Ultrathin Mixed Ionic-Electronic Conducting Interlayer via the Solution Shearing Technique for High-Performance Lithium-Sulfur Batteries.

The commercialization of lithium-sulfur (Li-S) batteries has been hampered by diverse challenges, including the shuttle phenomenon and low electrical/ionic conductivity of lithium sulfide and sulfur. To address these issues, extensive research has been devoted to developing multifunctional interlayers. However, interlayers capable of simultaneously suppressing the polysulfide (PS) shuttle and ensuring stable electrical and ionic conductivity are relatively uncommon. Moreover, the use of thick and heavy interlayers results in an unavoidable decline in the energy density of Li-S batteries. We developed an ultrathin (750 nm), lightweight (0.182 mg cm-2) interlayer that facilitates mixed ionic-electronic conduction using the solution shearing technique. The interlayer, composed of carbon nanotube (CNT)/Nafion/poly-3,4-ethylenedioxythiophene:tetracyanoborate (PEDOT:TCB), effectively suppresses the shuttle phenomenon through the synergistic segregation and adsorption effects on PSs by Nafion and CNT/PEDOT, respectively. Furthermore, the electrical/ionic conductivity of the interlayer can be improved via counterion exchange and homogeneous Li+ ion flux/good wettability from SO3- functional group of Nafion, respectively. Enhanced sulfur utilization and reaction kinetics through polysulfide shuttle inhibition and facilitated electron/ion transfer by interlayer enable a high discharge capacity of 1029 mA h g-1 in the Li-S pouch cell under a high sulfur loading of 5.3 mg cm-2 and low electrolyte/sulfur ratio of 5 µL mg-1.

Mechanically Robust Ultrathin Solid Electrolyte Membranes Using a Porous Net Template for All-Solid-State Batteries.

All-solid-state batteries (ASBs) have been identified as a potential next-generation technology for safe energy storage. However, the current pellet form of solid electrolytes (SEs) exhibits low cell-level energy densities and mechanical brittleness, and this has hampered the commercialization of ASBs. In this work, we report on the development of an ultrathin SE membrane that can be reduced to a thickness of 31 µm with minimal thermal shrinkage at 140 °C, while exhibiting robust mechanical properties (tensile strength of 19.6 MPa). Due to its exceptional ionic conductivity of 0.55 mS/cm and the corresponding areal conductance of 84 mS/cm2, the SE membrane-incorporated ASB displays cell-level gravimetric and volumetric energy densities of 127.9 Wh/kgcell and 140.7 Wh/Lcell, respectively. These values represent a 7.6- and 5.7-fold increase over those achieved with conventional SE pellet cells. Our results demonstrate the potential of the developed SE membrane to overcome the critical challenges in the commercialization of ASBs.

Effect of Lithium Substitution Ratio of Polymeric Binders on Interfacial Conduction within All-Solid-State Battery Anodes.

Problematic issues with electrically inert binders have been less serious in the conventional lithium-ion batteries by virtue of permeable liquid electrolytes (LEs) for ionic connection and/or carbonaceous additives for electronic connection in the electrodes. Contrary to electron-conductive binders used to maximize an active loading level, the development of ion-conductive binders has been lacking owing to the LE-filled electrode configuration. Herein, we represent a tactical strategy for improving the interfacial Li+ conduction in all-solid-state electrolyte-free graphite (EFG) electrodes where the solid electrolytes are entirely excluded, using lithium-substitution-modulated (LSM) binders. Finely tuning a lithium substitution ratio, a conductive LSM-carboxymethyl cellulose (CMC) binder is prepared from a controlled direct Na+/Li+ exchange reaction without a hazardous acid involvement. The EFG electrode employing LSM with a maximum degree of substitution of lithium (DSLi) of ∼68% in our study shows a considerably higher rate capability of 1.05 mA h cm-2 at 1 C and a capacity retention of ∼61.9% after 200 cycles at 0.5 C than those using sodium-CMC (Na-CMC) (0.78 mA h cm-2, ∼49.5%) and LSM with ∼35% lithium substitution (0.93 mA h cm-2, ∼55.4%). More importantly, the correlation between the phase transition near the bottom region of the EFG electrode and the state of charge (SOC) is systematically investigated, clarifying that the improvement of the interfacial conduction is proportional to the DSLi of the CMC binders. Theoretical calculations combined with experimental results further verify that creating the continuous interface through abundant pathways for mobile ions using the Li+-conductive binder is the enhancement mechanism of the interfacial conduction in the EFG electrode, mitigating serious charge transfer resistance.

Cooperative Electronic Structure Modulator of Fe Single-Atom Electrocatalyst for High Energy and Long Cycle Li-S Pouch Cell.

High-energy and long cycle lithium-sulfur (Li-S) pouch cells are limited by the insufficient capacities and stabilities of their cathodes under practical electrolyte/sulfur (E/S), electrolyte/capacity (E/C), and negative/positive (N/P) ratios. Herein, an advanced cathode comprising highly active Fe single-atom catalysts (SACs) is reported to form 320.2 W h kg-1 multistacked Li-S pouch cells with total capacity of ≈1 A h level, satisfying low E/S (3.0), E/C (2.8), and N/P (2.3) ratios and high sulfur loadings (8.4 mg cm-2 ). The high-activity Fe SAC is designed by manipulating its local environments using electron-exchangeable binding (EEB) sites. Introducing EEB sites comprising two different types of S species, namely, thiophene-like-S (-S) and oxidized-S (-SO2 ), adjacent to Fe SACs promotes the kinetics of the Li2 S redox reaction by providing additional binding sites and modulating the Fe d-orbital levels via electron exchange with Fe. The -S donates the electrons to the Fe SACs, whereas -SO2 withdraws electrons from the Fe SACs. Thus, the Fe d-orbital energy level can be modulated by the different -SO2 /-S ratios of the EEB site, controlling the electron donating/withdrawing characteristics. This desirable electrocatalysis is maximized by the intimate contact of the Fe SACs with the S species, which are confined together in porous carbon.

CNT-rGO Hydrogel-Integrated Fabric Composite Synthesized via an Interfacial Gelation Process for Wearable Supercapacitor Electrodes.

We demonstrate a flexible and stretchable supercapacitor assembled via straightforward interfacial gelation of reduced graphene oxide (rGO) with carbon nanotube (CNT) on a stretchable fabric surface. The difference between the redox potential of aqueous graphene oxide (GO) dispersion, prepared using a modified Hummers' method, and of a solid Zn plate, which was used as an external stimulus, induces a spontaneous reduction of GO flakes forming porous CNT-rGO hydrogel at the liquid-solid interface. With the aid of Zn, a macroporous and flexible CNT-rGO hydrogel was fabricated on a stretchable fabric platform using a facile fabrication method, and the CNT-rGO fabric composite was assembled into a supercapacitor to demonstrate its feasibility as a wearable electrode. The porous structure of the as-formed CNT-rGO fabric composite allows excellent electrolyte accessibility and ion transport that result in a fast charge/discharge rate up to 100 mV/s and a large areal capacity of 10.13 mF/cm2 at a discharge rate of 0.5 mA (0.1 mA/cm2). The inclusion of one-dimensional CNT as conductive bridges allows an excellent capacity retention of 95.2% after complete folding of the electrode and a capacity retention of 93.3% after 1000 bending cycles. Additional stretching test displayed a high capacity retention of 90.0% even at an applied strain as high as 50%, overcoming previous limitations of brittle graphene-based electrodes. This low-cost, lightweight, easy to synthesize, stretchable supercapacitor holds promise for next-generation wearable electronics and energy storage applications.

Graphene Oxide Induced Surface Modification for Functional Separators in Lithium Secondary Batteries.

Functional separators, which have additional functions apart from the ionic conduction and electronic insulation of conventional separators, are highly in demand to realize the development of advanced lithium ion secondary batteries with high safety, high power density, and so on. Their fabrication is simply performed by additional deposition of diverse functional materials on conventional separators. However, the hydrophobic wetting nature of conventional separators induces the polarity-dependent wetting feature of slurries. Thus, an eco-friendly coating process of water-based slurry that is highly polar is hard to realize, which restricts the use of various functional materials dispersible in the polar solvent. This paper presents a surface modification of conventional separators that uses a solution-based coating of graphene oxide with a hydrophilic group. The simple method enables the large-scale tuning of surface wetting properties by altering the morphology and the surface polarity of conventional separators, without significant degradation of lithium ion transport. On the surface modified separator, superior wetting properties are realized and a functional separator, applicable to lithium metal secondary batteries, is demonstrated as an example. We believe that this simple surface modification using graphene oxide contributes to successful fabrication of various functional separators that are suitable for advanced secondary batteries.

Omnidirectional Deformable Energy Textile for Human Joint Movement Compatible Energy Storage.

Omnidirectional deformability is an unavoidable basic requirement for wearable devices to accommodate human daily motion particularly at human joints. We demonstrate omnidirectionally bendable and stretchable textile-based electrochemical capacitor that retains high power performance under complex mechanical deformation. Judicious synergistic hybrid structure of woven elastic polymer yarns with carbon nanotubes and conductive polymers offers reliable electrical and electrochemical activity even under repeated cycles of severe complex deformation modes. The textile-based electrochemical capacitors exhibit omnidirectional stretchability with 93% of capacitance retention under repeated 50% omnidirectional stretching condition while demonstrating excellent specific capacitance (412 mF cm-2) and cycle stability (>2000 stretch). The wearable power source stably powers red LED under omnidirectional stretching that accompanies human elbow joint motion.

Dopant-specific unzipping of carbon nanotubes for intact crystalline graphene nanostructures.

Atomic level engineering of graphene-based materials is in high demand to enable customize structures and properties for different applications. Unzipping of the graphene plane is a potential means to this end, but uncontrollable damage of the two-dimensional crystalline framework during harsh unzipping reaction has remained a key challenge. Here we present heteroatom dopant-specific unzipping of carbon nanotubes as a reliable and controllable route to customized intact crystalline graphene-based nanostructures. Substitutional pyridinic nitrogen dopant sites at carbon nanotubes can selectively initiate the unzipping of graphene side walls at a relatively low electrochemical potential (0.6 V). The resultant nanostructures consisting of unzipped graphene nanoribbons wrapping around carbon nanotube cores maintain the intact two-dimensional crystallinity with well-defined atomic configuration at the unzipped edges. Large surface area and robust electrical connectivity of the synergistic nanostructure demonstrate ultrahigh-power supercapacitor performance, which can serve for AC filtering with the record high rate capability of -85° of phase angle at 120 Hz.