Langli Luo

Electrochemically Formed Ultrafine Metal Oxide Nanocatalysts for High-Performance Lithium–Oxygen Batteries

Lithium-oxygen (Li-O2) batteries have an extremely high theoretical specific energy density when compared with conventional energy-storage systems. However, practical application of the Li-O2 battery system still faces significant challenges. In this work, we report a new approach for synthesis of ultrafine metal oxide nanocatalysts through an electrochemical prelithiation process. This process reduces the size of NiCo2O4 (NCO) particles from 20-30 nm to a uniformly distributed domain of ∼2 nm and significantly improves their catalytic activity. Structurally, the prelithiated NCO nanowires feature ultrafine NiO/CoO nanoparticles that are highly stable during prolonged cycles in terms of morphology and particle size, thus maintaining an excellent catalytic effect to oxygen reduction and evolution reactions. A Li-O2 battery using this catalyst demonstrated an initial capacity of 29 280 mAh g(-1) and retained a capacity of >1000 mAh g(-1) after 100 cycles based on the weight of the NCO active material. Direct in situ transmission electron microscopy observations conclusively revealed the lithiation/delithiation process of as-prepared NCO nanowires and provided in-depth understanding for both catalyst and battery chemistries of transition-metal oxides. This unique electrochemical approach could also be used to form ultrafine nanoparticles of a broad range of materials for catalyst and other applications.

Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy

The performances of a Li-O2 battery depend on a complex interplay between the reaction mechanism at the cathode, the chemical structure and the morphology of the reaction products, and their spatial and temporal evolution; all parameters that, in turn, are dependent on the choice of the electrolyte. In an aprotic cell, for example, the discharge product, Li2O2, forms through a combination of solution and surface chemistries that results in the formation of a baffling toroidal morphology. In a solid electrolyte, neither the reaction mechanism at the cathode nor the nature of the reaction product is known. Here we report the full-cycle reaction pathway for Li-O2 batteries and show how this correlates with the morphology of the reaction products. Using aberration-corrected environmental transmission electron microscopy (TEM) under an oxygen environment, we image the product morphology evolution on a carbon nanotube (CNT) cathode of a working solid-state Li-O2 nanobattery and correlate these features with the electrochemical reaction at the electrode. We find that the oxygen-reduction reaction (ORR) on CNTs initially produces LiO2, which subsequently disproportionates into Li2O2 and O2. The release of O2 creates a hollow nanostructure with Li2O outer-shell and Li2O2 inner-shell surfaces. Our findings show that, in general, the way the released O2 is accommodated is linked to lithium-ion diffusion and electron-transport paths across both spatial and temporal scales; in turn, this interplay governs the morphology of the discharging/charging products in Li-O2 cells.

Complete Decomposition of Li2CO3 in Li–O2 Batteries Using Ir/B4C as Noncarbon-Based Oxygen Electrode

Instability of carbon-based oxygen electrodes and incomplete decomposition of Li2CO3 during charge process are critical barriers for rechargeable Li-O2 batteries. Here we report the complete decomposition of Li2CO3 in Li-O2 batteries using the ultrafine iridium-decorated boron carbide (Ir/B4C) nanocomposite as a noncarbon based oxygen electrode. The systematic investigation on charging the Li2CO3 preloaded Ir/B4C electrode in an ether-based electrolyte demonstrates that the Ir/B4C electrode can decompose Li2CO3 with an efficiency close to 100% at a voltage below 4.37 V. In contrast, the bare B4C without Ir electrocatalyst can only decompose 4.7% of the preloaded Li2CO3. Theoretical analysis indicates that the high efficiency decomposition of Li2CO3 can be attributed to the synergistic effects of Ir and B4C. Ir has a high affinity for oxygen species, which could lower the energy barrier for electrochemical oxidation of Li2CO3. B4C exhibits much higher chemical and electrochemical stability than carbon-based electrodes and high catalytic activity for Li-O2 reactions. A Li-O2 battery using Ir/B4C as the oxygen electrode material shows highly enhanced cycling stability than those using the bare B4C oxygen electrode. Further development of these stable oxygen-electrodes could accelerate practical applications of Li-O2 batteries.

Highly Reversible Zinc-Ion Intercalation into Chevrel Phase Mo6S8 Nanocubes and Applications for Advanced Zinc-Ion Batteries

This work describes the synthesis of Chevrel phase Mo6S8 nanocubes and its application as the anode material for rechargeable Zn-ion batteries. Mo6S8 can host Zn(2+) ions reversibly in both aqueous and nonaqueous electrolytes with specific capacities around 90 mAh/g, and exhibited remarkable intercalation kinetics and cyclic stability. In addition, we assembled full cells by integrating Mo6S8 anodes with zinc-polyiodide (I(-)/I3(-))-based catholytes, and demonstrated that such full cells were also able to deliver outstanding rate performance and cyclic stability. This first demonstration of a zinc-intercalating anode could inspire the design of advanced Zn-ion batteries.

Wide temperature electrolytes for lithium-ion batteries

Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service-temperature range of lithium (Li)-ion batteries (LIBs). In this study, we report such wide-temperature electrolyte formulations by optimizing the ethylene carbonate (EC) content in the ternary solvent system of EC, propylene carbonate (PC), and ethyl methyl carbonate (EMC) with LiPF6 salt and CsPF6 additive. An extended service-temperature range from -40 to 60 °C was obtained in LIBs with lithium nickel cobalt aluminum oxide (LiNi0.80Co0.15Al0.05O2, NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room temperature and elevated temperatures were systematically investigated together with the ionic conductivity and phase-transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by wt) with 0.05 M CsPF6, which was demonstrated in both coin cells of graphite∥NCA and 1 Ah pouch cells of graphite∥LiNi1/3Mn1/3Co1/3O2. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the high capacity retention (68%) at -40 °C and C/5 rate, significantly higher than that (20%) of the conventional LIB electrolyte, and the nearly identical stable cycle life as the conventional LIB electrolyte at room temperature and elevated temperatures up to 60 °C.

Size-dependent dynamic structures of supported gold nanoparticles in CO oxidation reaction condition

Significance Gold is the noblest metal. However, when the size decreases to nanoscale and is supported on reducible oxides, the gold nanoparticle shows exceptionally high catalytic performance even at low temperatures. Here, through state-of-the-art in situ aberration-corrected environmental transmission electron microscopy and ab initio molecular-dynamic simulations, we discovered that, upon exposing to reactant gas (carbon monoxide and oxygen), ultrasmall gold clusters on ceria show a size-dependent order-to-disorder transformation with generation of dynamic low-coordinated atoms, which presumably can effectively boost the oxidation reaction of carbon monoxide. The findings provide much-needed insights on the origin of size-dependent catalytic properties of supported gold and demonstrate a size effect in absorbent–particle interactions that may widely exist and play an essential role in heterogeneous catalysts. Gold (Au) catalysts exhibit a significant size effect, but its origin has been puzzling for a long time. It is generally believed that supported Au clusters are more or less rigid in working condition, which inevitably leads to the general speculation that the active sites are immobile. Here, by using atomic resolution in situ environmental transmission electron microscopy, we report size-dependent structure dynamics of single Au nanoparticles on ceria (CeO2) in CO oxidation reaction condition at room temperature. While large Au nanoparticles remain rigid in the catalytic working condition, ultrasmall Au clusters lose their intrinsic structures and become disordered, featuring vigorous structural rearrangements and formation of dynamic low-coordinated atoms on surface. Ab initio molecular-dynamics simulations reveal that the interaction between ultrasmall Au cluster and CO molecules leads to the dynamic structural responses, demonstrating that the shape of the catalytic particle under the working condition may totally differ from the shape under the static condition. The present observation provides insight on the origin of superior catalytic properties of ultrasmall gold clusters.

Li+-Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances

Lithium (Li) ion battery has penetrated almost every aspect of human life, from portable electronics, vehicles, to grids, and its operation stability in extreme environments is becoming increasingly important. Among these, subzero temperature presents a kinetic challenge to the electrochemical reactions required to deliver the stored energy. In this work, we attempted to identify the rate-determining process for Li+ migration under such low temperatures, so that an optimum electrolyte formulation could be designed to maximize the energy output. Substantial increase in the available capacities from graphite∥LiNi0.80Co0.15Al0.05O2 chemistry down to -40 °C is achieved by reducing the solvent molecule that more tightly binds to Li+ and thus constitutes a high desolvation energy barrier. The fundamental understanding is applicable universally to a wide spectrum of electrochemical devices that have to operate in similar environments.

Real-time Observation of Sintering Process of Carbon Supported Platinum Nanoparticles in Oxygen and Water through Environment TEM

Sintering of Pt electrocatalyst largely determines the life-time of PEM fuel cells. While extensive efforts have been made to increase the durability and explore the sintering mechanism of carbon supported Pt NPs, the real behaviors of Pt catalysts in working ambient of PEM fuel cells remain elusive. It has long been recognized that deactivation of the Pt-based electrocatalyst is directly related to the coarsening of the Pt nanoparticles under working conditions of PEMFC. In situ TEM is inherently an effective and straightforward technique to visualize the sintering process and reveal the mechanisms of the sintering process of Pt NPs.

Surface Coating Effect on Si Nanowires Anodes for Lithium Ion Batteries

Silicon based materials holds promise for next generation negative electrode for high-capacity Li-ion batteries, yet tremendous research effort have been made for tackling the chemo-mechanical failure that is associated with the intrinsic large volume change of Si during lithiation and delithiation process. Surface modification of Si nanostructures have successfully alleviated this problem and improved the cyclability of Si based anodes. Successful surface modifications are expected to provide both good protection and conduction between Si nanostructures without sacrificing the electrochemical performance. However, how these surface modifications will affect the lithiation and delithiation behavior of the Si nanostructures and whey they improve or deteriorate the performance of electrodes are largely unknown.