Electrolyte-cathode interactions in 5-V lithium-ion cells

The electrolyte/electrode interactions on the anode side of a lithium-ion cell and the formation of the solid electrolyte interphase (SEI) have been investigated intensively in the past and are fairly well understood. Present knowledge about the reactions on the cathode side and the resulting cathode electrolyte interphase (CEI) is less detailed. In this study, the electrolyte/electrode interactions on the surface of the high-voltage cathode material LiNi_0.5Mn_1.5O₄ (LNMO), both bare and FePO₄-coated, were investigated. The gases evolving upon first time charging of the system were investigated using a GC/MS combination. The degradation products included THF, dimethyl peroxide, phosphor trifluoride, 1,3-dioxolane and dimethyl difluor silane, formed in the GC’s column as its coating reacts with HF from the experiments. Although these substances and their formation are in themselves interesting, the absence of many degradation products which have been mentioned in the existing literature is of equal interest. Our results clearly indicate that coating a cathode material can have a major influence on the amount and composition of the gaseous decomposition products in the formation phase.     

α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films by liquid phase deposition: low-cost option for supercapacitor

In the present study, iron oxide (α-Fe₂O₃) thin films with good adhesion on stainless steel substrates are deposited by liquid phase deposition (LPD) technique, which is additive and binder-free. Iron oxyhydroxide (FeOOH) thin films are formed by means of a ligand-exchange equilibrium reaction of metal-fluoro complex ions and an F^?ions consuming reaction by using boric acid (H₃BO₃) as a scavenging agent. These films are annealed at 500 °C to get α-Fe₂O₃ thin films. The transformation from hydrophobic to hydrophilic nature of the films is observed due to annealing. The films are characterized by different techniques. The α-Fe₂O₃ film is checked for electrochemical supercapacitive performance in Na₂SO₃ solutions of various concentrations. Specific capacitance is calculated from cyclic voltammetry at numerous scan rates (5–200) mV s^?1. The highest obtained value of specific capacitance is 582 F g^?1 at 5 mV s^?1 for 0.5 M Na₂SO₃ electrolyte. The maximum values of specific power and specific energy are 6.9 and 53.4 Wh kg^?1 from the charge-discharge curve at the current density 2 mA cm^?2 in 0.5 M Na₂SO₃ electrolyte.     

A sustainable synthesis of biomass carbon sheets as excellent performance sodium ion batteries anode

Biomass-derived carbon (BMC) materials have attracted much attention due to their high performance and properties of abundant source. Herein, biomass carbon sheets (BMCS) from wheat straws had been successfully synthesized via a facile high temperature carbonization and expansion processes. The morphology of BMCS keeps the natural honeycomb-like shape of the cross section and the hollow tubular array structure of the vertical section with rich pores, which provides low-resistant ion channels to support fast diffusion. The (002) crystal plane reveals that the intercalation distance of carbon sheets is 0.383 nm larger than that graphite (0.335 nm), which benefits the larger sodium ion de/intercalation. By comparing different carbonization temperatures, wheat straws carbonized at 1200 °C (BMCS-1200) with well graphite microcrystallites show more excellent sodium ion storage performance than that of 900 °C (BMC-900). BMCS-1200 shows a stable reversible capacity of 221 mAh g^?1 after 200 cycles at 0.05 A g^?1, while BMC-900 is 162 mAh g^?1 after 100 cycles. And it also exhibits better rate capability (220, 109 mAh g^?1) than that of BMC-900 (125, 77 mAh g^?1) at 0.2 and 1 A g^?1, respectively. Finally, it delivers 89 mAh g^?1 stable capacity after 1400 cycles at 1 A g^?1 to prove its excellent long-term cycling stability.

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Graphical abstract High temperature carbon sheets with well graphite microcrystallites synthesized from wheat straw forexcellent sodium ion storage performance

     

Hexagram-like CoS-MoS<Subscript>2</Subscript> composites with enhanced activity for hydrogen evolution reaction

Hexagram-like CoS-MoS₂ composites were prepared on indium tin oxide (ITO) conductive glasses via cyclic voltammetry electrodeposition using Co(NO₃)₂ and (NH₄)₂MoS₂ as precursors and tested for application in hydrogen evolution reaction (HER). The structure of CoS-MoS₂ composites was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectrum (XPS). Electrochemical characterizations indicate that CoS-MoS₂ composites exhibit more excellent catalytic activity and stability than MoS₂. Compared with pure MoS₂, the hexagram-like CoS-MoS₂ composites with increased specific surface area improved the density of exposed active sites, and the Co binding S edges in CoS-MoS₂ composites promote the number of highly catalytic edge sites and decreased the binding energy △G _H. Moreover, the effects of different substrates on the CoS-MoS₂ composites were also investigated. Our further understanding of this highly active hydrogen evolution catalyst can facilitate the development of economical electrochemical hydrogen production systems.     

Aprotic metal-oxygen batteries: recent findings and insights

During the last two decades, we have observed a dramatic increase in the electrification of many technologies. What has enabled this transition to take place was the commercialization of Li-ion batteries in the early nineties. Mobile technologies such as cellular phones, laptops, and medical devices make these batteries crucial for our contemporary lifestyle. Like any other electrochemical cell, the Li-ion batteries are restricted to the thermodynamic limitations of the materials. It might be that the energy density of the most advance Li-ion battery is still too low for demanding technologies such as a full electric vehicle. To really convince future customers to switch from the internal combustion engine, new batteries and chemistry need to be developed. Non-aqueous metal-oxygen batteries—such as lithium–oxygen, sodium–oxygen, magnesium–oxygen, and potassium–oxygen—offer high capacity and high operation voltages. Also, by using suitable polar aprotic solvents, the oxygen reduction process that occurs during discharge can be reversed by applying an external potential during the charge process. Thus, in theory, these batteries could be electrically recharged a number of times. However, there are many scientific and technical challenges that need to be addressed. The current review highlights recent scientific insights related to these promising batteries. Nevertheless, the reader will note that many conclusions are applicable in other kinds of batteries as well.     

Determination of the thermal modification degree of beech wood using thermogravimetry

Thermal modification is one of the environmental friendly wood preservation technologies. During this process, changes of the main woody cell wall components occur, which lead to improved dimensional stability, lower hygroscopicity and improvement in biological durability. Several chemical reactions which occur during thermal treatment of wood caused changes in wood properties. During TG measurements, thermal decomposition reactions, which was not completed during previous thermal modification process, continued in wood samples, meaning that more thermally treated samples exhibited lower mass losses in a certain or whole temperature range up to 600 °C. Therefore, mass loss, obtained within selected temperature range, could be used as a marker of previous thermal treatment. The aim of the present work is to evaluate suitability of a thermogravimetric method (TG) for determination of a degree of thermal treatment of beech wood. On the basis of thermally untreated sample and those which were thermally modified at 180, 190, 200, 210, 215 and 220 °C in the absence of oxygen, respectively, and with known values of mass loss during the modification processes, several calibration curves were constructed. They represent mass loss in a certain temperature range during TG measurement versus mass loss during previous thermal modification. In a temperature range from 130 to 300 °C and from 130 to 320 °C under nitrogen atmosphere, a linear dependence was observed; correlation coefficients R ² were 0.87 and 0.91, respectively. In wider temperature range and under air atmosphere, lower correlation coefficients were obtained. High correlation coefficient, higher than 0.95, was observed in a temperature range from 25 to 130 °C under both atmospheres. In this region, dehydration due to rehydration of thermally modified samples occurs. The results of this work were compared with those obtained for Norway spruce.     

Template synthesis of imine-based covalent organic framework core-shell structure and hollow sphere: a case of COF<Subscript>TTA-DHTA</Subscript>

Controllably synthesizing well-dispersed covalent organic frameworks (COFs) with uniform both morphology and size is still a challenge. Herein, we report the template-directed synthesis of COF_TTA-DHTA-based core-shell hybrids under solvothermal conditions by using amino-functionalized SiO₂ microspheres as templates coupled with stepwise addition of initial monomer molecules. The modified amino groups on the surfaces of SiO₂ templates play an important role in the formation of well-defined NH₂-f-SiO₂@COF_TTA-DHTA core-shell hybrids. COF_TTA-DHTA hollow spheres can be obtained by etching SiO₂ cores of NH₂-f-SiO₂@COF_TTA-DHTA. Both the NH₂-f-SiO₂@COF_TTA-DHTA and COF_TTA-DHTA hollow spheres possess the well-defined morphology, high crystallinity and porosity, excellent dispersion property and high chemical stability. The template synthesis method demonstrated in this work provides a general method for the shape-controlled synthesis of COF-based materials, which is important for the further applications in the fields such as energy storage, drug delivery and catalysis.     

Encapsulation of RNA by negatively charged human serum albumin via physical interactions

Human serum albumin (HSA) is the most abundant plasma protein and has an inherent ability to target tumor cells. It is an excellent candidate for drug delivery. However, HSA cannot form complex with DNA or RNA, because it is negatively charged under physiological conditions. In this work, we reported a simple method to prepare HSA/RNA nanoparticles mainly by physical interaction. Firstly, the solution pH is adjusted to 4.0, under which condition HSA is positively charged. It forms complex with RNA via electrostatic interaction. The solution is then heated at 75 oC for 15 min to stabilize the structure and the size of the formed complex. The HSA/RNA nanoparticle prepared by this method has a diameter about 110 nm and a narrow distribution. It is also stable for days under physiological conditions. Cellular essays demonstrate that these particles exhibit a high cellular uptake efficiency and non-toxicity to HeLa cells.     

A facile chemical reduction method for synthesis of platinum–iron catalysts on carbon fiber papers for methanol oxidation

To enhance catalytic activity and durability for methanol oxidation reaction (MOR), we have fabricated bimetallic Pt–Fe catalysts on carbon fiber papers (denoted as Pt–Fe@CFP) by a facile chemical reduction method using iron as the precursor, ascorbic acid and sodium hypophosphite as the reductants, respectively. When ascorbic acid is using as the reductant, the Pt–Fe@CFP catalysts are composed of platinum and disordered Pt–Fe phases. The atomic ratio between Pt and Fe can be adjusted by altering deposition conditions. The Pt–Fe@CFP catalysts with Pt/Fe ratio of 1.1, which deposited with surfactant CTAB in bath at room temperature, exhibit excellent catalytic activity and stability in MOR. However, when sodium hypophosphite is employed as the reductant, the co-deposition of phosphorus would lead to a decreased catalytic performance in MOR.     

BiVO<Subscript>4</Subscript>-NPs: an efficient nano-catalyst for the synthesis of biscoumarins,bis(indolyl)methanes and 3,4-dihydropyrimidin-2(1<Emphasis Type="Italic">H</Emphasis>)-ones (thiones) derivatives

BiVO₄-NPs can be used as an efficient and reusable nano-catalyst for the promotion of the synthesis of biscoumarins, bis(indolyl)methanes and 3,4-dihydropyrimidin-2(1H)-ones (thiones) derivatives. The structures of the products were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and comparison with the authentic samples. Easy work-up procedure, excellent yields, short reaction times and reusability of the catalyst are some advantages of this work. In addition, in this article and for the first time, the preparation of 3,4-dihydropyrimidin-2(1H)-ones and -thiones from the protected derivatives of aldehydes including oximes, semicarbazones and 1,1-diacetates is reported.