Tuning fermi level and band gap in Li4Ti5O12 by doping and vacancy for ultrafast Li+ insertion/extraction

Li₄T_i5O₁₂ (LTO) attracts great interest due to the “zero strain” during cycles but the poor electronic and ionic conductivity critically impede the practical application. Herein, we report a synergy strategy of tuning localized electrons to shift Fermi level and band gap by Mg/Zr co-doping and oxygen vacancy incorporation, which significantly improves Li⁺ and electronic transport. More importantly, the intrinsic synergistic mechanism has been revealed by neutron diffraction, X-ray absorption spectra, and first-principles calculations. The “elastic effect” of lattice induced by Mg/Zr co-doping allows LTO to accommodate more oxygen vacancies to a certain degree without a severe lattice distortion, which largely improves the electronic conductivity. Mg/Zr co-doping and oxygen vacancy incorporation effectively enhanced the dynamic characteristics of LTO electrode, achieving the excellent rate performance (90 mAh/g at 20C) and cycle stability (96.9% after 500 cycles at 10C). First-principles calculations confirm Fermi level shifts to the conduction band, and the band gap becomes narrowed due to the synergistic modulation, and the intrinsic mechanism of the enhanced electronic and Li-ion conductivity is clarified. This study offers some insights into achieving the fast Li⁺ insertion/extraction by tuning the crystal and electronic structure with lattice doping and oxygen vacancy engineering.     

Electrochemical investigation of La0.4Sr0.6TiO3 synthesized in air for SOFC application

Journal of Applied Electrochemistry - La-doped titanate materials have been widely investigated as alternative Ni-free anodes for solid oxide fuel cells (SOFCs). In this study, La0.4Sr0.6TiO3 (LST)...     

Mechanical nondiscoloring and antistretching photonic crystal films based on Zn2+ coordination and hydroxypropyl methylcellulose

Mechanical nondiscoloring and antistretching photonic crystal (PC) films, especially those with stable structure colors during deformation, have great potential applications in wearable display devices, decoration, and packaging. Here, PC films with antistretching and invariant structural colors during deformation were prepared, by combining Zn²⁺ coordinated elastic material and hydroxypropyl methylcellulose (HPMC) with polystyrene@silica (PS@SiO₂) colloidal crystals. The PC films release energy by forming local fractures at a microscopic level during the straining process but the lattice spacing and effective refractive index of the local array do not change. According to the Bragg law, the structure color remains unchanged. The introduction of HPMC gave the PC films excellent tensile properties, and the maximum tensile strength reached 10 MPa. And after 100 times of stretching, bending and compression cycles, the structural color remained unchanged.     

Extension-dominated improved dispersive mixing in single-screw extrusion. Part 2: Comparative analysis with twin-screw extruder

In Part 1 of this work, the possibility of improving single-screw extruders (SSE) better dispersive mixer was explored by harnessing extensional flows provided by the hyperbolic contracting–diverging channels of extensional mixing elements (EME). Addition of the EME to the pin screw generated enhanced breakup for polymer blends and nanocomposite systems without significant penalty in flow rate. In Part 2, experiments are performed on immiscible polymer blends (low-viscosity ratio and high-viscosity ratio) and nanocomposites on both SSE and twin-screw extruder (TSE) with the same rotation speed and throughput. Morphological results show tremendous improvement in dispersive mixing capability of SSE when equipped with EME that are mainly comparable to conventional TSE that is, with kneading blocks as mixing sections, although not as good as TSEs equipped with EMEs. Mechanical results also show enhanced modulus when EME is used in SSE operations.     

Effect of electric field on storage modulus of dielectric composites

DCs composed by dielectric particles and elastomer matrix present electric field dependent deformation. Viscoelasticity dominates their electric field response, which has to be considered in their applications. Although the influence of strain amplitude and oscillation frequency on the viscoelasticity of DCs has been investigated, the effect of electric field has been seldom studied. In this study, DCs were prepared by dispersing TiO₂ particles with different concentrations and different distributions within silicone rubbers. The areal strain and the storage modulus of the DCs under different electric fields were tested. The results indicated the electric field has significant influence on the storage modulus of the DCs. Such an electric field dependent storage modulus is more significant for the DCs with higher particle fraction, or with aligned distributed particles. The enhanced electrostatic interaction between the adjacent particles by applying electric field is responsible for the phenomena.     

High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant

The flame retardant polypropylene containing the micro-envelope core-shell structure flame retardant, which encapsulated ammonium polyphosphate into melamine-formaldehyde resin and sodium silicate through in situ polymerization was prepared with polyamide 6, added as a carbon-forming agent. The composition of ammonium polyphosphate, encapsulated ammonium polyphosphate with melamine-formaldehyde resin and the micro-envelope core-shell structure flame retardant were characterized. The fire safety and thermal stability were investigated and showed an improvement including limiting oxygen index, thermogravimetric analysis, vertical burning tests, and microscale combustion calorimeter. The burned compounds were also studied to confirm the burning mechanism. The results showed the flame retardant performance had been greatly improved, while polyamide 6 had better char-forming effect. Besides, the water solubility of flame retardants and their influence on the mechanical properties of polypropylene were also investigated. The results on the effects of additives demonstrated a high efficiency flame retardant to polypropylene. A core-shell flame retardant that sodium silicate and melamine-formaldehyde resin-coated ammonium polyphosphate had been constructed. The effect of the built flame retardant system on the combustion performance of polypropylene was studied from the mechanism and performance. The LOI of the most flame retardant polypropylene reached 28.6%, and UL-94 reached the V-0 level.     

Simultaneously improved solid particle erosion resistant and strength of graphene nanoplates/carbon nanotube enhanced thermoplastic polyurethane films

Up to now, it is a major challenge to protect leading edge of the blades from solid particle erosion. Herein, we propose a structure optimization strategy to fabricate non-woven (NW) enhanced thermoplastic polyurethane nanocomposite films (thermoplastic polyurethane [TPU] - NW@G/C_x) with “sandwich - like” structure by hot pressing technology. TPU NW/graphene nanoplates/carbon nanotube (NW@G/C_x) interlayer film were first fabricated by spraying method. Then the interlayer film was laminated between TPU films to fabricate nanocomposite films. Such prepared TPU - NW@G/C_x film shows excellent solid particle erosion resistance and high-tensile strength. For example, the “steel-and-mortar” structure of NW fabric in TPU film results in high-tensile strength of 45 MPa and storage modulus of 21.2 MPa for TPU - NW@G/C_1.0, increasing by 25% and 171% compared with original TPU film (35 MPa, 8 MPa), respectively. In addition, compared with pure TPU film, the “sandwich - like” structure endows TPU - NW@G/C_1.2 with excellent solid particle erosion resistance and the thermal conductivity (0.251 W/m·K). These superior properties extends application of the TPU - NW@G/C_x film on wind turbine blades.     

Synergistic improvement of mechanical and thermal properties in epoxy composites via polyimide microspheres

Achieving synergetic improvements of mechanical strength, toughness, and thermal stability of epoxy resin has been a crucial but very challenging issue. Herein, to explore a new solution for circumventing this issue, polyimide microspheres were successfully prepared through the inverse nonaqueous emulsion process, and the structure, size distribution and morphologies of polyimide (PI) microspheres were comprehensively investigated. Then the PI microspheres were incorporated in epoxy resin matrix to systematically investigate the mechanical and thermal properties of obtained epoxy/PI microspheres composites. It was found that the PI microspheres can not only enhance the mechanical strength of epoxy resin, but also significantly improve the toughness. Specially, the epoxy-based composites containing 3 wt% PI microspheres exhibit a 47% increase in tensile strength, while the G_IC and Charpy impact strength increase by 106% and 200%, respectively. The toughing mechanism of epoxy/PI microspheres composites was discussed. Moreover, the PI microspheres can also endow the epoxy resin with excellent thermal stability and heat resistance. Thus, this work may open a new opportunity to synergistically enhance the mechanical and thermal properties of epoxy-based composites and may also give some valuable inspiration for the rational design of other high-performance thermosetting composites.     

Enzymatic degradability and release properties of graphene oxide/silk fibroin nanocomposite films

The structure evolution of silk fibroin (SF) in the nanocomposite films with graphene oxide (GO) was investigated and related to the enzymatic degradability and release property. The interaction with GO was found to induce conformation transition of SF from random coil to β-sheet. However, the surface binding constrained the rearrangement of the silk chains, leading to a decrease of β-sheet when GO content was more than 1.0%. The crystal structure of SF played a key role in the degradation of GO/SF composites. The preferential degradation of the hydrophilic blocks resulted in a faster degradation of SF films with higher β-sheet content. The addition of GO to SF matrix led to a slower release and a reduction of the burst release of RhB, the model compound. The release profile was well fitted to the Rigter–Peppas equation, from which the characteristic constant decreased and the diffusional exponent increased with increasing GO content but quickly leveled off when GO content was more than 1.0%. Degradation of the composites had little influence on the characteristic constant of RhB release, however, led to an increased diffusional exponent, which was more evident for the composites with higher β-sheet content.     

Hydrogen bonding induced enhancement for constructing anisotropic sugarcane composite hydrogels

Anisotropic hydrogels are appealing with their merits of similar biochemical and structural properties to the biological tissues. However, the mechanical properties of current anisotropic hydrogels need to be further improved. Herein, three kinds of novel anisotropic poly(2-hydroxyethyl methacrylate) (pHEMA), poly(acrylamide) (pAM), and poly(acrylamide-co-acrylic acid) (p[AM-co-AA]) sugarcane composite hydrogels were prepared successfully by filling the hydrogel monomer precursor into porous aligned sugarcane nanofibers network and then performing subsequent free radical polymerization. The hydrogel matrix and sugarcane nanofibers network were combined closely together through hydrogen bonding interaction. The anisotropic sugarcane composite hydrogels exhibit good flexibility and elastic recovery properties upon encountering mechanical crimping and twisting. In typical case, the as-prepared pHEMA sugarcane composite hydrogel can exhibit high anisotropic tensile strength of 2.37 and 0.54 MPa, while differential tear strength of 0.36 and 0.78 N/mm, along the parallel and vertical nanofibers directions. Finally, anisotropic lubrication behaviors were found and investigated systematically for those three kinds of sugarcane composite hydrogels when water was used as lubricant. Our current work proposes a simple and universal strategy for developing bioinspired anisotropic functional composite matters such as artificial skin, flexible sensor, and cartilage lubrication materials.