, mostly arise from electrode–electrolyte interface instability. Here, as a polymeric ionic liquid (PIL)-mediated interfacial control strategy to address this long-standing issue, we demonstrate a new class of molecularly designed, ion/electron-conductive nanoshields based on single-walled carbon nanotube (SWCNT)-embedded, dual-doped mesoporous carbon (referred to as “SMC”) shells for electrode materials. The SMC shell is formed on cathode materials through solution deposition of the SWCNT/PIL mixture and subsequent carbonization. The PIL (denoted as “PVIm[DS]”) synthesized in this study consists of poly(1-vinyl-3-ethylimidazolium) cations and dodecyl sulfate counter anions, whose molecular structures are rationally designed to achieve the following multiple functions: (i) precursor for the conformal/continuous nanothickness carbon shell, (ii) dual (N and S)-doping source, (iii) porogen for the mesoporous structure, and (iv) SWCNT dispersant. Driven by such chemical/structural uniqueness, the SMC shell prevents direct exposure of cathode materials to bulk liquid electrolytes while facilitating redox reaction kinetics. As a consequence, the SMC-coated cathode materials enable significant improvements in cell performance and also thermal stability. We envision that the SMC shell can be suggested as a new concept of effective and versatile surface modification strategy for next-generation high-performance electrode materials.

Monolithic heterojunction quasi-solid-state battery electrolytes based on thermodynamically immiscible dual phases

Traditional single-phase electrolytes, which are widely used in current state-of-the-art rechargeable batteries, have difficulties simultaneously fulfilling different chemical/electrochemical requirements of anodes and cathodes. Here, we demonstrate a new class of monolithic heterojunction quasi-solid-state electrolytes (MH-QEs) based on thermodynamically immiscible dual phases. As a proof-of-concept of the MH-QEs, their application to lithium–sulfur batteries is explored. Driven by combined effects of structural uniqueness and thermodynamic immiscibility, the electrode-customized MH-QEs provide exceptional electrochemical performance that lies far beyond those accessible with conventional battery electrolytes.

Nanomat Li–S batteries based on all-fibrous cathode/separator assemblies and reinforced Li metal anodes: towards ultrahigh energy density and flexibility

Lithium–sulfur (Li–S) batteries have attracted considerable attention as a promising alternative to current state-of-the-art lithium-ion batteries (LIBs), however, their practical use remains elusive, which becomes more serious upon application to flexible/wearable electronics. Here, we demonstrate a new class of nanomat Li–S batteries based on all-fibrous cathode–separator assemblies and conductive nonwoven-reinforced Li metal anodes as an unprecedented strategy toward ultrahigh energy density and mechanical flexibility. Sulfur cathodes, which are fibrous mixtures of sulfur-deposited multi-walled carbon nanotubes and single-walled carbon nanotubes, are monolithically integrated with bi-layered (pristine cellulose nanofiber (CNF)–anionic CNF) paper separators, resulting in metallic foil current collector-free, all-fibrous cathode–separator assemblies. The cathode–separator assemblies, driven by their all-fibrous structure (contributing to three-dimensional bi-continuous electron/ion conduction pathways) and anionic CNFs (suppressing the shuttle effect via electrostatic repulsion), improve redox kinetics, cyclability and flexibility. Nickel-/copper-plated conductive poly(ethylene terephthalate) nonwovens are physically embedded into Li foils to fabricate reinforced Li metal anodes with dimensional/electrochemical superiority. Driven by the structural uniqueness and chemical functionalities, the nanomat Li–S cells provide exceptional improvements in electrochemical performance (the (cell-based) gravimetric/volumetric energy density = 457 W h kgcell−1/565 W h Lcell−1 and the cycling performance (over 500 cycles) under 110% capacity excess of the Li metal anode) and mechanical deformability (they even can be crumpled).