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At least 379 records · Page 21

Elucidating the Synergic Effect in Nanoscale MoS 2 /TiO 2 Heterointerface for Na‐Ion Storage

Abstract Interface engineering in electrode materials is an attractive strategy for enhancing charge storage, enabling fast kinetics, and improving cycling stability for energy storage systems. Nevertheless, the performance improvement is usually ambiguously ascribed to the “synergetic effect”, the fundamental understanding toward the effect of the interface at molecular level in composite materials remains elusive. In this work, a well‐defined nanoscale MoS 2 /TiO 2 interface is rationally designed by immobilizing TiO 2 nanocrystals on MoS 2 nanosheets. The role of heterostructure interface between TiO 2 and MoS 2 by operando synchrotron X‐ray diffraction (sXRD), solid‐state nuclear magnetic resonance, and density functional theory calculations is investigated. It is found that the existence of a hetero‐interfacial electric field can promote charge transfer kinetics. Based on operando sXRD, it is revealed that the heterostructure follows a solid‐solution reaction mechanism with small volume changes during cycling. As such, the electrode demonstrates ultrafast Na + ions storage of 300 mAh g −1 at 10 A g −1 and excellent reversible capacity of 540 mAh g −1 at 0.2 A g −1 . This work provides significant insights into understanding of heterostructure interface at molecular level, which suggests new strategies for creating unconventional nanocomposite electrode materials for energy storage systems.

25 ENERGY STORAGE↗

Flux Synthesis of A-site Disordered Perovskite La 0.5 M 0.5 TiO 3 (M$=$Li, Na, K) Nanorods Tailored for Solid Composite Electrolytes

Inorganic fillers play an important role in improving the ionic conductivity of solid composite electrolytes (SCEs) for Li-ion batteries. Among inorganic fillers, perovskite-type lithium lanthanum titanate (LLTO) stands out for its high bulk Li + conductivity on the order of 10 -3 S cm -1 at room temperature. According to a literature survey, the optimal LLTO filler should possess the following characteristics: i) a single-crystal structure to minimize grain boundaries; ii) a small particle size to increase the filler/polymer interface area; iii) a 1D morphology for efficient interface channels; and iv) cubic symmetry to facilitate rapid bulk Li + diffusion within the filler. However, the synthesis of single crystal, 1D LLTO nanomaterials with cubic symmetry is challenging. Herein, a flux strategy is developed to synthesize La 0.5 M 0.5 TiO 3 (LMTO, M$=$Li, Na, and K) single-crystal nanorods with an A-site-disordered, cubic perovskite phase. The flux media promotes the oriented growth of nanorods, prevents nanorods from sintering, and provides multiple alkali metal ion doping at M sites to stabilize the cubic phase. SCEs compositing the Li + -conducting LMTO nanorods as fillers and poly[vinylene carbonate- co -lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] matrix exhibit more than twice the conductivity of the neat polymer electrolyte (30.6 vs 14.0 µS cm -1 at 303 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operando Interaction and Transformation of Metastable Defects in Layered Oxides for Na‐Ion Batteries

Non-equilibrium defects often dictate the macroscopic properties of materials. They largely define the reversibility and kinetics of processes in intercalation hosts in rechargeable batteries. Recently, imaging methods have demonstrated that transient dislocations briefly appear in intercalation hosts during ion diffusion. Despite new discoveries, the understanding of impact, formation and self-healing mechanisms of transient defects, including and beyond dislocations, is lacking. Here, operando X-ray Bragg Coherent Diffractive Imaging (BCDI) and diffraction peak analysis capture the stages of formation of a unique metastable domain boundary, defect self-healing, and resolve the local impact of defects on ionic diffusion in Na x Ni 1-y MnyO 2 intercalation hosts in a charging sodium-ion battery. Results, applicable to a wide range of layered intercalation materials due to the shared nature of framework layers, elucidate new dynamics of transient defects and their connection to macroscopic properties, and suggest how to control the nanostructure dynamics.

36 MATERIALS SCIENCE↗

Bipolar Organic Cathodes for Stable and Sustainable Na‐Ion and Rechargeable Al Batteries

Bipolar organic materials have emerged as promising cathode materials for rechargeable batteries because of their high voltage and high capacity. However, they suffer from poor cyclic stability and slow reaction kinetics. In this work, we designed and synthesized two bipolar organic cathode materials, containing carbonyl (n‐type) and amine (p‐type) functional groups, as well as extended conjugation structures, for Na‐ion batteries (NIBs) and rechargeable aluminum batteries (RABs). As universal electrode materials, bipolar organic materials exhibited exceptional electrochemical performance in terms of high capacity, high voltage, long cycle life, and fast rate capability. Further, the extended conjugation structures in backbones of the bipolar organic materials facilitate the π–π stacking with graphene, playing a critical role in the high performance. Furthermore, the formation of a stable and robust NaF‐rich cathode electrolyte interphase was shown to stabilize the bipolar organic cathode in NIBs. Electrochemical kinetic measurements reveal that both functional groups undergo reversible redox reactions. Specifically, the electron transfer rate constant of the p‐type amine group is one order of magnitude higher than that of the n‐type carbonyl group. These results highlight the efficacy of developing bipolar organic materials for achieving high‐performance organic cathode in NIBs and RABs.

25 ENERGY STORAGE↗

Influence of ion site occupancies on the unit cell parameters, specific volumes, and densities of M 8 (AlSiO 4 ) 6 X 2 sodalites where M = Li, Na, K, Rb, and Ag and X = Cl, Br, and I

Here, this paper discusses the effects of composition on the unit cell parameter (a), unit cell volume (V), specific volume (v), and density (ρ) of various sodalite compositions including $M^+_8$(AlSiO 4 ) 6 Cl 2 (M = Li, Na, K, Rb, and/or Ag) and Na8(AlSiO 4 ) 6 $X^-_2$(X = Cl, Br, and/or I). Compositional models were developed, and the results show that the models are successful at predicting a, V, and v (and thus ρ) within the compositional range available in the literature. Discussion is included on the correlation between the ionic radii of the alkali metals and halides in the sodalite β-cages and the measured values of a, V, v, and ρ. The data show linear increases in a and ρ with increases in the average ionic radii of the M + and X - constituents (data for v show a linear decrease).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mutual Diffusion Coefficients of Na 2 SO 4 at C = 0.02989 mol·dm -3 and 298.15 K by Using Rayleigh Interferometry with Free Diffusion Boundary Conditions: Experimental Test of the Effect of the C 3/2 Concentration Dependence of Refractive Index at Low Concentration

Rayleigh interferometry is one of the most precise and accurate methods for the experimental determination of the mutual diffusion coefficients of both electrolytes and non-electrolytes in liquid solutions. For binary solutions at moderate and high concentrations where the concentration dependences of both diffusion coefficient and refractive index can be assumed to be linear or almost linear and the concentration difference ΔC between a pair of solutions undergoing free diffusion is not large compared to their average concentration, and by using proper combinations of the interference fringe positions as they vary with time, under these conditions diffusion coefficients are obtained that are independent of the size of ΔC. However, this situation becomes more complicated at low concentrations for electrolyte solutions where the concentration dependences of both the diffusion coefficient and refractive index are non-linear, with C 1/2 dependence for the diffusion coefficient and C 3/2 dependence for the refractive index. As a test of these effects on calculated mutual diffusion of electrolyte solutions at low concentrations as measured by Rayleigh interferometry, apparent mutual diffusion coefficients D v,a (volume-fixed reference frame) were measured for fixed average concentrations C=(0.02989 ± 0.00001) mol·dm –3 of Na 2 SO 4 (aq) at 298.15 K while varying ΔC/C from 0.66673 to 2, a threefold variation. The dependence of the diffusion coefficient on ΔC/C was found to be linear, yielding D v = 1.041 6 × 10 –9 m 2 ·s –1 for an infinitely small concentration difference between the diffusing solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Strain Response and Dielectric Properties of Bi 1/2 (Na 0.78 K 0.22 ) 1/2 TiO 3 Ceramics Doped with (Fe 1/2 Nb 1/2 ) 4+

Environmentally friendly piezoceramics Bi 1/2 (Na 0.78 K 0.22 ) 1/2 Ti 1-x (Fe 1/2 Nb 1/2 ) x O 3 (BNKT-FN) with FeNb (FN) ratios 0, 0.01, 0.02, 0.03 and 0.04 were synthesized via conventional solid-state reaction (CSSR). X-ray diffraction (XRD) analysis revealed that the FN complexes were completely dissolved in BNKT perovskite and the structural transition occurred from ferroelectric to relaxor state. The average grain sizes for x = 0, 0.01, 0.02, 0.03 and 0.04 were found to be 0.34 μm, 0.35 μm, 0.38 μm, 0.32 μm and 0.39 μm, respectively. It is observed that the grain size increased with the addition of FN, except for x = 0.03. Here, the coercive field (E c ) and remnant polarization (P r ) of the system were decreased with increasing FN concentration and the highest E c of 21.1 kV/cm and P r of 29.2 μC/cm 2 were noted for the base pure sample. In addition, the increase of FN content steadily broadened the dielectric anomaly at maximum dielectric constant temperature (T m ) in the BNKT-FN system. Consequently, unipolar normalized strain (S max /E max ) was found to be enhanced monotonically achieving the highest value of around 654 pm/V (x = 0.02). These properties suggest that the investigated system could be a promising eco-friendly candidate for piezoelectric actuators and many other applications requiring high piezoelectric induced strain.

25 ENERGY STORAGE↗

Electronic structural and lattice thermodynamic properties of MAlO2 and M5AlO4 (M = Li, Na, K) sorbents for CO2 capture applications

Abstract The electronic properties and thermal stabilities of MAlO 2 and M 5 AlO 4 (M = Li, Na, K) are investigated by density functional theory and lattice phonon dynamics. Based on the calculated electronic and lattice thermodynamic properties, their abilities to capture CO 2 as solid sorbents are analyzed. The calculated electronic structural properties of MAlO 2 and M 5 AlO 4 indicate that all these alkali aluminates are semiconductors with a bandgap range of 2.4 ~ 6.4 eV. The 1st valence bands of these alkali aluminates are located 0 ~ − 6 eV under Fermi levels and are mainly contributed by p orbitals of O, s and p orbitals of Al and M. The phonon vibrational frequencies of M 5 AlO 4 spread at a lower frequency range compared to their MAlO 2 phases. With increasing temperature, the calculated phonon free energies of M 5 AlO 4 decrease faster than their corresponding MAlO 2 while their entropies have opposite trends. The reaction 2MAlO 2 + CO 2 = M 2 CO 3 + Al 2 O 3 has higher reaction heat and Gibbs free energy change than those of corresponding reaction 2 / 5 M 5 AlO 4 + CO 2 = M 2 CO 3 + 1 / 5 Al 2 O 3 , which shows the former reaction possesses lower turnover temperature. Among the alkali aluminates studied, the β-NaAlO 2 , lt-KAlO 2 , and γ-LiAlO 2 are better candidates that could be applied for CO 2 capture technologies. Graphical Abstract

36 MATERIALS SCIENCE↗

Phase-field simulation of domain size effect on dielectric and piezoelectric responses in K 0.5 Na 0.5 NbO 3 epitaxial thin films with superdomain structures

Size effects of mesoscale ferroelectric domains on the macroscopic dielectric and piezoelectric responses in domain-engineered bulk piezocrystals have been extensively studied for more than two decades. However, less is known about the domain size effects in ferroelectric epitaxial thin films, especially for films consisting of low-symmetry ferroelectric phases and exhibits hierarchical superdomain structures. Herein, using phase-field simulations, we systemically evaluate the effective out-of-plane dielectric and piezoelectric coefficients, κ$^{*}_{33}$ and d$^{*}_{33}$, as a function of the domain periods for two types of superdomain structures in ferroelectric K 0.5 Na 0.5 NbO 3 epitaxial thin films. In one type of the superdomain structures, we find that more than 70% increase of κ$^{*}_{33}$ and nearly 20% increase of d$^{*}_{33}$ can be achieved by tuning the domain period by a few tens of nanometers. Dissimilar behaviors are found when the domain period varies along different lateral directions, suggesting anisotropic domain size effects in thin films. By analyzing the local dielectric and piezoelectric responses from each domain variants and domain walls, we reveal that the domain size effect is governed by the variation of out-of-plane polarization inside the domains. Moreover, we also demonstrate enhanced domain size effects by modulating the misfit strains and temperature to approach the polymorphic phase boundaries, suggesting tunability of the size effect by doping and strain engineering. Furthermore, our results reveal multimodal domain size dependence of dielectric and piezoelectric responses in low-symmetry ferroelectric epitaxial thin films, implying that domain size engineering can be used to tune macroscopic properties of thin-film ferroelectrics, similar to their bulk counterparts.

36 MATERIALS SCIENCE↗

Dual function materials (Ru+Na 2 O/Al 2 O 3 ) for direct air capture of CO 2 and in situ catalytic methanation: The impact of realistic ambient conditions

Here a dual function material (DFM) comprised of 1% Ru, 10% Na 2 O/γ–Al 2 O 3 was studied for combined direct air capture (DAC) of CO 2 and catalytic methanation in a temperature swing operation. In the newly proposed operation, the DFM captures CO 2 (400 ppm) from air at ambient conditions. The material is then heated in H 2 to a temperature sufficient for catalytic conversion of the captured CO 2 to renewable natural gas. In this study, we demonstrate high CO 2 adsorption capacity and rates at ambient conditions (25 °C); the adsorbed CO 2 is then successfully catalytically methanated upon heating in H 2 . Adsorption was also carried out in humid conditions, more closely simulating ambient air. Adsorption and methane production were greatly improved with stable initial performance. The rate of adsorption is shown to be flowrate-dependent, which is critical for future reactor design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence of formation of an amorphous magnesium silicate (AMS) phase during alkali activation of (Na-Mg) aluminosilicate glasses

Highlights: • No hydrotalcite-group phase is formed as Al preferentially incorporates into zeolites. • Mg forms an amorphous Mg silicate (AMS) phase. • AMS is a more depolymerized phase when compared to Mg silicate hydrate (M-S-H). • High charge density of Mg effectively stabilizes depolymerized silicates in AMS phase. • Existence of AMS phase should be considered as possibility in Mg-rich AAMs. There is some ambiguity regarding the fate of Mg during the alkali activation of Mg-rich precursors within the broader field of alkali activated materials (AAMs). The present work addresses this issue by studying the reaction products in AAMs synthesized from (Na-Mg) aluminosilicate glasses. Here, instead of magnesium silicate hydrate (M-S-H) phase, Mg exclusively forms an amorphous magnesium silicate (AMS) phase. Compared to M-S-H, AMS is a more depolymerized phase, which has not previously been well documented. The formation of AMS seems to be driven by the high charge density of the Mg cation which effectively stabilizes the depolymerized silicate species. We also show that the lack of hydrotalcite-group phases is due to aluminum depletion by zeolite formation. This work highlights the need to consider the existence of the AMS phase in Mg-containing AAMs, especially in complex systems, where its identification may be difficult.

36 MATERIALS SCIENCE↗

Unraveling the Synergistic effects of La and Al co-doping on Ni/Co-free P2-type Na 0.67 Mn 0.67 Fe 0.33 O 2 layered oxide cathodes for sodium-ion batteries

Recent developments in high-performance cathodes for sodium-ion batteries (SIBs) tend to mitigate use of critical Ni and Co active species to satisfy sustainability. P2-type layered oxide cathodes based on Mn and Fe promise high capacity, sustainability, and low cost on account of the abundance and multiple redox characteristics of Mn and Fe. However, their commercialization is still challenged due to poor cycling stability caused by phase changes emanating from inherent Jahn-Teller distortions. Herein, we propose a novel strategy of trivalent La and Al co-doping to alleviate the drawbacks, innovating a new cathode of Na 0.67 Mn 0.62 Al 0.05 Fe 0.31 La 0.02 O 2 (AlLa). The co-doped cathode delivers an impressive capacity of 128.7 mAh/g at 1C and 106.5 mAh/g at high rate of 5C with a good capacity retention of 85% after 100 cycles. These are superior to the unmodified material, whose specific capacity was 118.6 mAh/g at 1C and 61.1 mAh/g at 5C with a retention of only 65% after 100 cycles. The synergistic contribution from La and Al associated with their improved oxygen bonding, pillaring, and local electronic structural modification stemming from rigid Lasingle bondO and Alsingle bondO bonding resulted in the observed structural and electrochemical improvement. Overall, this research offers novel strategies for designing high-performance cathode materials for sodium-ion batteries.

25 ENERGY STORAGE↗

An advanced low-cost cathode composed of graphene-coated Na 2.4 Fe 1.8 (SO 4 ) 3 nanograins in a 3D graphene network for ultra-stable sodium storage

Iron-based electrodes have attracted great attention for sodium storage because of the distinct cost effectiveness. However, exploring suitable iron-based electrodes with high power density and long duration remains a big challenge. Herein, a spray-drying strategy is adopted to construct graphene-coated Na 2.4 Fe 1.8 (SO 4 ) 3 nanograins in a 3D graphene microsphere network. The unique structural and compositional advantages endow these electrodes to exhibit outstanding electrochemical properties with remarkable rate performance and long cycle life. Additionally, mechanism analyses further explain the outstanding electrochemical properties from the structural aspect.

25 ENERGY STORAGE↗

Multinuclear PFGSTE NMR description of 39 K, 23 Na, 7 Li, and 1 H specific activation energies governing diffusion in alkali nitrite solutions

While pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has found widespread use in the quantification of self-diffusivity for many NMR-active nuclei, extending this technique to uncommon nuclei with unfavorable NMR properties remains an active area of research. Potassium-39 ( 39 K) is an archetypical NMR nucleus exhibiting an unfavorable gyromagnetic ratio combined with a very low Larmor frequency. Despite these unfavorable properties, this work demonstrates that 39 K PFGSTE NMR experiments are possible in aqueous solutions of concentrated potassium nitrite. Further, analysis of the results indicates that 39 K NMR diffusometry is feasible when the nuclei exhibit spin–lattice and spin–spin relaxation coefficients on the order of 60–100 ms and 50–100 ms, respectively. The diffusivity of 39 K followed Arrhenius behavior, and comparative 23 Na, 7 Li, and 1 H PFGSTE NMR studies of equimolal sodium nitrite and lithium nitrite solutions led to correlations between the enthalpy of hydration with the activation energy governing self-diffusion of the cations and also of water. Realizing the feasibility of 39 K PFGSTE NMR spectroscopy has a widespread impact across energy sciences because potassium is a common alkali element in energy storage materials and other applications.

74 ATOMIC AND MOLECULAR PHYSICS↗

Glass formation and structure of melt quenched mixed oxy-sulfide Na 4 P 2 S 7-x O x glasses for 0 ≤ x ≤ 5

The structures of Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 5, glasses were investigated using melt quench (MQ) samples. The short-range order (SRO) structures of these glasses were examined using a combination of Raman, Fourier Transform Infrared (FT-IR), and 31 P Magic Angle Spinning NMR ( 31 P MAS NMR) spectroscopies to determine how oxygen is incorporated into the sulfide structure. Using vibrational spectroscopy, semi-quantitative 31 P MAS NMR, and charge balancing, a complete compositional map of all the SRO structures present in these glasses has been generated. From these findings, full incorporation of the oxygen into the sulfide melt was found to occur across the compositional series through a structural disproportionation reaction where oxygen systematically replaces bridging sulfurs (BSs), before replacing the remaining non-bridging sulfurs (NBSs). Under the melting and quenching conditions used in this study, it was found that the melts crystallize too quickly to form homogeneous crystallite-free glasses for x > 5.

36 MATERIALS SCIENCE↗

Glass transition temperature studies of planetary ball milled glasses: Accessing the rapidly cooled glassy state in Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 7, Oxy-thio phosphate glasses

This paper details the very first in-depth study of the glass transition temperature (T g ) for planetary balled milled (PBM) Na 4 P 2 S 7-x O x (NaPSO), where 0 ≤ x ≤ 7, glasses. For 0 ≤ x ≤ 5, fully amorphous, homogeneous, and chemically reacted compositions can be prepared. For samples with 5 < x ≤ 7, partially amorphous but fully chemically reacted glass-ceramics can be produced. The reproducible, thermally cyclable onset T g and the onset crystallization temperature, T c , were investigated as a function of the composition and of the short-range order (SRO) structures of the glasses. Additionally, we examined the extreme sub-T g exothermic relaxations present due to the high energy milling processing and correspondingly high effective quenching rate. Using a differential scanning calorimeter (DSC) and scanning from well below the onset T g , the glasses are observed to relax exothermally below T g . The integrated relaxation enthalpy, ΔH rel , is ~ 0 for the x = 2 glass, but is significantly exothermic for lower and higher values of x. Once the high fictive state of these glasses has been erased by scanning to above the T g , but below the T c of the glass, the DSC scans of the glasses recover normal behavior for a normally cooled glass without any relaxation exotherm. The T g s of these glasses remain relatively constant for 0 ≤ x ≤ 3, but for glasses with 3 < x ≤ 5, T g increases sharply following the combined effects of the phosphate chain length increasing caused by the formation of bridging oxygens and the increasing concentration of more charge dense non-bridging oxygens (NBOs). For x > 5, both T g and Tc decrease sharply, becoming nearly identical at x = 7 where glass formation essentially ceases. For smaller values of x, T c increases with both chain length and the structural complexity of the composition but decreases sharply for glass-ceramics of x > 5.

36 MATERIALS SCIENCE↗

Redox effects on the structure and properties of Na-Mo-Fe-phosphate glasses

Na-Mo-Fe-phosphate glasses were prepared with reducing and oxidizing raw materials and the effects of the different Fe 2+ /Fe 3+ and Mo 5+ /Mo 6+ ratios on glass structure and properties were determined. Mssbauer spectroscopy confirms significantly greater concentrations of Fe 2+ ions in the reduced glasses and distorted Fe 3+ O 4 sites preferred over the Fe 3+ O 6 sites in the oxidized glasses. Raman spectroscopy reveals the presence of isolated Mo 6+ O 6 sites in the oxidized glasses, and highly distorted Mo 5+ O 5 sites in reduced Mo-rich glasses. The presence of specific Fe- and Mo-polyhedra is correlated with the average phosphate anion length, as characterized by high-pressure liquid chromatography. Generally, for the similar compositions, oxidized glasses have greater molar volumes than the reduced glasses, associated with the formation of isolated Mo 6+ O 6 octahedra and the absence of highly crosslinked Mo 5+ OPO 4 units. Tg increases with increasing Fe 3+ fractions in the Fe-rich glasses, whereas for the Mo-rich glasses, T g increases with greater Mo 5+ fractions.

36 MATERIALS SCIENCE↗

Origin of deactivation of aqueous Na–CO 2 battery and mitigation for long-duration energy storage

Here, the development of long-duration energy storage technology is crucial to facilitate the efficient utilization of renewable energy sources while mitigating carbon dioxide production. In this study, we investigate the deactivation and reactivation mechanisms of the aqueous Na–CO 2 battery during extended cycling. We have designed the cathode to include non-precious intermetallic catalysts. As the cell undergoes repeated cycles, the voltage polarization during discharge progressively rises, eventually leading to the cell's deactivation and formation of decomposition products clogging the electrode surface. Results obtained from comprehensive characterization techniques, including conductive atomic force microscopy (cAFM), Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and inductively coupled plasma-mass spectrometry provide insight into the decomposition products. We also showcase an electrochemical approach for regeneration of these aqueous cells. Our findings, along with the insights we have gained, provide a path toward creating long-duration systems with self-healing properties.

25 ENERGY STORAGE↗