Nanostructured Transition Metal Oxides on Carbon Fibers for Supercapacitor and Li-Ion Battery Electrodes: An Overview.

Nowadays, owing to the new technological and industrial requirements for equipment, such as flexibility or multifunctionally, the development of all-solid-state supercapacitors and Li-ion batteries has become a goal for researchers. For these purposes, the composite material approach has been widely proposed due to the promising features of woven carbon fiber as a substrate material for this type of material. Carbon fiber displays excellent mechanical properties, flexibility, and high electrical conductivity, allowing it to act as a substrate and a collector at the same time. However, carbon fiber's energy-storage capability is limited. Several coatings have been proposed for this, with nanostructured transition metal oxides being one of the most popular due to their high theoretical capacity and surface area. In this overview, the main techniques used to achieve these coatings-such as solvothermal synthesis, MOF-derived obtention, and electrochemical deposition-are summarized, as well as the main strategies for alleviating the low electrical conductivity of transition metal oxides, which is the main drawback of these materials.

Optimizing the Ion Conductivity and Mechanical Stability of Polymer Electrolyte Membranes Designed for Use in Lithium Ion Batteries: Combining Imidazolium-Containing Poly(ionic liquids) and Poly(propylene carbonate).

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young's modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10-6 S·cm-1 at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10-5 S·cm-1 and further increases to 10-3 S·cm-1 in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries.

Micellar cathodes from self-assembled nitroxide-containing block copolymers in battery electrolytes.

This contribution describes the synthesis of block copolymers containing electrochemically active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 m lithium trifluoromethanesulfonate dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate(1:1:1, in volume). Dynamic light scattering and atomic force micro-scopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochemical properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs Li(+) /Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs Li(+) /Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured organic radical batteries.

Poly[poly(ethylene glycol) methacrylate]-modified starch-based solid and gel polymer electrolytes for high performance Li-ion batteries.

The idea of replacing liquid electrolytes with polymer electrolytes has been successful and the development of these electrolytes has provided acceptable results. With the start of using natural polymers in the polymer industry, as well as starch, these materials can be one of the most important candidates for the polymer matrix in electrolytes. In this study, starch has been investigated as a polymer electrolyte, poly[poly(ethylene glycol) methacrylate] (PEGMA) is grafted to the starch by radical polymerization, and synthesized copolymers are used as solid polymer electrolytes (SPEs). Furthermore, by adding N,N'-methylenebisacrylamide (MBA) as a cross-linking agent, gel polymer electrolytes (GPEs) are produced after swelling in the liquid electrolyte. After characterization, the synthesized polymer electrolytes are investigated in terms of electrochemical properties. The best ionic conductivity of 3.8 × 10-5 S cm-1 is obtained for SPEs whereas it is obtained 4.3 × 10-3 S cm-1 for GPEs at room temperature. The ion transfer number in the range of 0.47-0.91 confirms the compatibility between the electrolytes and electrode. Also, the prepared polymer electrolytes present excellent electrochemical properties, including, a wide electrochemical stability window above 4.7 V, good specific capacities in the range of 170-200 mAh g-1 with a storage capacity of more than 92 %, and Coulombic efficiency of about 98 % after 100 cycles at 0.2 C.

Aramid nanofiber/bacterial cellulose composite separators for lithium-ion batteries.

Aramid nanofibers (ANFs) are expected to serve as new nanoscale building blocks which could improve both the mechanical performance and ionic conductivity of bacterial cellulose (BC) membranes due to their high interfacial bonding, matching of fiber size and the polar aramid groups in ANFs. Herein, composite membranes of BC and ANFs with different ANFs loadings of 2%, 4%, 6% and 8% were prepared by a traditional paper-making method after homogeneous mixing. The achieved membranes with relatively low ANFs loadings exhibited the increased tensile strength and ionic conductivity. The Li/LiFePO4 half-cells based on the 2%ANFs/BC separator demonstrated the best electrochemical performance (including discharge capacity, C-rate capability and cycling stability). Thus, the proposed ANFs/BC separators are a promising candidate for high-performance Li-ion batteries.

Preparation of novel carbon microfiber/carbon nanofiber-dispersed polyvinyl alcohol-based nanocomposite material for lithium-ion electrolyte battery separator.

A novel nanocomposite polyvinyl alcohol precursor-based material dispersed with the web of carbon microfibers and carbon nanofibers is developed as lithium (Li)-ion electrolyte battery separator. The primary synthesis steps of the separator material consist of esterification of polyvinyl acetate to produce polyvinyl alcohol gel, ball-milling of the surfactant dispersed carbon micro-nanofibers, mixing of the milled micron size (~500 nm) fibers to the reactant mixture at the incipience of the polyvinyl alcohol gel formation, and the mixing of hydrophobic reagents along with polyethylene glycol as a plasticizer, to produce a thin film of ~25 µm. The produced film, uniformly dispersed with carbon micro-nanofibers, has dramatically improved performance as a battery separator, with the ion conductivity of the electrolytes (LiPF6) saturated film measured as 0.119 S-cm(-1), approximately two orders of magnitude higher than that of polyvinyl alcohol. The other primary characteristics of the produced film, such as tensile strength, contact angle, and thermal stability, are also found to be superior to the materials made of other precursors, including polypropylene and polyethylene, discussed in the literature. The method of producing the films in this study is novel, simple, environmentally benign, and economically viable.