Diagnosing the Electrostatic Shielding Mechanism for Dendrite Suppression in Aqueous Zinc Batteries.

Aqueous zinc electrolytes offer the potential for cheaper rechargeable batteries due to their safe compatibility with the high capacity metal anode; yet, they are stymied by irregular zinc deposition and consequent dendrite growth. Suppressing dendrite formation by tailoring the electrolyte is a proven approach from lithium batteries; yet, the underlying mechanistic understanding that guides such tailoring does not necessarily directly translate from one system to the other. Here, it is shown that the electrostatic shielding mechanism, a fundamental concept in electrolyte engineering for stable metal anodes, has different consequences for the plating morphology in aqueous zinc batteries. Operando electrochemical transmission electron microscopy is used to directly observe the zinc nucleation and growth under different electrolyte compositions and reveal that electrostatic shielding additive suppresses dendrites by inhibiting secondary zinc nucleation along the (100) edges of existing primary deposits and encouraging preferential deposition on the (002) faces, leading to a dense and block-like zinc morphology. The strong influence of the crystallography of Zn on the electrostatic shielding mechanism is further confirmed with Zn||Ti cells and density functional theory modeling. This work demonstrates the importance of considering the unique aspects of the aqueous zinc battery system when using concepts from other battery chemistries.

Synthesis of Li1.20Mn0.432+Nb0.39O2 disordered rock-salt under reducing conditions for Li-ion batteries.

A Mn2+-Li-Nb disordered rock-salt oxide cathode is prepared by a solid-state reaction under 5% H2/N2, and its electrochemical property shows a high voltage plateau at 4.8 V, with irreversible structural changes in the 1st cycle due to O redox processes; this is supported by powder X-ray diffraction and ex situ laboratory Mn K-edge XANES data.

Surface Reduction Stabilizes the Single-Crystalline Ni-Rich Layered Cathode for Li-Ion Batteries.

The surface of the layered transition metal oxide cathode plays an important role in its function and degradation. Modification of the surface structure and chemistry is often necessary to overcome the debilitating effect of the native surface. Here, we employ a chemical reduction method using CaI2 to modify the native surface of single-crystalline layered transition metal oxide cathode particles. High-resolution transmission electron microscopy shows the formation of a conformal cubic phase at the particle surface, where the outmost layer is enriched with Ca. The modified surface significantly improves the long-term capacity retention at low rates of cycling, yet the rate capability is compromised by the impeded interfacial kinetics at high voltages. The lack of oxygen vacancy generation in the chemically induced surface phase transformation likely results in a dense surface layer that accounts for the improved electrochemical stability and impeded Li-ion diffusion. This work highlights the strong dependence of the electrode's (electro)chemical stability and intercalation kinetics on the surface structure and chemistry, which can be further tailored by the chemical reduction method.

Spontaneous Lithiation of Binary Oxides during Epitaxial Growth on LiCoO2.

Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. However, interfacial mixing can readily occur and significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here, we show a two-step sequence involving the growth of an epitaxial LiCoO2 cathode layer followed by the deposition of a binary transition metal oxide. Orientation-controlled epitaxial synthesis of the model solid-state-electrolyte Li2WO4 and anode material Li4Ti5O12 occurs as WO3 and TiO2 nucleate and react with Li ions from the underlying cathode. We demonstrate that this lithiation-assisted epitaxy approach can be used for energy materials discovery and exploring different combinations of epitaxial interfaces that can serve as well-defined model systems for mechanistic studies of energy storage and conversion processes.

Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation.

Layered lithium transition metal oxides derived from LiMO2 (M = Co, Ni, Mn, etc.) have been widely adopted as the cathodes of Li-ion batteries for portable electronics, electric vehicles, and energy storage. Oxygen loss in the layered oxides is one of the major factors leading to cycling-induced structural degradation and its associated fade in electrochemical performance. Herein, we review recent progress in understanding the phenomena of oxygen loss and the resulting structural degradation in layered oxide cathodes. We first present the major driving forces leading to the oxygen loss and then describe the associated structural degradation resulting from the oxygen loss. We follow this analysis with a discussion of the kinetic pathways that enable oxygen loss, and then we address the resulting electrochemical fade. Finally, we review the possible approaches toward mitigating oxygen loss and the associated electrochemical fade as well as detail novel analytical methods for probing the oxygen loss.

Could Irradiation Introduce Oxidized Oxygen Signals in Resonant Inelastic X-ray Scattering of Battery Electrodes?

The characterization of oxidized oxygen states through high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) has become a crucial approach for studying the oxygen redox activities in high-energy battery cathodes. However, this approach has been recently challenged due to the concern of irradiation damage. Here we revisited a typical Li-rich electrode, Li1.144Ni0.136Mn0.544Co0.136O2, in both lithiated and delithiated states and evaluated the X-ray irradiation effect in the lengthy mRIXS experiments. Our results show that irradiation cannot introduce any oxidized oxygen feature, and the features of oxidized oxygen are weakened with a high X-ray dose. The results confirm again that mRIXS detects the intrinsic oxidized oxygen state in battery electrodes. However, the distinct irradiation effects in different systems imply that irradiation could selectively target the least stable elemental or chemical states, which should be analyzed with caution in the study of active chemical states.

The morphology of VO2/TiO2(001): terraces, facets, and cracks.

Vanadium dioxide (VO2) features a pronounced, thermally-driven metal-to-insulator transition at 340 K. Employing epitaxial stress on rutile [Formula: see text] substrates, the transition can be tuned to occur close to room temperature. Striving for applications in oxide-electronic devices, the lateral homogeneity of such samples must be considered as an important prerequisite for efforts towards miniaturization. Moreover, the preparation of smooth surfaces is crucial for vertically stacked devices and, hence, the design of functional interfaces. Here, the surface morphology of [Formula: see text] films was analyzed by low-energy electron microscopy and diffraction as well as scanning probe microscopy. The formation of large terraces could be achieved under temperature-induced annealing, but also the occurrence of facets was observed and characterized. Further, we report on quasi-periodic arrangements of crack defects which evolve due to thermal stress under cooling. While these might impair some applicational endeavours, they may also present crystallographically well-oriented nano-templates of bulk-like properties for advanced approaches.

Directly measuring the structural transition pathways of strain-engineered VO2 thin films.

Epitaxial films of vanadium dioxide (VO2) on rutile TiO2 substrates provide a means of strain-engineering the transition pathways and stabilizing of the intermediate phases between monoclinic (insulating) M1 and rutile (metal) R end phases. In this work, we investigate structural behavior of epitaxial VO2 thin films deposited on isostructural MgF2 (001) and (110) substrates via temperature-dependent Raman microscopy analysis. The choice of MgF2 substrate clearly reveals how elongation of V-V dimers accompanied by the shortening of V-O bonds triggers the intermediate M2 phase in the temperature range between 70-80 °C upon the heating-cooling cycles. Consistent with earlier claims of strain-induced electron correlation enhancement destabilizing the M2 phase our temperature-dependent Raman study supports a small temperature window for this phase. The similarity of the hysteretic behavior of structural and electronic transitions suggests that the structural transitions play key roles in the switching properties of epitaxial VO2 thin films.

Elucidating the Mechanistic Origins of Photocatalytic Hydrogen Evolution Mediated by MoS2/CdS Quantum-Dot Heterostructures.

Solar fuel generation mediated by semiconductor heterostructures represents a promising strategy for sustainable energy conversion and storage. The design of semiconductor heterostructures for photocatalytic energy conversion requires the separation of photogenerated charge carriers in real space and their delivery to active catalytic sites at the appropriate overpotentials to initiate redox reactions. Operation of the desired sequence of light harvesting, charge separation, and charge transport events within heterostructures is governed by the thermodynamic energy offsets of the two components and their photoexcited charge-transfer reactivity, which determine the extent to which desirable processes can outcompete unproductive recombination channels. Here, we map energetic offsets and track the dynamics of electron transfer in MoS2/CdS architectures, prepared by interfacing two-dimensional MoS2 nanosheets with CdS quantum dots (QDs), and correlate the observed charge separation to photocatalytic activity in the hydrogen evolution reaction. The energetic offsets between MoS2 and CdS have been determined using hard and soft X-ray photoemission spectroscopy (XPS) in conjunction with density functional theory. A staggered type-II interface is observed, which facilitates electron and hole separation across the interface. Transient absorption spectroscopy measurements demonstrate ultrafast electron injection occurring within sub-5 ps from CdS QDs to MoS2, allowing for creation of a long-lived charge-separated state. The increase of electron concentration in MoS2 is evidenced with the aid of spectroelectrochemical measurements and by identifying the distinctive signatures of electron-phonon scattering in picosecond-resolution transient absorption spectra. Ultrafast charge separation across the type-II interface of MoS2/CdS heterostructures enables a high Faradaic efficiency of ∼99.4 ± 1.2% to be achieved in the hydrogen evolution reaction (HER) and provides a 40-fold increase in the photocatalytic activity of dispersed photocatalysts for H2 generation. The accurate mapping of thermodynamic driving forces and dynamics of charge transfer in these heterostructures suggests a means of engineering ultrafast electron transfer and effective charge separation to design viable photocatalytic architectures.

Simultaneous Structural and Electronic Transitions in Epitaxial VO_{2}/TiO_{2}(001).

Recent reports have identified new metaphases of VO_{2} with strain and/or doping, suggesting the structural phase transition and the metal-to-insulator transition might be decoupled. Using epitaxially strained VO_{2}/TiO_{2} (001) thin films, which display a bulklike abrupt metal-to-insulator transition and rutile to monoclinic transition structural phase transition, we employ x-ray standing waves combined with hard x-ray photoelectron spectroscopy to simultaneously measure the structural and electronic transitions. This x-ray standing waves study elegantly demonstrates the structural and electronic transitions occur concurrently within experimental limits (±1 K).

Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox.

Sensitivity to the "bulk" oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes-Li2MnO3, Li-rich NMC, and NMC 442-that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.

Type-II heterostructures of α-V2O5 nanowires interfaced with cadmium chalcogenide quantum dots: Programmable energetic offsets, ultrafast charge transfer, and photocatalytic hydrogen evolution.

We synthesized a new class of heterostructures by depositing CdS, CdSe, or CdTe quantum dots (QDs) onto α-V2O5 nanowires (NWs) via either successive ionic layer adsorption and reaction (SILAR) or linker-assisted assembly (LAA). SILAR yielded the highest loadings of QDs per NW, whereas LAA enabled better control over the size and properties of QDs. Soft and hard x-ray photoelectron spectroscopy in conjunction with density functional theory calculations revealed that all α-V2O5/QD heterostructures exhibited Type-II band offset energetics, with a staggered gap where the conduction- and valence-band edges of α-V2O5 NWs lie at lower energies (relative to the vacuum level) than their QD counterparts. Transient absorption spectroscopy measurements revealed that the Type-II energetic offsets promoted the ultrafast (10-12-10-11 s) separation of photogenerated electrons and holes across the NW/QD interface to yield long-lived (10-6 s) charge-separated states. Charge-transfer dynamics and charge-recombination time scales varied subtly with the composition of heterostructures and the nature of the NW/QD interface, with both charge separation and recombination occurring more rapidly within SILAR-derived heterostructures. LAA-derived α-V2O5/CdSe heterostructures promoted the photocatalytic reduction of aqueous protons to H2 with a 20-fold or greater enhancement relative to isolated colloidal CdSe QDs or dispersed α-V2O5 NWs. The separation of photoexcited electrons and holes across the NW/QD interface could thus be exploited in redox photocatalysis. In light of their programmable compositions and properties and their Type-II energetics that drive ultrafast charge separation, the α-V2O5/QD heterostructures are a promising new class of photocatalyst architectures ripe for continued exploration.

Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes.

Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2-yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite.

Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na0.27MnO2) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g-1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.

Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation.

Metal-organic frameworks (MOFs) containing redox active linkers have led to hybrid compounds exhibiting high electrical conductivity, which enables their use in applications in electronics and electrocatalysis. While many computational studies predict two-dimensional (2D) MOFs to be metallic, the majority of experiments show decreasing conductivity on cooling, indicative of a gap in the electronic band structure. To date, only a handful of MOFs have been reported that exhibit increased electrical conductivity upon cooling indicative of a metallic character, which highlights the need for a better understanding of the origin of the conductivity. A 2D MOF containing iron bis(dithiolene) motifs was recently reported to exhibit semiconducting behavior with record carrier mobility. Herein, we report that high crystallinity and the elimination of guest species results in an iron 2,3,6,7,10,11-tripheylenehexathiolate (THT) MOF, FeTHT, exhibiting a complex transition from semiconducting to metallic upon cooling, similar to what was shown for the analogous CoTHT. Remarkably, exposing the FeTHT to air significantly influences the semiconducting-to-metallic transition temperature (100 to 300 K) and ultimately results in a material showing metallic-like character at, and above, room temperature. This study indicates these materials can tolerate a substantial degree of doping that ultimately results in charge delocalization and metallic-like conductivity, an important step toward enabling their use in chemiresistive sensing and optoelectronics.

An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research.

X-ray absorption fine structure (XAFS) and x-ray emission spectroscopy (XES) are advanced x-ray spectroscopies that impact a wide range of disciplines. However, unlike the majority of other spectroscopic methods, XAFS and XES are accompanied by an unusual access model, wherein the dominant use of the technique is for premier research studies at world-class facilities, i.e., synchrotron x-ray light sources. In this paper, we report the design and performance of an improved XAFS and XES spectrometer based on the general conceptual design of Seidler et al. [Rev. Sci. Instrum. 85, 113906 (2014)]. New developments include reduced mechanical degrees of freedom, much-increased flux, and a wider Bragg angle range to enable extended x-ray absorption fine structure (EXAFS) measurement and analysis for the first time with this type of modern laboratory XAFS configuration. This instrument enables a new class of routine applications that are incompatible with the mission and access model of the synchrotron light sources. To illustrate this, we provide numerous examples of x-ray absorption near edge structure (XANES), EXAFS, and XES results for a variety of problems and energy ranges. Highlights include XAFS and XES measurements of battery electrode materials, EXAFS of Ni with full modeling of results to validate monochromator performance, valence-to-core XES for 3d transition metal compounds, and uranium XANES and XES for different oxidation states. Taken en masse, these results further support the growing perspective that modern laboratory-based XAFS and XES have the potential to develop a new branch of analytical chemistry.

The Middle Road Less Taken: Electronic-Structure-Inspired Design of Hybrid Photocatalytic Platforms for Solar Fuel Generation.

The development of efficient solar energy conversion to augment other renewable energy approaches is one of the grand challenges of our time. Water splitting, or the disproportionation of H2O into energy-dense fuels, H2 and O2, is undoubtedly a promising strategy. Solar water splitting involves the concerted transfer of four electrons and four protons, which requires the synergistic operation of solar light harvesting, charge separation, mass and charge transport, and redox catalysis processes. It is unlikely that individual materials can mediate the entire sequence of charge and mass transport as well as energy conversion processes necessary for photocatalytic water splitting. An alternative approach, emulating the functioning of photosynthetic systems, involves the utilization of hybrid systems wherein different components perform the various functions required for solar water splitting. The design of such hybrid systems requires the multiple components to operate in lockstep with optimal thermodynamic driving forces and interfacial charge transfer kinetics. This Account describes a new class of nanoscale heterostructures comprising M xV2O5 nanowires, where M is a p-block cation with a ( n - 1) d10 ns2 np0 electronic configuration characterized by a stereoactive lone pair of electrons and x is its stoichiometry, interfaced with II-VI semiconductor quantum dots (QDs). Photocatalytic water splitting involves the transfer of excited-state holes from QDs to mid-gap states (derived from the stereoactive lone pairs of p-block cations) of nanowires, hole transport through nanowires, the reduction of protons at a QD-immobilized catalyst, and water oxidation at an anode. The M xV2O5/QD architectures provide a vast design space for evolutionary optimization of function with considerable tunability of composition and structure of the individual components as well as of the interfacial structure, thereby facilitating programmability of absorption spectra, energetic offsets, and charge-transfer reactivity. The available design space spans choice of the p-block cation M, its stoichiometry x, the composition and size of various QDs, and the nature of the nanowire/QD interface. This multivariate parameter space has been navigated by integrating first-principles modeling, diversified synthesis, spectroscopic measurements, and catalytic evaluation to facilitate the rational design of several generations of heterostructures and the systematic improvement of their photocatalytic performance. The electronic structures of the target heterostructures are predicted by DFT calculations in light of the revised lone pair model of stereoactive structural distortions and evaluated by hard X-ray photoelectron spectroscopy such as to systematically tune the interfacial band offsets. Central to this approach is the development of a topochemical "etch-a-sketch" intercalation approach that allows for facile installation of p-block cations in metastable polymorphs of V2O5. The interfacial charge transfer kinetics of M xV2O5/QD heterostructures is further evaluated by transient absorption spectroscopy to measure excited-state charge-transfer dynamics and is found to depend sensitively on interfacial structure and the thermodynamic driving forces in accordance with Marcus theory. The integration of theory and experiment has allowed for the design of viable photocatalytic architectures exemplified by the exceptional catalytic performance of ß-Pb xV2O5/CdX (X= S, Se) architectures, which has subsequently been elaborated to other lone-pair M xV2O5 compounds, demonstrating the effective exploitation of the opportunities for programmability available in the design space.

Hole Extraction by Design in Photocatalytic Architectures Interfacing CdSe Quantum Dots with Topochemically Stabilized Tin Vanadium Oxide.

Tackling the complex challenge of harvesting solar energy to generate energy-dense fuels such as hydrogen requires the design of photocatalytic nanoarchitectures interfacing components that synergistically mediate a closely interlinked sequence of light-harvesting, charge separation, charge/mass transport, and catalytic processes. The design of such architectures requires careful consideration of both thermodynamic offsets and interfacial charge-transfer kinetics to ensure long-lived charge carriers that can be delivered at low overpotentials to the appropriate catalytic sites while mitigating parasitic reactions such as photocorrosion. Here we detail the theory-guided design and synthesis of nanowire/quantum dot heterostructures with interfacial electronic structure specifically tailored to promote light-induced charge separation and photocatalytic proton reduction. Topochemical synthesis yields a metastable ß-Sn0.23V2O5 compound exhibiting Sn 5s-derived midgap states ideally positioned to extract photogenerated holes from interfaced CdSe quantum dots. The existence of these midgap states near the upper edge of the valence band (VB) has been confirmed, and ß-Sn0.23V2O5/CdSe heterostructures have been shown to exhibit a 0 eV midgap state-VB offset, which underpins ultrafast subpicosecond hole transfer. The ß-Sn0.23V2O5/CdSe heterostructures are further shown to be viable photocatalytic architectures capable of efficacious hydrogen evolution. The results of this study underscore the criticality of precisely tailoring the electronic structure of semiconductor components to effect rapid charge separation necessary for photocatalysis.

Scalable Memdiodes Exhibiting Rectification and Hysteresis for Neuromorphic Computing.

Metal-Nb2O5-x-metal memdiodes exhibiting rectification, hysteresis, and capacitance are demonstrated for applications in neuromorphic circuitry. These devices do not require any post-fabrication treatments such as filament creation by electroforming that would impede circuit scalability. Instead these devices operate due to Poole-Frenkel defect controlled transport where the high defect density is inherent to the Nb2O5-x deposition rather than post-fabrication treatments. Temperature dependent measurements reveal that the dominant trap energy is 0.22 eV suggesting it results from the oxygen deficiencies in the amorphous Nb2O5-x. Rectification occurs due to a transition from thermionic emission to tunneling current and is present even in thick devices (>100 nm) due to charge trapping which controls the tunneling distance. The turn-on voltage is linearly proportional to the Schottky barrier height and, in contrast to traditional metal-insulator-metal diodes, is logarithmically proportional to the device thickness. Hysteresis in the I-V curve occurs due to the current limited filling of traps.