Xiahui Yao

Enabling unassisted solar water splitting by iron oxide and silicon

Photoelectrochemical (PEC) water splitting promises a solution to the problem of large-scale solar energy storage. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. Here we show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. This result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

Three Dimensionally Ordered Mesoporous Carbon as a Stable, High‐Performance Li–O2 Battery Cathode

Enabled by the reversible conversion between Li2O2 and O2, Li-O2 batteries promise theoretical gravimetric capacities significantly greater than Li-ion batteries. The poor cycling performance, however, has greatly hindered the development of this technology. At the heart of the problem is the reactivity exhibited by the carbon cathode support under cell operation conditions. One strategy is to conceal the carbon surface from reactive intermediates. Herein, we show that long cyclability can be achieved on three dimensionally ordered mesoporous (3DOm) carbon by growing a thin layer of FeO(x) using atomic layer deposition (ALD). 3DOm carbon distinguishes itself from other carbon materials with well-defined pore structures, providing a unique material to gain insight into processes key to the operations of Li-O2 batteries. When decorated with Pd nanoparticle catalysts, the new cathode exhibits a capacity greater than 6000 mAh g(carbon) (-1) and cyclability of more than 68 cycles.

Selective Deposition of Ru Nanoparticles on TiSi2 Nanonet and Its Utilization for Li2O2 Formation and Decomposition

The Li-O2 battery promises high capacity to meet the need for electrochemical energy storage applications. Successful development of the technology hinges on the availability of stable cathodes. The reactivity exhibited by a carbon support compromises the cyclability of Li-O2 operation. A noncarbon cathode support has therefore become a necessity. Using a TiSi2 nanonet as a high surface area, conductive support, we obtained a new noncarbon cathode material that corrects the deficiency. To enable oxygen reduction and evolution, Ru nanoparticles were deposited by atomic layer deposition onto TiSi2 nanonets. A surprising site-selective growth whereupon Ru nanoparticles only deposit onto the b planes of TiSi2 was observed. DFT calculations show that the selectivity is a result of different interface energetics. The resulting heteronanostructure proves to be a highly effective cathode material. It enables Li-O2 test cells that can be recharged more than 100 cycles with average round-trip efficiencies >70%.

Why Do Lithium–Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect

Abstract As an electrochemical energy‐storage technology with the highest theoretical capacity, lithium–oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round‐trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium–oxygen batteries for high‐performance operations and how to eventually materialize the full potentials of this promising technology.

Comparison of heterogenized molecular and heterogeneous oxide catalysts for photoelectrochemical water oxidation

Photoelectrochemical (PEC) reactions, such as water splitting, promise a direct route for solar-to-chemical energy conversion. Successful implementations of these reactions often require the combination of catalysts with photoelectrodes. How these catalysts improve the performance of photoelectrodes, however, is not well understood, making it difficult to further improve these systems for practical applications. Here, we present a systematic study that directly compares two water-oxidation catalysts (WOCs) on a hematite (α-Fe2O3)-based PEC system. We observe that when a thin layer of a heterogenized molecular Ir catalyst (het-WOC) is applied to a hematite photoanode, the systems performance is improved primarily due to improved charge transfer (>2 fold), while the surface recombination rate remains unchanged. In stark contrast, heterogeneous oxide catalysts (IrOx) improve the PEC performance of hematite by significantly reducing the surface recombination rate. These results suggest that the het-WOC provides additional charge-transfer pathways across the Fe2O3|H2O interface, while IrOx and similar bulk metal-oxide catalysts replace the Fe2O3|H2O interface with a fundamentally different one.

Hematite‐Based Solar Water Splitting in Acidic Solutions: Functionalization by Mono‐ and Multilayers of Iridium Oxygen‐Evolution Catalysts

Solar water splitting in acidic solutions has important technological implications, but has not been demonstrated to date in a dual absorber photoelectrochemical cell. The lack of functionally stable water-oxidation catalysts (WOCs) in acids is a key reason for this slow development. The only WOCs that are stable at low pH are Ir-based systems, which are typically too expensive to be implemented broadly. It is now shown that this deficiency may be corrected by applying an ultra-thin monolayer of a molecular Ir WOC to hematite for solar water splitting in acidic solutions. The turn-on voltage is observed to shift cathodically by 250 mV upon the application of a monolayer of the molecular Ir WOC. When the molecular WOC is replaced by a heterogeneous multilayer derivative, stable solar water splitting for over 5 h is achieved with near-unity Faradaic efficiency.

Achieving Low Overpotential Li-O₂ Battery Operations by Li₂O₂ Decomposition through One-Electron Processes.

As a promising high-capacity energy storage technology, Li-O2 batteries face two critical challenges, poor cycle lifetime and low round-trip efficiencies, both of which are connected to the high overpotentials. The problem is particularly acute during recharge, where the reactions typically follow two-electron mechanisms that are inherently slow. Here we present a strategy that can significantly reduce recharge overpotentials. Our approach seeks to promote Li2O2 decomposition by one-electron processes, and the key is to stabilize the important intermediate of superoxide species. With the introduction of a highly polarizing electrolyte, we observe that recharge processes are successfully switched from a two-electron pathway to a single-electron one. While a similar one-electron route has been reported for the discharge processes, it has rarely been described for recharge except for the initial stage due to the poor mobilities of surface bound superoxide ions (O2(-)), a necessary intermediate for the mechanism. Key to our observation is the solvation of O2(-) by an ionic liquid electrolyte (PYR14TFSI). Recharge overpotentials as low as 0.19 V at 100 mA/g(carbon) are measured.

Functionalizing Titanium Disilicide Nanonets with Cobalt Oxide and Palladium for Stable Li Oxygen Battery Operations.

Li oxygen (Li-O2) batteries promise high energy densities but suffer from challenges such as poor cycling lifetime and low round-trip efficiencies. Recently, the instability of carbon cathode support has been recognized to contribute significantly to the problems faced by Li-O2 batteries. One strategy to address the challenge is to replace carbon materials with carbon-free ones. Here, we present titanium silicide nanonets (TiSi2) as such a new material platform for this purpose. Because TiSi2 exhibits no oxygen reduction reaction (ORR) or oxygen evolution reaction (OER) activities, catalysts are required to promote discharge and recharge reactions at reduced overpotentials. Pd nanoparticles grown by atomic layer deposition (ALD) were observed to provide the bifunctionalities of ORR and OER. Their adhesion to TiSi2 nanonets, however, was found to be poor, leading to drastic performance decay due to Pd detachments and aggregation. The problem was solved by adding another layer of Co3O4, also prepared by ALD. Together, the Pd/Co3O4/TiSi2 combination affords the desired functionalities and stability. Li-O2 test cells that lasted more than 126 cycles were achieved. The reversible formation and decomposition of Li2O2 was verified by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), ferrocenium back-titration, and gas-chromatography and mass spectrometry (GC-MS). Our results provide a new material platform for detailed studies of Li-O2 operations for better understanding of the chemistries involved, which is expected to help pave the way toward practical Li-O2 battery realizations.

Enabling rechargeable non-aqueous Mg–O2 battery operations with dual redox mediators

Dual redox mediators (RMs) were introduced for Mg-O2 batteries. 1,4-Benzoquinone (BQ) facilitates the discharge with an overpotential reduction of 0.3 V. 5,10,15,20-Tetraphenyl-21H,23H-porphine cobalt(ii) (Co(ii)TPP) facilitates the recharge with an overpotential decrease of up to 0.3 V. Importantly, the two redox mediators are compatible in the same DMSO-based electrolyte.

Free-standing porous carbon electrodes derived from wood for high-performance Li-O2 battery applications

Porous carbon materials are widely used in particulate forms for energy applications such as fuel cells, batteries, and (super) capacitors. To better hold the particles together, polymeric additives are utilized as binders, which not only increase the weight and volume of the devices, but also cause adverse side effects. We developed a wood-derived, free-standing porous carbon electrode and successfully applied it as a cathode in Li-O2 batteries. The spontaneously formed hierarchical porous structure exhibits good performance in facilitating the mass transport and hosting the discharge products of Li2O2. Heteroatom (N) doping further improves the catalytic activity of the carbon cathode with lower overpotential and higher capacity. Overall, the Li-O2 battery based on the new carbon cathode affords a stable energy efficiency of 65% and can be operated for 20 cycles at a discharge depth of 70%. The wood-derived free-standing carbon represents a new, unique structure for energy applications.