Understanding Ion-Beam Damage to Air-Sensitive Lithium Metal With Cryogenic Electron and Ion Microscopy.

It is essential to understand the nanoscale structure and chemistry of energy storage materials due to their profound impact on battery performance. However, it is often challenging to characterize them at high resolution, as they are often fundamentally altered by sample preparation methods. Here, we use the cryogenic lift-out technique in a plasma-focused ion beam (PFIB)/scanning electron microscope (SEM) to prepare air-sensitive lithium metal to understand ion-beam damage during sample preparation. Through the use of cryogenic transmission electron microscopy, we find that lithium was not damaged by ion-beam milling although lithium oxide shells form in the PFIB/SEM chamber, as evidenced by diffraction information from cryogenic lift-out lithium lamellae prepared at two different thicknesses (130 and 225 nm). Cryogenic energy loss spectroscopy further confirms that lithium was oxidized during the process of sample preparation. The Ellingham diagram suggests that lithium can react with trace oxygen gas in the FIB/SEM chamber at cryogenic temperatures, and we show that liquid oxygen does not contribute to the oxidation of lithium process. Our results suggest the importance of understanding how cryogenic lift-out sample preparation has an impact on the high-resolution characterization of reactive battery materials.

Sub-100 mA/cm2 CO2-to-CO Reduction Current Densities in Hierarchical Porous Gold Electrocatalysts Made by Direct Ink Writing and Dealloying.

While most research efforts on CO2-to-CO reduction electrocatalysts focus on boosting their selectivity, the reduction rate, directly proportional to the reduction current density, is another critical parameter to be considered in practical applications. This is because mass transport associated with the diffusion of reactant/product species becomes a major concern at a high reduction rate. Nanostructured Au is a promising CO2-to-CO reduction electrocatalyst for its very high selectivity. However, the CO2-to-CO reduction current density commonly achieved in conventional nanostructured Au electrocatalysts is relatively low (in the range of 1-10 mA/cm2) for practical applications. In this work, we combine direct ink writing-based additive manufacturing and dealloying to design a robust hierarchical porous Au electrocatalyst to improve the mass transport and achieve high CO2-to-CO reduction current densities on the order of 64.9 mA/cm2 with CO partial current density of 33.8 mA/cm2 at 0.55 V overpotential using an H-cell configuration. Although the current density achieved in our robust hierarchical porous Au electrocatalyst is one order of magnitude higher than the one achieved in conventional nanostructured electrocatalysts, we found that the selectivity of our system is relatively low, namely 52%, which suggests that mass transport remains a critical issue despite the hierarchical porous architecture. We further show that the bulk dimension of our electrocatalyst is a critical parameter governing the interplay between selectivity and reduction rate. The insights gained in this work shed new light on the design of electrocatalysts toward scale-up CO2 reduction and beyond.

Effect of Nanoscale Confinement on Polymer-Infiltrated Scaffold Metal Composites.

Most research on polymer composites has focused on adding discrete inorganic nanofillers to a polymer matrix to impart properties not found in polymers alone. However, properties such as ion conductivity and mechanical reinforcement would be greatly improved if the composite exhibited an interconnected network of inorganic and polymer phases. Here, we fabricate bicontinuous polymer-infiltrated scaffold metal (PrISM) composites by infiltrating polymer into nanoporous gold (NPG) films. Polystyrene (PS) and poly(2-vinylpyridine) (P2VP) films are infiltrated into the ∼43 nm diameter NPG pores via capillary forces during thermal annealing above the polymer glass transition temperature (Tg). The infiltration process is characterized in situ using spectroscopic ellipsometry. PS and P2VP, which have different affinities for the metal scaffold, exhibit slower segmental dynamics compared to their bulk counterparts when confined within the nanopores, as measured through Tg. The more attractive P2VP shows a 20 °C increase in Tg relative to its bulk, while PS only shows a 6 °C increase at a comparable molecular weight. The infiltrated polymer, in turn, stabilizes the gold nanopores against temporal coarsening. The broad tunability of these polymer/metal hybrids represents a unique template for designing functional network composite structures with applications ranging from flexible electronics to fuel cell membranes.

Surface Facet Engineering in Nanoporous Gold for Low-Loading Catalysts in Aluminum-Air Batteries.

The performance of metal-air batteries and fuel cells depends on the speed and efficiency of electrochemical oxygen reduction reactions at the cathode, which can be improved by engineering the atomic arrangement of cathode catalysts. It is, however, difficult to improve upon the performance of platinum nanoparticles in alkaline electrolytes with low-loading catalysts that can be manufactured at scale. Here, the authors synthesized nanoporous gold catalysts with increased (100) surface facets using electrochemical dealloying in sodium citrate surfactant electrolytes. These modified nanoporous gold catalysts achieved an 8% higher operating voltage and 30% greater power density in aluminum-air batteries over traditionally prepared nanoporous gold, and their performance was superior to commercial platinum nanoparticle electrodes at a 10 times lower mass loading. The authors used rotation disc electrode studies, backscattering of electrons, and underpotential deposition to show that the increased (100) facets improved the catalytic activity of citrate dealloyed nanoporous gold compared to conventional nanoporous gold. The citrate dealloyed samples also had the highest stability and least concentration of steps and kinks. The developed synthesis and characterization techniques will enable the design and synthesis of metal nanostructured catalysts with controlled facets for low-cost and mass production of metal-air battery cathodes.

Using X-Ray Scattering to Elucidate the Microstructural Instability of 3D Bicontinuous Nanoporous Metal Scaffolds for Use in an Aperiodic 3D Tricontinuous Conductor-Insulator-Conductor Nanocapacitor.

The development of three-dimensional aperiodic energy storage devices is in part impeded by the lack of appropriate aperiodic templates that can withstand the thermal conditions required to deposit energy storage materials within their void space. Herein, the feasibility of an aperiodic three-dimensional architecture for energy storage is demonstrated for the first time by constructing a tricontinuous conductor-insulator-conductor (CIC) nanocapacitor on an aperiodic nanoporous gold scaffold. To accomplish this, the scaffold was characterized using in situ small-angle X-ray scattering (SAXS) during exposure to a thermal environment, revealing that its microstructure eventually stabilizes after undergoing a phase of rapid coarsening, indicating a departure from the 1/4 time-dependent power-law coarsening behavior usually observed at the early stage of the coarsening process. Using this stability regime, we created the CIC by intentionally precoarsening and stabilizing the scaffold before depositing two dissimilar metal oxide films in its void space by atomic layer deposition. Current-voltage characteristics and electrochemical impedance spectroscopy measurements revealed that the un-optimized 3D CIC outperformed its 2D counterpart by ∼4× in terms of capacitance. This proof-of-concept device will pave the way to the development of aperiodic three-dimensional energy storage systems with enhanced energy and power densities.

Enhancing the free corrosion dealloying rate with a catalytically driven reaction.

Despite its high popularity, chemical dealloying that is widely used for the fabrication of nanoporous metals is a relatively slow process: dealloying a few milligrams of bulk material may take from several hours up to a few days, depending on the material system. Raising the temperature of the corroding medium is a common approach to speed up the dealloying process. However, high temperatures cause undesired ligament growth in dealloyed materials. Here we report for the first time the use of a catalytically driven reaction to speed up the dealloying process at ambient temperature and pressure. To demonstrate the concept, we show that the free corrosion dealloying of a silver-aluminum alloy is significantly faster with the help of a platinum catalyst. More importantly, the corresponding characteristic nanostructured size is much smaller than that without a catalyst. Our finding is expected to play a central role in scaling up the dealloying process from the laboratory to the industrial scale.

Tuning Porosity and Surface Area in Mesoporous Silicon for Application in Li-Ion Battery Electrodes.

This work aims to improve the poor cycle lifetime of silicon-based anodes for Li-ion batteries by tuning microstructural parameters such as pore size, pore volume, and specific surface area in chemically synthesized mesoporous silicon. Here we have specifically produced two different mesoporous silicon samples from the magnesiothermic reduction of ordered mesoporous silica in either argon or forming gas. In situ X-ray diffraction studies indicate that samples made in Ar proceed through a Mg2Si intermediate, and this results in samples with larger pores (diameter ≈ 90 nm), modest total porosity (34%), and modest specific surface area (50 m2 g-1). Reduction in forming gas, by contrast, results in direct conversion of silica to silicon, and this produces samples with smaller pores (diameter ≈ 40 nm), higher porosity (41%), and a larger specific surface area (70 m2 g-1). The material with smaller pores outperforms the one with larger pores, delivering a capacity of 1121 mAh g-1 at 10 A g-1 and retains 1292 mAh g-1 at 5 A g-1 after 500 cycles. For comparison, the sample with larger pores delivers a capacity of 731 mAh g-1 at 10 A g-1 and retains 845 mAh g-1 at 5 A g-1 after 500 cycles. The dependence of capacity retention and charge storage kinetics on the nanoscale architecture clearly suggests that these microstructural parameters significantly impact the performance of mesoporous alloy type anodes. Our work is therefore expected to contribute to the design and synthesis of optimal mesoporous architectures for advanced Li-ion battery anodes.

Using X-ray Microscopy To Understand How Nanoporous Materials Can Be Used To Reduce the Large Volume Change in Alloy Anodes.

Tin metal is an attractive negative electrode material to replace graphite in Li-ion batteries due to its high energy density. However, tin undergoes a large volume change upon alloying with Li, which pulverizes the particles, and ultimately leads to short cycling lifetimes. Nevertheless, nanoporous materials have been shown to extend battery life well past what is observed in nonporous material. Despite the exciting potential of porous alloying anodes to significantly increase the energy density in Li-ion batteries, the fundamental physics of how nanoscale architectures accommodate the electrochemically induced volume changes are poorly understood. Here, operando transmission X-ray microscopy has been used to develop an understanding of the mechanisms that govern the enhanced cycling stability in nanoporous tin. We found that in comparison to dense tin, nanoporous tin undergoes a 6-fold smaller areal expansion after lithiation, as a result of the internal porosity and unique nanoscale architecture. The expansion is also more gradual in nanoporous tin compared to the dense material. The nanoscale resolution of the microscope used in this study is ∼30 nm, which allowed us to directly observe the pore structure during lithiation and delithiation. We found that nanoporous tin remains porous during the first insertion and desinsertion cycle. This observation is key, as fully closed pores could lead to mechanical instability, electrolyte inaccessibility, and short lifetimes. While tin was chosen for this study because of its high X-ray contrast, the results of this work should be general to other alloy-type systems, such as Si, that also suffer from volume change based cycling degradation.

Nanoporous Tin with a Granular Hierarchical Ligament Morphology as a Highly Stable Li-Ion Battery Anode.

Next generation Li-ion batteries will require negative electrode materials with energy densities many-fold higher than that found in the graphitic carbon currently used in commercial Li-ion batteries. While various nanostructured alloying-type anode materials may satisfy that requirement, such materials do not always exhibit long cycle lifetimes and/or their processing routes are not always suitable for large-scale synthesis. Here, we report on a high-performance anode material for next generation Li-ion batteries made of nanoporous Sn powders with hierarchical ligament morphology. This material system combines both long cycle lifetimes (more than 72% capacity retention after 350 cycles), high capacity (693 mAh/g, nearly twice that of commercial graphitic carbon), good charging/discharging capabilities (545 mAh/g at 1 A/g, 1.5C), and a scalable processing route that involves selective alloy corrosion. The good cycling performance of this system is attributed to its nanoporous architecture and its unique hierarchical ligament morphology, which accommodates the large volume changes taking place during lithiation, as confirmed by synchrotron-based ex-situ X-ray 3D tomography analysis. Our findings are an important step for the development of high-performance Li-ion batteries.

Mesoporous Ni60Fe30Mn10-alloy based metal/metal oxide composite thick films as highly active and robust oxygen evolution catalysts †.

A major challenge in the field of water electrolysis is the scarcity of oxygen-evolving catalysts that are inexpensive, highly corrosion-resistant, suitable for large-scale applications and able to oxidize water at high current densities and low overpotentials. Most unsupported, non-precious metals oxygen-evolution catalysts require at least ~350 mV overpotential to oxidize water with a current density of 10 mA/cm2 in 1 M alkaline solution. Here we report on a robust nanostructured porous NiFe-based oxygen evolution catalyst made by selective alloy corrosion. In 1 M KOH, our material exhibits a catalytic activity towards water oxidation of 500 mA/cm2 at 360 mV overpotential and is stable for over eleven days. This exceptional performance is attributed to three factors. First, the small size of the ligaments and pores in our mesoporous catalyst (~10 nm) results in a high BET surface area (43 m2/g) and therefore a high density of oxygen-evolution catalytic sites per unit mass. Second, the open porosity facilitates effective mass transfer at the catalyst/electrolyte interface. Third and finally, the high bulk electrical conductivity of the mesoporous catalyst allows for effective current flow through the electrocatalyst, making it possible to use thick films with a high density of active sites and ~3×104 cm2 of catalytic area per cm2 of electrode area. Our mesoporous catalyst is thus attractive for alkaline electrolyzers where water-based solutions are decomposed into hydrogen and oxygen as the only products, driven either conventionally or by photovoltaics.

Metallic muscles at work: high rate actuation in nanoporous gold/polyaniline composites.

Metallic muscles made of nanoporous metals suffer from serious drawbacks caused by the usage of an aqueous electrolyte for actuation. An aqueous electrolyte prohibits metallic muscles from operating in dry environments and hampers a high actuation rate due to the low ionic conductivity of electrolytes. In addition, redox reactions involved in electrochemical actuation severely coarsen the ligaments of nanoporous metals, leading to a substantial loss in performance of the actuator. Here we present an electrolyte-free approach to put metallic muscles to work via a metal/polymer interface. A nanocoating of polyaniline doped with sulfuric acid was grown onto the ligaments of nanoporous gold. Dopant sulfate anions coadsorbed into the polymer coating matrix were exploited to tune the nanoporous metal surface stress and subsequently generate macroscopic dimensional changes in the metal. Strain rates achieved in the single-component nanoporous metal/polymer composite actuator are 3 orders of magnitude higher than that of the standard three-component nanoporous metal/electrolyte hybrid actuator.

Enhanced strain in functional nanoporous gold with a dual microscopic length scale structure.

We have synthesized nanoporous Au with a dual microscopic length scale by exploiting the crystal structure of the alloy precursor. The synthesized mesoscopic material is characterized by stacked Au layers of submicrometer thickness. In addition, each layer displays nanoporosity through the entire bulk. It is shown that the thickness of these layers can be tailored via the grain size of the alloy precursor. The two-length-scale structure enhances the functional properties of nanoporous gold, leading to charge-induced strains of amplitude up to 6%, which are roughly 2 orders of magnitude larger than in nanoporous Au with the standard one-length-scale porous morphology. A model is presented to describe these phenomena.