Health diagnosis and recuperation of aged Li-ion batteries with data analytics and equivalent circuit modeling.

Battery health assessment and recuperation play crucial roles in the utilization of second-life Li-ion batteries. However, due to ambiguous aging mechanisms, it is challenging to estimate battery health and devise an effective strategy for cell rejuvenation. This paper presents aging and reconditioning experiments of 62 commercial lithium iron phosphate cells, which allow us to use machine learning models to predict cycle life and identify important indicators of recoverable capacity. An average test error of 16.84% ± 1.87% (mean absolute percentage error) for cycle life prediction is achieved by gradient boosting regressor. Some of the recoverable lost capacity is found to be attributed to the non-uniformity in electrodes. An experimentally validated equivalent circuit model is built to demonstrate how such non-uniformity can be accumulated, and how it can give rise to recoverable capacity loss. Furthermore, Shapley additive explanations (SHAP) analysis also reveals that battery operation history significantly affects the capacity recovery.

Efficient Ternary Mn-Based Spinel Oxide with Multiple Active Sites for Oxygen Evolution Reaction Discovered via High-Throughput Screening Methods.

The discovery of more efficient and stable catalysts for oxygen evolution reaction (OER) is vital in improving the efficiency of renewable energy generation devices. Given the large numbers of possible binary and ternary metal oxide OER catalysts, high-throughput methods are necessary to accelerate the rate of discovery. Herein, Mn-based spinel oxide, Fe10 Co40 Mn50 O, is identified for the first time using high-throughput methods demonstrating remarkable catalytic activity (overpotential of 310 mV on fluorine-doped tin oxide (FTO) substrate and 237 mV on Ni foam at 10 mA cm-2 ). Using a combination of soft X-ray absorption spectroscopy and electrochemical measurements, the high catalytic activity is attributed to 1) the formation of multiple active sites in different geometric sites, tetrahedral and octahedral sites; and 2) the formation of active oxyhydroxide phase due to the strong interaction of Co2+ and Fe3+ . Structural and surface characterizations after OER show preservation of Fe10 Co40 Mn50 O surface structure highlighting its durability against irreversible redox damage on the catalytic surface. This work demonstrates the use of a high-throughput approach for the rapid identification of a new catalyst, provides a deeper understanding of catalyst design, and addresses the urgent need for a better and stable catalyst to target greener fuel.

An energy efficient bi-functional electrode for continuous cation-selective capacitive deionization.

Effective ion intercalation nanomaterials provide tremendous opportunities to various deionization systems such as capacitive deionization (CDI) to significantly improve the removal capacity of brackish water desalination. However, the asymmetric design of CDI devices causes a low removal rate due to the indispensable regeneration half-cycle. Furthermore, choices of chloride selective electrodes for such devices are limited. This imposes a big challenge on further improvement of CDI systems. Herein, we report a cation-selective CDI system using a single bi-functional Na2VTi(PO4)3@carbon nanomaterial with redox couples of V4+/V3+ and Ti3+/Ti4+ as an advanced symmetric electrode. The as-prepared continuous desalination set-up shows a superior removal rate of 0.022 mg g-1 s-1 (1.32 mg g-1 min-1) with a high half-cycle removal capacity of 35 mg g-1, and extremely low energy consumption of 0.14 W h g-1 (at a current density of 100 mA g-1). In addition, an extremely high cycle-stability of at least 50 cycles is achieved. The bi-functional intercalation mechanism is investigated by in situ XRD and ex situ XPS. The symmetric device yields a simplified and low-cost configuration with improved energy efficiency and high removal capacity. This opens a new horizon towards the commercialization of CDI technologies.

Surface Modification of Hematite Photoanodes with CeOx Cocatalyst for Improved Photoelectrochemical Water Oxidation Kinetics.

Hematite is a promising photoanode for solar water splitting by photoelectrochemical (PEC) cells, but its performance is limited by the slow kinetics of water oxidation reaction or oxygen evolution reaction (OER). Surface modification of hematite photoanodes with a suitable water oxidation cocatalyst is a key strategy for improving the kinetics of water oxidation. In this study, a CeOx overlayer is deposited on the surface of the hematite photoanode by a water-based solution method with ceric ammonium nitrate (CAN) followed by heat treatment. The photocurrent of CeOx -modified hematite is 3 times higher than that of pristine hematite (at 1.23 V vs. RHE) under AM 1.5G, 1 sun conditions. Through hole-scavenger measurements, Tafel plot analysis, and electrochemical impedance spectroscopy, it is concluded that CeOx overlayer increases the hole injection efficiency, improves the surface catalytic activity, and enhances charge transfer across the photoanode/electrolyte interface. These observations are attributed to the synergistic effects of Ce3+ /Ce4+ redox species in CeOx and the oxygen vacancies. This work elucidates the role of CeOx as an efficient cocatalyst overlayer to improve the OER kinetics of photoanodes.

Understanding the Roles of NiOx in Enhancing the Photoelectrochemical Performance of BiVO4 Photoanodes for Solar Water Splitting.

Solar water oxidation is considered as a promising method for efficient utilization of solar energy and bismuth vanadate (BiVO4 ) is a potential photoanode. Catalyst loading on BiVO4 is often used to tackle the limitations of charge recombination and sluggish kinetics. In this study, amorphous nickel oxide (NiOx ) is loaded onto Mo-doped BiVO4 by photochemical metal-organic deposition method. The resulting NiOx /Mo:BiVO4 photoanodes demonstrate a two-fold improvement in photocurrent density (2.44 mA cm-2 ) at 1.23 V versus reversible hydrogen electrode (RHE) compared with the uncatalyzed samples. After NiOx modification the charge-separation and charge-transfer efficiencies improve significantly across the entire potential range. It is further elucidated by open-circuit photovoltage (OCP), time-resolved-microwave conductivity (TRMC), and rapid-scan voltammetry (RSV) measurements that NiOx modification induces larger band bending and promotes efficient charge transfer on the surface of BiVO4 . This work provides insight into designing BiVO4 -catalyst assemblies by using a simple surface-modification route for efficient solar water oxidation.

Ruthenium-Tungsten Composite Catalyst for the Efficient and Contamination-Resistant Electrochemical Evolution of Hydrogen.

A new catalyst, prepared by a simple physical mixing of ruthenium (Ru) and tungsten (W) powders, has been discovered to interact synergistically to enhance the electrochemical hydrogen evolution reaction (HER). In an aqueous 0.5 M H2SO4 electrolyte, this catalyst, which contained a miniscule loading of 2-5 nm sized Ru nanoparticles (5.6 µg Ru per cm2 of geometric surface area of the working electrode), required an overpotential of only 85 mV to drive 10 mA/cm2 of H2 evolution. Interestingly, our catalyst also exhibited good immunity against deactivation during HER from ionic contaminants, such as Cu2+ (over 24 h). We unravel the mechanism of synergy between W and Ru for catalyzing H2 evolution using Cu underpotential deposition, photoelectron spectroscopy, and density functional theory (DFT) calculations. We found a decrease in the d-band and an increase in the electron work function of Ru in the mixed composite, which made it bind to H more weakly (more Pt-like). The H-adsorption energy on Ru deposited on W was found, by DFT, to be very close to that of Pt(111), explaining the improved HER activity.

Self-Anchored Catalyst Interface Enables Ordered Via Array Formation from Submicrometer to Millimeter Scale for Polycrystalline and Single-Crystalline Silicon.

Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO2 are also formed with excellent vertical registry through the polystack, even though they are separated by SiO2 which is readily removed by HF alone with no anisotropy. In addition, 320 µm square through-Si-via (TSV) arrays in 550 µm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide range of feature sizes has significant implications for 2.5D/3D photonic and electronic device applications.

Damage-Free Smooth-Sidewall InGaAs Nanopillar Array by Metal-Assisted Chemical Etching.

Producing densely packed high aspect ratio In0.53Ga0.47As nanostructures without surface damage is critical for beyond Si-CMOS nanoelectronic and optoelectronic devices. However, conventional dry etching methods are known to produce irreversible damage to III-V compound semiconductors because of the inherent high-energy ion-driven process. In this work, we demonstrate the realization of ordered, uniform, array-based In0.53Ga0.47As pillars with diameters as small as 200 nm using the damage-free metal-assisted chemical etching (MacEtch) technology combined with the post-MacEtch digital etching smoothing. The etching mechanism of InxGa1-xAs is explored through the characterization of pillar morphology and porosity as a function of etching condition and indium composition. The etching behavior of In0.53Ga0.47As, in contrast to higher bandgap semiconductors (e.g., Si or GaAs), can be interpreted by a Schottky barrier height model that dictates the etching mechanism constantly in the mass transport limited regime because of the low barrier height. A broader impact of this work relates to the complete elimination of surface roughness or porosity related defects, which can be prevalent byproducts of MacEtch, by post-MacEtch digital etching. Side-by-side comparison of the midgap interface state density and flat-band capacitance hysteresis of both the unprocessed planar and MacEtched pillar In0.53Ga0.47As metal-oxide-semiconductor capacitors further confirms that the surface of the resultant pillars is as smooth and defect-free as before etching. MacEtch combined with digital etching offers a simple, room-temperature, and low-cost method for the formation of high-quality In0.53Ga0.47As nanostructures that will potentially enable large-volume production of In0.53Ga0.47As-based devices including three-dimensional transistors and high-efficiency infrared photodetectors.

Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array.

The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12.

Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

In this work, we investigate the transport processes governing the metal-assisted chemical etching (MacEtch) of silicon (Si). We show that in the oxidation of Si during the MacEtch process, the transport of the hole charges can be accomplished by the diffusion of metal ions. The oxidation of Si is subsequently governed by a redox reaction between the ions and Si. This represents a fundamentally different proposition in MacEtch whereby such transport is understood to occur through hole carrier conduction followed by hole injection into (or electron extraction from) Si. Consistent with the ion transport model introduced, we showed the possibility in the dynamic redistribution of the metal atoms that resulted in the formation of pores/cracks for catalyst thin films that are ≲30 nm thick. As such, the transport of the reagents and by-products are accomplished via these pores/cracks for the thin catalyst films. For thicker films, we show a saturation in the etch rate demonstrating a transport process that is dominated by diffusion via metal/Si boundaries. The new understanding in transport processes described in this work reconcile competing models in reagents/by-products transport, and also solution ions and thin film etching, which can form the foundation of future studies in the MacEtch process.

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide.

Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13](2-) building blocks. Of the three terminal disulfide (S2(2-)) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.

Antimony Doping in Solution-processed Cu2 ZnSn(S,Se)4 Solar Cells.

Kesterite Cu2 ZnSn(S,Se)4 (CZTSSe) is obtained using a facile precursor-solution method followed by selenization. Power-conversion efficiency of 6.0 % is achieved and further improved to 8.2 % after doping the absorber with 0.5 mol % Sb. XRD and Raman spectroscopy show similar characteristics for the undoped and doped CZTSSe. Increasing the Sb concentration increases the grain size and lowers the series resistance. However, further Sb doping beyond 0.5 mol % degrades device performance due to lower open-circuit voltage (and therefore lower fill factor). The effect of Sb doping and the doping concentration are investigated by power-dependent and temperature-dependent photoluminescence studies, revealing that trap density is significant reduced with 0.5 mol % Sb doping. Additional doping beyond 0.5 mol % creates more defects that quench the photoexcited carriers and decrease the open-circuit voltage.

Efficient polymer solar cells enabled by low temperature processed ternary metal oxide as electron transport interlayer with large stoichiometry window.

Highly efficient organic photovoltaic cells are demonstrated by incorporating low temperature solution processed indium zinc oxide (IZO) as cathode interlayers. The IZOs are synthesized using a combustion synthesis method, which enables low temperature processes (150-250 °C). We investigated the IZO films with different electron mobilities (1.4×10(-3) to 0.23 cm2/(V·s)), hydroxide-oxide content (38% to 47%), and surface roughness (0.19-5.16 nm) by modulating the ternary metal oxide stoichiometry. The photovoltaic performance was found to be relatively insensitive to the composition ratio of In:Zn over the range of 0.8:0.2 to 0.5:0.5 despite the differences in their electrical and surface properties, achieving high power conversion efficiencies of 6.61%-7.04%. Changes in composition ratio of IZO do not lead to obvious differences in energy levels, diode parameters and morphology of the photoactive layer, as revealed by ultraviolet photoelectron spectroscopy (UPS), dark current analysis and time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements, correlating well with the large IZO stoichiometry window that enables efficient photovoltaic devices. Our results demonstrate the robustness of this ETL system and provide a convenient approach to realize a wide range of multicomponent oxides and compatible with processing on flexible plastic substrates.

Silicon decorated with amorphous cobalt molybdenum sulfide catalyst as an efficient photocathode for solar hydrogen generation.

The construction of viable photoelectrochemical (PEC) devices for solar-driven water splitting can be achieved by first identifying an efficient independent photoanode for water oxidation and a photocathode for hydrogen generation. These two photoelectrodes then must be assembled with a proton exchange membrane within a complete coupled system. Here we report the preparation of a Si/a-CoMoSx hybrid photocathode which shows impressive performance (onset potential of 0.25 V vs RHE and photocurrent jsc of 17.5 mA cm(-2) at 0 V vs RHE) in pH 4.25 phosphate solution and under simulated AM 1.5 solar illumination. This performance is among the best reported for Si photocathodes decorated with noble-metal-free catalysts. The electrode preparation is scalable because it relies on a photoassisted electrodeposition process employing an available p-type Si electrode and [Co(MoS4)2](2-) precursor. Investigation of the mechanism of the Si/a-CoMoSx electrode revealed that under conditions of H2 photogeneration this bimetallic sulfide catalyst is highly efficient in extracting electrons from illuminated Si and subsequently in reducing protons into H2. The Si/a-CoMoSx photocathode is functional over a wide range of pH values, thus making it a promising candidate for the construction of a complete solar-driven water splitting PEC device.

Hydrothermal grown nanoporous iron based titanate, Fe2TiO5 for light driven water splitting.

We report the synthesis of iron based titanate (Fe2TiO5) thin films using a simple low cost hydrothermal technique. We show that this Fe2TiO5 works well as a photoanode for the photoelectrochemical splitting of water due to favorable band energetic. Further characterization of thin films including band positions with respect to water redox levels has been investigated. We conclude that Fe2TiO5 is a promising material comparable to hematite for constructing PEC cells.

Improving the efficiency of hematite nanorods for photoelectrochemical water splitting by doping with manganese.

Here, we report a significant improvement of the photoelectrochemical (PEC) properties of hematite (α-Fe2O3) to oxidize water by doping with manganese. Hematite nanorods were grown on a fluorine-treated tin oxide (FTO) substrate by a hydrothermal method in the presence on Mn. Systematic physical analyses were performed to investigate the presence of Mn in the samples. Fe2O3 nanorods with 5 mol % Mn treatment showed a photocurrent density of 1.6 mA cm(-2) (75% higher than that of pristine Fe2O3) at 1.23 V versus RHE and a plateau photocurrent density of 3.2 mA cm(-2) at 1.8 V versus RHE in a 1 M NaOH electrolyte solution (pH 13.6). We attribute the increase in the photocurrent density, and thus in the oxygen evolving capacity, to the increased donor density resulting from Mn doping of the Fe2O3 nanorods, as confirmed by Mott-Schottky measurement, as well as the suppression of electron-hole recombination and enhancement in hole transport, as detected by chronoamperometry measurements.

Nanostructuring of nickel hydroxide via a template solution approach for efficient electrochemical devices.

Nanostructuring is a key approach in enhancing the performance of electrochemical devices. In this work, nanostructuring is achieved by the electrodeposition of nickel hydroxide nanowire arrays, with both open-ended and close-ended structures, through anodized aluminium oxide (AAO) templates that are directly fabricated on indium tin oxide/glass substrates. The open-ended and close-ended nanostructures are compared together with identically fabricated thin films to show the effects of nanostructuring. Open-ended nanowire arrays demonstrated the best electrochemical activity with superior transmittance modulation and faster activation, while the thin film showed the worst performance. In comparing with the close-ended structures, enhanced performance is observed for the open-ended structures despite the use of less material for the latter. This demonstrates that in designing nanostructures or porous materials, it is important for the porosity to have both interconnectivity and exposure to the electrolyte in electrochemical reactions.

Joining copper oxide nanotube arrays driven by the nanoscale Kirkendall effect.

Various annealing conditions (environment, temperature, and duration) are applied to study the nanoscale Kirkendall effect of copper (Cu) nanowire (NW) arrays on a Si substrate. The results show that an appropriate amount of oxygen supply is crucial for uniform transformation from Cu NWs (average diameter ∼50 nm) into Cu oxide nanotube arrays. An annealing duration of 30 min at 200 °C in a low vacuum environment reveals that the voids are not uniformly distributed at the Cu/Cu oxide interface. This suggests that void growth is due to surface diffusion of Cu along void surfaces. Annealing above 200 °C for 60 min resulted in complete transformation from Cu NWs into Cu oxide nanotubes. X-ray photoelectron spectroscopy characterization indicates that the Cu oxides formed at 200 °C and 300 °C are Cu2O and CuO, respectively. It is demonstrated that the transformation from Cu NW arrays into Cu oxide nanotube arrays can be combined with the joining of stacked Si chips in a single-process step with reasonable joint shear strength. Transmission electron microscopy-electron energy loss spectroscopy elemental mapping analysis reveals that the joint interface is Cu oxide. The outward diffusion of Cu driven by the nanoscale Kirkendall effect is believed to enhance the joining process. By controlling the environment, temperature, and duration, joined Cu2O or CuO nanotube stacked chips can be achieved, which serve as a platform for the further development of nanostructured, stacked devices.

Novel assembly of an MoS2 electrocatalyst onto a silicon nanowire array electrode to construct a photocathode composed of elements abundant on the earth for hydrogen generation.

Mild-mannered catalyst: a novel procedure to load a MoS(2) co-catalyst onto the surface of silicon under mild-conditions (room temperature, atmospheric pressure, aqueous solution) by a photo-assisted electrodeposition process employing commercially available precursors is reported. The obtained Si-NW@MoS(2) photocathode showed similar catalytic activity for light-driven H(2) generation compared with a Si-NW@Pt photocathode.

Surface treatment of hematite photoanodes with zinc acetate for water oxidation.

A simple and inexpensive method to form a hematite photoanode for efficient water oxidation is reported. A very thin ZnO overlayer was deposited on top of a thin film of hematite and found, compared with non-treated hematite, to increase the photocurrent and reduce the onset potential for generating oxygen from water. After 3 cycles of ZnAc treatment, the photocurrent increased more than 40% to 1.08 mA cm(-2) at 0.23 V vs. Ag/AgCl and onset potential for water oxidation shifted by -170 mV. It is proposed that the ZnO overlayer changes the flat band potential of hematite and reduces the surface defects.