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Register a new userIn situ kinetics studies of Zn-Al LDH intercalation with corrosion related species
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Kinetics parameters for three anion exchange reactions - Zn-LDH-NO3 - Zn-LDH-Cl, Zn-LDH-NO3 - Zn-LDH-SO4 and Zn-LDH-NO3 - Zn-LDH-VOx - were obtained by in situ synchrotron study. The first and the second ones are two-stage reactions; the first stage is characterized by the two-dimensional diffusion-controlled reaction following deceleratory nucleation and the second stage is a one-dimensional diffusion-controlled reaction also with a decelerator nucleation effect. In the case of exchange NO3 - Cl host anions are completely released, while in the case of NO3 - SO42 the reaction ends without complete release of nitrate anions. The exchange of Zn-LDH-NO3 - Zn-LDH-VOx is one-stage reaction and goes much slower than the previous two cases. It is characterized by a one stage two-dimensional reaction and nucleation considered to be instantaneous in this case. As a result, at the end of this process there are two crystalline phases with different polyvanadate species, presumably V4O124 and V2O74, nitrate anions were not completely released. The rate of replacing NO3 anions by guest ones can be represented as Cl > SO42 > VOxy.
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The Mg-Zn and Al-Zn binary alloys have been investigated theoretically under static isotropic pressure. The stable phases of these binaries on both initially hexagonal-close-packed (HCP) and face-centered-cubic (FCC) lattices have been determined by utilizing an iterative approach that uses a configurational cluster expansion method, Monte Carlo search algorithm, and density functional theory (DFT) calculations. Based on 64-atom models, it is shown that the most stable phases of the Mg-Zn binary alloy under ambient condition are $rm MgZn_3$, $rm Mg_{19}Zn_{45}$, $rm MgZn$, and $rm Mg_{34}Zn_{30}$ for the HCP, and $rm MgZn_3$ and $rm MgZn$ for the FCC lattice, whereas the Al-Zn binary is energetically unfavorable throughout the entire composition range for both the HCP and FCC lattices under all conditions. By applying an isotropic pressure in the HCP lattice, $rm Mg_{19}Zn_{45}$ turns into an unstable phase at P$approx$$10$~GPa, a new stable phase $rm Mg_{3}Zn$ appears at P$gtrsim$$20$~GPa, and $rm Mg_{34}Zn_{30}$ becomes unstable for P$gtrsim$$30$~GPa. For FCC lattice, the $rm Mg_{3}Zn$ phase weakly touches the convex hull at P$gtrsim$$20$~GPa while the other stable phases remain intact up to $approx$$120$~GPa. Furthermore, making use of the obtained DFT results, bulk modulus has been computed for several compositions up to pressure values of the order of $approx$$120$~GPa. The findings suggest that one can switch between $rm Mg$-rich and $rm Zn$-rich early-stage clusters simply by applying external pressure. $rm Zn$-rich alloys and precipitates are more favorable in terms of stiffness and stability against external deformation.
To meet growing energy demands, degradation mechanisms of energy storage devices must be better understood. As a non-destructive tool, X-ray Computed Tomography (CT) has been increasingly used by the battery community to perform $textit{in-situ}$ experiments that can investigate dynamic phenomena. However, few have used X-ray CT to study representative battery systems over long cycle lifetimes (>100 cycles). Here, we report the $textit{in-situ}$ CT study of Zn-Ag batteries and demonstrate the effects of current collector parasitic gassing over long-term storage and cycling. We design performance representative $textit{in-situ}$ CT cells that can achieve >250 cycles at a high areal capacity of $mathrm{12.5;mAh/cm^2}$. Combined with electrochemical experiments, the effects of current collector parasitic gassing are revealed with micro-scale CT (MicroCT). The volume expansion and evolution of ZnO and Zn depletion is quantified with cycling and elevated temperature testing. The experimental insights are then utilized to develop larger form-factor $mathrm{4;cm^2}$ cells with electrochemically compatible current collectors. With this, we demonstrate over 325 cycles at a high capacity of $mathrm{12.5;mAh/cm^2}$ for a $mathrm{4;cm^2}$ form-factor. This work demonstrates that $textit{in-situ}$ X-ray CT used in long cycle-lifetime studies can be applied to examine a multitude of other battery chemistries to improve their performances.
Amorphous solids, which show characteristic differences from crystals, are common in daily usage. Glasses, gels, and polymers are familiar examples, and polymers are particularly important in terms of their role in construction and crafting. Previous studies have mainly focused on the bulk properties of polymeric products, and the local properties are less discussed. Here, we designed a distinctive protocol using the negatively charged nitrogen vacancy center in nanodiamond to study properties inside polymeric products in situ. Choosing the curing of poly dimethylsiloxane and the polymerization of cyanoacrylate as subjects of investigation, we measured the time dependence of local pressure and strain in the materials during the chemical processes. From the measurements, we were able to probe the local shear stress inside the two polymeric substances in situ. By regarding the surprisingly large shear stress as the internal tension, we attempted to provide a microscopic explanation for the ultimate tensile strength of a bulk solid. Our current methodology is applicable to any kind of transparent amorphous solids with the stress in the order of MPa and to the study of in situ properties in nanoscale. With better apparatus, we expect the limit can be pushed to sub-MPa scale.
Lithium-intercalated layered transition-metal oxides, LixTMO2, brought about a paradigm change in rechargeable batteries in recent decades and show promise for use in memristors, a type of device for future neural computing and on-chip storage. Thermal transport properties, although being a crucial element in limiting the charging/discharging rate, package density, energy efficiency, and safety of batteries as well as the controllability and energy consumption of memristors, are poorly managed or even understood yet. Here, for the first time, we employ quantum calculations including high-order lattice anharmonicity and find that the thermal conductivity k of LixTMO2 materials is significantly lower than hitherto believed. More specifically, the theoretical upper limit of k of LiCoO2 is 6 W/m-K, 2-6 times lower than the prior theoretical predictions. Delithiation further reduces k by 40-70% for LiCoO2 and LiNbO2. Grain boundaries, strains, and porosity are yet additional causes of thermal-conductivity reduction, while Li-ion diffusion and electrical transport are found to have only a minor effect on phonon thermal transport. The results elucidate several long-standing issues regarding the thermal transport in lithium-intercalated materials and provide guidance toward designing high-energy-density batteries and controllable memristors.
The sub-gap density of states of amorphous indium gallium zinc oxide ($a$-IGZO) is obtained using the ultrabroadband photoconduction (UBPC) response of thin-film transistors (TFTs). Density functional theory simulations classify the origin of the measured sub-gap density of states peaks as a series of donor-like oxygen vacancy states and acceptor-like Zn vacancy states. Donor peaks are found both near the conduction band and deep in the sub-gap, with peak densities of $10^{17}-10^{18}$ cm$^{-3}$eV$^{-1}$. Two deep acceptor-like metal vacancy peaks with peak densities in the range of $10^{18}$ cm$^{-3}$eV$^{-1}$ and lie adjacent to the valance band Urbach tail region at 2.0 to 2.5 eV below the conduction band edge. By applying detailed charge balance, we show increasing the density of metal vacancy deep-acceptors strongly shifts the $a$-IGZO TFT threshold voltage to more positive values. Photoionization (h$ u$ > 2.0 eV) of metal vacancy acceptors is one cause of transfer curve hysteresis in $a$-IGZO TFTs owing to longer recombination lifetimes as they get captured into acceptor-like vacancies.
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