Compositionally complex doping for zero-strain zero-cobalt layered cathodes.

The high volatility of the price of cobalt and the geopolitical limitations of cobalt mining have made the elimination of Co a pressing need for the automotive industry1. Owing to their high energy density and low-cost advantages, high-Ni and low-Co or Co-free (zero-Co) layered cathodes have become the most promising cathodes for next-generation lithium-ion batteries2,3. However, current high-Ni cathode materials, without exception, suffer severely from their intrinsic thermal and chemo-mechanical instabilities and insufficient cycle life. Here, by using a new compositionally complex (high-entropy) doping strategy, we successfully fabricate a high-Ni, zero-Co layered cathode that has extremely high thermal and cycling stability. Combining X-ray diffraction, transmission electron microscopy and nanotomography, we find that the cathode exhibits nearly zero volumetric change over a wide electrochemical window, resulting in greatly reduced lattice defects and local strain-induced cracks. In-situ heating experiments reveal that the thermal stability of the new cathode is significantly improved, reaching the level of the ultra-stable NMC-532. Owing to the considerably increased thermal stability and the zero volumetric change, it exhibits greatly improved capacity retention. This work, by resolving the long-standing safety and stability concerns for high-Ni, zero-Co cathode materials, offers a commercially viable cathode for safe, long-life lithium-ion batteries and a universal strategy for suppressing strain and phase transformation in intercalation electrodes.

Exploring Cr and molten salt interfacial interactions for molten salt applications.

Molten salts play an important role in various energy-related applications such as high-temperature heat transfer fluids and reaction media. However, the extreme molten salt environment causes the degradation of materials, raising safety and sustainability challenges. A fundamental understanding of material-molten salt interfacial evolution is needed. This work studies the transformation of metallic Cr in molten 50/50 mol% KCl-MgCl2via multi-modal in situ synchrotron X-ray nano-tomography, diffraction and spectroscopy combined with density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Notably, in addition to the dissolution of Cr in the molten salt to form porous structures, a δ-A15 Cr phase was found to gradually form as a result of the metal-salt interaction. This phase change of Cr is associated with a change in the coordination environment of Cr at the interface. DFT and AIMD simulations provide a basis for understanding the enhanced stability of δ-A15 Cr vs. bcc Cr, by revealing their competitive phase thermodynamics at elevated temperatures and probing the interfacial behavior of the molten salt at relevant facets. This study provides critical insights into the morphological and chemical evolution of metal-molten salt interfaces. The combination of multimodal synchrotron analysis and atomic simulation also offers an opportunity to explore a broader range of systems critical to energy applications.

Interdependence of Support Wettability -Electrodeposition Rate - Sodium Metal Anode and SEI Microstructure.

This study examines how current collector support chemistry (sodiophilic intermetallic Na2Te vs. sodiophobic baseline Cu) and electrodeposition rate affect microstructure of sodium metal and its solid electrolyte interphase (SEI). Capacity and current (6 mAh cm-2, 0.5-3 mA cm-2) representative of commercially relevant mass loading in anode-free sodium metal battery (AF-SMBs) are analyzed. Synchrotron X-ray nanotomography and grazing-incidence wide-angle X-ray scattering (GIWAXS) are combined with cryogenic focused ion beam (cryo-FIB) microscopy. Highlighted are major differences in film morphology, internal porosity, and crystallographic preferred orientation e.g. (110) vs. (100) and (211) with support and deposition rate. Within the SEI, sodium fluoride (NaF) is more prevalent with Te-Cu versus sodium hydride (NaH) and sodium hydroxide (NaOH) with baseline Cu. Due to competitive grain growth the preferred orientation of sodium crystallites depends on film thickness. Mesoscale modelling delineates the role of SEI (ionic conductivity, morphology) on electrodeposit growth and onset of electrochemical instability.

CLIP-Based Adaptive Graph Attention Network for Large-Scale Unsupervised Multi-Modal Hashing Retrieval.

With the proliferation of multi-modal data generated by various sensors, unsupervised multi-modal hashing retrieval has been extensively studied due to its advantages in storage, retrieval efficiency, and label independence. However, there are still two obstacles to existing unsupervised methods: (1) As existing methods cannot fully capture the complementary and co-occurrence information of multi-modal data, existing methods suffer from inaccurate similarity measures. (2) Existing methods suffer from unbalanced multi-modal learning and data semantic structure being corrupted in the process of hash codes binarization. To address these obstacles, we devise an effective CLIP-based Adaptive Graph Attention Network (CAGAN) for large-scale unsupervised multi-modal hashing retrieval. Firstly, we use the multi-modal model CLIP to extract fine-grained semantic features, mine similar information from different perspectives of multi-modal data and perform similarity fusion and enhancement. In addition, this paper proposes an adaptive graph attention network to assist the learning of hash codes, which uses an attention mechanism to learn adaptive graph similarity across modalities. It further aggregates the intrinsic neighborhood information of neighboring data nodes through a graph convolutional network to generate more discriminative hash codes. Finally, this paper employs an iterative approximate optimization strategy to mitigate the information loss in the binarization process. Extensive experiments on three benchmark datasets demonstrate that the proposed method significantly outperforms several representative hashing methods in unsupervised multi-modal retrieval tasks.

Accelerated Degradation in a Quasi-Single-Crystalline Layered Oxide Cathode for Lithium-Ion Batteries Caused by Residual Grain Boundaries.

The rapidly growing demand of electrical vehicles (EVs) requires high-energy-density lithium-ion batteries (LIBs) with excellent cycling stability and safety performance. However, conventional polycrystalline high-Ni cathodes severely suffer from intrinsic chemomechanical degradation and fast capacity fade. The emerging single-crystallization strategy offers a promising pathway to improve the cathode's chemomechanical stability; however, the single-crystallinity of the cathode is not always guaranteed, and residual grain boundaries (GBs) could persist in nonideal synthesis conditions, leading to the formation of "quasi-single-crystalline" (QSC) cathodes. So far, there has been a lack of understanding of the influence of these residual GBs on the electrochemical performance and structural stability. Herein, we investigate the degradation pathway of a QSC high-Ni cathode through transmission electron microscopy and X-ray techniques. The residual GBs caused by insufficient calcination time dramatically exacerbate the cathode's chemomechanical instability and cycling performance. Our work offers important guidance for next-generation cathodes for long-life LIBs.

Influence of Potassium Metal-Support Interactions on Dendrite Growth.

Combined synchrotron X-ray nanotomography imaging, cryogenic electron microscopy (cryo-EM) and modeling elucidate how potassium (K) metal-support energetics influence electrodeposit microstructure. Three model supports are employed: O-functionalized carbon cloth (potassiophilic, fully-wetted), non-functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo-FIB) cross-sections yield complementary three-dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub-10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore-free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate-metal interaction on K metal film nucleation and growth, as well as the associated stress state.

Chemomechanically Stable Ultrahigh-Ni Single-Crystalline Cathodes with Improved Oxygen Retention and Delayed Phase Degradations.

The pressing demand in electrical vehicle (EV) markets for high-energy-density lithium-ion batteries (LIBs) requires further increasing the Ni content in high-Ni and low-Co cathodes. However, the commercialization of high-Ni cathodes is hindered by their intrinsic chemomechanical instabilities and fast capacity fade. The emerging single-crystalline strategy offers a promising solution, yet the operation and degradation mechanism of single-crystalline cathodes remain elusive, especially in the extremely challenging ultrahigh-Ni (Ni > 90%) regime whereby the phase transformation, oxygen loss, and mechanical instability are exacerbated with increased Ni content. Herein, we decipher the atomic-scale stabilization mechanism controlling the enhanced cycling performance of an ultrahigh-Ni single-crystalline cathode. We find that the charge/discharge inhomogeneity, the intergranular cracking, and oxygen-loss-related phase degradations that are prominent in ultrahigh-Ni polycrystalline cathodes are considerably suppressed in their single-crystalline counterparts, leading to improved chemomechanical and cycling stabilities of the single-crystalline cathodes. Our work offers important guidance for designing next-generation single-crystalline cathodes for high-capacity, long-life LIBs.

Kinetic Limitations in Single-Crystal High-Nickel Cathodes.

High-nickel cathodes attract immense interest for use in lithium-ion batteries to boost Li-storage capacity while reducing cost. For overcoming the intergranular-cracking issue in polycrystals, single-crystals are considered an appealing alternative, but aggravating concerns on compromising the ionic transport and kinetic properties. We report here a quantitative assessment of redox reaction in single-crystal LiNi0.8 Mn0.1 Co0.1 O2 using operando hard X-ray microscopy/spectroscopy, revealing a strong dependence of redox kinetics on the state of charge (SOC). Specifically, the redox is sluggish at low SOC but increases rapidly as SOC increases, both in bulk electrodes and individual particles. The observation is corroborated by transport measurements and finite-element simulation, indicating that the sluggish kinetics in single-crystals is governed by ionic transport at low SOC and may be alleviated through synergistic interaction with polycrystals integrated into a same electrode.

Lanthanide-Binding Tags for 3D X-ray Imaging of Proteins in Cells at Nanoscale Resolution.

We report the application of lanthanide-binding tags (LBTs) for two- and three-dimensional X-ray imaging of individual proteins in cells with a sub-15 nm beam. The method combines encoded LBTs, which are tags of minimal size (ca. 15-20 amino acids) affording high-affinity lanthanide ion binding, and X-ray fluorescence microscopy (XFM). This approach enables visualization of LBT-tagged proteins while simultaneously measuring the elemental distribution in cells at a spatial resolution necessary for visualizing cell membranes and eukaryotic subcellular organelles.

PyXAS - an open-source package for 2D X-ray near-edge spectroscopy analysis.

In the synchrotron X-ray community, X-ray absorption near-edge spectroscopy (XANES) is a widely used technique to probe the local coordination environment and the oxidation states of specific elements within a sample. Although this technique is usually applied to bulk samples, the advent of new synchrotron sources has enabled spatially resolved versions of this technique (2D XANES). This development has been extremely powerful for the study of heterogeneous systems, which is the case for nearly all real applications. However, associated with the development of 2D XANES comes the challenge of analyzing very large volumes of data. As an example, a single 2D XANES measurement at a synchrotron can easily produce ∼106 spatially resolved XANES spectra. Conventional manual analysis of an individual XANES spectrum is no longer feasible. Here, a software package is described that has been developed for high-throughput 2D XANES analysis. A detailed description of the software as well as example applications are provided.

Versatile compact heater design for in situ nano-tomography by transmission X-ray microscopy.

A versatile, compact heater designed at National Synchrotron Light Source-II for in situ X-ray nano-imaging in a full-field transmission X-ray microscope is presented. Heater design for nano-imaging is challenging, combining tight spatial constraints with stringent design requirements for the temperature range and stability. Finite-element modeling and analytical calculations were used to determine the heater design parameters. Performance tests demonstrated reliable and stable performance, including maintaining the exterior casing close to room temperature while the heater is operating at above 1100°C, a homogenous heating zone and small temperature fluctuations. Two scientific experiments are presented to demonstrate the heater capabilities: (i) in situ 3D nano-tomography including a study of metal dealloying in a liquid molten salt extreme environment, and (ii) a study of pore formation in icosahedral quasicrystals. The progression of structural changes in both studies were clearly resolved in 3D, showing that the new heater enables powerful capabilities to directly visualize and quantify 3D morphological evolution of materials under real conditions by X-ray nano-imaging at elevated temperature during synthesis, fabrication and operation processes. This heater design concept can be applied to other applications where a precise, compact heater design is required.

Origin of Plasticity in Nanostructured Silicon.

The mechanism of plasticity in nanostructured Si has been intensively studied over the past decade but still remains elusive. Here, we used in situ high-pressure radial x-ray diffraction to simultaneously monitor the deformation and structural evolution of a large number of randomly oriented Si nanoparticles (SiNPs). In contrast to the high-pressure ß-Sn phase dominated plasticity observed in large SiNPs (∼100 nm), small SiNPs (∼9 nm) display a high-pressure simple hexagonal phase dominated plasticity. Meanwhile, dislocation activity exists in all of the phases, but significantly weakens as the particle size decreases and only leads to subtle plasticity in the initial diamond cubic phase. Furthermore, texture simulations identify major active slip systems in all of the phases. These findings elucidate the origin of plasticity in nanostructured Si under stress and provide key guidance for the application of nanostructured Si.

Anisotropically Electrochemical-Mechanical Evolution in Solid-State Batteries and Interfacial Tailored Strategy.

All-solid-state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid-state batteries, which is largely attributed to the solid-solid interface issues. A fundamental elucidation of electrode-electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid-state battery were probed, revealing a heterogeneous phase transition evolution at solid-solid interfaces. The strain-induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid-state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid-solid interface. Our study enlightens new insights into the mechanism behind solid-solid interfacial reaction for optimizing advanced solid-state batteries.

Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques.

The structure of pristine AgFeO2 and phase makeup of Ag0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO2 and amorphous γ-Fe2O3 phases) was investigated using synchrotron X-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO2 and Ag0.2FeO1.6 were investigated using ex situ, in situ, and operando characterization techniques. An amorphous γ-Fe2O3 component in the Ag0.2FeO1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO2 and Ag0.2FeO1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO2 component. As complimentary techniques to XRD, ex situ X-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in situ high energy X-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag+ to Ag0 and partial reduction of Fe3+ to Fe2+ occur on reduction to 1.0 V, resulting in a Li1+yFeIIIFeIIyO2 phase. The Li1+yFeIIIFeIIyO2 phase can then reversibly cycle between Fe3+ and Fe2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag0.2FeO1.6 composite, a substantial amorphous γ-Fe2O3 component is observed which discharges to rock salt LiFe2O3 and Fe0 metal phase in the 3.5-1.0 V voltage range (in parallel with the AgFeO2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.

Artificial Photosynthesis on TiO2-Passivated InP Nanopillars.

Here, we report photocatalytic CO2 reduction with water to produce methanol using TiO2-passivated InP nanopillar photocathodes under 532 nm wavelength illumination. In addition to providing a stable photocatalytic surface, the TiO2-passivation layer provides substantial enhancement in the photoconversion efficiency through the introduction of O vacancies associated with the nonstoichiometric growth of TiO2 by atomic layer deposition. Plane wave-density functional theory (PW-DFT) calculations confirm the role of oxygen vacancies in the TiO2 surface, which serve as catalytically active sites in the CO2 reduction process. PW-DFT shows that CO2 binds stably to these oxygen vacancies and CO2 gains an electron (-0.897e) spontaneously from the TiO2 support. This calculation indicates that the O vacancies provide active sites for CO2 absorption, and no overpotential is required to form the CO2(-) intermediate. The TiO2 film increases the Faraday efficiency of methanol production by 5.7× to 4.79% under an applied potential of -0.6 V vs NHE, which is 1.3 V below the E(o)(CO2/CO2(-)) = -1.9 eV standard redox potential. Copper nanoparticles deposited on the TiO2 act as a cocatalyst and further improve the selectivity and yield of methanol production by up to 8-fold with a Faraday efficiency of 8.7%.

Capacity retention behavior and morphology evolution of SixGe1-x nanoparticles as lithium-ion battery anode.

Engineering silicon into nanostructures has been a well-adopted strategy to improve the cyclic performance of silicon as a lithium-ion battery anode. Here, we show that the electrode performance can be further improved by alloying silicon with germanium. We have evaluated the electrode performance of SixGe1-x nanoparticles (NPs) with different compositions. Experimentally, SixGe1-x NPs with compositions approaching Si50Ge50 are found to have better cyclic retention than both Si-rich and Ge-rich NPs. During the charge/discharge process, NP merging and Si-Ge homogenization are observed. In addition, a distinct morphology difference is observed after 100 cycles, which is believed to be responsible for the different capacity retention behavior. The present study on SixGe1-x alloy NPs sheds light on the development of Si-based electrode materials for stable operation in lithium-ion batteries (e.g., through a comprehensive design of material structure and chemical composition). The investigation of composition-dependent morphology evolution in the delithiated Li-SiGe ternary alloy also significantly broadens our understanding of dealloying in complex systems, and it is complementary to the well-established understanding of dealloying behavior in binary systems (e.g., Au-Ag alloys).

Solution ionic strength engineering as a generic strategy to coat graphene oxide (GO) on various functional particles and its application in high-performance lithium-sulfur (Li-S) batteries.

A generic and facile method of coating graphene oxide (GO) on particles is reported, with sulfur/GO core-shell particles demonstrated as an example for lithium-sulfur (Li-S) battery application with superior performance. Particles of different diameters (ranging from 100 nm to 10 µm), geometries, and compositions (sulfur, silicon, and carbon) are successfully wrapped up by GO, by engineering the ionic strength in solutions. Importantly, our method does not involve any chemical reaction between GO and the wrapped particles, and therefore, it can be extended to vast kinds of functional particles. The applications of sulfur/GO core-shell particles as Li-S battery cathode materials are further investigated, and the results show that sulfur/GO exhibit significant improvements over bare sulfur particles without coating. Galvanic charge-discharge test using GO/sulfur particles shows a specific capacity of 800 mAh/g is retained after 1000 cycles at 1 A/g current rate if only the mass of sulfur is taken into calculation, and 400 mAh/g if the total mass of sulfur/GO is considered. Most importantly, the capacity decay over 1000 cycles is less than 0.02% per cycle. The coating method developed in this study is facile, robust, and versatile and is expected to have wide range of applications in improving the properties of particle materials.

Large-scale fabrication, 3D tomography, and lithium-ion battery application of porous silicon.

Recently, silicon-based lithium-ion battery anodes have shown encouraging results, as they can offer high capacities and long cyclic lifetimes. The applications of this technology are largely impeded by the complicated and expensive approaches in producing Si with desired nanostructures. We report a cost-efficient method to produce nanoporous Si particles from metallurgical Si through ball-milling and inexpensive stain-etching. The porosity of porous Si is derived from particle's three-dimensional reconstructions by scanning transmission electron microscopy (STEM) tomography, which shows the particles' highly porous structure when etched under proper conditions. Nanoporous Si anodes with a reversible capacity of 2900 mAh/g was attained at a charging rate of 400 mA/g, and a stable capacity above 1100 mAh/g was retained for extended 600 cycles tested at 2000 mA/g. The synthetic route is low-cost and scalable for mass production, promising Si as a potential anode material for the next-generation lithium-ion batteries with enhanced capacity and energy density.

Unrecoverable lattice rotation governs structural degradation of single-crystalline cathodes.

Transitioning from polycrystalline to single-crystalline nickel-rich cathodes has garnered considerable attention in both academia and industry, driven by advantages of high tap density and enhanced mechanical properties. However, cathodes with high nickel content (>70%) suffer from substantial capacity degradation, which poses a challenge to their commercial viability. Leveraging multiscale spatial resolution diffraction and imaging techniques, we observe that lattice rotations occur universally in single-crystalline cathodes and play a pivotal role in the structure degradation. These lattice rotations prove unrecoverable and govern the accumulation of adverse lattice distortions over repeated cycles, contributing to structural and mechanical degradation and fast capacity fade. These findings bridge the previous knowledge gap that exists in the mechanistic link between fast performance failure and atomic-scale structure degradation.

Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries.

Lithium-ion batteries play a crucial role in decarbonizing transportation and power grids, but their reliance on high-cost, earth-scarce cobalt in the commonly employed high-energy layered Li(NiMnCo)O2 cathodes raises supply-chain and sustainability concerns. Despite numerous attempts to address this challenge, eliminating Co from Li(NiMnCo)O2 remains elusive, as doing so detrimentally affects its layering and cycling stability. Here, we report on the rational stoichiometry control in synthesizing Li-deficient composite-structured LiNi0.95Mn0.05O2, comprising intergrown layered and rocksalt phases, which outperforms traditional layered counterparts. Through multiscale-correlated experimental characterization and computational modeling on the calcination process, we unveil the role of Li-deficiency in suppressing the rocksalt-to-layered phase transformation and crystal growth, leading to small-sized composites with the desired low anisotropic lattice expansion/contraction during charging and discharging. As a consequence, Li-deficient LiNi0.95Mn0.05O2 delivers 90% first-cycle Coulombic efficiency, 90% capacity retention, and close-to-zero voltage fade for 100 deep cycles, showing its potential as a Co-free cathode for sustainable Li-ion batteries.