Establishing Ultralow Self-Discharge Zn-I2 Battery by Optimizing ZnSO4 Electrolyte Concentration.

As one of promising candidates for large-scale energy-storage systems, Zn-I2 aqueous battery exhibits multifaceted advantages including low cost, high energy/powder density, and intrinsic operational safety, but also suffers from fast self-discharge and short cycle/shelf lifespan associating with I3 - shuttle, Zn dendrite growth, and corrosion. In this paper, the battery's self-discharge rate is successfully suppressed down to an unprecedent level of 17.1% after an ultralong shelf-time of 1 000 h (i.e., 82.9% capacity retention after 41 days open-circuit storage), by means of manipulating solvation structures of traditional ZnSO4 electrolyte via simply adjusting electrolyte concentration. Better yet, the optimized 2.7 m ZnSO4 electrolyte further prolongs the cycle lifespan of the battery up to >10 000 and 43 000 cycles at current density of 1 and 5 A g-1, respectively, thanks to the synthetic benefits from reduced free water content, modified solvation structure and lowered I2 dissolution in the electrolyte. With both long lifespan and ultralow self-discharge, this reliable and affordable Zn-I2 battery may provide a feasible alternative to the centuries-old lead-acid battery.

A Low Driving-Voltage Hybrid-Electrolyte Electrochromic Window with Only Ferreous Redox Couples.

Even after decades of development, the widespread application of electrochromic windows (ECW) is still seriously restricted by their high price and inadequate performance associated with structural/fabrication complexity and electrochemical instability. Herein, a simple hybrid electrochromic system based on PFSA (perfluorosulfonic acid)-coated Prussian blue (PB, Fe4III [FeII(CN)6]3) film and Ferricyanide-Ferrocyanide ([Fe(CN)6]4-/[Fe(CN)6]3-)-containing hybrid electrolyte is reported. The PB film and the [Fe(CN)6]4-/[Fe(CN)6]3- couple show near redox potentials well inside the electrochemical window of water, resulting in a low driven voltage (0.4 V for coloring and -0.6 V for bleaching) and a relatively long lifespan (300 cycles with 76.9% transmittance contrast retained). The PFSA layer, as a cation-exchange structure, significantly improves the transmittance modulation amplitude (ΔT: 23.3% vs. 71.9% at a wavelength of 633 nm) and optical memory abilities (ΔT retention: 10.1% vs. 67.0% after 300 s open-circuit rest increases) of the device, by means of preventing the direct contact and charge transfer between the PB film and the [Fe(CN)6]4-/[Fe(CN)6]3- couple. This "hybrid electrolyte + electron barrier layer" design provides an effective way for the construction of simple structured electrochromic devices.

Boosting Zn||I2 Battery's Performance by Coating a Zeolite-Based Cation-Exchange Protecting Layer.

HIGHLIGHTS: High-performance Zn||I2 batteries were established by coating zeolite protecting layers. The Zn2+-conductive layer suppresses I3- shuttling, Zn corrosion/dendrite growth. The Zeolite-Zn||I2 batteries achieve long lifespan (91.92% capacity retention after 5600 cycles), high coulombic efficiencies (99.76% in average) and large capacity (203-196 mAh g-1 at 0.2 A g-1) simultaneously. The intrinsically safe Zn||I2 battery, one of the leading candidates aiming to replace traditional Pb-acid batteries, is still seriously suffering from short shelf and cycling lifespan, due to the uncontrolled I3--shuttling and dynamic parasitic reactions on Zn anodes. Considering the fact that almost all these detrimental processes terminate on the surfaces of Zn anodes, modifying Zn anodes' surface with protecting layers should be one of the most straightforward and thorough approaches to restrain these processes. Herein, a facile zeolite-based cation-exchange protecting layer is designed to comprehensively suppress the unfavored parasitic reactions on the Zn anodes. The negatively-charged cavities in the zeolite lattice provide highly accessible migration channels for Zn2+, while blocking anions and electrolyte from passing through. This low-cost cation-exchange protecting layer can simultaneously suppress self-discharge, anode corrosion/passivation, and Zn dendrite growth, awarding the Zn||I2 batteries with ultra-long cycle life (91.92% capacity retention after 5600 cycles at 2 A g-1), high coulombic efficiencies (99.76% in average) and large capacity (203-196 mAh g-1 at 0.2 A g-1). This work provides a highly affordable approach for the construction of high-performance Zn-I2 aqueous batteries.

Establishing High-Performance Quasi-Solid Zn/I2 Batteries with Alginate-Based Hydrogel Electrolytes.

Zinc-iodine (Zn/I2) batteries are recognized as a kind of leading candidate for large-scale energy storage systems, owing to the high-capacity dissolution-deposition reactions on both electrodes. Nevertheless, the lifespan of Zn/I2 batteries is severely limited by the uncontrolled shuttling of triiodide ions (I3-) and unfavorable side reactions on Zn anodes. Herein, an alginate-based polyanionic hydrogel electrolyte is designed and synthesized by ion exchange and Zn2+-induced cross-linking. The immobile, negatively charged polyanionic chains on the hydrogel skeleton effectively block I3- from shuttling, while simultaneously transporting cations that are indispensable for battery chemistry. Moreover, this hydrogel can also enhance the cycling durability of Zn anodes by alleviating Zn's dendritic growth and corrosion reactions, due to the homogenized Zn2+ flux and reduced interfacial contact between free water and metallic Zn. Consequently, this alginate-based hydrogel electrolyte enables stable Zn plating/stripping for over 600 h at 2 mA cm-2 and 2 mAh cm-2 (corresponding to 10% depth of discharge). Serving as an electrolyte for Zn/I2 full batteries, this hydrogel helps the battery to achieve a high capacity of 183.4 mAh g-1 (capacity retention = 97.6%) after even 200 cycles at 0.2 A g-1, 77.4% higher than that of the traditional ZnSO4 aqueous counterpart (residual capacity = 41.5 mAh g-1). This work indicates the promising potential of electrolyte design on the performance improvement of aqueous Zn/I2 batteries.

Straightforward preparation of Na2(TiO)SiO4 hollow nanotubes as anodes for ultralong cycle life lithium ion battery.

One-dimensional Na2(TiO)SiO4 (SNTO) nanotubes have been successfully synthesized by a straightforward hydrothermal method with the assistance of cetyltetramethyl ammonium bromide (CTAB). Herein, the influence of the Si/Ti ratio on the morphology or composition of SNTO hollow nanotubes has been investigated, and the result shows that the optimum molar ratio of the optimal morphology is 1 : 1. The prepared samples were first applied as anodes in lithium ion batteries (LIBs) for the time being and superior rate capability, ultralong and stable cycling lifespan performance were obtained. The facile and uniquely designed one-dimensional SNTO nanotube electrodes delivered a high reversible capacity of 121.9 mA h g-1 after 5000 cycles at a high current of 1.0 A g-1 without significant attenuation. The superior electrochemical properties are attributed to their special nanotube structure with a high specific surface area, which could shorten the ion/electron transport pathway, and increase the number of active sites and the contact area between the electrolyte and active electrodes. Meanwhile, the kinetic analysis of the electrochemical behaviors of SNTO hollow nanotube electrodes was carried out by performing calculations using cyclic voltammograms recorded at different scan rates, and the results showed that the obtained reversible capacity is mainly due to the capacitive contribution. This work expands the types of anode materials for LIBs, which will further promote the development of LIBs.

2D/1D V2O5 Nanoplates Anchored Carbon Nanofibers as Efficient Separator Interlayer for Highly Stable Lithium-Sulfur Battery.

Quick capacity loss due to the polysulfide shuttle effects is a critical challenge for high-performance lithium-sulfur (Li-S) batteries. Herein, a novel 2D/1D V2O5 nanoplates anchored carbon nanofiber (V-CF) interlayer coated on standard polypropylene (PP) separator is constructed, and a stabilization mechanism derived from a quasi-confined cushion space (QCCS) that can flexibly accommodate the polysulfide utilization is demonstrated. The incorporation of the V-CF interlayer ensures stable electron and ion pathway, and significantly enhanced long-term cycling performances are obtained. A Li-S battery assembled with the V-CF membrane exhibited a high initial capacity of 1140.8 mAh·g-1 and a reversed capacitance of 1110.2 mAh·g-1 after 100 cycles at 0.2 C. A high reversible capacity of 887.2 mAh·g-1 is also maintained after 500 cycles at 1 C, reaching an ultra-low decay rate of 0.0093% per cycle. The excellent electrochemical properties, especially the long-term cycling stability, can offer a promising designer protocol for developing highly stable Li-S batteries by introducing well-designed fine architectures to the separator.

Fe3O4 Hollow Nanosphere-Coated Spherical-Graphite Composites: A High-Rate Capacity and Ultra-Long Cycle Life Anode Material for Lithium Ion Batteries.

The spherical-graphite/Fe3O4 composite has been successfully fabricated by a simple two-step synthesis strategy. The oxygenous functional groups between spherical-graphite and Fe3O4 benefit the loading of hollow Fe3O4 nanospheres. All of the composites as anodes for half cells show higher lithium storage capacities and better rate performances in comparison with spherical-graphite. The composite containing 39 wt% of hollow Fe3O4 nanospheres exhibits a high reversible capacity of 806 mAh g-1 up to 200 cycles at 0.5 A g-1. When cycled at a higher current density of 2 A g-1, a high charge capacity of 510 mAh g-1 can be sustained, even after 1000 long cycles. Meanwhile, its electrochemical performance for full cells was investigated. When matching with LiCoO2 cathode, its specific capacity can remain at 137 mAh g-1 after 100 cycles. The outstanding lithium storage performance of the spherical-graphite/Fe3O4 composite may depend on the surface modification of high capacity hollow Fe3O4 nanospheres. This work indicates that the spherical-graphite/Fe3O4 composite is one kind of prospective anode material in future energy storage fields.

Non-Conjugated Dicarboxylate Anode Materials for Electrochemical Cells.

Classical organic anode materials for Na-ion batteries are mostly based on conjugated carboxylate compounds, which can stabilize added electrons by the double-bond reformation mechanism. Now, 1,4-cyclohexanedicarboxylic acid (C8 H12 O4 , CHDA) with a non-conjugated ring (-C6 H10 -) connected with carboxylates is shown to undergo electrochemical reactions with two Na ions, delivering a high charge specific capacity of 284 mA h g-1 (249 mA h g-1 after 100 cycles), and good rate performance. First-principles calculations indicate that hydrogen-transfer-mediated orbital conversion from antibonding π* to bonding σ stabilize two added electrons, and reactive intermediate with unpaired electron is suppressed by localization of σ-bonds and steric hindrance. An advantage of CHDA as an anode material is good reversibility and relatively constant voltage. A large variety of organic non-conjugated compounds are predicted to be promising anode materials for sodium-ion batteries.

Recycled Carbon Fiber-Supported Polyaniline/Manganese Dioxide Prepared via One-Step Electrodeposition for Flexible Supercapacitor Integrated Electrodes.

The exploration of multifunctional electrode materials has been a hotspot for the development of high-performance supercapacitors. We have used carbon fiber plates recovered from construction waste to prepare high-quality flexible carbon fiber materials by pyrolysis of epoxy resin. The as-prepared recycled carbon fiber has a diameter of 8 µm and is the perfect substrate material for flexible electrode materials. Furthermore, polyaniline and manganese dioxide are uniformly deposited on the recycled carbon fiber by one-step electrodeposition to form an active film. The recycled carbon fiber/polyaniline/MnO2 composite shows an excellent specific capacitance of 475.1 F·g-1 and capacitance retention of 86.1% after 5000 GCD cycles at 1 A·g-1 in 1 M Na2SO4 electrolyte. The composites optimized for electrodeposition time have more electroactive sites, faster ions and electron transfer, structural stability and higher conductivity, endowing the composites promising application prospect.

Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C8H8) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C8-C4-C8 (C16H12) and C8-C4-C8-C4-C8 (C24H16) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C16H12 and C24H16 exhibit discharge capacities of 525.3 and 357.2 mA h g-1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na+/Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C24H16-based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Nanoporous thermochromic VO(2) films with low optical constants, enhanced luminous transmittance and thermochromic properties.

Nanoporous thermochromic VO(2) films with low optical constants and tunable thicknesses have been prepared by polymer-assisted deposition. The film porosity and thickness change the interference relationship of light reflected from the film-substrate and the air-film interfaces, strongly influencing the optical properties of these VO(2) films. Our optimized single-layered VO(2) films exhibit high integrated luminous transmittance (T(lum,l) = 43.3%, T(lum,h) = 39.9%) and solar modulation (ΔT(sol) = 14.1%, from T(sol,l) = 42.9% to T(sol,h) = 28.8%), which are comparable to those of five-layered TiO(2)/VO(2)/TiO(2)/VO(2)/TiO(2) films (T(lum,l) = 45%, T(lum,h) = 42% and ΔT(sol) = 12%, from T(sol,l) = 52% to T(sol,h) = 40%, from Phys. Status Solidi A2009, 206, 2155-2160.). Optical calculations suggest that the performance could be further improved by increasing the porosity.

Thermochromic VO2 thin films: solution-based processing, improved optical properties, and lowered phase transformation temperature.

This paper describes a solution-phase synthesis of high-quality vanadium dioxide thermochromic thin films. The films obtained showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal-insulator phase transition (MIPT). For a 59 nm thick single-layer VO(2) thin film, the integral values of visible transmittance (T(int)) for metallic (M) and semiconductive (S) states were 54.1% and 49.1%, respectively, while the NIR switching efficiencies (DeltaT) were as high as 50% at 2000 nm. Thinner films can provide much higher transmittance of visible light, but they suffer from an attenuation of the switching efficiency in the near-infrared region. By varying the film thickness, ultrahigh T(int) values of 75.2% and 75.7% for the M and S states, respectively, were obtained, while the DeltaT at 2000 nm remained high. These results represent the best data for VO(2) to date. Thicker films in an optimized range can give enhanced NIR switching efficiencies and excellent NIR blocking abilities; in a particularly impressive experiment, one film provided near-zero NIR transmittance in the switched state. The thickness-dependent performance suggests that VO(2) will be of great use in the objective-specific applications. The reflectance and emissivity at the wavelength range of 2.5-25 microm before and after the MIPT were dependent on the film thickness; large contrasts were observed for relatively thick films. This work also showed that the MIPT temperature can be reduced simply by selecting the annealing temperature that induces local nonstoichiometry; a MIPT temperature as low as 42.7 degrees C was obtained by annealing the film at 440 degrees C. These properties (the high visible transmittance, the large change in infrared transmittance, and the near room-temperature MIPT) suggest that the current method is a landmark in the development of this interesting material toward applications in energy-saving smart windows.

A novel solution process for the synthesis of VO2 thin films with excellent thermochromic properties.

This article describes a novel and simple route to preparing VO(2) thermochromic films by using a VOCl(2) solution with poly(vinylpyrrolidone) (PVP). X-ray diffraction and Raman spectra showed that the VO(2) films deposited with PVP consisted of a nearly pure monoclinic/rutile (M/R) phase. Conversely, films prepared without PVP contained obviously impure crystalline phases. The as-prepared films with PVP showed excellent optical properties compared to those prepared by common gas-phase methods: an integral visible transmittance of 54.5% and an IR reduction (change in transmittance) of 41.5% at 2000 nm. The phase-transition temperatures were adjusted from 69 to 54 degrees C by tungsten doping. Equipment analyses revealed that PVP plays two roles in the film formation. First, it fundamentally acts as a film-forming promoter to improve physical gelation via interactions among oppositely charged carbonyl groups and amine groups of the polymer. Second, the negatively charged carbonyl groups can interact with VO(2+) to form a uniform mixed-gel film after solvent evaporation. Thus, the addition of PVP can stabilize the solution and improve the as-prepared film quality and phase purity. The current study suggests that the process has promise in applications of smart windows.