ON THE MECHANISM OF “HYDROPHOBIC” INTERACTIONS

It is shown that the interfacial attraction between low-energy bodies immersed in aqueous media, known as “hydrophobic” interaction, can be quantitatively accounted for by, mainly, the hydrogen-bonding energy of cohesion of water, plus, to a very minor extent, a van der Waals-Lifshitz attraction between the Immersed law-energy bodies.     

Asymmetric double-layer composite electrolyte with enhanced ionic conductivity and interface stability for all-solid-state lithium metal batteries

All-solid-state Li metal battery has been regarded as a promising battery technology due to its high energy density based on the high capacity of lithium metal anode and high safety based on the all solid state electrolyte without inflammable solvent.However,challenges still exist mainly in the poor contact and unstable interface between electrolyte and electrodes.Herein,we demonstrate an asymmetric design of the composite polymer electrolyte with two different layers to overcome the interface issues at both the cathode and the anode side simultaneously.At the cathode side,the polypropylene carbonate layer has enough viscosity and flexibility to reduce the inter-facial resistance,while at the Li anode side,the polyethylene oxide layer modified with hexagonal boron nitride has high mechanical strength to suppress the Li dendrite growth.Owing to the synergetic effect between different components,the asprepared double layer composite polymer electrolyte demonstrates a large electrochemical window of5.17 V,a high ionic conductivity of 6.1×10~(-4) S/cm,and a transfe rence number of 0.56,featuring excellent ion transport kinetics and good chemical stability.All-solid-state Li metal battery assembled with LiFePO_4 cathode and Li anode delivers a high capacity of 150.9 mAh/g at 25℃ and 0.1 C-rate,showing great potential for practical applications.     

Low-Temperature Electrolyte Design for Lithium-Ion Batteries: Prospect and Challenges

Lithium-ion batteries have dominated the energy market from portable electronic devices to electric vehicles. However, the LIBs applications are limited seriously when they were operated in the cold regions and seasons if there is no thermal protection. This is because the Li+ transportation capability within the electrode and particularly in the electrolyte dropped significantly due to the decreased electrolyte liquidity, leading to a sudden decline in performance and short cycle-life. Thus, design a low-temperature electrolyte becomes ever more important to enable the further applications of LIBs. Herein, we summarize the low-temperature electrolyte development from the aspects of solvent, salt, additives, electrolyte analysis, and performance in the different battery systems. Then, we also introduce the recent new insight about the cation solvation structure, which is significant to understand the interfacial behaviors at the low temperature, aiming to guide the design of a low-temperature electrolyte more effectively.     

Densification and lithium ion conductivity of garnet-type Li7-xLa3Zr2-xTaxO12 （x=0.25） solid electrolytes

The garnet-type Li7La3Zr2O12 ceramic is a promising solid electrolyte for all-solid-state secondary lithium batteries. However, it faces the problem of lithium volatilization during sintering, which may cause low density and deterioration of ionic conductivity. In this work, the effects of sintering temperature and addition on the density as well as the lithium ion conductivity of Li7-xLa3Zr2-xTaxO12 (LLZTO, x=0.25) ceramics prepared by solid state reaction have been studied. It is found that optimization of the sintering temperature leads to a minor increase in the ceramic density, yielding an optimum ionic conductivity of 2.9×10-4 S·cm-1 at 25℃. Introduction of Li 3 PO 4 addition in an appropriate concentration can obviously increase the density, leading to an optimum ionic conductivity of 7.2×10-4 S·cm-1 at 25℃. This value is superior to the conductivity data in most recent reports on the LLZTO ceramics.     

Preparation of safe water–lipid mixed electrolytes for application in ion capacitor

Aqueous electrolytes are safe, economic, and environmentally friendly. However, they have a narrow potential window. On the other hand, organic electrolytes exhibit good thermodynamic stability but are inflammable and moisture sensitive. In this study, we prepared water–PEG–lipid ternary electrolytes(TEs). To combine the advantages of water, polyethylene glycol(PEG) and propylene carbonate(PC). The nonflammable mixed electrolytes exhibited a wide potential window of about 2.8 V due to the beneficial effects of PEG and PC. Using these TEs, a lithium manganate–active carbon ion capacitor could be operated at 2.4 V with an energy density of 32 Wh/kg, based on the total active electrode material(current density of 3.3 m A/cm~2). This value was significantly higher than that achieved using an aqueous electrolyte, thereby rationalizing the higher energy density.     

High temperature creep behavior of phosphoric acid‐polybenzimidazole gel membranes

This work investigates the effects of polymer solids content and macromolecular structure on the high temperature creep behavior of polybenzimidazole (PBI) gel membranes imbibed with phosphoric acid (PA) after preparation via a polyphosphoric acid (PPA) mediated sol‐gel process Low‐solids, highly acid‐doped PBI membranes demonstrate outstanding fuel cell performance under anhydrous, ambient pressure, and high temperature (120–200 °C) operating conditions. However, PBI membranes are susceptible to creep under compressive loads at elevated temperatures, so their long‐term mechanical durability is a major concern. Here, we report results for the creep behavior of PBI membranes subject to compression at 180 °C. For para‐ and meta‐PBI homopolymers, increasing polymer solids content results in lower creep compliance and higher extensional viscosity, which may be rationalized by increasing chain density in the sol‐gel network. Comparing various homo‐ and copolymers at similar solids loading, differences in creep behavior may be rationalized in terms of chain–chain and chain‐solvent interactions that control macromolecular solubility and stiffness in the PA solvent. The results demonstrate the feasibility of improving the mechanical properties of PA‐doped PBI membranes by control of polymer solids content and rational design of PBI macromolecular structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1527–1538     

Tailored side‐chain architecture of benzil voltage stabilizers for enhanced dielectric strength of cross‐linked polyethylene

The synthesis and physico‐chemical properties of seven benzil‐type voltage stabilizers are reported. The benzil core is substituted with alkyl chains of different length that are linked to the benzil core via an ester, ether, or tertiary amine group. All additives can be melt‐processed with low‐density polyethylene (LDPE). Fourier‐transform infrared spectroscopy confirms that benzil compounds are not affected by the LDPE cross‐linking reaction induced by dicumyl peroxide. Moreover, a combination of gel content measurements, thermal analysis, and small‐angle X‐ray scattering indicates that the presence of benzil voltage stabilizers does not significantly alter the microstructure of cross‐linked polyethylene (XLPE). Electrical tree inhibition experiments under high‐voltage alternating current conditions show that all investigated additives substantially enhance the dielectric strength of the insulating material at a concentration of only 10 mmol kg^?1. The highest improvement in dielectric strength, of more than 70% with respect to reference XLPE, is obtained with voltage stabilizers, which carry short (methyl) side chains that are linked to the benzil core via an ester or tertiary amine group. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1047–1054     

Electrolytes for quasi solid‐state dye‐sensitized solar cells based on block copolymers

The first use of PS_n‐b‐PEO_m‐b‐PS_n block copolymers (PS = polystyrene, PEO = poly(ethylene oxide)) as solid hosts for iodine/iodide electrolytes in dye‐sensitized solar cells (DSSCs) is described. Using the benchmark photosensitizer N719, DSSC based on the quasi solid‐state electrolytes afforded efficiencies up to 6.7%, to be compared with an efficiency of 7.3% obtained in similar conditions with a conventional iodine/iodide liquid electrolyte. By varying the PS:PEO relative volume ratio in the block copolymers different properties and morphologies were obtained. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 719–727     

Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott–Schottky or Gouy–Chapman–Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments.