Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Crystallization and spectroscopic properties in Er3+ doped oxyfluorogermanate glass ceramics containing Na

The Er³⁺ doped oxyfluorogermanate glasses, with a composition containing Na element, were synthesized by the conventional melting–quenching technique. When Na element was introduced into the composition of oxyfluorogermanate glass, the crystals behavior was investigated in details. Depending on the annealing procedure supplied, thermal annealing of precursor glasses in the system GeO₂/BaF₂/AlF₃/Na₂O/NaF/ZnO/GdF₃/ErF₃ led to the precipitation of different crystal phase nanocrystals. It was confirmed the nanocrystals in GC600 is orthorhombic NaBaAlF₆ which led to enhance obviously in the UC luminescence of Er³⁺. However, the nanocrystals in G585 led to decrease in the UC luminescence, which indicated few Er ions enter into the lattice of this nanocrystal phase. The reason of the decrease in UC emission intensity of GC585 was analyzed.     

Effect of sodium doping on graded Cu(In1−xGax)Se2 thin films prepared by chemical spray pyrolysis

In the present work we have studied the effect of Na on the properties of graded Cu(In_1−xGa_x)Se₂ (CIGS) layer. Graded CIGS structures were prepared by chemical spray pyrolysis at a substrate temperature of 350 °C on soda lime glass. Sodium chloride is used as a dopant along with metal (Cu/In/Ga) chlorides and n, n-dimethyl selenourea precursors. The addition of Na exhibited better crystallinity with chalcopyrite phase and an improvement in preferential orientation along the (112) plane. Energy dispersive analysis of X-rays (line/point mapping) revealed a graded nature of the film and percentage incorporation of Na (0.86 at%). Raman studies showed that the film without sodium doping consists of mixed phase of chalcopyrite and CuAu ordering. Influence of sodium showed a remarkable decrease in electrical resistivity (0.49–0.087 Ω cm) as well as an increase in carrier concentration (3.0×10¹⁸–2.5×10¹⁹ cm⁻³) compared to the un-doped films. As carrier concentration increased after sodium doping, the band gap shifted from 1.32 eV to 1.20 eV. Activation energies for un-doped and Na doped films from modified Arrhenius plot were calculated to be 0.49 eV and 0.20 eV, respectively. Extremely short carrier lifetimes in the CIGS thin films were measured by a novel, non-destructive, noncontact method (transmission modulated photoconductive decay). Minority carrier lifetimes of graded CIGS layers without and with external Na doping are found to be 3.0 and 5.6 ns, respectively.     

Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials

Layered sodium transition metal oxides of NaTMO₂ (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO₂. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X‐ray diffraction, Cs‐corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO₆ octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.     

Phase equilibria in CaNaPO4-CaKPO4 system and their influence on formation of bioceramics based on mixed Ca-K-Na phosphates

An investigation of the two-component phase diagram of the CaNaPO₄- CaKPO₄system performed using various analysis techniques is reported. The continuous solid solution series of α-CaMPO₄ existing above 700 °C undergoes eutectoid decomposition during cooling to β-CaMPO₄-based solid solutions enriched with Na and K, and to an intermediate nonstoichiometric compound with an ideal composition of CaK_0.6Na_0.4PO₄. All three compounds exhibit significant volumetric effects associated with first-order phase transitions, with positive volume changes under cooling for the intermediate compound. Increased K content in ceramics based on CaK_yNa_1-yPO₄ compositions enhances the strength properties of those ceramics, including their fracture toughness, which is associated with increased density. Increased K content also has a smaller effect of inducing phase transformations accompanied by strong volume changes.     

The deactivation effect of Na2O and NaCl on CeO2–TiO2 catalysts for selective catalytic reduction of NO with NH3

The effect of Na₂O and NaCl on CeO₂–TiO₂ catalyst for the selective catalytic reduction of NO with NH₃ was investigated with BET, XRD, XPS, NH₃-TPD, H₂-TPR, in-situ DRIFT and catalytic activity measurements. The results showed that both Na species could deactivate the CeO₂–TiO₂ catalyst and Na₂O had a stronger effect than NaCl. The more serious deactivation by Na₂O could be ascribed to smaller surface area, fewer surface Ce³⁺ and chemical adsorbed oxygen, lower surface acidity, and worse reducibility. The introduction of NaCl and Na₂O facilitated the formation of new surface NO_x adspecies, but were inactive in NH₃-SCR reaction. The adsorption of NH₃ were inhibited. The NH₃-SCR reaction over the CeO₂–TiO₂ catalyst was governed by both E-R and L-H mechanisms. The introduction of NaCl and Na₂O didn't change the NH₃-SCR reaction mechanisms.     

Thermal depolarization and electromechanical hardening in Zn2+-doped Na1/2Bi1/2TiO3-BaTiO3

Na_1/2Bi_1/2TiO₃-based materials have been earmarked for one of the first large-volume applications of lead-free piezoceramics in high-power ultrasonics. Zn²⁺-doping is demonstrated as a viable route to enhance the thermal depolarization temperature and electromechanically harden (1-y)Na_1/2Bi_1/2TiO₃-yBaTiO₃ (NBT100yBT) with a maximum achievable operating temperature of 150 °C and mechanical quality factor of 627 for 1 mole % Zn²⁺-doped NBT6BT. Although quenching from sintering temperatures has been recently touted to enhance T_F-R, with quenching the doped compositions featuring an additional increase in T_F-R by 17 °C, it exhibits negligible effect on the electromechanical properties. The effect is rationalized considering the missing influence on conductivity and therefore, negligible changes in the defect chemistry upon quenching. High-resolution diffraction indicates that Zn²⁺-doped samples favor the tetragonal phase with enhanced lattice distortion, further corroborated by ²³Na Nuclear Magnetic Resonance investigations.     

Influence of Zn2+ doping on the morphotropic phase boundary in lead-free piezoelectric (1 – x)Na1/2Bi1/2TiO3-xBaTiO3

A series of morphotropic phase boundary (MPB) compositions of (1–x)Na_1/2Bi_1/2TiO₃-xBaTiO₃ (x = 0.05, 0.055, 0.06, 0.065, 0.07), with and without 0.5 mol% Zn-doping was synthesized using the solid-state route. The samples were characterized using X-ray diffraction, dielectric analysis, and electromechanical measurements (piezoelectric d₃₃ coefficient, coupling factor k_p, mechanical quality factor Q_m, and internal bias field E_bias). The increase in the ferroelectric-relaxor transition temperature upon Zn-doping was accompanied by a shift of the MPB toward the Na_1/2Bi_1/2TiO₃-rich side of the phase diagram. Higher tetragonal phase fraction and increased tetragonal distortion were noted for Zn-doped (1 – x)Na_1/2Bi_1/2TiO₃-xBaTiO₃. In addition, ferroelectric hardening and the presence of an internal bias field (E_bias) were observed for all doped compositions. The piezoelectric constant d₃₃ and the coupling coefficient k_p decreased by up to ∼30%, while a 4- to 6-fold increase in Q_m was observed for the doped compositions. Apart from establishing a structure–property correlation, these results highlight the chemically induced shift of the phase diagram upon doping, which is a crucial factor in material selection for optimal performance and commercialization.     

对武安高岭土除铁工艺研究

河北武安硬质高岭土粉含Fe2O31.23%，经高梯度磁选后降至0.77%，再用Na2S2O3进行还原溶解后降至0.62%，白度提高了13％，本文介绍了流程及条件试验过程和结果。