Joint Charge Storage for High-Rate Aqueous Zinc-Manganese Dioxide Batteries.

Aqueous rechargeable zinc-manganese dioxide batteries show great promise for large-scale energy storage due to their use of environmentally friendly, abundant, and rechargeable Zn metal anodes and MnO2 cathodes. In the literature various intercalation and conversion reaction mechanisms in MnO2 have been reported, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. A systematical study to understand the charge storage mechanisms in a layered δ-MnO2 cathode is reported. An electrolyte-dependent reaction mechanism in δ-MnO2 is identified. Nondiffusion controlled Zn2+ intercalation in bulky δ-MnO2 and control of H+ conversion reaction pathways over a wide C-rate charge-discharge range facilitate high rate performance of the δ-MnO2 cathode without sacrificing the energy density in optimal electrolytes. The Zn-δ-MnO2 system delivers a discharge capacity of 136.9 mAh g-1 at 20 C and capacity retention of 93% over 4000 cycles with this joint charge storage mechanism. This study opens a new gateway for the design of high-rate electrode materials by manipulating the effective redox reactions in electrode materials for rechargeable batteries.

Boosting the Electrochemical Performance of Li1.2Mn0.54Ni0.13Co0.13O2 by Atomic Layer-Deposited CeO2 Coating.

It has been demonstrated that atomic layer deposition (ALD) provides an initially safeguarding, uniform ultrathin film of controllable thickness for lithium-ion battery electrodes. In this work, CeO2 thin films were deposited to modify the surface of lithium-rich Li1.2Mn0.54Ni0.13Co0.13O2 (LRNMC) particles via ALD. The film thicknesses were measured by transmission electron microscopy. For electrochemical performance, ∼2.5 nm CeO2 film, deposited by 50 ALD cycles (50Ce), was found to have the optimal thickness. At a 1 C rate and 55 °C in a voltage range of 2.0-4.8 V, an initial capacity of 199 mAh/g was achieved, which was 8% higher than that of the uncoated (UC) LRNMC particles. Also, 60.2% of the initial capacity was retained after 400 cycles of charge-discharge, compared to 22% capacity retention of UC after only 180 cycles of charge-discharge. A robust kinetic of electrochemical reaction was found on the CeO2-coated samples at 55 °C through electrochemical impedance spectroscopy. The conductivity of 50Ce was observed to be around 3 times higher than that of UC at 60-140 °C. The function of the CeO2 thin-film coating was interpreted as being to increase substrate conductivity and to block the dissolution of metal ions during the charge-discharge process.

Significant improvement in TiO2 photocatalytic activity through controllable ZrO2 deposition.

ZrO2 was deposited on anatase TiO2 nanoparticles using 5-80 cycles of atomic layer deposition (ALD). The photocatalytic activity of all samples was evaluated based on the degradation of methylene blue (MB) solution under UV light. The TiO2 sample with 45 cycles of ZrO2 deposition (45c-Zr/TiO2, 1.1 wt% ZrO2) was proved to be the most efficient catalyst with a degradation kinetic constant 10 times larger than that of the pure TiO2 sample. All samples were characterized using inductively coupled plasma atomic emission spectroscopy (ICP-AES), nitrogen adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra analysis (UV-DRS), Raman and photoluminescence (PL) techniques. The high photocatalytic activity of 45c-Zr/TiO2 can be attributed to stronger adsorption in the ultraviolet region and a reduction in the recombination rate of electron/hole pairs.

Unveiling the Role of CeO2 Atomic Layer Deposition Coatings on LiMn2O4 Cathode Materials: An Experimental and Theoretical Study.

An atomic layer deposition (ALD) coating on active materials of a lithium ion battery is a more effective strategy for improving battery performance than other coating technologies. However, substantial uncertainty still remains about the underlying physics and role of the ALD coating in improving battery performance. Although improvement in the stability and capacity of CeO2 thin film coated particles for batteries has been reported, a detailed and accurate description of the mechanism has not been provided. We have developed a multiphysics-based model that takes into consideration stress mechanics, diffusion of lithium ion, and dissolution of transition-metal ions of spinel LiMn2O4 cathode. The model analyzes how different coating thicknesses affect diffusion-induced stress generation and, ultimately, crack propagation. Experimentally measured diffusivity and dissolution rates were incorporated into the model to account for a trade-off between delayed transport and prevention of side reactions. Along with experimental results, density functional theory results are used to explain how a change in volume, due to dissolution of active material, can affect battery performance. The predicted behavior from the model is well-matched with experimental results obtained on coated and uncoated LiMn2O4-Li foil cells. The proposed approach and explanations will serve as important guidelines for thin film coating strategies for various battery materials.

Employing Synergetic Effect of Doping and Thin Film Coating to Boost the Performance of Lithium-Ion Battery Cathode Particles.

Atomic layer deposition (ALD) has evolved as an important technique to coat conformal protective thin films on cathode and anode particles of lithium ion batteries to enhance their electrochemical performance. Coating a conformal, conductive and optimal ultrathin film on cathode particles has significantly increased the capacity retention and cycle life as demonstrated in our previous work. In this work, we have unearthed the synergetic effect of electrochemically active iron oxide films coating and partial doping of iron on LiMn1.5Ni0.5O4 (LMNO) particles. The ionic Fe penetrates into the lattice structure of LMNO during the ALD process. After the structural defects were saturated, the iron started participating in formation of ultrathin oxide films on LMNO particle surface. Owing to the conductive nature of iron oxide films, with an optimal film thickness of ~0.6 nm, the initial capacity improved by ~25% at room temperature and by ~26% at an elevated temperature of 55 °C at a 1C cycling rate. The synergy of doping of LMNO with iron combined with the conductive and protective nature of the optimal iron oxide film led to a high capacity retention (~93% at room temperature and ~91% at 55 °C) even after 1,000 cycles at a 1C cycling rate.

Stabilizing nanostructured solid oxide fuel cell cathode with atomic layer deposition.

We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.

Encapsulation of supported metal nanoparticles with an ultra-thin porous shell for size-selective reactions.

A novel nanostructured catalyst with an ultra-thin porous shell obtained from the thermal decomposition of an aluminium alkoxide film deposited by molecular layer deposition for size-selective reactions was developed. The molecular sieving capability of the porous metal oxide films was verified by examining the liquid-phase hydrogenation of n-hexene versus cis-cyclooctene.