In Situ Formed Ag-Li Intermetallic Layer for Stable Cycling of All-Solid-State Lithium Batteries.

With the timely advent of the electric vehicle era, where battery stability has emerged as a major issue, all-solid-state batteries (ASSBs) have attracted significant attention as the game changer owing to their high stability. However, despite the introduction of a densely packed solid electrolyte (SE) layer, when Li is used to increase the energy density of the cell, the short-circuit problem caused by Li protrusion is unavoidable. Furthermore, most strategies to control nonuniform Li growth are so complicated that they hinder the practical application of ASSBs. To overcome these limitations, this study proposes an Ag-Li alloy anode via mass-producible roll pressing method. Unlike previous studies reporting solid-solution-based metal alloys containing a small amount of lithiophilic Ag, the in situ formed and Ag-enriched Ag-Li intermetallic layer mitigates uneven Li deposition and maintains a stable SE/Ag-Li interface, facilitating reversible Li operation. Contrary to Li cells showing frequent initial short-circuit, the cell incorporating the Ag-Li anode exhibits a better capacity retention of 94.3% for 140 cycles, as well as stable cycling even under 12 C. Through a facile approach enabling the fabrication of a large-area anode with controllable Li growth, this study provides practical insight for developing ASSBs with stable cyclabilities.

A Novel Strategy to Overcome the Hurdle for Commercial All-Solid-State Batteries via Low-Cost Synthesis of Sulfide Solid Electrolytes.

Unlike commercial lithium-ion batteries, the high cost and low ionic conductivity of solid electrolytes (SEs) continues to be a big hurdle in commercially available all-solid-state batteries (ASSBs). Rather than the conventional dry-process and high-energy ball milling processes, the productive solution synthesis of bulk-type SEs is the most crucial issue in the successful application of high-energy-density ASSBs. In this study, the way is paved to overcome the hurdle for commercial lithium phosphorus sulfide chloride (LPSCl) SEs via a readily processable bulk-type solution-based synthesis without acquiring any high-energy ball-milling processes. By incorporating an elemental sulfur additive during the preparation process, Li2 S and S form a polysulfide, and P2 S5 is induced to react readily to provide LPSCl with excellent ion conductivity as high as 1.8 mS cm-1 . Surprisingly, the purity of bulk type precursors does not affect the final composition and ionic conductivity of sulfide electrolytes, which show the same electrochemical characteristics of ASSB cells with a high discharge capacity of 185.6 mA h g-1 . The study offers a promising strategy for saving the production cost of sulfide SEs, possibly up to 92%, and their commercial ASSBs are expected to be achieving a competitive cost per energy density of ≈0.46 $ W-1 .

Vertically Aligned Binder-Free TiO2 Nanotube Arrays Doped with Fe, S and Fe-S for Li-ion Batteries.

Vertically aligned Fe, S, and Fe-S doped anatase TiO2 nanotube arrays are prepared by an electrochemical anodization process using an organic electrolyte in which lactic acid is added as an additive. In the electrolyte, highly ordered TiO2 nanotube layers with greater thickness of 12 µm, inner diameter of approx. 90 nm and outer diameter of approx. 170 nm are successfully obtained. Doping of Fe, S, and Fe-S via simple wet impregnation method substituted Ti and O sites with Fe and S, which leads to enhance the rate performance at high discharge C-rates. Discharge capacities of TiO2 tubes increased from 0.13 mAh cm-2(bare) to 0.28 mAh cm-2 for Fe-S doped TiO2 at 0.5 C after 100 cycles with exceptional capacity retention of 85 % after 100 cycles. Owing to the enhancement of thermodynamic and kinetic properties by doping of Fe-S, Li-diffusion increased resulting in remarkable discharge capacities of 0.27 mAh cm-2 and 0.16 mAh cm-2 at 10 C, and 30 C, respectively.

Facile fabrication of solution-processed solid-electrolytes for high-energy-density all-solid-state-batteries by enhanced interfacial contact.

Instead of commercial lithium-ion batteries (LIBs) using organic liquid electrolytes, all-solid-state lithium-ion batteries (ASSBs) employing solid electrolytes (SEs) are promising for applications in high-energy-density power applications and electric vehicles due to their potential for improving safety and achieving high capacity. Although remarkable progress in SEs has been achieved and has resulted in high ionic conductivity, which now reaches values comparable to those of liquid electrolytes, the typical use of a slurry process for the fabrication of conventional ASSBs inevitably causes harmful reactions between sulfide materials and polar solvents. Here, we studied the efficient infiltration process of SE slurry into conventional composite LIB electrodes (NCM622) for achieving high-energy-density ASSBs via a scalable solution-based fabrication process. Two methods are proposed to ensure that SE materials are evenly distributed and sufficiently infiltrated into the porous structures of LIB electrodes. The LPSCl SE solutions were effectively infiltrated into the electrodes at higher processing temperatures and the temperature was subsequently optimized at above the boiling point of the ethanol solvent due to the dynamic motion of SE molecules via a convective flow during solvent vaporization. Moreover, the porous LIB composite electrodes with a mixture of active materials of different particle sizes formed and filled capillary pores resulting in a high electrode density. The LPSCl SE-infiltrated NCM622 electrodes that used this strategy could remarkably improve the initial discharge capacity of ASSBs to as high as 177 mAh/g. These ASSBs also showed excellent performance even at high loading values (about 17 mg/cm2), making them competitive with LIBs using conventional liquid electrolytes.

Graphitic Hollow Nanocarbon as a Promising Conducting Agent for Solid-State Lithium Batteries.

All-solid-state batteries (ASSBs) have lately received enormous attention for electric vehicle applications because of their exceptional stability by engaging all-solidified cell components. However, there are many formidable hurdles such as low ionic conductivity, interface instability, and difficulty in the manufacturing process, for its practical use. Recently, carbon, one of the representative conducting agents, turns out to largely participate in side reactions with the solid electrolyte, which finally leads to the formation of insulating side products at the interface. Although the battery community mentioned that parasitic reactions are presumably attributed to carbon itself or the generation of electronic conducting paths lowering the kinetic barrier for reactions, the underlying origin for such reactions as well as appropriate solutions have not been provided yet. In this study, for the first time, it is verified that the functional group on carbon is an origin for causing negative effects on interfacial stability and a graphitized hollow nanocarbon as a promising solution for improving-electrochemical performance is introduced. This work offers an invaluable lesson that a relatively minor part, such as a conducting agent, in ASSBs sometimes gives more positive impact on improving electrochemical performance than huge efforts for resolving other parts.

Enhanced osteogenic differentiation of human mesenchymal stem cells on Ti surfaces with electrochemical nanopattern formation.

Titanium (Ti) and its alloys are mainly used for dental and orthopedic applications due to their excellent biocompatibility and mechanical properties. However, their intrinsic bioinertness often quotes as a common complaint for biomedical applications. Herein, we produced nanopattern Ti surfaces with 10 nm nanopores in 120 nm dimples by electrochemical nanopattern formation (ENF), and evaluated the osteogenic differentiation of human mesenchymal stem cells (hMSCs) on the nanopattern Ti surfaces. The ENF surfaces were obtained by removing the TiO2 nanotube (NT) layers prepared by an anodization process. To determine the in vitro effects of the ENF surface, cell proliferation assay, alkaline phosphatase activity assay, alizarin red staining, western blotting, and immunocytochemistry were performed. Atomic force microscopy and scanning electron microscopy analysis show that the ENF surface has an ultrafine surface roughness with highly aligned nanoporous morphology. hMSCs on ENF surfaces exhibit increased proliferation and enhanced osteogenic differentiation as compared to the ordered TiO2 nanotubular and compact TiO2 surfaces. Surface modification with the ENF process is a promising technique for fabricating osteointegrative implant materials with a highly bioactive, rigid and purified nano surfaces.

LiI-Doped Sulfide Solid Electrolyte: Enabling a High-Capacity Slurry-Cast Electrode by Low-Temperature Post-Sintering for Practical All-Solid-State Lithium Batteries.

All-solid-state lithium batteries (ASSLBs) based on sulfide solid electrolytes (SEs) have received great attention because of the high ionic conductivity of the SEs, intrinsic thermal safety, and higher energy density achievable with a Li metal anode. However, studies on practical slurry-cast composite electrodes show an extremely limited battery performance than the binder-free pelletized electrodes because of the poor interfacial robustness between the active materials and SEs by the presence of a polymeric binder. Here, we employ a low-temperature post-sintering process for the slurry-cast composite electrodes in order to overcome the binder-induced detrimental effects on the electrochemical performance. The LiI-doped Li3PS4 SEs are chosen because the addition of iodine not only improves the Li-ion conductivity and Li metal compatibility but also lowers the glass-transition and crystallization temperatures. Low-temperature post-sintering of composite cathodes consisting of a LiNi0.6Co0.2Mn0.2O2-active material, LiI-doped Li3PS4 SE, polymeric binder, and conducting agent shows a significantly improved electrochemical performance as compared to a conventional slurry-cast electrode containing pre-annealed SEs. Detailed analyses by electrochemical impedance spectroscopy and galvanostatic intermittent titration technique confirm that post-sintering effectively reduces the interfacial resistance and enhances the chemomechanical robustness at solid-solid interfaces, which enables the development of practical slurry-cast ASSLBs with sulfide SEs.

Production of Oxidation-Resistant Cu-Based Nanoparticles by Wire Explosion.

The low performance or high cost of commercially available conductive inks limits the advancement of printed electronics. This article studies the explosion of metal wires in aqueous solutions as a simple, low-cost, and environmentally friendly method to prepare metallic nanoparticles consisting of Cu and Cu alloys for use in affordable, highly conductive inks. Addition of 0.2 M ascorbic acid to an aqueous explosion medium prevented the formation of Cu2O shells around Cu nanoparticles, and allowed for the printing of conductive lines directly from these nanoparticles with no post-treatment. Cu alloy nanoparticles were generated from metal wires that were alloyed as purchased, or from two wires of different metals that were twisted together. Cu nanoparticles alloyed with 1% Sn, 5% Ag, 5% Ni and 30% Ni had electrical conductivities similar to Cu but unlike Cu, remained conductive after 24 hrs at 85 °C and 85% RH.

Real-time visualization of diffusion-controlled nanowire growth in solution.

This Letter shows that copper nanowires grow through the diffusion-controlled reduction of dihydroxycopper(I), Cu(OH)2(-). A combination of potentiostatic coulometry, UV-visible spectroscopy, and thermodynamic calculations was used to determine the species adding to growing Cu nanowires is Cu(OH)2(-). Cyclic voltammetry was then used to measure the diffusion coefficient of Cu(OH)2(-) in the reaction solution. Given the diameter of a Cu nanowire and the diffusion coefficient of Cu(OH)2(-), we calculated the dependence of the diffusion-limited growth rate on the concentration of copper ions to be 26 nm s(-1) mM(-1). Independent measurements of the nanowire growth rate with dark-field optical microscopy yielded 24 nm s(-1) mM(-1) for the growth rate dependence on the concentration of copper. Dependence of the nanowire growth rate on temperature yielded a low activation energy of 11.5 kJ mol(-1), consistent with diffusion-limited growth.

The role of cuprous oxide seeds in the one-pot and seeded syntheses of copper nanowires.

This paper demonstrates that Cu2O nanoparticles form in the early stages of a solution-phase synthesis of copper nanowires, and aggregate to form the seeds from which copper nanowires grow. Removal of ethylenediamine from the synthesis leads to the rapid formation of Cu2O octahedra. These octahedra are introduced as seeds in the same copper nanowire synthesis to improve the yield of copper nanowires from 12% to >55%, and to enable independent control over the length of the nanowires. Transparent conducting films are made from nanowires with different lengths to examine the effect of nanowire aspect ratio on the film performance.

A rapid synthesis of high aspect ratio copper nanowires for high-performance transparent conducting films.

This communication presents a way to produce copper nanowires with aspect ratios as high as 5700 in 30 min, and describes the growth processes responsible for their formation. These nanowires were used to make transparent conducting films with a transmittance >95% at a sheet resistance <100 Ω sq(-1).

Extended self-ordering regime in hard anodization and its application to make asymmetric AAO membranes for large pitch-distance nanostructures.

We report here a fast and reliable hard anodization process to make asymmetric anodic aluminum oxide (AAO) membranes which can serve as a template for large pitch-distance nanostructures. In order to make larger pitch distances possible, the common burning failure associated with the high current density during the conventional constant voltage hard anodization, especially at a voltage higher than a known limit, i.e., 155 V for oxalic acid, was effectively suppressed by using a burning-protective agent. A new self-ordering regime beyond the voltage limit was observed with a different voltage-interpore distance relationship of 2.2 nm V(-1) compared to the reported 2.0 nm V(-1) for hard anodization. Combining a sulfuric acid mild anodization with this new regime of hard anodization, we further demonstrate a scalable process to make an asymmetric membrane with size up to ~47 mm in diameter and ~60 µm in thickness. This free-standing membrane can be used as a template for novel nanopatterned structures such as arrays of quantum dots, nanowires or nanotubes with diameters of a few tens of nanometers and pitch distance of over 400 nm.

Toxicity and clearance of intratracheally administered multiwalled carbon nanotubes from murine lung.

Carbon nanotubes (CNT) are known to have widespread industrial applications; however, several reports indicated that these compounds may be associated with adverse effects in humans. In this study, multiwalled carbon nanotubes were administered to murine lungs intratracheally to determine whether acute and chronic pulmonary toxicity occurred. In particular, pristine multiwalled carbon nanotubes (PMWCNT) and acid-treated multiwalled carbon nanotubes (TMWCNT) were used in this study. In broncheoalveolar lavage fluid (BALF) cell analysis, PMWCNT induced more severe acute inflammatory cell recruitment than TMWCNT. Histopathologically, both PMWCNT and TMWCNT induced multifocal inflammatory granulomas in a dose-dependent manner. The observed granulomas were reversible, with TMWCNT-induced granulomas diminishing faster than PMWCNT-induced granulomas. Although the area of granuloma reduced with time, hyperplasia and dysplastic characteristics such as mitotic figures, anisokaryosis, and anisocytosis were still observed. These findings demonstrate that MWCNT induces granulomatous inflammation, and the duration and pattern of inflammation seem to vary depending upon the types of MWCNT to which mice are exposed. Therefore, toxicity studies on various types of CNT are needed as the responsiveness to these compounds differs.

Low dietary inorganic phosphate stimulates lung tumorigenesis through altering protein translation and cell cycle in K-ras(LA1) mice.

Recent surveys indicate that Pi intake has increased steadily as Pi-containing foods have increased. Our previous study demonstrated that high dietary Pi strongly stimulated lung tumorigeneis. In order to answer the issue whether low Pi may be chemopreventive, we examined the effects of low Pi on lung cancer. Eighteen 5-wk-old male K-ras(LA1) lung cancer model mice were randomly allocated to 2 groups. One group was fed a normal diet (0.5% Pi) and other group was fed low Pi (0.1% Pi) diet for 4 wk. Lung cancer development was evaluated by histopathological examination, Western blot, kinase assay, and immunohistochemistry. Low Pi increased the expression of sodium-dependent phosphate co-transporter 2b, and activated Akt signal with decreased PTEN expression in the lungs of K-ras(LA1) mice. Low Pi increased the Akt/mTOR-mediated protein translation through upregulating the phosphorylation of p70S6K and 4E-BP1. In addition, low Pi stimulated cell cycling as evidenced by altered cell cycle regulators such as cyclin D1 and D3. Finally, low Pi increased lung tumorigenesis in K-ras(LA1) mice compared to the normal diet group. Our results clearly demonstrated that low Pi also promoted lung tumorigenesis, thus suggesting that an appropriate intake of dietary Pi may be critical for lung cancer prevention as well as treatment.

High dietary inorganic phosphate increases lung tumorigenesis and alters Akt signaling.

RATIONALE: Phosphate (Pi) is an essential nutrient to living organisms. Recent surveys indicate that the intake of Pi has increased steadily. Our previous studies have indicated that elevated Pi activates the Akt signaling pathway. An increased knowledge of the response of lung cancer tissue to high dietary Pi may provide an important link between diet and lung tumorigenesis. OBJECTIVES: The current study was performed to elucidate the potential effects of high dietary Pi on lung cancer development. METHODS: Experiments were performed on 5-week-old male K-ras(LA1) lung cancer model mice and 6-week-old male urethane-induced lung cancer model mice. Mice were fed a diet containing 0.5% Pi (normal Pi) and 1.0% Pi (high Pi) for 4 weeks. At the end of the experiment, all mice were killed. Lung cancer development was evaluated by diverse methods. MEASUREMENT AND MAIN RESULTS: A diet high in Pi increased lung tumor progression and growth compared with normal diet. High dietary Pi increased the sodium-dependent inorganic phosphate transporter-2b protein levels in the lungs. High dietary consumption of Pi stimulated pulmonary Akt activity while suppressing the protein levels of tumor suppressor phosphatase and tensin homolog deleted on chromosome 10 as well as Akt binding partner carboxyl-terminal modulator protein, resulting in facilitated cap-dependent protein translation. In addition, high dietary Pi significantly stimulated cell proliferation in the lungs of K-ras(LA1) mice. CONCLUSIONS: Our results showed that high dietary Pi promoted tumorigenesis and altered Akt signaling, thus suggesting that careful regulation of dietary Pi may be critical for lung cancer prevention as well as treatment.