Search

Free-standing electrode (FSE) architectures hold the potential to dramatically increase the gravimetric and volumetric energy density of lithium-ion batteries (LIBs) by eliminating the parasitic dead weight and volume associated with traditional metal foil current collectors. However, current FSE fabrication methods suffer from insufficient mechanical stability, electrochemical performance, or industrial adoptability. Here, we demonstrate a scalable camphene-assisted fabrication method that allows simultaneous casting and templating of FSEs comprising common LIB materials with a performance superior to their foil-cast counterparts. These porous, lightweight, and robust electrodes simultaneously enable enhanced rate performance by improving the mass and ion transport within the percolating conductive carbon pore network and eliminating current collectors for efficient and stable Li

Alkaline water electrolysis, a promising technology for clean energy storage, is constrained by extrinsic factors in addition to intrinsic electrocatalytic activity. To begin to compare between catalytic materials for electrolysis applications, these extrinsic factors must first be understood and controlled. Here, we modify extrinsic electrode properties and study the effects of bubble release to examine how the electrode and surface design impact the performance of water electrolysis. We fabricate robust and cost-effective electrodes through a sequential three-dimensional (3D) printing and metal deposition procedure. Through a systematic assessment of the deposition procedure, we confirm the close relationship between extrinsic electrode properties (

Though potassium activation is one of the most common methods for producing high surface area porous carbons, a detailed understanding of the influence of precursor properties on the resulting physicochemical properties is lacking. To this end, polycondensation products of sucrose and melamine served as a useful platform to understand the role of precursor N content on the surface chemistry and porosity after potassium activation. By manipulating the nitrogen:carbon:potassium ratios in the precursors, a suite of porous carbons with variable surface areas (528–2740 m2/g) and nitrogen contents (0–22 at%) were synthesized. Analysis of both the byproducts and the carbons’ resulting physicochemical properties revealed a complex interplay of various known reaction schemes (viz., gas evolution, carbothermal reduction, chemical etching, and molten salt templating), which are not mutually exclusive and can each contribute to the resulting porosity and surface chemistry. With this comprehensive study and careful control of the precursor composition, we define specific nitrogen:potassium regimes where certain porogenesis pathways dominate. Our work emphasizes that straightforward mechanisms focused on carbothermal reduction and exfoliation cannot always explain porogenesis in nitrogen-rich carbons. This work endeavors to serve as a roadmap for greater understanding and control of the structure and chemistry of nitrogen-rich, potassium-activated porous carbons.

Carbons with varying porosity and N-content exhibit tunable thermodynamics of CO2 adsorption, stemming from synergy between confinement and surface chemistry. Further, size-sieving CO2/N2 adsorption selectivity occurs in sub-nanoscale interlayers.

Passivation of stainless steel by additives forming mass-transport blocking layers is widely practiced, where Cr element is added into bulk Fe-C forming the Cr2O3-rich protective layer. Here we extend the long-practiced passivation concept to Si anodes for lithium-ion batteries, incorporating the passivator of LiF/Li2CO3 into bulk Si. The passivation mechanism is studied by various ex situ characterizations, redox peak contour maps, thickness evolution tests, and finite element simulations. The results demonstrate that the passivation can enhance the lithiation of Li2Si and de-lithiation of Li3.75Si, induce the formation of F-rich robust solid electrolyte interphase, stabilize the Si/LiF/Li2CO3 composite, and mitigate the volume change of Si anodes upon cycling. The 3D passivated Si anode can fully retain a high capacity of 3701 mAh g-1 after 1500 cycles and tolerate high rates up to 50 C. This work provides insight into how to construct durable Si anodes through effective passivation.

In this paper we activate carbons from precursors of varying nitrogen content with different activating cations. The charge density of the cation helped to tune material properties and influence CO2 adsorption thermodynamics.

Doping is a well-known strategy to enhance the electrochemical energy storage performance of layered cathode materials. Many studies on various dopants have been reported; however, a general relationship between the dopants and their effect on the stability of the positive electrode upon prolonged cell cycling has yet to be established. Here, we explore the impact of the oxidation states of various dopants (i.e., Mg2+, Al3+, Ti4+, Ta5+, and Mo6+) on the electrochemical, morphological, and structural properties of a Ni-rich cathode material (i.e., Li[Ni0.91Co0.09]O2). Galvanostatic cycling measurements in pouch-type Li-ion full cells show that cathodes featuring dopants with high oxidation states significantly outperform their undoped counterparts and the dopants with low oxidation states. In particular, Li-ion pouch cells with Ta5+- and Mo6+-doped Li[Ni0.91Co0.09]O2 cathodes retain about 81.5% of their initial specific capacity after 3000 cycles at 200 mA g−1. Furthermore, physicochemical measurements and analyses suggest substantial differences in the grain geometries and crystal lattice structures of the various cathode materials, which contribute to their widely different battery performances and correlate with the oxidation states of their dopants., Long-term efficient cycling stability is of paramount importance for the development of high-energy Li-ion batteries. Here, the authors investigate the effect of transition metal dopants on the electrochemical, morphological, and structural properties of Ni-rich cathode active materials.

Electrochemical conditioning via chronopotentiometry (CP) and cyclic voltammetry (CV) is essential for the activation of oxygen evolution reaction (OER) electrocatalysts. While many reports have activated OER electrocatalysts using either CP or CV, the inherent differences between these two electrochemical conditioning methods for the activation of OER electrocatalytic materials have yet to be explored. Here, we investigate the effects of CP and CV electrochemical conditioning on a Ni-based OER precatalyst and substrate in Fe-purified and Fe-unpurified KOH electrolytes by employing (ⅰ) Ni foil, (ⅱ) NiSe precatalyst films with different thicknesses on the fluorine-doped tin oxide glass substrate, and (ⅲ) NiSe precatalyst films on Ni foil substrates. It was found that CV electrochemical conditioning can result in a higher degree of in situ oxidation and Fe incorporation for Ni-based precatalysts and substrates compared to CP electrochemical conditioning. In turn, this brought about different material properties (e.g., in situ oxidized layer thickness, composition, crystallinity, and morphology) and electrochemical characteristics (e.g., active surface area, electron transport limitation, and intrinsic activity) of Ni-based electrocatalysts, thereby not only affecting their OER activity but also complicating the interpretation of the origin of OER activity. This study identifies the distinct effects of CP and CV electrochemical conditioning on Ni-based OER electrocatalysts and provides insight into the choice of the electrochemical conditioning method to better investigate OER electrocatalysts.

The highly reactive nature and rough surface of Li foil can lead to the uncontrollable formation of Li dendrites when employed as an anode in a lithium metal battery. Thus, it could be of great practical utility to create uniform, electrochemically stable, and "lithiophilic" surfaces to realize homogeneous deposition of Li. Herein, a LiZn alloy layer is deposited on the surface of Li foil by e-beam evaporation. The idea is to introduce a uniform alloy surface to increase the active area and make use of the Zn sites to induce homogeneous nucleation of Li. The results show that the alloy film protected the Li metal anode, allowing for a longer cycling life with a lower deposition overpotential over a pure-Li metal anode in symmetric Li cells. Furthermore, full cells pairing the modified lithium anode with a LiFePO4 cathode showed an incremental increase in Coulombic efficiency compared with pure-Li. The concept of using only an alloy modifying layer by an in-situ e-beam deposition synthesis method offers a potential method for enabling lithium metal anodes for next-generation lithium batteries.

Nickel nitride (Ni3N) is known as one of the promising precatalysts for the electrochemical oxygen evolution reaction (OER) under alkaline conditions. Due to its relatively low oxidation resistance, Ni3N is electrochemically self-oxidized into nickel oxides/oxyhydroxides (electroactive sites) during the OER. However, we lack a full understanding of the effects of Ni3N self-oxidation and Fe impurity incorporation into Ni3N from electrolyte towards OER activity. Here, we report on our examination of the compositional and structural transformation of Ni3N precatalyst layers on Ni foams (Ni3N/Ni foam) during extended periods of OER testing in Fe-purified and unpurified KOH media using both a standard three-electrode cell and a flow cell, and discuss their electrocatalytic properties. After the OER tests in both KOH media, the Ni3N surfaces were converted into amorphous, nano-porous nickel oxide/(oxy)hydroxide surfaces. In the Fe-purified electrolyte, a decrease in OER activity was confirmed after the OER test because of the formation of pure NiOOH with low OER activity and electrical conductivity. Conversely, in the unpurified electrolyte, a continuous increase in OER activity was observed over the OER testing, which may have resulted from the Fe incorporation into the self-oxidation-formed NiOOH. Our experimental findings revealed that Fe impurities play an essential role in obtaining notable OER activity using the Ni3N precatalyst. Additionally, our Ni3N/Ni foam electrode exhibited a low OER overpotential of 262 mV to reach a geometric current density of 10 mA cmgeo−2 in a flow cell with unpurified electrolyte.

Electrochemical water splitting is one of the most promising approaches for sustainable energy conversion and storage toward a future hydrogen society. This demands durable and affordable electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). In this study, we report the preparation of uniform Ni–P–O, Ni–S–O, and Ni–S–P–O electrocatalytic films on nickel foam (NF) substrates via flow cell-assisted electrodeposition. Remarkably, electrodeposition onto 12 cm2 substrates was optimized by strategically varying critical parameters. The high quality and reproducibility of the materials is attributed to the use of a 3D-printed flow cell with a tailored design. Then, the as-fabricated electrodes were tested for overall water splitting in the same flow cell under alkaline conditions. The best-performing sample, NiSP/NF, required relatively low overpotentials of 93 mV for the HER and 259 mV for the OER to produce a current density of 10 mA cm−2. Importantly, the electrodeposited films underwent oxidation into amorphous nickel (oxy)hydroxides and oxidized S and P species, improving both HER and OER performance. The superior electrocatalytic performance of the Ni–S–P–O films originates from the unique reconstruction process during the HER/OER. Furthermore, the overall water splitting test using the NiSP/NF couple required a low cell voltage of only 1.85 V to deliver a current density of 100 mA cm−2. Overall, we demonstrate that high-quality electrocatalysts can be obtained using a simple and reproducible electrodeposition method in a robust 3D-printed flow cell.

This paper reports a highly active and stable nonprecious metal electrocatalyst based on bimetallic nanoscale nickel molybdenum nitride developed for the hydrogen evolution reaction (HER). A composite of 7 nm Ni2Mo3N nanoparticles grown on nickel foam (Ni2Mo3N/NF) was prepared through a simple and economical synthetic method involving one-step annealing of Ni foam, MoCl5, and urea without a Ni precursor. The Ni2Mo3N/NF exhibits high activity with low overpotential (η10 of 21.3 mV and η100 of 123.8 mV) and excellent stability for the HER, achieving one of the best performances among state-of-the-art transition metal nitride based catalysts in alkaline media. Supporting density functional theory (DFT) calculations indicate that N sites in Ni2Mo3N with a N–Mo coordination number of four have a hydrogen adsorption energy close to that of Pt and hence may be responsible for the enhanced HER performance.

ConspectusThe enhanced catalytic activity of Pd-Au catalysts originates from ensemble effects related to the local composition of Pd and Au. The study of Pd-Au planar model catalysts in an ultrahigh vacuum (UHV) environment allows the observation of molecular level catalytic reactions between the Pd-Au surface and target molecules. Recently, there has been progress in understanding the behavior of simple molecules (H2, O2, CO, etc.) employing UHV surface science techniques, the results of which can be applied not only to heterogeneous catalysis but also to electro- and photochemical catalysis.Employing UHV methods in the investigation of Pd-Au model catalysts has shown that single Pd atoms can dissociatively adsorb H2 molecules. The recombinative desorption temperature of H2 varies with Pd ensemble size, which allows the use of H2 as a probe molecule for quantifying surface composition. In particular, H2 desorption from Pd-Au interface sites (or small Pd ensembles) is observed from 150-300 K, which is between the H2 desorption temperature from pure Au (∼110 K) and Pd (∼350 K) surfaces. When the Pd ensembles are large enough to form Pd(111)-like islands, H2 desorption occurs from 300-400 K, as with pure Pd surfaces. The different H2 desorption behavior, which depends on Pd ensemble size, has also been applied to the analysis of dehydrogenation mechanisms for potential liquid storage mediums for H2, namely formic acid and ethanol. In both cases, the Pd-Au interface is the main reaction site for generating H2 from formic acid and ethanol with less overall decomposition of the two molecules (compared to pure Pd).The chemistry behind O2 activation has also been informed through the control of Pd ensembles on a gold model catalyst for acetaldehyde and ethanol oxidation reactions under UHV conditions. O2 molecules molecularly adsorbed on continuous Pd clusters can be dissociated into O adatoms above 180 K. This O2 activation process is improved by coadsorbed H2O molecules. It is also possible to directly (through a precursor mechanism) introduce O adatoms on the Pd-Au surface by exposure to O2 at 300 K. The quantity of dissociatively adsorbed O adatoms is proportional to the Pd coverage. However, the O adatoms are more reactive on a less Pd covered surface, especially at the Pd-Au interface sites, which can initiate CO oxidation at temperatures as low as 140 K. Acetaldehyde molecules can be selectively oxidized to acetic acid on the Pd-Au surface with O adatoms, in which the selectivity toward acetic acid originates from preventing the decarboxylation of acetate species. Moreover, the O adatoms on the Pd-Au surface accelerate ethanol dehydrogenation, which causes the increase in acetaldehyde production. Hydrogen is continuously abstracted from the formed acetaldehyde and remaining ethanol molecules, and they ultimately combine as ethyl acetate on the Pd-Au surface.Using Pd-Au model catalysts under UHV conditions allows the discovery of molecular level mechanistic details regarding the catalytic behavior of H and O adatoms with other molecules. We also expect that these findings will be applicable regarding other chemistry on Pd-Au catalysts.

Nickel adds to the capacity of layered oxide cathodes of lithium-ion batteries but comprises their stability. We report a petal-grained Li[Ni0.89Co0.10Sb0.01]O2 cathode that is, nevertheless, stable. The stability originates from the ordering of the nanosized grains in a dense, flower-petal-like array, where the elongated and nearly parallel grains radiate from the center to the surface. The ordering of the grains prevents microcrack generation from abrupt lattice changes of the stressful H2-H3 phase transition. The tight packing of the nanograins is conserved upon cycling, preventing destructive seepage of the electrolytic solution into the particles. The half-cell, cycling between 2.7-4.3 V versus Li/Li+ at a 0.5 C rate retains 95.0% of its initial capacity of 220 mAh g-1 after 100 cycles. The full-cell, cycling with a graphite anode and between 3.0-4.2 V at a 1 C rate, retains 83.9% of its initial capacity after 1000 cycles.

Deposition of materials as a thin film is important for various applications, such as sensors, microelectronic devices, and membranes. There have been breakthroughs in gas-phase metal-organic framework (MOF) thin-film growth, which is more applicable to micro- and nanofabrication processes and also less harmful to the environment than solvent-based methods. Three different types of gas-phase MOF thin film deposition methods have been developed using chemical vapor deposition (CVD), atomic layer deposition (ALD), and physical vapor deposition (PVD)-CVD combined techniques. The CVD-based method basically converts metal oxide layers into MOF thin films by exposing the surface to ligand vapor. The ALD-based method allows growing MOF thin films following layer-by-layer (LBL) growth by sequentially exposing gas-phase metal and ligand precursors. The PVD-CVD method uses PVD for metal deposition and CVD for ligand deposition, which is similar to LBL growth. These gas-phase growth methods can broaden the use of MOFs in diverse areas. Herein, the current progress of gas-phase MOF thin film growth is discussed and future directions suggested.

Metallic vanadium carbide (V8C7) with cubic symmetry is examined as an oxygen evolution reaction (OER) precatalyst in alkaline media. Herein, we used quasi in situ scanning electron microscopy and ...

Direct conversion of methane to methanol has been a long-sought objective. Partial oxidation by thermal catalysis is possible but suffers from a rapid loss in methanol selectivity with increasing m...

The low cost, abundance, and high capacity of sodium and sulfur make them attractive battery materials. However, formation and migration of polysulfides in sulfur batteries causes rapid capacity fade, limiting battery cycle life. Most strategies to mitigate polysulfide shuttling address migration rather than formation and require complicated or expensive synthetic steps. Here, we introduce an amorphous, sulfur-rich molybdenum sulfide as a sulfur equivalent cathode that is simple and easy to make and shows excellent cycling performance with a specific capacity of 537 mAh g–1 at 50 mA g–1, retaining over 200 mAh g–1 at a rate of 1 A g–1.

Selenium-doped germanium (GeSe) micrometer-sized particles have been reported with good cycling performance and rate capability due to a Li–Se–Ge network formed during the first lithiation that pro...

Ruddlesden–Popper phase quasi-2-D organolead halide perovskites like n-butylammonium methylammonium lead iodide (nBA-MAPI) exhibit improved moisture stability over typical 3-D perovskite materials,...

Bulk carbon nitride (C3N4) was transformed into hierarchically nanoporous, nitrogen-rich (N-rich) carbons via calcium chloride (CaCl2) mediated thermal activation. By systematically varying the ann...

The long-term instability of typical organolead halide perovskites has led to increased interest in Ruddlesden–Popper phase (RPP) perovskites. These materials have been shown to possess high stabil...

This work evaluates the use of potassium hydroxide (KOH) and potassium oxalate monohydrate (K2C2O4•H2O) for the formation of nitrogen- and oxygen-doped porous carbons. Based on molar equivalent amo...

The photoelectrochemical water splitting of monoclinic bismuth vanadate (BiVO4) suffers from sluggish charge mobility as well as substantial charge recombination losses. Here, we treated the BiVO4 ...

Metal-organic framework (MOF) thin films allow the unique properties of MOFs to be incorporated into membranes and micro-electronic devices and also permit studies of catalysis employing powerful u...

Silicon (Si) films are promising anode materials in thin-film lithium batteries due to their high capacity of 3578 mAh g-1, but the huge volume expansion of lithiated Li15Si4 and the unstable solid electrolyte interphase (SEI) preclude their practical application. Here lithium fluoride (LiF) coated Si nanocolumns are fabricated by glancing angle evaporation to address the obstacle. The LiF coating can elevate the lithium ion diffusion coefficient (LDC) of Si electrodes upon the alloying reaction and reduce the LDC upon the SEI formation. The composition evolution of the outer SEI layer in the LiF/Si electrodes is studied by ex situ X-ray photoelectron spectroscopy. The modified surface and mitigated volume expansion enable the LiF/Si nanocolumns to exhibit superior rate capability and higher cycling stability compared with the pristine Si nanocolumns. This work demonstrates the positive effect of LiF coating for reducing the polarization and forming a robust SEI film on Si anodes.

This Perspective discusses the prospective strategies for overcoming the stability and capacity trade-off associated with increased Ni content in layered Ni-rich Li[NixCoyMnz]O2 (NCM) and Li[NixCoy...

Microspheres of cobalt metal–cobalt carbide (Co−CoxC , CoxC = Co2C and Co3C) composite with carbon shells were prepared via an OH−- and Cl−-assisted polyol method and investigated for electrocataly...

Mass spectrometry (MS) has emerged as a valuable technology for molecular and spatial evaluation of biological samples. Ambient ionization MS techniques, in particular, allow direct analysis of tissue samples with minimal pretreatment. Here, we describe the design and optimization of an alternative ambient liquid extraction MS approach for metabolite and lipid profiling and imaging from biological samples. The system combines a piezoelectric picoliter dispenser to form solvent nanodroplets onto the sample surface with controlled and tunable spatial resolution and a conductive capillary to directly aspirate/ionize the nanodroplets for efficient analyte transmission and detection. Using this approach, we performed spatial profiling of mouse brain tissue sections with different droplet sizes (390, 420, and 500 μm). MS analysis of normal and cancerous human brain and ovarian tissues yielded rich metabolic profiles that were characteristic of disease state and enabled visualization of tissue regions with different histologic composition. This method was also used to analyze the lipid profiles of human ovarian cell lines. Overall, our results demonstrate the capabilities of this system for spatially controlled MS analysis of biological samples.

Although Li-ion batteries have emerged as the battery of choice for electric vehicles and large-scale smart grids, significant research efforts are devoted to identifying materials that offer higher energy density, longer cycle life, lower cost, and/or improved safety compared to those of conventional Li-ion batteries based on intercalation electrodes. By moving beyond intercalation chemistry, gravimetric capacities that are 2-5 times higher than that of conventional intercalation materials (e.g., LiCoO2 and graphite) can be achieved. The transition to higher-capacity electrode materials in commercial applications is complicated by several factors. This Review highlights the developments of electrode materials and characterization tools for rechargeable lithium-ion batteries, with a focus on the structural and electrochemical degradation mechanisms that plague these systems.

We observe that metallic manganese alloyed with polycrystalline cobalt promotes the dissociation of CO. Increasing coverages of Mn on Co facillitate stronger molecular CO binding energies and stronger C(ad) + O(ad) binding energies. These findings show the role of metallic manganese in promoting model Co Fischer-Tropsch catalysis.

To understand the effect of selenium doping on the good cycling performance and rate capability of a Ge0.9Se0.1 electrode, the dynamic morphological and phase changes of the Ge0.9Se0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge0.9Se0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge0.9Se0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge0.9Se0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li15Ge4 phase. These in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials.

Imaging of lithium electrodepositions revealed that in the absence of a compressed porous separator, achieved via a plastic washer, dendrite-free lithium was deposited from glyme solutions of 1 M LiNO3. When the 1 M LiNO3 in glyme was coupled with a 1 M LiFSI salt, high coulombic efficiencies were also attainable in both Li|Cu and anode-free LFP|Cu cells. However, dendrite resurgence was observed in cycled lithium coin cell electrodes when a porous separator was utilized. This was attributed to the restriction of Li+ flux to the electrode surface induced by the porous and tortuous structure of the polymer separator. At these pores, localized current densities, which exceeded the applied current density, and a non-uniform Li+ flux resulted in dendritic lithium growth. Replacement of the separator by a washer normalized the current distribution and provided for non-dendritic lithium deposits in coin cells.

Strategies to improve the catalytic efficiency of the hydrogen evolution reaction (HER), an integral electrochemical reaction in solar-to-hydrogen technologies, frequently include the use of porous...

A tin oxide-carbon composite (SnOx-C) was fabricated as a candidate for use as an anode in lithium-ion batteries through the pyrolysis of a ditin citrate precursor. The simultaneous formation of ti...

Through a simple gelation-solvothermal method with graphene oxide as the additive, a Cu4SnS4-rich composite of nanoparticles and nanotubes is synthesized and applied for thin and flexible Li-metal batteries. Unlike the Cu2SnS3-rich electrode, the Cu4SnS4-rich electrode cycles stably with an enhanced conversion capacity of ∼416 mAh g-1 (∼52% of total capacity) after 200 cycles. The lithiation/delithiation mechanisms of Cu-Sn-S electrodes and the voltage ranges of conversion and alloying reactions are informed by in situ X-ray diffraction tests. The conversion process of three Cu-Sn-S compounds is compared by density functional theory (DFT) calculations based on three algorithms, elucidating the enhanced conversion stability and superior diffusion kinetics of Cu4SnS4 electrodes. The reaction pathway of Cu-Sn-S electrodes and the root cause for the unstable capacity are revealed by in situ/ex situ characterizations, DFT calculations, and various electrochemical tests. This work provides insight into developing energy materials and power devices based on multiple lithiation mechanisms.

Amorphous molybdenum sulfides (a-MoSx) are known to be active electrocatalysts for the hydrogen evolution reaction (HER), but the role stoichiometry of the sulfur atoms plays in the HER activity remains unclear. In this work, we deposited thin films of a-MoSx from two thiomolybdate deposition baths with different sulfur ratios (MoS42– and Mo2S122–) and showed that the sulfur stoichiometry, as determined by X-ray photoelectron spectroscopy, is controlled by the precursor of choice and the electrochemical method used to deposit the thin films. Using the Mo2S122– precursor allows access to a MoS6 thin film, with a higher S/Mo ratio compared with that of any previously reported electrodeposited films. We also examined the effect of electrochemistry on the resulting S/Mo ratio in the as-prepared a-MoSx thin films. Samples with S/Mo ratios ranging from 2 to 6 were electrodeposited on glassy carbon (GC) substrates by using anodic, cathodic, or cyclic voltammetry deposition. The a-MoSx thin films deposited on GC ...

Layered nickel-rich cathode particles for lithium-ion batteries can fail and severely limit the cycling performance via cracking from anisotropic strain which allows electrolyte penetration and the...

Different WO3 facets have different surface energies and electronic structures, and exhibit different water oxidation abilities and photocatalytic performance as a result. Because of the material’s limited photoresponse region, loading a narrow bandgap material on WO3 is a generally known method for improving photo-harvesting. In this paper, we have synthesized WO3 films with different crystal facet ratios. After loading BiVO4 on these WO3 films, we measured the photoelectrochemical (PEC) performance to investigate the effects of WO3 facet choice on the heterojunction film electrode’s performance. We found that a high-intensity ratio of the (002) WO3 facet in X-ray diffraction (XRD) leads to a more negative onset potential and higher photocurrents in a lower potential region. The ultraviolet photoelectron spectra show a lower work function for the 002-dominant WO3 film compared to other WO3 films, which may result in a higher quasi-fermi level for the heterojunction electrode. Based on the XRD results, the high-intensity ratio of the (002) WO3 facet preferentially exposes the (020) BiVO4 facet, which may be a reason for the better charge extraction observed at low applied potential and high faradic efficiency on PEC water splitting. Together, this results in a high hole injection efficiency for 002-dominant WO3/BiVO4 films compared with WO3/BiVO4 films favoring other WO3 facet ratios.