Polymeric films can be grown by a sequential, self-limiting surface chemistry process known as molecular layer deposition (MLD). The MLD reactants are typically bifunctional monomers for stepwise condensation polymerization and can yield completely organic films. The MLD of organic–inorganic hybrid polymers can also be accomplished using a bifunctional organic monomer and a multifunctional inorganic monomer. In this work, the growth of a poly(aluminum ethylene glycol) polymer is demonstrated using the sequential exposures of trimethylaluminum (TMA) and ethylene glycol (EG). These hybrid polymers, known as alucones, were grown over a wide range of temperatures from 85 to 175 °C. In situ quartz crystal microbalance and ex situ X-ray reflectivity experiments confirmed linear growth of the alucone film versus number of TMA/EG reaction cycles at all temperatures. The alucone growth rates decreased at higher temperatures. Growth rates varied from 4.0 Å per cycle at 85 °C to 0.4 Å per cycle at 175 °C. In situ Fourier transform infrared spectroscopy was used to monitor the surface reactions during alucone MLD. Ex situ FTIR spectroscopy, X-ray photoelectron spectroscopy, and X-ray reflectivity measurements were also employed to determine the chemical composition, thickness, and density of the alucone films. These ex situ studies revealed that the alucone films grown on Al2O3 ALD surfaces evolved under ambient conditions before reaching a stable state. Alucone films capped with rapid SiO2 ALD displayed much more stability than alucone films grown on Al2O3 ALD surfaces. These results indicated that H2O may facilitate the chemical transformation of the alucone MLD films. The alucone films represent a new class of organic–inorganic hybrid polymers. Modification of this basic alucone MLD chemistry with use of other diols or other bifunctional monomers can produce different alucone polymers with variable properties.
In order to employ Li-ion batteries (LIBs) in next-generation hybrid electric and/or plug-in hybrid electric vehicles (HEVs and PHEVs), LIBs must satisfy many requirements: electrodes with long lifetimes (fabricated from inexpensive environmentally benign materials), stability over a wide temperature range, high energy density, and high rate capability. Establishing long-term durability while operating at realistic temperatures (5000 charge-depleting cycles, 15 year calendar life, and a range from À46 8C to þ66 8C) for a battery that does not fail catastrophically remains a significant challenge. [1] Recently, surface modifications of electrode materials have been explored as viable paths to improve the performance of LIBs for vehicular applications.[2] The cycle life and safety issues have been largely satisfied for Li x MO 2 (M ¼ Co, Ni, Mn, etc.) cathodes by coating the active material particles with a metal oxide and/or metal phosphate. [2a,2b,3] For anode, state-of-the-art materials such as Si suffer from significant volume expansion/contraction during charge-discharge leading to rapid capacity fade.[4] Natural graphite (NG) is a realistic candidate anode, for vehicular applications, due to its high reversible capacity, low and flat potential relative to Li/Li þ , moderate volume change, and low cost.[5] In previous reports, the performance of NG was improved by surface modifications with mild oxidation, [6] coating with amorphous carbon,[5c] metal oxides (Al 2 O 3 , ZrO 2 ), [5a,7] and metal phosphate (AlPO 4 ).[5b] These efforts were performed in order to mitigate the solid electrolyte interphase (SEI) [8] that is formed on the NG surface by reductive decomposition of the electrolyte during initial charge-discharge especially at elevated temperatures. The decomposition of the SEI at elevated temperature ($80 8C) is exothermic and initiates thermal runaway. [9] In most previous reports films of metal oxides and metal phosphates have been deposited on powder electrode materials with 'sol-gel' wet-chemical methods.
To deploy Li-ion batteries in next-generation vehicles, it is essential to develop electrodes with durability, high energy density, and high power. Here we report a breakthrough in controlled full-electrode nanoscale coatings that enables nanosized materials to cycle with durable high energy and remarkable rate performance. The nanoparticle electrodes are coated with Al(2)O(3) using atomic layer deposition (ALD). The coated nano-LiCoO(2) electrodes with 2 ALD cycles deliver a discharge capacity of 133 mAh/g with currents of 1400 mA/g (7.8C), corresponding to a 250% improvement in reversible capacity compared to bare nanoparticles (br-nLCO), when cycled at this high rate. The simple ALD process is broadly applicable and provides new opportunities for the battery industry to design other novel nanostructured electrodes that are highly durable even while cycling at high rate.
Ultrathin atomic layer deposition (ALD) coatings enhance the performance of lithium-ion batteries (LIBs). Previous studies have demonstrated that LiCoO2 cathode powders coated with metal oxides with thicknesses of ∼100 to 1000Å grown using wet chemical techniques improved LIB performance. In this study, LiCoO2 powders were coated with conformal Al2normalO3 ALD films with thicknesses of only ∼3 to 4Å established using two ALD cycles. The coated LiCoO2 powders exhibited a capacity retention of 89% after 120 charge–discharge cycles in the 3.3–4.5 V (vs Li/Li+ ) range. In contrast, the bare LiCoO2 powders displayed only a 45% capacity retention. Al2normalO3 ALD films coated directly on the composite electrode also produced improved capacity retention. This dramatic improvement may result from the ultrathin Al2normalO3 ALD film acting to minimize Co dissolution or reduce surface electrolyte reactions. Similar experiments with ultrathin ZnO ALD films did not display enhanced performance.
Passivating lithium ion (Li) battery electrode surfaces to prevent electrolyte decomposition is critical for battery operations. Recent work on conformal atomic layer deposition (ALD) coating of anodes and cathodes has shown significant technological promise. ALD further provides well-characterized model platforms for understanding electrolyte decomposition initiated by electron tunneling through a passivating layer. First-principles calculations reveal two regimes of electron transfer to adsorbed ethylene carbonate molecules (EC, a main component of commercial electrolyte), depending on whether the electrode is alumina coated. On bare Li metal electrode surfaces, EC accepts electrons and decomposes within picoseconds. In contrast, constrained density functional theory calculations in an ultrahigh vacuum setting show that, with the oxide coating, e(-) tunneling to the adsorbed EC falls within the nonadiabatic regime. Here the molecular reorganization energy, computed in the harmonic approximation, plays a key role in slowing down electron transfer. Ab initio molecular dynamics simulations conducted at liquid EC electrode interfaces are consistent with the view that reactions and electron transfer occur right at the interface. Microgravimetric measurements demonstrate that the ALD coating decreases electrolyte decomposition and corroborates the theoretical predictions.
Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 Å on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 Å and ZnO films with a thickness of ~250 Å dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 Å on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
334 Leonard St
Brooklyn, NY 11211
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.