Revealing the Simultaneous Effects of Conductivity and Amorphous Nature of Atomic-Layer-Deposited Double-Anion-Based Zinc Oxysulfide as Superior Anodes in Na-Ion Batteries.

Although sodium-ion batteries (SIBs) are considered promising alternatives to their Li counterparts, they still suffer from challenges like slow kinetics of the sodiation process, large volume change, and inferior cycling stability. On the other hand, the presence of additional reversible conversion reactions makes the metal compounds the preferred anode materials over carbon. However, conductivity and crystallinity of such materials often play the pivotal role in this regard. To address these issues, atomic layer deposited double-anion-based ternary zinc oxysulfide (ZnOS) thin films as an anode material in SIBs are reported. Electrochemical studies are carried out with different O/(O+S) ratios, including O-rich and S-rich crystalline ZnOS along with the amorphous phase. Amorphous ZnOS with the O/(O+S) ratio of ≈0.4 delivers the most stable and considerably high specific (and volumetric) capacities of 271.9 (≈1315.6 mAh cm-3 ) and 173.1 mAh g-1 (≈837.7 mAh cm-3 ) at the current densities of 500 and 1000 mA g-1 , respectively. A dominant capacitive-controlled contribution of the amorphous ZnOS anode indicates faster electrochemical reaction kinetics. An electrochemical reaction mechanism is also proposed via X-ray photoelectron spectroscopy analyses. A comparison of the cycling stability further establishes the advantage of this double-anion-based material over pristine ZnO and ZnS anodes.

Atomic layer deposited tungsten nitride thin films as a new lithium-ion battery anode.

This article demonstrates the atomic layer deposition (ALD) of tungsten nitride using tungsten hexacarbonyl [W(CO)6] and ammonia [NH3] and its use as a lithium-ion battery anode. In situ quartz crystal microbalance (QCM), ellipsometry and X-ray reflectivity (XRR) measurements are carried out to confirm the self-limiting behaviour of the deposition. A saturated growth rate of ca. 0.35 Å per ALD cycle is found within a narrow temperature window of 180-195 °C. In situ Fourier transform infrared (FTIR) vibrational spectroscopy is used to determine the reaction pathways of the surface bound species after each ALD half cycle. The elemental presence and chemical composition is determined by XPS. The as-deposited material is found to be amorphous and crystallized to h-W2N upon annealing at an elevated temperature under an ammonia atmosphere. The as-deposited materials are found to be n-type, conducting with an average carrier concentration of ca. 10(20) at room temperature. Electrochemical studies of the as-deposited films open up the possibility of this material to be used as an anode material in Li-ion batteries. The incorporation of MWCNTs as a scaffold layer further enhances the electrochemical storage capacity of the ALD grown tungsten nitride (WNx). Ex situ XRD analysis confirms the conversion based reaction mechanism of the as-grown material with Li under operation.

Atomic layer deposition of Al2O3 on P2-Na0.5Mn0.5Co0.5O2 as interfacial layer for high power sodium-ion batteries.

Surface modification is one of the impressive and widely used technique to improve the electrochemical performance of sodium-ion batteries by modifying the electrode-electrolyte interface. Herein, we used the atomic layer deposition (ALD) to modify the surface of P2-Na0.5Mn0.5Co0.5O2 by sub-monolayer Al2O3 coating on the prefabricated electrodes. Phase purity is confirmed using various structural and morphological studies. The pristine electrode delivered an initial discharge capacity of 154 mAh g-1 at 0.5C, and inferior rate performance of 23 mAh g-1 at 40C rate. On the other hand, the interfacial modified cathode with 5 cycles of ALD coating delivers a high capacity of 174 and 45 mAh g-1 at 0.5C and 40C rate, respectively. The Co2+/3+ redox couple is utilized for the faradaic process with high reversibility along with suppressed P2-O2 phase transition. The presence of the Al2O3 layer acts as an artificial cathode electrolyte interface by suppressing the electrolyte oxidation at higher cutoff potentials. This is clearly validated by the reduced charge transfer resistance of surface modified electrodes after cycling at various current rates. Even at an elevated temperature condition (50 °C), interfacial layer significantly improves the safety of the cell and ensures the stability of the cathode.

Solution-Processed ZnxCd1-xS Buffer Layers for Vapor Transport-Deposited SnS Thin-Film Solar Cells: Achieving High Open-Circuit Voltage.

As an alternative buffer material to CdS, ZnxCd1-xS buffer layers for vapor transport-deposited SnS thin-film solar cells (TFSCs) were fabricated using the successive ionic layer adsorption and reaction (SILAR) method. Varying the Zn-to-Cd ratio resulted in a series of ZnxCd1-xS thin films with controllable band gaps in the range of 2.40-3.65 eV. The influence of the Zn-to-Cd ratio on the cell performance was investigated in detail. The Zn0.34Cd0.66S buffer layer was found to be the optimal composition for SnS TFSCs, and a record open-circuit voltage (Voc) of 0.405 V was achieved with an efficiency of 3.72%, whereas the SILAR-CdS buffer layer rendered a Voc of 0.324 V. The improvement in Voc when using the Zn0.34Cd0.66S buffer layer was corroborated by the spike-type conduction band offset of 0.35 eV with the SnS absorber, as revealed by the X-ray photoelectron spectroscopy analysis. In addition, minimized interfacial recombination at the SnS/Zn0.34Cd0.66S heterojunction was confirmed by the temperature-dependent Voc analysis under illuminated conditions.

Facile Phase Control of Multivalent Vanadium Oxide Thin Films (V2O5 and VO2) by Atomic Layer Deposition and Postdeposition Annealing.

Atomic layer deposition was adopted to deposit VOx thin films using vanadyl tri-isopropoxide {VO[O(C3H7)]3, VTIP} and water (H2O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VOx. The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO2 and V2O5 phases, respectively. The possible band structures of the crystalline VO2 and V2O5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V2O5 and VO2 films, respectively.

Highly Uniform Atomic Layer-Deposited MoS2@3D-Ni-Foam: A Novel Approach To Prepare an Electrode for Supercapacitors.

This article takes an effort to establish the potential of atomic layer deposition (ALD) technique toward the field of supercapacitors by preparing molybdenum disulfide (MoS2) as its electrode. While molybdenum hexacarbonyl [Mo(CO)6] serves as a novel precursor toward the low-temperature synthesis of ALD-grown MoS2, H2S plasma helps to deposit its polycrystalline phase at 200 °C. Several ex situ characterizations such as X-ray diffractometry (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and so forth are performed in detail to study the as-grown MoS2 film on a Si/SiO2 substrate. While stoichiometric MoS2 with very negligible amount of C and O impurities was evident from XPS, the XRD and high-resolution transmission electron microscopy analyses confirmed the (002)-oriented polycrystalline h-MoS2 phase of the as-grown film. A comparative study of ALD-grown MoS2 as a supercapacitor electrode on 2-dimensional stainless steel and on 3-dimensional (3D) Ni-foam substrates clearly reflects the advantage and the potential of ALD for growing a uniform and conformal electrode material on a 3D-scaffold layer. Cyclic voltammetry measurements showed both double-layer capacitance and capacitance contributed by the faradic reaction at the MoS2 electrode surface. The optimum number of ALD cycles was also found out for achieving maximum capacitance for such a MoS2@3D-Ni-foam electrode. A record high areal capacitance of 3400 mF/cm2 was achieved for MoS2@3D-Ni-foam grown by 400 ALD cycles at a current density of 3 mA/cm2. Moreover, the ALD-grown MoS2@3D-Ni-foam composite also retains high areal capacitance, even up to a high current density of 50 mA/cm2. Finally, this directly grown MoS2 electrode on 3D-Ni-foam by ALD shows high cyclic stability (>80%) over 4500 charge-discharge cycles which must invoke the research community to further explore the potential of ALD for such applications.