Engineering topics
Xiao, Xianghui
Publications and source records attributed to Xiao, Xianghui.
Integrated rocksalt–polyanion cathodes with excess lithium and stabilized cycling
Co- and Ni-free disordered rocksalt cathodes utilize oxygen redox to increase the energy density of lithium-ion batteries, but it is challenging to achieve good cycle life at high voltages >4.5 V (versus Li/Li + ). Here, in this study, we report a family of Li-excess Mn-rich cathodes that integrates rocksalt- and polyanion-type structures. Following design rules for cation filling and ordering, we demonstrate the bulk incorporation of polyanion groups into the rocksalt lattice. This integration bridges the two primary families of lithium-ion battery cathodes—layered/spinel and phosphate oxides—dramatically enhancing the cycling stability of disordered rocksalt cathodes with 4.8 V upper cut-off voltage. The cathode exhibits high gravimetric energy densities above 1,100 Wh kg -1 and >70% retention over 100 cycles. This study opens up a broad compositional space for developing battery cathodes using earth-abundant elements such as Mn and Fe.
From irregular to regular eutectic growth in the Al-Al 3 Ni system: In situ observations during directional solidification
Here we investigate the irregular eutectic growth dynamics of the Al-Al 3 Ni alloy, in which one of the solid phases (Al 3 Ni) grows faceted from the liquid. Leveraging in situ optical microscopy and synchrotron transmission x-ray microscopy, we address the question of the degree of coupling between Al and Al 3 Ni at the growth front and that of the shape of the microstructures left behind in the bulk solid during directional solidification. Real-time optical observations bring evidence for a morphological transition from a eutectic-grain dependent, irregular eutectic growth at low solidification velocity V (typically 1 μm s -1 ), to a weakly anisotropic, regular growth at higher V ( reaching 10 μm s -1 ). Unprecedented x-ray nano-imaging of the solid–liquid interface, and 3D characterization of the growth patterns, were made possible by a new DS setup at Brookhaven National Laboratory’s NSLS-II. At low V, the leading tips of partly faceted Al 3 Ni crystals are observed to grow not far ahead of the Al growth front. Correlating in situ images and postmortem 3D tomographic reconstructions reveals that the presence of faceted and non-faceted regions of Al 3 Ni crystals in the solid is a direct consequence of coupling and decoupling during DS, respectively. Upon increasing V, the lead distance of Al 3 Ni vanishes, and the shape of Al 3 Ni ceases to be governed by faceted growth. These observations cast light onto the basic mechanisms (faceted growth, diffusive coupling, and the dynamics of trijunctions) governing a faceted to rod-like transition upon increasing V in the Al 3 Ni system, with broad implications to a large class of irregular eutectics.
Elucidating the Transition of 3D Morphological Evolution of Binary Alloys in Molten Salts with Metal Ion Additives
Molten salts serve as effective high-temperature heat transfer fluids and thermal storage media used in a wide range of energy generation and storage facilities, including concentrated solar power plants, molten salt reactors and high-temperature batteries. However, at the salt–metal interfaces, a complex interplay of charge-transfer reactions involving various metal ions, generated either as fission products or through corrosion of structural materials, takes place. Simultaneously, there is a mass transport of ions or atoms within the molten salt and the parent alloys. The precise physical and chemical mechanisms leading to the diverse morphological changes in these materials remain unclear. Here, to address this knowledge gap, this work employed a combination of synchrotron X-ray nanotomography and electron microscopy to study the morphological and chemical evolution of Ni-20Cr in molten KCl-MgCl 2 , while considering the influence of metal ions (Ni 2+ , Ce 3+ , and Eu 3+ ) and variations in salt composition. Our research suggests that the interplay between interfacial diffusivity and reactivity determines the morphological evolution. The summary of the associated mass transport and reaction processes presented in this work is a step forward toward achieving a fundamental comprehension of the interactions between molten salts and alloys. Overall, the findings offer valuable insights for predicting the diverse chemical and structural alterations experienced by alloys in molten salt environments, thus aiding in the development of protective strategies for future applications involving molten salts.
Ultrastable cathodes enabled by compositional and structural dual-gradient design
Cathodes for next-generation batteries are pressed for higher voltage operation (≥4.5 V) to achieve high capacity with long cyclability and thermal tolerance. Current cathodes fail to meet these requirements owing to structural and electrochemical strains at high voltages, leading to fast capacity fading. Here, in this work, we present a cathode with a coherent architecture ranging from ordered to disordered frameworks with concentration gradient and controllable Ni oxidation activities, which can overcome voltage ceilings imposed by existing cathodes. This design enables simultaneous high-capacity and high-voltage operation at 4.5 V without capacity fading, and up to 4.7 V with negligible capacity decay. Multiscale diffraction and imaging techniques reveal the disordered surface is electrochemically and structurally indestructible, preventing surface parasitic reactions and phase transitions. Structural coherence from ordering to disordering limits lattice parameter changes, mitigating lattice strain and enhancing morphological integrity. The dual-gradient design also notably improves thermal stability, driving the advancement of high-performance cathode materials.
A Green, Fire–Retarding Ether Solvent for Sustainable High–Voltage Li–Ion Batteries at Standard Salt Concentration
Lithium-ion batteries (LIBs) are increasingly encouraged to enhance their environmental friendliness and safety while maintaining optimal energy density and cost-effectiveness. Although various electrolytes using greener and safer glyme solvents have been reported, the low charge voltage (usually lower than 4.0 V vs Li/Li + ) restricts the energy density of LIBs. Herein, tetraglyme, a less-toxic, non-volatile, and non-flammable ether solvent, is exploited to build safer and greener LIBs. It is demonstrated that ether electrolytes, at a standard salt concentration (1 m), can be reversibly cycled to 4.5 V vs Li/Li + . Anchored with Boron-rich cathode-electrolyte interphase (CEI) and mitigated current collector corrosion, the LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode delivers competitive cyclability versus commercial carbonate electrolytes when charged to 4.5 V. Synchrotron spectroscopic and imaging analyses show that the tetraglyme electrolyte can sufficiently suppress the overcharge behavior associated with the high-voltage electrolyte decomposition, which is advantageous over previously reported glyme electrolytes. The new electrolyte also enables minimal transition metal dissolution and deposition. NMC811||hard carbon full cell delivers excellent cycling stability at C/3 with a high average Coulombic efficiency of 99.77%. In conclusion, this work reports an oxidation-resilient tetraglyme electrolyte with record-high 4.5 V stability and enlightens further applications of glyme solvents for sustainable LIBs by designing Boron-rich interphases.
In Situ and Operando Observation of Zinc Moss Growth and Dissolution in Alkaline Electrolyte for Zinc–Air Batteries
As a promising battery technology, zinc–air batteries still face significant challenges, including the formation of a mossy structure on the zinc metal anode in alkaline electrolyte. Because a similar phenomenon also plagues lithium and sodium metal batteries, elucidating its mechanism has important implications for progress in energy storage. Herein, operando X-ray nanotomography was employed to visualize zinc moss growth and dissolution at the individual colony level. By tracking its microstructure evolution, zinc moss was found to display irreversible plating/stripping behavior. While zinc moss exhibits self-limiting growth and zinc deposition occurs mainly in its outer region, zinc dissolution is more uniformly distributed inside the moss colony upon stripping, leading to the formation of “dead” zinc and capacity loss. A direct correlation is established between the moss amount and zinc plating/stripping efficiency. Finally, results from this study offer new insights into mitigating the unstable zinc plating morphology and improving the cycle life of aqueous zinc–air batteries.
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. Here, 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.
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–MgCl 2 via 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. Finally, the combination of multimodal synchrotron analysis and atomic simulation also offers an opportunity to explore a broader range of systems critical to energy applications.
Cross-length-scale investigation reveals the spatial thermo-chemical dynamics hidden in Ni-rich layered Li-ion cathodes
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The pore structure and water absorption in Portland/slag blended hardened cement paste determined by synchrotron X-ray microtomography and neutron radiography
The development of the pore structures of hardened Portland/slag cement pastes for sample ages up to 1 year, and the absorption of moisture through these pores, are monitored and quantified using X-ray and neutron techniques.
High‐Nickel Heterostructured Cathodes with Local Stoichiometry Control for High‐Voltage Operation
The growing demand for lithium‐ion batteries to power electric vehicles and other energy‐dense devices continues to fuel the need for cathodes of increasingly higher nickel in cathodes. The relentless pursuit of high Ni content, however, raises concerns on compromising cell lifetime and safety, especially under high‐voltage operation. Alternative to the traditional design of uniform or core–shell composition, we report a rational control of local stoichiometry in high‐Ni cathodes, enabling their high thermal and cycling stabilities—up to 258 °C at the fully charged state and 91.4% capacity retention for 100 cycles between 2.7 and 4.4 V. Multimodal synchrotron X‐ray characterization unveils the heterostructure of secondary particles, featuring a high‐Ni core (LiNi 0.90 Mn 0.05 Co 0.05 O 2 ) covered by a thin Ni‐gradient layer that remains stable over prolonged cycling due to suppressed oxygen release and structural deterioration. This work underlines, the intricate interplay between local stoichiometry and redox reactions in stabilizing high‐Ni cathodes for high‐voltage operation while ensuring safety.
Convolutional Neural Network for Segmenting Micro-X-ray Computed Tomography Images of Wood Cellular Structures
To further enhance the performance of wood products, improved tools are needed to study in situ cellular scale phenomena like mechanical deformations and moisture swelling. Micro-X-ray computed tomography (μXCT) using brilliant synchrotron light sources now has the spatial and temporal resolution for real-time visualization of phenomena in three-dimensional cellular structures. However, the tradeoff for speed includes the loss of intensity contrast between different types of materials within the imaged structure, such as cell wall and air in wood. This loss of contrast prevents traditional histogram-based segmentation methods from being used effectively. A new convolutional neural network (CNN) approach was therefore developed to segment fast μXCT images of wood into cell wall and air volumes. The fast μXCT and segmentation were demonstrated in the study of moisture swelling in loblolly pine (Pinus taeda) earlywood and latewood cellular structures conditioned at 0%, 33%, 75%, and 95% relative humidity (RH). The CNN segmentation results had a mean intersection over union (IoU) metric accuracy of 96%. Initial analysis of the swelling in the latewood revealed cell walls swelled about 25% when conditioned from 0% to 95% RH. Additionally, the widths of ray cell lumina in the transverse plane of latewood could be observed to increase at higher RH. The segmentation method presented here will facilitate future quantitative analyses in in situ μXCT studies of wood and other similar cellular materials.
Nanotomography Investigation of 3D Printed Batteries with a Water-in-Salt Gel Polymer Electrolyte
3D printing, also known as additive manufacturing, has emerged as a promising strategy to design and fabricate future energy storage devices. Although significant progress has been reported, current 3D printed battery designs are still limited by the choice of the electrolyte, such as ceramic or conventional toxic organic electrolytes. Here, we incorporated the latest developments in aqueous batteries into a novel 3D printable battery that can be fabricated directly in an ambient environment that is also more environmentally friendly. Specifically, a gel polymer electrolyte with a water-in-salt concept was introduced in our 3D-printed batteries. Combining their advantages, the resulting 3D printable batteries show promise for much simplified processing conditions. Further, the structural, (electro-)chemical, and morphological evolution batteries are being investigated by synchrotron X-ray nanotomography and electrochemical analysis. Overall, our research explores the possibility of an easier and more environmentally friendly way to build 3D printable, customizable batteries for future technologies.
Temperature-Dependent Morphological Evolution during Corrosion of the Ni-20Cr Alloy in Molten Salt Revealed by Multiscale Imaging
Understanding the mechanisms leading to the degradation of alloys in molten salts at elevated temperatures is significant for developing several key energy generation and storage technologies, including concentrated solar and next-generation nuclear power plants. Specifically, the fundamental mechanisms of different types of corrosion leading to various morphological evolution characteristics for changing reaction conditions between the molten salt and alloy remain unclear. Here, in this work, the three-dimensional (3D) morphological evolution of Ni–20Cr in KCl–MgCl 2 is studied at 600 °C by combining in situ synchrotron X-ray and electron microscopy techniques. By further comparing different morphology evolution characteristics in the temperature range of 500–800 °C, the relative rates between diffusion and reaction at the salt–metal interface lead to different morphological evolution pathways, including intergranular corrosion and percolation dealloying. In this work, the temperature-dependent mechanisms of the interactions between metals and molten salts are discussed, providing insights for predicting molten salt corrosion in real-world applications.
Heterogeneous 3D Morphological Evolution of Ni Microparticles in Molten Salts: Visualized by Operando Synchrotron X-ray Nano-tomography
Ni-based superalloys are promising materials for high-temperature molten salt (MS) energy generation and storage. Studying morphological and chemical evolution of pure Ni in MS provides fundamental knowledge for MS technologies and corrosion mitigation. Here, in this study, real-time 3D morphological changes of Ni microparticles in molten KCl-MgCl 2 were studied by operando synchrotron X-ray nano-tomography at 700°C. Rapid Ni particle agglomeration occurred, without significant chemical reactions, such as oxide or chloride formation. The morphological growth evolved differently from classical coarsening or sintering behaviors and occurred nonuniformly, with other regions showing slight dissolution of Ni. Ni nanoparticles were found to be dispersed in many areas of the samples, either from microparticle dissolution or other radiation-induced nanoparticle formation mechanisms. This study discusses important factors, i.e., thermal gradient, amounts of salt and metals, and radiation effect, that influence morphological changes of materials in MS, critical for fundamental understanding of material–MS interactions as well as for practical applications.
Unveiling the Mechanical and Electrochemical Evolution of Nanosilicon Composite Anodes in Sulfide-Based All-Solid-State Batteries
The utilization of silicon anodes in all-solid-state lithium batteries provides good prospects for facilitating high energy density. However, the compatibility of sulfide solid-state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. Here, in this paper, operando X-ray absorption near-edge structure (XANES) spectroscopy, ex situ scanning electron microscopy (SEM), and ex situ X-ray nanotomography (XnT) are utilized to investigate the chemistry and structure evolution of nano-Si composite anodes. Results from XANES demonstrate a partial decomposition of SEs during the first lithiation stage, which is intensified by the presence of carbon. Nevertheless, the performances of first three cycles in Si–SE–C are stable, which proves that the generated media is ionically conductive. XnT and SEM results show that the addition of SEs and carbon improves the structural stability of the anode, with fewer pores and voids. A chemo-elasto-plastic model reveals that SEs and carbon buffer the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enables the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and a better rate than pure Si and Si composite anodes with only SEs.
Pre-zeolite framework super-MIEC anodes for high-rate lithium-ion batteries
New physical insights and a robust approach are provided to develop super-MIEC anodes for high-rate batteries, which would bridge two materials families—nanoporous framework materials and conductive oxides.