Ultrafast-Laser Micro-Structuring of LiNi0.8Mn0.1Co0.1O2 Cathode for High-Rate Capability of Three-Dimensional Li-ion Batteries.

Femtosecond ultrafast-laser micro-patterning was employed to prepare a three-dimensional (3D) structure for the tape-casting Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. The influences of laser structuring on the electrochemical performance of NMC811 were investigated. The 3D-NMC811 cathode retained capacities of 77.8% at 2 C of initial capacity at 0.1 C, which was thrice that of 2D-NMC811 with an initial capacity of 27.8%. Cyclic voltammetry (CV) and impedance spectroscopy demonstrated that the 3D electrode improved the Li+ ion transportation at the electrode-electrolyte interface, resulting in a higher rate capability. The diffusivity coefficient DLi+, calculated by both CV and electrochemical impedance spectroscopy, revealed that 3D-NMC811 delivered faster Li+ ion transportation with higher DLi+ than that of 2D-NMC811. The laser ablation of the active material also led to a lower charge-transfer resistance, which represented lower polarization and improved Li+ ion diffusivity.

Stable Zn Metal Anodes with Limited Zn-Doping in MgF2 Interphase for Fast and Uniformly Ionic Flux.

The practical applications of aqueous Zn metal batteries are currently restricted by the inherent drawbacks of Zn such as the hydrogen evolution reaction, sluggish kinetics, and dendrite formation. To address these problems, herein, a limitedly Zn-doped MgF2 interphase comprising an upper region of pure, porous MgF2 and a lower region of gradient Zn-doped MgF2 is achieved via radio frequency sputtering technique. The porous MgF2 region is a polar insulator whose high corrosion resistance facilitates the de-solvation of the solvated Zn ions and suppression of hydrogen evolution, resulting in Zn metal electrodes with a low interfacial resistance. The Zn-doped MgF2 region facilitates fast transfer kinetics and homogeneous deposition of Zn ions owing to the interfacial polarization between the Zn dopant and MgF2 matrix, and the high concentration of the Zn dopant on the surface of the metal substrate as fine nuclei. Consequently, a symmetric cell incorporating the proposed Zn metal exhibits low overpotentials of ~ 27.2 and ~ 99.7 mV without Zn dendrites over 250 to 8000 cycles at current densities of 1.0 and 10.0 mA cm-2, respectively. The developed Zn/MnO2 full cell exhibits superior capacity retentions of 97.5% and 84.0% with average Coulombic efficiencies of 99.96% after 1000 and 3000 cycles, respectively.

Plasma-Assisted Surface Modification on the Electrode Interface for Flexible Fiber-Shaped Zn-Polyaniline Batteries.

A novel flexible fiber-shaped zinc-polyaniline battery (FZPB) is proposed to enhance the electrochemical performance, mass loading, and stability of polyaniline cathodes. To this end, electron-cyclotron-resonance oxygen plasma-modified carbon fibers are employed. During plasma treatment, on the carbon-fiber surface, O2+ plasma breaks the C-C, C-H, and C-N bonds to form C radicals, while the O2 molecules are broken down to reactive oxygen species (O+, O2+, O2+, and O22+). The C radicals and the reactive oxygen species are combined to homogeneously form oxygen functional groups, such as -OH, -COOH, and -C═O. The surface area and total pore volume of the treated carbon fibers increase as the plasma attacks. During electrodeposition, aniline interacts with the oxygen functional groups to form N-O and N-H bonds and π-π stacking, resulting in a homogeneous and high-loading polyaniline structure and improved adhesion between polyaniline and carbon fibers. In an FZPB, the cathode with plasma-treated carbon fibers and a polyaniline loading of 0.158 mg mgCF-1 (i.e., 2.36 mg cmCF-1) exhibits a capacity retention of 95.39% after 200 cycles at 100 mA g-1 and a discharge capacity of 83.96 mA h g-1 at such a high current density of 2000 mA g-1, which are ∼1.67 and 1.24 times those of the pristine carbon-fiber-based one, respectively. Furthermore, the FZPB exhibits high flexibility with a capacity retention of 86.4% after bending to a radius of 2.5 mm for 100 cycles as a wearable energy device.

Self-Relaxant Superelastic Matrix Derived from C60 Incorporated Sn Nanoparticles for Ultra-High-Performance Li-Ion Batteries.

Homogeneously dispersed Sn nanoparticles approximately ⩽10 nm in a polymerized C60 (PC60) matrix, employed as the anode of a Li-ion battery, are prepared using plasma-assisted thermal evaporation coupled by chemical vapor deposition. The self-relaxant superelastic characteristics of the PC60 possess the ability to absorb the stress-strain generated by the Sn nanoparticles and can thus alleviate the problem of their extreme volume changes. Meanwhile, well-dispersed dot-like Sn nanoparticles, which are surrounded by a thin SnO2 layer, have suitable interparticle spacing and multilayer structures for alleviating the aggregation of Sn nanoparticles during repeated cycles. The Ohmic characteristic and the built-in electric field formed in the interparticle junction play important roles in enhancing the diffusion and transport rate of Li ions. SPC-50, a Sn-PC60 anode consisting of 50 wt % Sn and 50 wt % PC60, as confirmed by energy-dispersive X-ray spectroscopy analysis, exhibited the highest electrochemical performance. The resulting SPC-50 anode, in a half-cell configuration, exhibited an excellent capacity retention of 97.18%, even after 5000 cycles at a current density of 1000 mA g-1 with a discharge capacity of 834.25 mAh g-1. In addition, the rate-capability performance of this SPC-50 half-cell exhibited a discharge capacity of 544.33 mAh g-1 at a high current density of 10 000 mA g-1, even after the current density was increased 100-fold. Moreover, a very high discharge capacity of 1040.09 mAh g-1 was achieved with a capacity retention of 98.67% after 50 cycles at a current density of 100 mA g-1. Futhermore, a SPC-50 full-cell containing the LiCoO2 cathode exhibited a discharge capacity of 801.04 mAh g-1 and an areal capacity of 1.57 mAh cm-2 with a capacity retention of 95.27% after 350 cycles at a current density of 1000 mA g-1.

ZnO Nanorod Array Modified PVDF Membrane with Superhydrophobic Surface for Vacuum Membrane Distillation Application.

The vacuum membrane distillation (VMD) is a promising technology for lots of applications. To solve the membrane fouling and wetting problems, in this paper, a novel ZnO nanorods 1 H,1 H,2 H,2 H-perfluorodecyltriethoxysilane (PDTS) modified poly(vinylidene fluoride) (PVDF) membrane with a micro/nanoscale hierarchical structure and a superhydrophobic surface has been prepared and applied to the VMD process for distilling highly salty water, for the first time. Among these, a pyrolysis-adhesion method is created to obtain the ZnO seeds and fasten them on the PVDF substrate firmly. The novel modified membrane shows a stable superhydrophobic surface with a water contact angle of 152°, easy cleaning property, excellent thermal and mechanical stability, because of the Cassie's state caused by pocketing much air in the hydrophobized ZnO nanorods, the low surface energy of PDTS coating, and the strong adhesion between ZnO nanorods and PVDF membrane, which has built an ideal structure for VMD application. After 8 h VMD of 200 g L-1 NaCl solution, compared to the virgin PVDF membrane, the novel membrane shows a similar permeate flux but a much higher quality permeated liquid because of its unique antifouling and antiwetting caused by the several microns gap between the feed and the membrane. Due to its easy cleaning property, the novel membrane also exhibits an excellent reusability.

Li4SiO4-Based Artificial Passivation Thin Film for Improving Interfacial Stability of Li Metal Anodes.

An amorphous SiO2 (a-SiO2) thin film was developed as an artificial passivation layer to stabilize Li metal anodes during electrochemical reactions. The thin film was prepared using an electron cyclotron resonance-chemical vapor deposition apparatus. The obtained passivation layer has a hierarchical structure, which is composed of lithium silicide, lithiated silicon oxide, and a-SiO2. The thickness of the a-SiO2 passivation layer could be varied by changing the processing time, whereas that of the lithium silicide and lithiated silicon oxide layers was almost constant. During cycling, the surface of the a-SiO2 passivation layer is converted into lithium silicate (Li4SiO4), and the portion of Li4SiO4 depends on the thickness of a-SiO2. A minimum overpotential of 21.7 mV was observed at the Li metal electrode at a current density of 3 mA cm-2 with flat voltage profiles, when an a-SiO2 passivation layer of 92.5 nm was used. The Li metal with this optimized thin passivation layer also showed the lowest charge-transfer resistance (3.948 Ω cm) and the highest Li ion diffusivity (7.06 × 10-14 cm2 s-1) after cycling in a Li-S battery. The existence of the Li4SiO4 artificial passivation layer prevents the corrosion of Li metal by suppressing Li dendritic growth and improving the ionic conductivity, which contribute to the low charge-transfer resistance and high Li ion diffusivity of the electrode.

Pseudocapacitive Characteristics of Low-Carbon Silicon Oxycarbide for Lithium-Ion Capacitors.

Lithium-ion capacitors (LICs) and lithium-ion batteries (LIBs) are important energy storage devices. As a material with good mechanical, thermal, and chemical properties, low-carbon silicon oxycarbide (LC-SiOC), a kind of silicone oil-derived SiOC, is of interest as an anode material, and we have examined the electrochemical behavior of LC-SiOC in LIB and LIC devices. We found that the lithium storage mechanism in LC-SiOC, prepared by pyrolysis of phenyl-rich silicon oil, depends on an oxygen-driven rather than a carbon-driven mechanism within our experimental scope. An investigation of the electrochemical performance of LC-SiOC in half- and full-cell LIBs revealed that LC-SiOC might not be suitable for full-cell LIBs because it has a lower capacity (238 mAh g-1) than that of graphite (290 mAh g-1) in a cutoff voltage range of 0-1 V versus Li/Li+, as well as a substantial irreversible capacity. Surprisingly, LC-SiOC acts as a pseudocapacitive material when it is tested in a half-cell configuration within a narrow cutoff voltage range of 0-1 V versus Li/Li+. Further investigation of a "hybrid" supercapacitor, also known as an LIC, in which LC-SiOC is coupled with an activated carbon electrode, demonstrated that a power density of 156 000 W kg-1 could be achieved while maintaining an energy density of 25 Wh kg-1. In addition, the resulting capacitor had an excellent cycle life, holding ∼90% of its energy density even after 75 000 cycles. Thus, LC-SiOC is a promising active material for LICs in applications such as heavy-duty electric vehicles.

One-Step Catalytic Synthesis of CuO/Cu2O in a Graphitized Porous C Matrix Derived from the Cu-Based Metal-Organic Framework for Li- and Na-Ion Batteries.

The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in a highly graphitized porous C matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increasing the rate capability and reversible capacity of metal oxide negative materials for Li- and Na-ion batteries. CuO/Cu2O-GPC is synthesized through a Cu-based metal-organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied and exhibit excellent capacities of 887.3 mAh g(-1) at 60 mA g(-1) after 200 cycles in a Li-ion battery and 302.9 mAh g(-1) at 50 mA g(-1) after 200 cycles in a Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micronanoparticles and highly graphitized porous C formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and resulting high electrochemical performance, CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.

Ionic Liquid-Based Polymer Electrolytes via Surfactant-Assisted Polymerization at the Plasma-Liquid Interface.

We first report an innovative method, which we refer to as interfacial liquid plasma polymerization, to chemically cross-link ionic liquids (ILs). By this method, a series of all-solid state, free-standing polymer electrolytes is successfully fabricated where ILs are used as building blocks and ethylene oxide-based surfactants are employed as an assisted-cross-linking agent. The thickness of the films is controlled by the plasma exposure time or the ratio of surfactant to ILs. The chemical structure and properties of the polymer electrolyte are characterized by scanning electron microscopy (SEM), Fourier transformation infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy (EIS). Importantly, the underlying polymerization mechanism of the cross-linked IL-based polymer electrolyte is studied to show that fluoroborate or halide anions of ILs together with the aid of a small amount of surfactants having ethylene oxide groups are necessary to form cross-linked network structures of the polymer electrolyte. The ionic conductivity of the obtained polymer electrolyte is 2.28 × 10(-3) S·cm(-1), which is a relatively high value for solid polymer electrolytes synthesized at room temperature. This study can serve as a cornerstone for developing all-solid state polymer electrolytes with promising properties for next-generation electrochemical devices.

Interfacial Engineering for Enhanced Light Absorption and Charge Transfer of a Solution-Processed Bulk Heterojunction Based on Heptazole as a Small Molecule Type of Donor.

In the present study, a solution-processed organic semiconductor based on indolocarbazole derivative (heptazole) is introduced as a p-type donor material for a bulk-heterojunction photovoltaic device. The heptazole has an optical band gap of 2.97 eV, and its highest occupied molecular orbital-lowest unoccupied molecular orbital energy levels are compactable with the PC60BM to construct a donor-acceptor heterojuction for energy harvesting and transfer. When the bulk-heterojunction photovoltaic devices consisting of ITO/PEDOT:PSS/heptazole:PC60BM/Al with different blending ratio of heptazole:PC60BM were constructed, the cell with 1:1 blending ratio exhibited the best power conversion efficiency. Further, when an indoline organic dye (D149) was introduced as an interfacial modifier to the above donor/acceptor bulk heterojunction, the device demonstrated an enhanced overall power conversion efficiency from 1.26% to 2.51% hence demonstrating enhancement by the factor of 100%. The device was further characterized using electronic absorption spectroscopy, photoluminescence spectroscopy, electrochemical impedance spectroscopy, and the photovoltage decay kinetics. These studies reveal that the enhanced power conversion efficiency of the device is due to the enhanced charge transfer with the complementary light absorption feature of the interfacial D149 dye molecules.

Oxidation-resistant hybrid metal oxides/metal nanodots/silver nanowires for high performance flexible transparent heaters.

Despite its excellent optical, electrical, mechanical, and thermal performances, a silver nanowire (AgNW)-based transparent conducting heater (TCH) still demonstrates several drawbacks such as facile nanowire breakdown on application of a high DC voltage, easy oxidation when exposed to harsh environments, leading to increased surface resistivity, and high resistance among wire junctions causing nonhomogeneous temperature profiles. To overcome these issues, the AgNW was hybridized with other transparent heating materials made of fluorine-doped tin oxide (FTO) thin films and NiCr nanodots (FTO/NiCr/AgNW). The dispersed NiCr nanodots (∼50 nm) and FTO thin films (∼20 nm) electrically bridge the nanowire junctions leading to a decreased sheet resistance and uniform temperature profiles. The hybrid transparent heater shows excellent optical transmittance (>90%) and high saturation temperature (162 °C) at low applied DC voltage (6 V). Moreover, the FTO/NiCr/AgNW heater exhibits a stable sheet resistance in a hostile environment, hence highlighting the excellent oxidation-resistance of the heating materials. These results indicate that the proposed hybrid transparent heaters could be a promising approach to combat the inherent problems associated with AgNW-based transparent heaters for various functional applications.

Carbon-Coated Li4Ti5O12 as Anode Material for Sodium-Ion Batteries.

The surface-coating of carbon was performed on the spinel Li4Ti5O12 materials for the electrochemical sodium insertion in sodium ion battery application. The carbon-coated Li4Ti5O12 was synthesized by using the citric acid sol-gel method. Carbon-coated Li4Ti5O12 exhibits superior cycle performance as well as the rate capability in comparison to the pristine Li4Ti5O12. Electrochemical impedance spectroscopy analyses also reveal that surface modification with carbon suppresses the increase in resistance concerning charge transfer reaction as well as solid electrolyte interface layer formation during cycle test.

Electrochemical Characteristics of Pyrolytic Carbon Coated Silicon for Anode Materials of Lithium Ion Batteries.

Pyrolytic carbon coated silicon is prepared and employ it as an anode material for lithium secondary batteries. The pyrolytic carbon coating of silicon with sucrose precursor not only provides a suitable carbon matrix but also suppresses the breaking away of Si from the current collector during the insertion and extraction of Li+. The increase of disordered carbon content leads to the increase of discharge capacity retention. The improvements of cycle stability are attributed to a decrease in the volume change of the silicon, good networking between Si particles, and good adhesion of the current collector with the active material. The nano Si combined with the disordered carbon leads to an increase of capacity retention and initial coulombic efficiency.

Formation of Semimetallic Cobalt Telluride Nanotube Film via Anion Exchange Tellurization Strategy in Aqueous Solution for Electrocatalytic Applications.

Metal telluride nanostructures have demonstrated several potential applications particularly in harvesting and storing green energy. Metal tellurides are synthesized by tellurization process performed basically at high temperature in reducing gas atmosphere, which makes the process expensive and complicated. The development of a facile and economical process for desirable metal telluride nanostructures without complicated manipulation is still a challenge. In an effort to develop an alternative strategy of tellurization, herein we report a thin film formation of self-standing cobalt telluride nanotubes on various conducting and nonconducting substrates using a simple binder-free synthetic strategy based on anion exchange transformation from a thin film of cobalt hydroxycarbonate nanostructures in aqueous solution at room temperature. The nanostructured films before and after ion exchange transformation reaction are characterized using field emission scanning electron microscope, energy dispersive X-ray analyzer, X-ray photoelectron spectroscopy, thin film X-ray diffraction technique, high resolution transmission electron microscope, and selected area electron diffraction analysis technique. After the ion exchange transformation of nanostructures, the film shows conversion from insulator to highly electrical conductive semimetallic characteristic. When used as a counter electrode in I3(-)/I(-) redox electrolyte based dye-sensitized solar cells, the telluride film exhibits an electrocatalytic reduction activity for I3(-) with a demonstration of solar-light to electrical power conversion efficiency of 8.10%, which is highly competitive to the efficiency of 8.20% exhibited by a benchmarked Pt-film counter electrode. On the other hand, the telluride film electrode also demonstrates electrocatalytic activity for oxygen evolution reaction from oxidation of water.

3D Woven-Like Carbon Micropattern Decorated with Silicon Nanoparticles for Use in Lithium-Ion Batteries.

Carbon/silicon composite materials are a promising anode substrate for use in lithium-ion batteries. In this study, we suggest a new architecture for a composite electrode made of a woven-like carbon material decorated with silicon nanoparticles. The 3D woven-like carbon (WLC) structure was fabricated using direct carbonization of multi-beam interference lithography polymer patterns. Subsequent solution coating was applied to decorate the WLC with silicon nanoparticles (SiNPs). The SiNP/WLC electrode exhibited a specific capacity of 930 mAh g(-1) , which is three times higher than the specific capacity of the bare electrode. Specifically, the SiNP/WLC electrode exhibited an outstanding retention capacity of 81 % after 50 cycles and a Coulombic efficiency of more than 98 %. This rate capability performance was attributed to the WLC structure and the uniform decoration of the SiNPs.

Si/Ti2O3/Reduced Graphene Oxide Nanocomposite Anodes for Lithium-Ion Batteries with Highly Enhanced Cyclic Stability.

Silicon (Si) has attracted tremendous attention as a high-capacity anode material for next generation Li-ion batteries (LIBs); unfortunately, it suffers from poor cyclic stability due to excessive volume expansion and reduced electrical conductivity after repeated cycles. To circumvent these issues, we propose that Si can be complexed with electrically conductive Ti2O3 to significantly enhance the reversible capacity and cyclic stability of Si-based anodes. We prepared a ternary nanocomposite of Si/Ti2O3/reduced graphene oxide (rGO) using mechanical blending and subsequent thermal reduction of the Si, TiO2 nanoparticles, and rGO nanosheets. As a result, the obtained ternary nanocomposite exhibited a specific capacity of 985 mAh/g and a Coulombic efficiency of 98.4% after 100 cycles at a current density of 100 mA/g. Furthermore, these ternary nanocomposite anodes exhibited outstanding rate capability characteristics, even with an increased current density of 10 A/g. This excellent electrochemical performance can be ascribed to the improved electron and ion transport provided by the Ti2O3 phase within the Si domains and the structurally reinforced conductive framework comprised of the rGO nanosheets. Therefore, it is expected that our approach can also be applied to other anode materials to enable large reversible capacity, excellent cyclic stability, and good rate capability for high-performance LIBs.

Charge Transfer-Induced Molecular Hole Doping into Thin Film of Metal-Organic Frameworks.

Despite the highly porous nature with significantly large surface area, metal-organic frameworks (MOFs) can be hardly used in electronic and optoelectronic devices due to their extremely poor electrical conductivity. Therefore, the study of MOF thin films that require electron transport or conductivity in combination with the everlasting porosity is highly desirable. In the present work, thin films of Co3(NDC)3DMF4 MOFs with improved electronic conductivity are synthesized using layer-by-layer and doctor blade coating techniques followed by iodine doping. The as-prepared and doped films are characterized using FE-SEM, EDX, UV/visible spectroscopy, XPS, current-voltage measurement, photoluminescence spectroscopy, cyclic voltammetry, and incident photon to current efficiency measurements. In addition, the electronic and semiconductor properties of the MOF films are characterized using Hall Effect measurement, which reveals that, in contrast to the insulator behavior of the as-prepared MOFs, the iodine doped MOFs behave as a p-type semiconductor. This is caused by charge transfer-induced hole doping into the frameworks. The observed charge transfer-induced hole doping phenomenon is also confirmed by calculating the densities of states of the as-prepared and iodine doped MOFs based on density functional theory. Photoluminescence spectroscopy demonstrates an efficient interfacial charge transfer between TiO2 and iodine doped MOFs, which can be applied to harvest solar radiations.

Coating lithium titanate with nitrogen-doped carbon by simple refluxing for high-power lithium-ion batteries.

Nitrogen-doped carbon is coated on lithium titanate (Li4Ti5O12, LTO) via a simple chemical refluxing process, using ethylenediamine (EDA) as the carbon and nitrogen source. The process incorporates a carbon coating doped with a relatively high amount of nitrogen to form a conducting network on the LTO matrix. The introduction of N dopants in the carbon matrix leads to a higher density of C vacancies, resulting in improved lithium-ion diffusion. The uniform coating of nitrogen-doped carbon on Li4Ti5O12 (CN-LTO) enhances the electronic conductivity of a CN-LTO electrode and the corresponding electrochemical properties of the cell employing the electrode. The results of our study demonstrate that the CN-LTO anode exhibits higher rate capability and cycling performance over 100 cycles. From the electrochemical tests performed, the specific capacity of CN-LTO electrode at higher rates of 20 and 50 C are found to be 140.7 and 82.3 mAh g(-1), respectively. In addition, the CN-Li4Ti5O12 anode attained higher capacity retention of 100% at 1 C rate after 100 cycles and 92.9% at 10 C rate after 300 cycles.

Interfacial Engineering of CdO-CdSe 3D Microarchitectures with in situ Photopolymerized PEDOT for an Enhanced Photovoltaic Performance.

In the present work, porous 3D CdO-microstructured electrode obtained by pyrolysis of 3D CdCO3 microstructures is self-sensitized with CdSe using an ion exchange reaction. After sensitization, an interfacial treatment of the CdO-CdSe interface is performed by depositing a thin film of PEDOT using a photoinduce polymerization route. The microstructured electrode before and after interfacial treatment is characterized using field-emission scanning microscope, energy dispersive X-ray analyzer, contact angle measurement, UV-Visible absorption spectrophotometer and X-ray photoelectron spectrometer. After constructing a liquid junction solar cell with a Pt counter electrode, the photovoltaic performance and interfacial charge transfer kinetics across the CdO-CdSe interface before and after PEDOT treatment are investigated. The results exhibit an improved interfacial charge-transfer resistance after the PEDOT treatment, which leads to enhance the short-circuit current by 15.81% and the power conversion efficiency by 19.82%.