Influence of surfactants on rheological behaviors of polyacrylonitrile/dimethyl sulfoxide/silicon blending polymer solutions

KH550, KH560, CTAB, and F127 were adopted to modify silicon (Si) to improve the dispersity and stability of Si in the polyacrylonitrile/dimethyl sulfoxide (PAN/DMSO) polymer solutions. The influence of surfactants on rheological behaviors of PAN/DMSO/Si blending polymer solutions was investigated by an advanced solution and melt rotation rheometer. The homogeneity and stability were also studied. The results showed that the surfactants could change the viscosity dependence of blending polymer solutions on shear rate, temperature and storage time by increase the steric hindrance of Si. Among the four solutions, PAN/DMSO/Si blending polymer solution with F127 exhibited the lowest viscosity, activation energy and the smallest structural viscosity index and exhibited the trend close to the Newtonian fluids. Moreover, PAN/DMSO/Si blending polymer solution with F127 exhibited the best dispersity and stability, indicating its best physical properties and machinability.     

Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g^?1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li⁺ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Strain‐rate‐dependent mechanical properties of polypropylene separator for lithium‐ion batteries

The mechanical integrity of battery separators is critical for battery safety and durability. A comprehensive study of strain‐rate‐dependent tensile and puncture properties of a polypropylene lithium‐ion battery separator is presented here with a new model. Due to anisotropy of the polymeric membrane, tensile testing was conducted for different directions. Results showed that tensile strength and elastic modulus were increased 1000% and 500%, respectively, for different directions. It was also demonstrated that tensile strength changed 10 to 25% with strain rate (1.67 × 10^?4 to 1.67 × 10^?1 s^?1) for different directions. An equation was obtained for the first time for flow stress versus strain rate at varied tensile directions with respect to machine direction. Moreover, puncture testing was performed and it was shown that puncture strength was increased 140% with increasing strain rate from 0.25 to 250 mm min^?1. Two failure modes were also observed in puncture samples. Finally, Eyring's model was used to calculate activation enthalpy of the porous polypropylene separator. © 2020 Society of Chemical Industry     

A review study on titanium niobium oxide-based composite anodes for Li-ion batteries: Synthesis,structure, and performance

The growing demands for Li-ion batteries (LIBs) in the electrification revolution, require the development of advanced electrode materials. Recently, intercalating titanium niobium oxide (TNO) anode materials with the general formula of TiNb_xO_2+2.5x have received lots of attention as an alternative to graphite and Li₄Ti₅O₁₂ commercial anodes. The desirability of this family of compounds stems from their high theoretical capacities (377–402 mAh/g), high safety, high working voltage, excellent cycling stability, and significant pseudocapacitive behavior. However, the rate performance of TNO-based anodes is poor owing to their low electronic and ionic conductivities. TNO-based composites generally are prepared with two aims of enhancing the conductivity of TNO and achieving a synergic effect between the TNO and the other component of the composite. Compositing with carbon matrices, such as graphene and carbon nanotubes (CNTs) are the most studied strategy for improving the conductivity of TNO and optimizing its high-rate performance. Also, for obtaining anode materials with high capacity and high long-term stability, the composites of TNO with transition metal dichalcogenides (TMDs) materials were proposed in previous literature. In this work, a comprehensive review of the TNO-based composites as the anodes for LIBs is presented which summarizes in detail the main recent literature from their synthesis procedure, optimum synthesis parameters, and the obtained morphology/structure to their electrochemical performance as the LIBs anode. Finally, the research gaps and the future perspective are proposed.     

The status of and opportunities for utility-scale battery storage in Australia: A regulatory and market perspective

Australia's electricity market is rapidly adding renewable energy generation. Utility-scale batteries could have a major role in facilitating these transitions; however, their deployment is still largely state-subsidized. We summarize the current and future roles for batteries from a legal-economic perspective in the context of Australia's electricity market framework. We find that the future of batteries in Australia is not only a function of the large-scale deployment of renewables, their cost development and the comparative future cost of competing gas turbines but also of national electricity market and state policy reforms focusing on reliability.     

A Complexing Agent to Enable a Wide-Temperature Range Bromine-Based Flow Battery for Stationary Energy Storage

Bromine-based flow batteries (Br-FBs) are considered one of the most promising energy storage systems due to their features of high energy density and low cost. However, they generally suffer from uncontrolled diffusion of corrosive bromine particularly at high temperatures. That is because the interaction between polybromide anions and the commonly used complexing agent (N–methyl–N–ethyl–pyrrolidinium bromide [MEP]) decreases with increasing temperatures, which causes serious self-discharge and capacity fade. Herein, a novel bromine complexing agent, 1–ethyl–2–methyl–pyridinium bromide (BCA), is introduced in Br-FBs to solve the above problems. It is proven that BCA can combine with polybromide anions very well even at a high temperature of 60 °C. Moreover, the BCA contributes to decreasing the electrochemical polarization of Br⁻/Br₂ couple, which in turn improves their power density. As a result, a zinc–bromine flow battery with BCA as the complexing agent can achieve a high energy efficiency of 84% at 40 mA cm⁻², even at high temperature of 60 °C and it can stably run for more than 400 cycles without obvious performance decay. This paper provides an effective complexing agent to enable a wide temperature range Br-FB.     

Biofortification with selenium and lithium improves nutraceutical properties of major winery grapes in the Midwestern United States

Enriching the micronutrients, selenium (Se) and lithium (Li), in grapes to improve their nutraceutical properties were implemented by foliar application of organic fertiliser rich in Se and Li onto five grape cultivars. The effects of this biofortification on vine vigour, fruit quality, overall micronutrients and phenolic compounds also were investigated. Agronomic biofortification was found greatly increased the Se and Li content in the whole grape by multiple times, meanwhile it did not significantly affect the vine vigour and fruit quality of grapes. However, the biofortification did impact the Ionome (including all the mineral nutrients and trace elements) and phenolic compounds in grapes and this varied among cultivars. This study demonstrated foliar spray of organic Se/Li fertiliser was a very effective strategy to biofortify these micronutrients in grape berries, particularly in the skin, and therefore might be a promising strategy to increase the consumption and awareness of these grapes.