Keun-Ho Choi

Progress in flexible energy storage and conversion systems, with a focus on cable-type lithium-ion batteries

The unending demand for portable, flexible, and even wearable electronic devices that have an aesthetic appeal and unique functionality stimulates the development of advanced power sources that have excellent electrochemical performance and, more importantly, shape versatility. The challenges in the fabrication of next-generation flexible power sources mainly arise from their limited form factors, which prevent their facile integration into differently shaped electronic devices, and from the lack of reliable electrochemical materials that exhibit optimized attributes and suitable processability. This review describes the technological innovations and challenges associated with flexible energy storage and conversion systems such as lithium-ion batteries and supercapacitors, along with an overview of the progress in flexible proton exchange membrane fuel cells (PEMFCs) and solar cells. In particular, recently highlighted cable-type flexible batteries with extreme omni-directional flexibility are comprehensively discussed.

All-inkjet-printed, solid-state flexible supercapacitors on paper

The forthcoming ubiquitous innovations driven by flexible/wearable electronics and Internet of Things (IoT) have inspired the relentless pursuit of advanced power sources with versatile aesthetics. Here, we demonstrate a new class of solid-state flexible power sources that are fabricated directly on conventional A4 paper using a commercial desktop inkjet printer. A salient feature of the inkjet-printed power sources is their monolithic integration with paper, i.e., they look like inkjet-printed letters or figures that are commonly found in office documents. A supercapacitor (SC), which is composed of activated carbon/carbon nanotubes (CNTs) and an ionic liquid/ultraviolet-cured triacrylate polymer-based solid-state electrolyte, is chosen as a model power source to explore the feasibility of the proposed concept. Cellulose nanofibril-mediated nanoporous mats are inkjet-printed on top of paper as a primer layer to enable high-resolution images. In addition, CNT-assisted photonic interwelded Ag nanowires are introduced onto the electrodes to further improve the electrical conductivity of the electrodes. The inkjet-printed SCs can be easily connected in series or parallel, leading to user-customized control of cell voltage and capacitance. Notably, a variety of all-inkjet-printed SCs featuring computer-designed artistic patterns/letters are aesthetically unitized with other inkjet-printed images and smart glass cups, underscoring their potential applicability as unprecedented object-tailored power sources.

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.

Compliant polymer network-mediated fabrication of a bendable plastic crystal polymer electrolyte for flexible lithium-ion batteries

We demonstrate a bendable plastic crystal polymer electrolyte (referred to as “B-PCPE”) for use in flexible lithium-ion batteries. The B-PCPE proposed herein is composed of a plastic crystal electrolyte (PCE, 1 M lithium bis-trifluoromethanesulphonimide (LiTFSI) in succinonitrile (SN)) and a UV (ultraviolet)-cured polymer network bearing long linear hydrocarbon chains (here, trimethylolpropane propoxylate triacrylate (TPPTA) polymer is exploited). The solid electrolyte characteristics of the B-PCPE are investigated in terms of plastic crystal behavior, mechanical bendability, ionic conductivity, and cell performance. Owing to the presence of long linear hydrocarbon chains attached to crosslinkable acrylate groups, the TPPTA polymer network in the B-PCPE acts as a compliant mechanical framework, thereby exerting a beneficial influence on bendability and also interfacial resistance with lithium metal electrodes. Meanwhile, the B-PCPE exhibits slightly lower ionic conductivity than a control sample (referred to as “R-PCPE”) incorporating a rigid and stiff polymer network of ethoxylated trimethylolpropane triacrylate (ETPTA). This unique behavior of the B-PCPE is discussed with an in-depth consideration of the polymer network structure and its specific interaction with the lattice defect phase of SN in the PCE. Although relatively sluggish ionic transport is observed in the B-PCPE, its intimate interfacial contact with electrodes (possibly due to the mechanically compliant TPPTA polymer network) may beneficially contribute to imparting satisfactory cycling performance.

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.