LiF-Rich Solid Electrolyte Interphase Formation by Establishing Sacrificial Layer on the Separator.

The formation of a stable solid electrolyte interphase (SEI) layer is crucial for enhancing the safety and lifespan of Li metal batteries. Fundamentally, a homogeneous Li+ behavior by controlling the chemical reaction at the anode/electrolyte interface is the key to establishing a stable SEI layer. However, due to the highly reactive nature of Li metal anodes (LMAs), controlling the movement of Li+ at the anode/electrolyte interface remains challenging. Here, an advanced approach is proposed for coating a sacrificial layer called fluorinated self-assembled monolayer (FSL) on a boehmite-coated polyethylene (BPE) separator to form a stable SEI layer. By leveraging the strong affinity between the fluorine functional group and Li+, the rapid formation of a LiF-rich SEI layer in the cell production and early cycling stage is facilitated. This initial stable SEI formation promotes the subsequent homogeneous Li+ flux, thereby improving the LMA stability and yielding an enhanced battery lifespan. Further, the mechanism behind the stable SEI layer generation by controlling the Li+ dynamics through the FSL-treated BPE separator is comprehensively verified. Overall, this research offers significant contributions to the energy storage field by addressing challenges associated with LMAs, thus highlighting the importance of interfacial control in achieving a stable SEI layer.

Electrochemical Analysis of Ion Effects on Electrolyte-Gated Synaptic Transistor Characteristics.

Electrolyte-gated transistors (EGTs) are promising candidates as artificial synapses owing to their precise conductance controllability, quick response times, and especially their low operating voltages resulting from ion-assisted signal transmission. However, it is still vague how ion-related physiochemical elements and working mechanisms impact synaptic performance. Here, to address the unclear correlations, we suggest a methodical approach based on electrochemical analysis using poly(ethylene oxide) EGTs with three alkali ions: Li+, Na+, and K+. Cyclic voltammetry is employed to identify the kind of electrochemical reactions taking place at the channel/electrolyte interface, which determines the nonvolatile memory functionality of the EGTs. Additionally, using electrochemical impedance spectroscopy and qualitative analysis of electrolytes, we confirm that the intrinsic properties of electrolytes (such as crystallinity, solubility, and ion conductivity) and ion dynamics ultimately define the linearity/symmetricity of conductance modulation. Through simple but systematic electrochemical analysis, these results offer useful insights for the selection of components for high-performing artificial synapses.

Valid design and evaluation of cathode and anode materials of aqueous zinc ion batteries with high-rate capability and cycle stability.

Although non-aqueous lithium-ion batteries have a high gravimetric density, aqueous zinc-ion batteries (ZIBs) have recently been in the spotlight as an alternative, because ZIBs have characteristics such as high volumetric density, high ionic conductivity, eco-friendliness, low cost, and high safety. However, the improvement in electrochemical performance is limited due to insufficient rate capability and severe cycle fading of the vanadium-oxide-based cathode and zinc-metal-based anode material, which are frequently used as active materials for ZIBs. In addition, complex methods are required to prepare high-performance cathode and anode materials. Therefore, a simple yet effective strategy is needed to obtain high-performance anodes and cathodes. Herein, an ammonium vanadate nanofiber (AVNF) intercalated with NH4+ and H2O as a cathode material for ZIBs was synthesized within 30 minutes through a facile sonochemical method. In addition, an effective Al2O3 layer of 9.9 nm was coated on the surface of zinc foil through an atomic layer deposition technique. As a result, AVNF//60Al2O3@Zn batteries showed a high rate capability of 108 mA h g-1 even at 20 A g-1, and exhibited ultra-high cycle stability with a capacity retention of 94% even after 5000 cycles at a current density of 10 A g-1.

Surface Oxygen Vacancy Inducing Li-Ion-Conducting Percolation Network in Composite Solid Electrolytes for All-Solid-State Lithium-Metal Batteries.

Composite solid electrolytes (CSEs) are newly emerging components for all-solid-state Li-metal batteries owing to their excellent processability and compatibility with the electrodes. Moreover, the ionic conductivity of the CSEs is one order of magnitude higher than the solid polymer electrolytes (SPEs) by incorporation of inorganic fillers into SPEs. However, their advancement has come to a standstill owing to unclear Li-ion conduction mechanism and pathway. Herein, the dominating effect of the oxygen vacancy (Ovac ) in the inorganic filler on the ionic conductivity of CSEs is demonstrated via Li-ion-conducting percolation network model. Based on density functional theory, indium tin oxide nanoparticles (ITO NPs) are selected as inorganic filler to determine the effect of Ovac on the ionic conductivity of the CSEs. Owing to the fast Li-ion conduction through the Ovac inducing percolation network on ITO NP-polymer interface, LiFePO4 /CSE/Li cells using CSEs exhibit a remarkable capacity in long-term cycling (154 mAh g-1 at 0.5C after 700 cycles). Moreover, by modifying the Ovac concentration of ITO NPs via UV-ozone oxygen-vacancy modification, the ionic conductivity dependence of the CSEs on the surface Ovac from the inorganic filler is directly verified.

Ionic Liquid Electrolytes for Electrochemical Energy Storage Devices.

For decades, improvements in electrolytes and electrodes have driven the development of electrochemical energy storage devices. Generally, electrodes and electrolytes should not be developed separately due to the importance of the interaction at their interface. The energy storage ability and safety of energy storage devices are in fact determined by the arrangement of ions and electrons between the electrode and the electrolyte. In this paper, the physicochemical and electrochemical properties of lithium-ion batteries and supercapacitors using ionic liquids (ILs) as an electrolyte are reviewed. Additionally, the energy storage device ILs developed over the last decade are introduced.

Electron Density-Change in Semiconductor by Ion-Adsorption at Solid-Liquid Interface.

The change in electrical properties of electrodes by adsorption or desorption at interfaces is a well-known phenomenon required for signal production in electrically transduced sensing technologies. Furthermore, in terms of electrolyte-insulator-semiconductor (EIS) structure, several studies of energy conversion techniques focused on ion-adsorption at the solid-liquid interface have suggested that the electric signal is generated by ionovoltaic phenomena. However, finding substantial clues for the ion-adsorption phenomena in the EIS structure is still a difficult task because direct evidence for carrier accumulation in semiconductors by Coulomb interactions is insufficient. Here, a sophisticated Hall measurement system is demonstrated to quantitatively analyze accumulated electron density-change inside the semiconductor depending on the ion-adsorption at the solid-liquid interface. Also, an enhanced EIS-structured device is designed in an aqueous-soaked system that works with the ionovoltaic principle to monitor the ion-dynamics in liquid electrolyte media, interestingly confirming ion-concentration dependence and ion-specificity by generated peak voltages. This newly introduced peculiar method contributes to an in-depth understanding of the ionovoltaic phenomena in terms of carrier actions in the semiconductors and ionic behaviors in the aqueous-bulk phases, providing informative analysis about interfacial adsorptions that can expand the scope of ion-sensing platforms.

Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode.

A novel copper oxide/graphite composite (GCuO) anode with high capacity and long cycle stability is proposed. A simple, one-step synthesis method is used to prepare the GCuO, through heat treatment of the Cu ion complex and pristine graphite. The gases generated during thermal decomposition of the Cu ion complex (H2 and CO2 ) induce interlayer expansion of the graphite planes, which assists effective ion intercalation. Copper oxide is formed simultaneously as a high-capacity anode material through thermal reduction of the Cu ion complex. Material analyses reveal the formation of Cu oxide nanoparticles and the expansion of the gaps between the graphite layers from 0.34 to 0.40 nm, which is enough to alleviate layer stress for reversible ion intercalation for Li or Na batteries. The GCuO cell exhibits excellent Li-ion battery half-cell performance, with a capacity of 532 mAh g-1 at 0.2 C (C-rate) and capacity retention of 83 % after 250 cycles. Moreover, the LiFePO4 /GCuO full cell is fabricated to verify the high performance of GCuO in practical applications. This cell has a capacity of 70 mAh g-1 and a coulombic efficiency of 99 %. The GCuO composite is therefore a promising candidate for use as an anode material in advanced Li- or Na-ion batteries.

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized ß-polytype porous silicon carbide electrodes.

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo2O4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo2O4) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g-1 at a scan rate of 5 mV s-1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe3O4 nanoparticles and SiCF (SiCF/Fe3O4) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g-1 at a scan rate of 5 mV s-1. Therefore, by pairing the SiCF/MgCo2O4 positive electrode and the SiCF/Fe3O4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g-1 at a scan rate of 5 mV s-1) and energy density (maximum energy density of 72.79 Wh kg-1 at a power density of 727.96 W kg-1).

Bridging Oriented Copper Nanowire-Graphene Composites for Solution-Processable, Annealing-Free, and Air-Stable Flexible Electrodes.

One-dimensional flexible metallic nanowires (NWs) are of considerable interest for next-generation wearable devices. The unavoidable challenge for a wearable electrode is the assurance of high conductivity, flexibility, and durability with economically feasible materials and simple manufacturing processes. Here, we use a straightforward solvothermal method to prepare a flexible conductive material that contains reduced graphene oxide (RGO) nanosheets bridging oriented copper NWs. The GO-assistance route can successfully meet the criteria listed above and help the composite films maintain high conductivity and durable flexibility without any extra treatment, such as annealing or acid processes. The composite film exhibits a high electrical performance (0.808 Ω·sq(-1)) without considerable change over 30 days under ambient conditions. Moreover, the Cu NW-RGO composites can be deposited on polyester cloth as a lightweight wearable electrode with high durability and simple processability and are very promising for a wide variety of electronic devices.

Novel Synthesis, Coating, and Networking of Curved Copper Nanowires for Flexible Transparent Conductive Electrodes.

In this work, a whole manufacturing process of the curved copper nanowires (CCNs) based flexible transparent conductive electrode (FTCE) is reported with all solution processes, including synthesis, coating, and networking. The CCNs with high purity and good quality are designed and synthesized by a binary polyol coreduction method. In this reaction, volume ratio and reaction time are the significant factors for the successful synthesis. These nanowires have an average 50 nm in width and 25-40 µm range in length with curved structure and high softness. Furthermore, a meniscus-dragging deposition (MDD) method is used to uniformly coat the well-dispersed CCNs on the glass or polyethylene terephthalate substrate with a simple process. The optoelectrical property of the CCNs thin films is precisely controlled by applying the MDD method. The FTCE is fabricated by networking of CCNs using solvent-dipped annealing method with vacuum-free, transfer-free, and low-temperature conditions. To remove the natural oxide layer, the CCNs thin films are reduced by glycerol or NaBH4 solution at low temperature. As a highly robust FTCE, the CCNs thin film exhibits excellent optoelectrical performance (T = 86.62%, R(s) = 99.14 Ω â—»(-1)), flexibility, and durability (R/R(0) < 1.05 at 2000 bending, 5 mm of bending radius).

Synthesis of Cu3Sn alloy nanocrystals through sequential reduction induced by gradual increase of the reaction temperature.

Cu3Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), UV/Vis spectroscopy, and X-ray diffraction (XRD) analyses, the alloy formation mechanism of Cu3Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu-Sn alloy nanocrystals, and then the formation of Cu3Sn alloy nanocrystals. We anticipate that the synthesis of Cu3Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.

Facile synthesis of oxidation-resistant copper nanowires toward solution-processable, flexible, foldable, and free-standing electrodes.

Oxidation-resistant copper nanowires (Cu NWs) are synthesized by a polyol reduction method. These Cu NWs show excellent oxidation resistance, good dispersibility, and have a low sintering temperature. A Cu NW-based flexible, foldable, and free-standing electrode is fabricated by filtration and a sintering process. The electrode also exhibits high electrical conductivity even bending, folding, and free-standing.