Conductive Polyaniline-Indium Oxide Composite Films Prepared by Sequential Infiltration Synthesis for Electrochemical Energy Storage.

Composites of conductive polymers (CP) and metal oxides (MO) have attracted continued interest in the past decade for diverse application fields because the synergistic effects of CP and MO enable the realization of unusual electronic, electrochemical, catalytic, and mechanical properties of the composites. Herein, we present a novel method for the sequential infiltration synthesis of composite films of polyaniline (PANI) and indium oxide (InO x ) with high electrical conductivities (4-9 S/cm). The synthesized composite films were composed of two phases of graded concentration: InO x with oxygen vacancies and PANI with partially protonated molecular units. The PANI-InO x composite films displayed enhanced electrochemical activity with a pair of well-defined redox peaks. The open interfacial regions between the InO x and PANI phases may provide efficient pathways for ion diffusion and active sites for improved charge transfer.

Polymer Electrolyte/Sulfur Double-Shelled Anisotropic Reduced Graphene Oxide Lamellar Scaffold Enables Stable and High-Loading Cathode for Quasi-Solid-State Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) can replace lithium-ion batteries by delivering a higher specific capacity. However, the areal capacity of current LSBs is low because the intrinsic limitations of sulfur make achieving a high sulfur loading difficult. Herein, the authors report vertically aligned reduced graphene oxide (rGO) with sulfur and poly(ethylene oxide)-based polymer electrolyte double-shell layers (VRG@S@PPE) as a high-loading sulfur cathode. The addition of vapor-grown carbon fiber (VGCF) into rGO is the key to success, as it allows for gas evacuation from internal nano/micropores without structural collapse, enabling perfect double-shell layer contact. Owing to the anisotropic rGO lamellar structure that enables straightforward ion/electron transport and provides numerous active sites, sulfur-infiltrated rGO reinforced via VGCF (VRG@S) exhibits a high capacity of 998 mAh g-1 after 100 cycles at 0.1 C under high sulfur loading (6 mg cm-2 ). Interestingly, an additional polymer electrolyte layer further increases the cycle retention (1005 and 718 mAh g-1 after 100 cycles at 0.1 and 1 C, respectively), because intimate contact between the solid polymer electrolyte and sulfur could suppress the loss of sulfur due to lithium polysulfide (LPS) shuttling or volume change during lithiation/delithiation. Therefore, it is possible to realize safe and stable quasi-solid-state LSBs with high sulfur loading.

Synergetic Effect of Li-Ion Concentration and Triple Doping on Ionic Conductivity of Li7La3Zr2O12 Solid Electrolyte.

Li7La3Zr2O12 (LLZO) is a promising and safe solid electrolyte for all-solid-state batteries. To achieve high ionic conductivity of LLZO, stabilizing the cubic phase and reducing Li loss during the sintering process is essential. Therefore, reducing the sintering temperature, which increases the sintering time for high-density pellets, is necessary. Herein, we investigate the change in the crystal structure, morphology, and Li ionic conductivity of LLZO pellets by triple doping with Al, Ga, and Ta and modulating the variation in initial Li concentrations. Interestingly, the proportion of the conductive cubic phase increased with increasing Li stoichiometry by 1.1 times, and this tendency was further accelerated by triple doping. The synergetic effects of triple doping and Li concentration also minimized Li loss during sintering. Accordingly, it provided a high-quality LLZO pellet with good ionic conductivity (3.6 × 10-4 S cm-1) and high relative density (97.8%). Notably, the LLZO pellet was obtained using a very short sintering process (40 min). Considering that the most time-consuming step is the sintering process for LLZO, this study can provide guidelines for the fast production and commercialization of LLZO electrolytes with high ionic conductivity.

In Situ Conversion of Metal-Organic Frameworks into VO2 -V3 S4 Heterocatalyst Embedded Layered Porous Carbon as an "All-in-One" Host for Lithium-Sulfur Batteries.

Although lithium-sulfur batteries exhibit a fivefold higher energy density than commercial lithium-ion batteries, their volume expansion and insulating nature, and intrinsic polysulfide shuttle have hindered their practical application. An alternative sulfur host is necessary to realize porous, conductive, and polar functions; however, there is a tradeoff among these three critical factors in material design. Here, the authors report a layered porous carbon (LPC) with VO2 /V3 S4 heterostructures using one-step carbonization-sulfidation of metal-organic framework templates as a sulfur host that meets all the criteria. In situ conversion of V-O ions into V3 S4 nuclei in the confined 2D space generated by dynamic formation of the LPC matrix creates {200}-facet-exposed V3 S4 nanosheets decorated with tiny VO2 nanoparticles. The VO2 /V3 S4  @ LPC composite facilitates high sulfur loading (70 wt%), superior energy density (1022 mA h g-1 at 0.2 C, 100 cycles), and long-term cyclability (665 mA h g-1 at 1 C, 1000 cycles). The enhanced Li-S chemistry is attributed to the synergistic heterocatalytic behavior of polar VO2 and conductive V3 S4 in the soft porous LPC scaffold, which accelerates polysulfide adsorption, conversion, and charge-transfer ability simultaneously.

Extremely stretchable and self-healing conductor based on thermoplastic elastomer for all-three-dimensional printed triboelectric nanogenerator.

Advances in next-generation soft electronic devices rely on the development of highly deformable, healable, and printable energy generators to power these electronics. Development of deformable or wearable energy generators that can simultaneously attain extreme stretchability with superior healability remains a daunting challenge. We address this issue by developing a highly conductive, extremely stretchable, and healable composite based on thermoplastic elastomer with liquid metal and silver flakes as the stretchable conductor for triboelectric nanogenerators. The elastomer is used both as the matrix for the conductor and as the triboelectric layer. The nanogenerator showed a stretchability of 2500% and it recovered its energy-harvesting performance after extreme mechanical damage, due to the supramolecular hydrogen bonding of the thermoplastic elastomer. The composite of the thermoplastic elastomer, liquid metal particles, and silver flakes exhibited an initial conductivity of 6250 S cm-1 and recovered 96.0% of its conductivity after healing.

Finite element analysis of knee and ankle joint during gait based on motion analysis.

Contact pressures in the articular cartilage during gait affect injuries and the degenerative arthritis of knee and ankle joints. However, only contact forces at the knee and ankle joints during gait can be estimated by using a rigid body dynamic model. The contact pressure distribution can be obtained quantitatively for a static posture by using finite element (FE) analysis in most cases. The purpose of this study is to develop a new method to obtain the contact pressure distribution at the knee and ankle joints during gait by integrating FE analysis with rigid body dynamic analysis. In this method, a reference FE model of the lower extremity is constructed first and is then transformed to each stance phase of the gait obtained from dynamic analysis by using homogeneous transformation. The muscle forces and ground reaction force (GRF) during gait obtained from the dynamic analysis were used as loading conditions for FE analysis. Finally, the contact pressure distribution at the tibia plateau cartilage and talus cartilage were estimated at the 1st peak, mid-stance, and the 2nd peak at the same time. The present method can provide the contact pressure distribution at the knee and ankle joints over the entire gait.

A Stretchable and Self-Healing Energy Storage Device Based on Mechanically and Electrically Restorative Liquid-Metal Particles and Carboxylated Polyurethane Composites.

Stretchable and self-healing (SH) energy storage devices are indispensable elements in energy-autonomous electronic skin. However, the current collectors are not self-healable nor intrinsically stretchable, they mostly rely on strain-accommodating structures that require complex processing, are often limited in stretchability, and suffer from low device packing density and fragility. Here, an SH conductor comprising nickel flakes, eutectic gallium indium particles (EGaInPs), and carboxylated polyurethane (CPU) is presented. An energy storage device is constructed by the two SH electrodes assembled with graphene nanoplatelets sandwiching an ionic-liquid electrolyte. An excellent electrochemical healability (94% capacity retention upon restretching at 100% after healing from bifurcation) is unveiled, stemming from the complexation modulated redox behavior of EGaIn in the presence of the ligand bis(trifluoromethanesulfonyl)imide, which enhances the reversible Faradaic reaction of Ga. Self-healing can be achieved where the damaged regions are electrically restored by the flow of liquid metal and mechanically healing activated by the interfacial hydrogen bonding of CPU with an efficiency of 97.5% can be achieved. The SH conductor has an initial conductivity of 2479 S cm-1 that attains a high stretchability with 700% strain, it restores 100% stretchability even after breaking/healing with the electrical healing efficiency of 75%.

Coaxial Ag-base metal nanowire networks with high electrochemical stability for transparent and stretchable asymmetric supercapacitors.

Transparent and stretchable Ag-Ni and Ag-Fe core-shell nanowire networks were fabricated as a cathode and anode, respectively, for asymmetric supercapacitors. Both electrodes showed a reversible stretchability at up to 100% strain and exhibited high electrochemical stability and specific capacitances of ∼3 mF cm-2 with 50% optical transmittance. The asymmetric device assembled with a PVA/KOH electrolyte demonstrated a high operating voltage of 1.6 V and an excellent capacitance retention (92%) over 5000 cycles even after stretching to 35% strain.

Enhanced Lithium Storage in Reduced Graphene Oxide-supported M-phase Vanadium(IV) Dioxide Nanoparticles.

Vanadium(IV) dioxide (VO2) has drawn attention as one of the most attractive electrode materials for lithium-ion batteries (LIBs), hence, much research has been conducted in various sectors in this field. However, to date, most of this research has focused on the VO2(B) polymorph, whereas electrochemical information on the use of VO2(M) in LIB electrodes is insufficient. Thus, it is worthwhile to explore the possibility of using VO2(M) for LIB electrode application, and to investigate whether its electrochemical properties can be improved. In this study, VO2(M) nanoparticles, incorporated with a reduced graphene oxide composite (NP-VO2/rGO), were successfully synthesized via a sol-gel assisted hydrothermal process by the chemical reduction of V2O5 gel, using hydrazine as the reducing agent. The particle size was less than 50 nm regardless of the presence of rGO. Also, NP-VO2/rGO exhibited a specific capacity of 283 mA h g(-1) up to the 200(th) cycle at a current density of 60 mA g(-1), indicating its potential to be used in LIBs.

Quantitative Evaluation of the Dispersion of Graphene Sheets With and Without Functional Groups Using Molecular Dynamics Simulations.

Nanofluids with enhanced thermal properties are candidates for thermal management in automotive systems, with scope for improving energy efficiency. In particular, many studies have reported on dispersions of nanoparticles with long-term stability in the base fluid, with qualitative evaluations of the dispersion stability via either the naked eye or optical instruments. Additives such as surfactants can be used to enhance the dispersion of nanoparticles; however, this may diminish their intrinsic thermal properties. Here, we describe molecular dynamics simulations of nanofluids containing graphene sheets dispersed in ethylene glycol and water. We go on to suggest a quantitative evaluation method for the degree of dispersion, based on the ratio of the total number of nanoparticles to the number of clustered nanoparticles. Moreover, we investigate the effects of functional groups on the surface of graphene, which are expected to improve the dispersion without requiring additives such as surfactants due to steric hindrance and chemical affinity for the surrounding fluid. We find that, for pure graphene, the degree of dispersion decreased as the quantity of graphene sheets increased, which is attributed to an increased probability of aggregation at higher loadings; however, the presence of functional groups inhibited the graphene sheets from forming aggregates.

Enhanced Photocatalytic Activity of Ultrathin Ba5Nb4O15 Two-Dimensional Nanosheets.

Anisotropic two-dimensional (2D) nanosheets of the layered perovskite, Ba5Nb4O15, with thicknesses of 5-10 nm and lateral sizes of 300-1200 nm, were synthesized by a hydrothermal route. The influences of the 2D morphology of the material on the crystal and electronic structures, light absorption properties, and photocatalytic activity were investigated. The ultrathin nanosheets showed much-enhanced photocatalytic activity compared to both thick nanosheets (∼30 nm) and micrometer-sized particles for the evolution of H2 from water splitting under UV light illumination. This enhanced activity is predominantly attributed to the larger surface area, higher optical absorption, and charge separation ability of the 2D nanosheet, which results from the variation of the local crystal structure arising from the ultrathin morphology of the Ba5Nb4O15.

Biomineralized multifunctional magnetite/carbon microspheres for applications in Li-ion batteries and water treatment.

Advanced functional materials incorporating well-defined multiscale architectures are a key focus for multiple nanotechnological applications. However, strategies for developing such materials, including nanostructuring, nano-/microcombination, hybridization, and so on, are still being developed. Here, we report a facile, scalable biomineralization process in which Micrococcus lylae bacteria are used as soft templates to synthesize 3D hierarchically structured magnetite (Fe3O4) microspheres for use as Li-ion battery anode materials and in water treatment applications. Self-assembled Fe3O4 microspheres with flower-like morphologies are systematically fabricated from biomineralized 2D FeO(OH) nanoflakes at room temperature and are subsequently subjected to post-annealing at 400 °C. In particular, because of their mesoporous properties with a hollow interior and the improved electrical conductivity resulting from the carbonized bacterial templates, the Fe3 O4 microspheres obtained by calcining the FeO(OH) in Ar exhibit enhanced cycle stability and rate capability as Li-ion battery anodes, as well as superior adsorption of organic pollutants and toxic heavy metals.

High-areal-capacity lithium storage of the Kirkendall effect-driven hollow hierarchical NiS(x) nanoarchitecture.

Three-dimensional (3-D) architectures can provide significant advantages as lithium ion microbattery electrodes by lengthening the vertical dimension. In addition, the nanoscale hierarchy and hollow properties are important factors for enhancing the performance. Here, we prepared a 3-D nickel sulfide nanoarchitecture via a facile low-temperature solution route. A Kirkendall effect-driven sulfidation of a 3-D nickel electrode was used to produce a hollow 3-D structure. Moreover, a nanoscale hierarchy can be formed with the use of highly concentrated sulfur species. The morphology, structure, and chemical composition of the 3-D nickel sulfide electrode are characterized in detail, and the formation mechanism is discussed based on a time-resolved study. The 3-D nickel sulfide electrodes show an outstanding areal capacity (1.5 mA h cm(-2) at a current rate of 0.5 mA cm(-2)), making this electrode a potential electrode for 3-D lithium ion microbatteries with a large energy density. Moreover, this strategy is expected to provide a general fabrication method for transition metal sulfide nanoarchitectures.

Transparent-conducting-oxide nanowire arrays for efficient photoelectrochemical energy conversion.

We report one dimensional (1-D) transparent-conducting-oxide arrays coated with light-absorbing semiconductors to simultaneously maximize light harvesting and charge collection in a photoelectrochemical (PEC) system. Tin-doped indium oxide (ITO) nanowire (NW) arrays are prepared on ITO thin-film substrates as the transparent-conducting-oxide, and TiO2 or CdSe/CdS/TiO2 thin layers were coated on the ITO NW arrays as the solar light-absorbing layers. The optimal PEC performance, 0.85% under 100 mW cm(-2) of light illumination, is obtained from ∼ 30 µm-long ITO NW, which is covered with ∼ 20 nm-thick TiO2 nanoshell. We finally demonstrate that the ITO NW-based photoelectrode is also compatible with one of the most efficient visible-light sensitizers, the CdS/CdSe quantum dot. Our approach using the transparent conducting 1-D array has wide potential to improve the PEC performances of conventional semiconducting materials through liberation from the poor charge transport.

Hierarchical assembly of TiO2-SrTiO3 heterostructures on conductive SnO2 backbone nanobelts for enhanced photoelectrochemical and photocatalytic performance.

Heterostructures can play a role in enhanced photoinduced electrochemical and catalytic reactions due to the advantageous combination of two compounds. Herein, we demonstrate the fabrication of Sb:SnO2@TiO2-SrTiO3 3D heterostructures via a simple hydrothermal method using a conductive Sb:SnO2@TiO2 nanobelt electrode as a template. XRD, FESEM, and TEM analyses confirm that a well-dispersed and crystalized SrTiO3 layer is formed on the surface of TiO2 nanorods. The photoelectrochemical (PEC) performance of the heterostructure is optimized by controlling the reaction time. Details about the effect of the hydrothermal reaction time on the PEC performance are discussed. The optimized Sb:SnO2@TiO2-SrTiO3 heterostructure exhibited a higher onset potential and a saturated photocurrent in comparison to the Sb:SnO2@TiO2 nanostructure. The result is attributed to a Fermi level shift and a blocking layer effect caused by the SrTiO3. Furthermore, the photocatalytic degradation of methylene blue was significantly enhanced on the optimized Sb:SnO2@TiO2-SrTiO3. This work demonstrates that a synergetic effect between three-dimensional nanoarchitecturing and a heterojunction structure is responsible for enhanced PEC as well as improved photocatalytic performance levels, both of which can be extended to other metal-oxide and/or ternary compounds.

Hydrated manganese(II) phosphate (Mn3(PO4)2·3H2O) as a water oxidation catalyst.

The development of a water oxidation catalyst has been a demanding challenge in realizing water splitting systems. The asymmetric geometry and flexible ligation of the biological Mn4CaO5 cluster are important properties for the function of photosystem II, and these properties can be applied to the design of new inorganic water oxidation catalysts. We identified a new crystal structure, Mn3(PO4)2·3H2O, that precipitates spontaneously in aqueous solution at room temperature and demonstrated its high catalytic performance under neutral conditions. The bulky phosphate polyhedron induces a less-ordered Mn geometry in Mn3(PO4)2·3H2O. Computational analysis indicated that the structural flexibility in Mn3(PO4)2·3H2O could stabilize the Jahn-Teller-distorted Mn(III) and thus facilitate Mn(II) oxidation. This study provides valuable insights into the interplay between atomic structure and catalytic activity.

A ferroelectric photocatalyst for enhancing hydrogen evolution: polarized particulate suspension.

A particle-based photocatalyst with a permanent internal field prepared by a corona poling method is presented as a novel approach to enhance the hydrogen evolution reaction in a particulate-suspension system. Photocatalytic activity of K0.5Na0.5NbO3 was significantly improved by 7.4 times after the polarization.

Three-dimensional hierarchical Li4Ti5O12 nanoarchitecture by a simple hydrothermal method.

The spinel Li4Ti5O12 (LTO) is a promising candidate as a superior electrode material for energy storage devices due to the extremely small volume expansion/contraction during the charge/discharge processes of a battery. There are various synthetic approaches for the nanostructured LTO electrode: sol-gel, sonochemical, solution-combustion, hydrothermal methods, and others. Herein, three-dimensional (3D) high-density heterogeneous LTO architectures are fabricated by employing the TiO2 nanorods (NRs) branched SnO2 nanowire (NW) arrays as the template. The TiO2 NRs were effectively converted by the hydrothermal method into the LTO NRs that have a width of 40-nm and length of 100-nm, which induce branch/backbone structured LTO-SnO2 composites. Interestingly, the 3D LTO architectures exhibit unique geometrical shapes because the NRs are surrounded by small nanoparticles. We also discuss how the temperature and solvent affect the LTO nanostructure formation in detail. These results suggest that using a template can provide a new method for designing and synthesizing various classes of 3D architecturing synthesis.

Enhanced performance of NaTaO3 using molecular co-catalyst [Mo3S4]4+ for water splitting into H2 and O2.

Photocatalytic activity of NaTaO(3) was significantly improved by using a molecular co-catalyst [Mo(3)S(4)](4+). Its hydrogen production rate is 28 times higher than pure NaTaO(3). This study presents the potential of bioinspired molecular metal clusters as efficient co-catalysts.

Fabrication of TiO2/Tin-doped indium oxide-based photoelectrode coated with overlayer materials and its photoelectrochemical behavior.

The photoelectrochemical properties of TiO2-based photoelectrodes with metal oxide overlayers (e.g., ZnO, ZrO2, MgO, and Al2O3) were investigated. The metal oxides were deposited on TiO2/tin-doped indium oxide (ITO) films by spin-coating metal-alkoxide precursors. The formation of the overlayers was confirmed by energy dispersive X-ray spectroscopy (EDS) and high resolution transmission electron microscopy (HRTEM). Each overlayers were well-coated on the TiO2-based films and have approximately 2 nm thickness. The prepared films were used as photoanodes in a photoelectrochemical system with a Pt counter electrode to evaluate hydrogen production performance. Comparing with other overlayers, the ZnO-coated photoelectrode exhibits the highest rate of hydrogen evolution and which is better than the uncoated one. From the photoelectrochemical and spectroscopic study, the superior hydrogen production property of the ZnO-coated TiO2 photoelectrode was attributed to both the higher light absorbance of ZnO compared to TiO2 and the formation of hydroxyl groups at the ZnO surface.