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.     

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.     

High-entropy oxide phases with magnetoplumbite structure

Sintering of oxides and carbonates at 1400 °C gives crystalline high-entropy single phase products with a BaFe₁₂O₁₉ (magnetoplumbite) structure containing 5 doping elements at high concentration level: Ba(Fe₆Ti_1·2Co_1·2In_1.2Ga_1.2Cr_1.2)O₁₉. The complete list of explored substitutions includes K, Ca, Sr, Pb, La, Bi, Al, Ga, In, Ti, V, Cr, Mn, Co, and Ni. Loading to the batch more than 5 dopants or introduction of NiO, or V₂O₅ initiates formation of second phases like spinels or vanadates. Bi₂O₃ and K₂O are too volatile at sintering temperature and were evaporated from the samples.Due to large ionic radius, the In³⁺ cation is likely to be incorporated not only on Fe³⁺ sites, but also on Ba²⁺ sites, that follow from resulting crystal composition. The smallest di-valent and tri-valent cations, Sr²⁺ and Al³⁺, are found to preferably concentrate together in the same magnetoplumbite phase crystals within one sample.According to elemental analysis of selected hexagonal crystals in the investigated 8 doped samples the most prospective compositions for obtaining high-entropy single phase with magnetoplumbite structure can be formulated as (Ca,Sr,Ba,Pb,La)Fe_x(Al,Ga,In,Ti,Cr,Mn,Co)_12-xO₁₉ where x = 1.5–6.     

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.     

Hydrogen storage properties of Mg98.5Gd1Zn0.5 and Mg98.5Gd0.5Y0.5Zn0.5 alloys containing LPSO phases

In this work, the as-cast Mg-rich Mg_98.5Gd₁Zn_0.5 and Mg_98.5Gd_0.5Y_0.5Zn_0.5 alloys are prepared by the semi-continuous casting method, and their hydrogen storage performance and catalytic mechanisms are investigated by experimental and first-principles calculations approaches. The results show that the LPSO phases decompose and in-situ form the RE(Gd/Y)H_x(x = 2,3) nano-hydrides upon hydrogenation. These nano-hydrides not only serve as the in-situ catalysts to promote the hydrogen ab/desorption of Mg matrix, but also present the pinning effect to inhibit the growth of Mg/MgH₂ grains during hydrogenation and dehydrogenation. Comparatively, the two alloys exhibit the similar hydrogen absorption kinetics, while the hydrogen desorption kinetics of Mg_98.5Gd₁Zn_0.5 is superior to that of Mg_98.5Gd_0.5Y_0.5Zn_0.5. The first-principles calculations reveal that the GdH₂ and YH₂ hydrides exhibit different catalytic effects on weakening the bond strength of H–H within H₂ and Mg–H within MgH₂, which interprets well the differences in the hydrogen ab/desorption kinetics between Mg_98.5Gd₁Zn_0.5 and Mg_98.5Gd_0.5Y_0.5Zn_0.5 alloys.     

Control of the particle microstructure during the synthesis of bulk-polymerized transparent methacrylate-acrylonitrile-butadiene-styrene resin

A series of methacrylate-acrylonitrile-butadiene-styrene (MABS) resins was prepared using bulk polymerization. The polarity of the continuous phase and the compatibility of two phases were changed by adjusting the methyl methacrylate (MMA) content, choosing values that were close to styrene-butadiene rubber solubility value. The possibility of controlling the microstructure of the MABS resin by changing the polarity of the components and the compatibility of two phases was assessed. The dynamic mechanical analysis shows that the compatibility of two phases varies with the MMA content. The morphological analysis shows that increasing MMA contents results in a gradual decrease in the sub-inclusion structure with a network skeleton of rubber particles, and that all the particles become solid rubber when the MMA content reaches 75%. The sub-inclusion structure reappears but does not have a network skeleton when the MMA content is 90%. The impact strength and morphological analysis indicate that the solid rubber particles and the sub-inclusion structure with a network skeleton provide excellent toughness, while the sub-inclusion structure without a network skeleton does not. In contrast, the transmittance of the ABS resin first increased and then decreased with increasing MMA content.     

Microstructure evolution and bonding strength of the Al2O3/Al2O3 interface brazed via Ni-Ti intermetallic phases

In this study, Al₂O₃ workpieces were vacuum brazed by using Ni-45Ti binary alloy. The interfacial microstructure evolution of the joints obtained at different brazing temperatures was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The bonding strength of the joints was measured by shear testing. The results indicated that Ni₂Ti₄O and AlNi₂Ti were the main reaction products in the joint areas. Moreover, the Ti₂Ni intermetallic compound formed in the brazing seam. The typical layer structure of the brazed joints was Al₂O₃/AlNi₂Ti/Ni₂Ti₄O/Ti₂Ni + NiTi/Ni₂Ti₄O/AlNi₂Ti/Al₂O₃. With the brazing temperature increasing, the thickness of the Ni₂Ti₄O reaction layer adjacent to the Al₂O₃ substrate increased significantly, while the AlNi₂Ti phase had a tendency to dissolve with the brazing temperature increasing. The mechanism for the microstructure evolution was also discussed. The maximum shear strength of 125.63±4.87 MPa of the joints was obtained when brazed at 1350 °C for 30min. The fracture occurred hardly in the interface between Al₂O₃ and Ni-45Ti filler alloy.     

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.     

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.