Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Formation mechanism of Ti(C,N) solid solution in Al-brown fused alumina refractory at 1973 K in flowing N2

Brown fused alumina is a cost-effective alumina material, and the state of Ti in alumina has a great influence on its high-temperature performance. In this paper, the Ti-containing phases in brown fused alumina particles and Al-brown fused alumina refractory were successfully transformed into Ti(C,N) at 1973 K in flowing N₂. The evolution of the Ti-containing phases in brown fused alumina under high temperature and nitrogen conditions was investigated by XRD, SEM and EDS. The results show that the Ti-containing phases in brown fused alumina include Ti₂O₃, Ti(C,N,O), TiFeSi₂, Ca_0·95Mg_0·9Al_10·1(Ti)O₁₇ and a low-melting point Ca₃Al₂Si₃(Mg,Ti)O₁₂ phase. Under high temperature and nitrogen conditions, the TiO_2[liquid], MgO_[liquid] and SiO_2[liquid] in the low-melting point phase are transformed into Ti(C,N), Mg(g) and SiO(g), while they are supplemented from Ti₂O₃, Ti(C,N,O) and Ca_0·95Mg_0·9Al_10·1(Ti)O₁₇. After heat treatment at 1973 K for 3 h, Ti₂O₃ and Ti(C,N,O) disappear, Ca_0·95Mg_0·9Al_10·1(Ti)O₁₇ is transformed into plate-like Ca_0·55Al₁₁O_17.05, and Ti(C,N) is formed on the surface of the corundum particles. The formation of Ti(C,N) reduces the porosity of the brown fused alumina particles and increases their strength.     

Hydrogen storage in Zr0.9Ti0.1(Ni0.5Cr0.5-xVx)2 Laves phase,with x = 0, 0.125, 0.25, 0.375, 0.5. A theoretical approach

Density functional calculations were performed on Zr_0.9Ti_0.1(Ni_0.5Cr_0.5-xV_x)₂ Laves Phase, with x = 0, 0.125, 0.25, 0.375 and 0.5, in order to study its H absorption capacity. Binding energy, electronic structure and bonding were analyzed for the intermetallic compound with different V content and increasing amounts of hydrogen.The optimized geometry was found in good agreement with experimental data of the C14 Laves phase. Hydrogen locates preferentially in A₂B₂ tetrahedral sites in the AB₂ matrix (A = Zr, Ti; B = Ni, Cr, V) but AB₃ and B₄sites are also stable. The volume of the intermetallic and the H binding energy increases with vanadium content. Theoretically H absorption is possible up to 4.5 H/F.U. but the strongest binding energy is achieved with 3 H/F. U.The main contribution to density of states is due to d states of all components of the structure and an H-metal bonding is observed in the range ?10 to ?4 eV.     

Oxidation mechanisms in bulk Ti2AlC: Influence of the grain size

In this work, oxidation mechanisms were studied in fine-grained (FG) and coarse-grained (CG) Ti₂AlC bulk samples. Results showed that the oxidation kinetics are controlled by the grain size of Ti₂AlC. Bigger are the grains, faster is the oxidation. A dense and protective Al₂O₃ layer forms at the surface of FG-Ti₂AlC samples while for the CG-Ti₂AlC samples, a thick TiO₂ layer forms on top of a discontinuous Al₂O₃. CG-Ti₂AlC was observed to simultaneously transform into Ti₃AlC₂ and TiC instead of being directly transformed into TiC. This transformation result in the following crystallographically sandwich-like structure: (0001) Ti₂AlC // (0001) Ti₃AlC₂ // (111) TiC. The volume shrinkage associated to this transformation produces elongated holes that are partially filled by α-Al₂O₃. The stress caused by the volume shrinkage generates cracks at the surface, which makes the oxygen inwards diffusion easier and thus worsens the oxidation resistance the CG-Ti₂AlC bulk.     

Coexistence of three ferroelectric phases and enhanced piezoelectric properties in BaTiO3–CaHfO3 lead-free ceramics

Perovskite ferroelectrics possess the fascinating piezoelectric properties near a morphotropic phase boundary, attributing to a low energy barrier that the results in structural instability and easy polarization rotation. In this work, a new lead-free system of (1-x)BaTiO₃-xCaHfO₃ was designed, and characterized by a coexistence of ferroelectric rhombohedral-orthorhombic-tetragonal (R-O-T) phases. With the increase amount of CaHfO₃ (x), a stable coexistence region of three ferroelectric phases (R-O-T) exists at 0.06 ≤ x ≤ 0.08. Both large piezoelectric coefficient (d₃₃～400 pC/N), inverse piezoelectric coefficient (d₃₃^*～547 pm/V) and planar electromechanical coupling factor (k_p～58.2%) can be achieved for the composition with x = 0.08 near the coexistence of three ferroelectric phases. Our results show that the materials with the composition located at a region where the three ferroelectric R-O-T phases coexist would have the lowest energy barrier and thus greatly promote the polarization rotation, resulting in a strong piezoelectric response.