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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18

Fluorinated Rocksalt‐Polyanion Cathode for Lithium‐Ion Batteries

Integrated rocksalt‐polyanion cathodes (DRXPS) are promising candidates for next‐generation lithium‐ion battery cathode materials that combine high energy density, stable cycling performance, and reduced reliance on Co and Ni. In this work, we investigated Li 3 Mn 1.6 P 0.4 O 5.4 F 0.6 , a new DRXPS cathode with fluoride incorporation. A pure spinel phase was formed and a discharge capacity retention of 84% was achieved after 200 cycles between 1.5 and 4.8 V versus Li/Li + . In comparison, the similarly synthesized Li 3 Mn 1.6 Nb 0.4 O 5.4 F 0.6 , in which all P 5+ was substituted by Nb 5+ while maintaining the same stoichiometry for all other elements, crystallized in a disordered rocksalt structure, and exhibited inferior capacity retention and rate capability than the P 5+ counterpart. Our findings expand the compositional space of DRXPS to include F − , justify the viability of integrating polyanion groups in rocksalt‐type cathodes, and highlight the superiority of P 5+ as a cation charge compensator compared to the commonly used Nb 5+ . This work thereby advances the design of robust, high‐performance cathode materials for sustainable batteries.

36 MATERIALS SCIENCE↗

A Mössbauer Spectroscopy Investigation of Nickel‐Zinc Ferrites Synthesized by a Self‐Combustion Method for Soft Magnetic Core Applications

Soft ferrites are materials of interest for magnetic cores, as used for wireless charging transformers. Their low permeabilities, high resistivity, and magnetic polarization make them interesting for high-power electric vehicle charging and drive systems. The nickel-zinc-doped ferrites are of particular interest; however, the compositional space is quite large with respect to dopant concentrations, stoichiometric ratios and synthesis technique. Nickel-zinc spinel ferrites with varying nickel-zinc ratios prepared by a self-combustion reaction followed by heat treatment exhibit good crystallinity, and their low-temperature Mössbauer spectra show local magnetism and site occupation in agreement with materials prepared by solid-state reaction. Thus, the combustion synthesis method offers a facile tunability of compositions, which, combined with the possibility of rapid characterization of atomic-scale magnetism by Mössbauer spectroscopy, enables advances in the compositional and processing space at a fast pace. Low-temperature Mössbauer spectroscopy data for samples with increasing nickel content reveals a systematic increase in average hyperfine field (2.8 T/Ni) and decrease in average isomer shift (−0.036 mm/s/Ni) that can determine the nickel/zinc content, even in the absence of applied magnetic field data. Furthermore, a gradual evolution of color is also observed with increasing nickel content, albeit trends in color depend on sintering conditions.

Mössbauer spectroscopy↗

3D LiMn 2 O 4 nThin Film Deposited by ALD: A Road toward High-Capacity Electrode for 3D Li-Ion Microbatteries

Miniaturized electronics suffer from a lack of energy autonomy. In that context, the fabrication of lithium-ion solid-state microbatteries with high performance is mandatory for powering the next generation of portable electronic devices. Here, the fabrication of a thin film positive electrode for 3D Li-ion microbatteries made by the atomic layer deposition (ALD) method and in situ lithiation step is demonstrated. The 3D electrodes based on spinel LiMn 2 O 4 films operate at high working potential (4.1 V vs Li/Li + ) and are capable of delivering a remarkable surface capacity (approximate to 180 mu Ah cm -2 ) at low C-rate while maintaining more than 40 mu Ah cm -2 at C/2 (time constant = 2 h). Both the thickness of the electrode material and the 3D gain of the template are carefully tuned to maximize the electrode performance. Further, advanced characterization techniques such as transmission electron and X-ray transmission microscopies are proposed as perfect tools to study the conformality of the deposited films and the interfaces between each layer: no interdiffusion or segregation are observed. This work represents a major issue towards the fabrication of 3D-lithiated electrode by ALD-without any prelithiation step by electrochemical technique-making it an attractive solution for the fabrication of 3D Li-ion solid-state microbatteries with semiconductor processing methods.

3D Li-ion micro-batteries↗

A Low-Voltage Layered Na 2 TiGeO 5 Anode for Lithium-Ion Battery

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. In this work, a titanium-based oxide of Na 2 TiGeO 5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g –1 with a current density of 50 mA g –1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na 2 TiGeO 5 anode material high security compared with graphite and high energy density compared with spinel Li 4 Ti 5 O 12 . Combining the electrochemical tests and the density functional theory calculations, the Li + storage mechanism of Na 2 TiGeO 5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

25 ENERGY STORAGE↗

Direct Nano‐Synthesis Methods Notably Benefit Mg‐Battery Cathode Performance

Abstract Rechargeable magnesium batteries are promising candidates for next‐generation electrochemical energy storage, but their development is severely hindered by sluggish solid‐state diffusion and significant desolvation penalties of the divalent cation. Studies suggest that nano‐sized electrode materials alleviate these issues by shortening diffusion lengths and increasing electrode/electrolyte interaction. Here, the effect of particle size and synthetic methodology on the electrochemical performance of four sulfide cathode materials in Mg batteries is investigated: layered TiS 2 , CuS, spinel Ti 2 S 4 , and CuCo 2 S 4 . In these sulfide hosts, the direct preparation of nano‐dimensional crystallites is critical to activate or improve electrochemistry. Even promising cathode materials can appear electrochemically inert when micron‐sized particles are investigated (e.g., CuCo 2 S 4 ), and mechanical milling leads to surface degradation of active material which severely limits performance. However, nano‐sized CuCo 2 S 4 prepared directly reaches a capacity nearly double that of ball‐milled material and delivers 350 mAh g −1 at 60 °C. This work provides synthetic considerations which may be crucial in the discovery and design of novel Mg cathode materials, so that promising candidates are not overlooked. By extension, in oxide materials where Mg 2+ diffusion is expected to be much more sluggish, this factor is anticipated to be even more important when screening for new hosts.

Blanc, Lauren E.↗

Oxidation Behavior of Candidate NiCr Alloys for Engine Exhaust Valves: Part I—Effect of Minor Alloying Elements

Oxidation-induced degradation of structural materials employed as exhaust valves within internal combustion engines (ICEs) will be a relevant life-limiting mechanism, in addition to creep and mechanical fatigue, due to ever-increasing severity of operating temperatures and pressures. Ni–Cr-based alloys, which form external chromia-based scales at the relevant operating temperatures are being considered as suitable candidate materials. Thermal cycling of these alloys in water vapor-containing atmospheres, such as those present during hydrocarbon fuel combustion within ICEs, can considerably influence their oxidation behavior. Here, the role of typical alloying additions such as Mn, Si, Al and Ti on the cyclic oxidation behavior of model NiCr–X (X = Mn,Si,Al,Ti) alloys exposed in dry air and air + 10% H 2 O at 800°C and 950°C was investigated. Combined additions of Mn and Si reduced scaling rates compared to binary Ni–22Cr alloys. The presence of water vapor possibly suppressed formation of NiMnCr spinel and thereby the Cr depletion in the alloy. Combined Al and Ti additions mainly resulted in accelerated oxidation kinetics due to the Ti doping of chromia scales. More porous external scales were observed in water vapor leading to a much deeper depth of nitridation in the Ni–22Cr–Al–Ti alloys.

36 MATERIALS SCIENCE↗

Mechanical and Corrosion Response of 316SS in Supercritical CO 2

The supercritical carbon dioxide (s-CO 2 ) Brayton cycle is currently being explored as a replacement for the steam Rankine cycle due to its potential for higher efficiency and lower cycle cost. 316 stainless steel is a candidate alloy for use in s-CO 2 up to roughly 600 °C, but the mechanical effects of prolonged exposure of base and welded material in s-CO 2 have not been analyzed. The potential for carburization makes this an important concern for the implementation of 316 and similar austenitic stainless steels in the s-CO 2 environment. In this study, welded and base material of two types of 316–316L and 316H–were exposed in either s-CO 2 or argon at 550 °C or 750 °C for 1000 h. 550 °C s-CO 2 exposure yielded a thin (< 1 µm) Cr oxide with occasional nodules of duplex Fe oxide and Fe–Cr spinel that were up to 5 microns thick. However, tensile results from s-CO –2 exposure matched those of 550 °C thermal aging in Ar, indicating that no mechanically detrimental carburization occurred in either 316 variant after 1000 h exposure. Conversely, 750 °C s-CO 2 exposure produced roughly 10 × the oxide thickness, with a more substantial Fe oxide (3–5 µm) on the majority of the surface and nodules of up to 40 µm thick. In comparison to aged samples, tensile testing of 750 °C CO 2 -exposed samples revealed ductility loss attributed to carburization. As a result, projections of 316L performance in s-CO 2 indicate that mechanically detrimental carburization—equal to that shown here for 750 °C, 1000 h—will likely be present after 7–14 years of service at 550 °C.

316 stainless steel↗

Characteristics of Nozzle Clogging and Evolution of Oxide Inclusion for Al-Killed Ti-Stabilized 18Cr Stainless Steel

Characteristics of nozzle clogging and evolution of oxide inclusion were studied by sampling the deposits of submerged entry nozzle (SEN) and the molten steel in tundish during Al-killed Ti-stabilized 18Cr stainless steelmaking process. The deposits found in the clogging of SEN were mainly composed of frozen steel and inclusions. The inclusions in the deposits and tundish were both mainly (MgO-Al{sub 2}O{sub 3}){sub rich}-CaO-TiO{sub x}. The compositions of most inclusions were Liquid+Spinel or Liquid+TiSp phase. The (MgO-Al{sub 2}O{sub 3}){sub rich}-CaO inclusions that were not effectively modified by calcium treatment could be a source of clogging. By combining both the experimental results and thermodynamic calculation, (MgO-Al{sub 2}O{sub 3}){sub rich}-TiO{sub x} inclusions (TiSp inclusions) would be formed with the decreasing temperature in steel during continuous casting, which could be transported and accumulated on the inner wall of the SEN. Increasing the calcium content in the molten steel could decrease the formation of TiSp inclusions. During continuous casting, these inclusions accumulated on the inner wall of the SEN and gradually formed porous network of clog. Molten steel would gradually solidify in the porous space of the clog due to the increased residence time of the molten steel when flowing through it. The clogging gradually increased and caused the shutdown of continuous casting.

36 MATERIALS SCIENCE↗

Magneto-structural and induction heating properties of MFe2O4 (M?=?Co, Mn, Zn) MNPs for magnetic particle hyperthermia application

The thermal decomposition approach was used for the synthesis of MFe2O4 magnetic nanoparticles (MNPs) by substituting M as Co, Mn, and Zn. The obtained MNPs were characterized for magneto-structural properties using X-Ray diffraction patterns, FTIR, Raman and Mossbauer spectroscopy techniques which confirm the formation of phase pure cubic spinel ferrite with space group Fd3m and five Raman active modes. The size, morphology, and compositional analysis was performed using HRTEM and EDX where the size of MNPs was found to be less than 10 nm that attains superparamagnetism. The magnetic hyperthermia performance of obtained MNPs was evaluated by induction heating experiments at magnetic field range 13.3 to 26.7 kAm-1. The specific absorption rate (SAR) and intrinsic loss power (ILP) values were determined at different magnetic fields within the human tolerable range and correlated with magneto-structural properties to evaluate its potential for possible magnetic particle hyperthermia therapy.

Magnetic nanoparticles, complex-decomposition, mag↗

Designing shape-memory-like microstructures in intercalation materials

During the reversible insertion of ions, lattices in intercalation materials undergo structural transformations. These lattice transformations generate misfit strains and volume changes that, in turn, contribute to the structural decay of intercalation materials and limit their reversible cycling. In this paper, we draw on insights from shape-memory alloys, another class of phase transformation materials, that also undergo large lattice transformations but do so with negligible macroscopic volume changes and internal stresses. We develop a theoretical framework to predict structural transformations in intercalation compounds and identify crystallographic design rules necessary for forming shape-memory-like microstructures in intercalation materials. We use our approach to systematically screen open-source structural databases comprising $n$ > 5000 pairs of intercalation compounds. We identify candidate compounds, such as Li x Mn 2 O 4 (Spinel), Li x Ti 2 (PO 4 ) 3 (NASICON), that approximately satisfy the crystallographic design rules and can be precisely doped to form shape-memory-like microstructures. Throughout, we compare our analytical results with experimental measurements of intercalation compounds. We find a direct correlation between structural transformations, microstructures, and increased capacity retention in these materials. These results, more generally, show that crystallographic designing of intercalation materials could be a novel route to discovering compounds that do not decay with continuous usage.

36 MATERIALS SCIENCE↗

Modification of LiMn 2 O 4 surfaces by controlling the Acid–Base surface chemistry of atomic layer deposition

In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al 2 O 3 coatings on spinel LiMn 2 O 4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid-base properties, were used to establish trends in the ALD Al 2 O 3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid-base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al 2 O 3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al 2 O 3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. Finally, we show how the ligand acid-base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fischer-Tropsch synthesis: Direct cobalt nitrate reduction of promoted Co/Al 2 O 3 catalysts

Direct reduction of cobalt nitrate versus conventional calcination/reduction treatment was conducted using alumina with identical methodology as previously applied to SiO 2 and TiO 2 . Similar BET surface areas, pore volumes and pore size distributions were obtained for the activated calcined and uncalcined catalysts indicating no significant difference on morphological properties. However, the reducibility slightly increases and Co crystallite size is smaller for activated uncalcined samples. Reduction phenomena were analyzed by TPR-MS and TPR-EXAFS/XANES. Combining these techniques allows an explanation of the complex phenomena occurring during the direct reduction of cobalt nitrate, as both nitrate decomposition and cobalt oxide reduction are involved. Cobalt nitrate species are converted to CoO x intermediates. These species are oxidized by NO X (from nitrate decomposition) to Co 3 O 4 spinel, which is converted to CoO prior to Co 0 formation. Noble metals (Pt, Re, Ru and Ag) improve cobalt oxide reducibility, especially for the final reduction step (i.e., CoO to Co 0 ). The effect of direct nitrate reduction on FT activity was investigated using a 1 L CSTR. Activated unpromoted and Pt-promoted uncalcined catalysts achieved higher initial and steady-state CO conversions in comparison to the corresponding calcined catalysts. The best performance was achieved with direct reduction of uncalcined 0.5%Pt-25%Co/Al 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Co doping on the structure and physicochemical properties of hausmannite (Mn 3 O 4 ) and its transformation during aging

Hausmannite is a common low-valence manganese oxide mineral with a distorted spinel structure in surficial sediments. Although natural Mn oxides often contain various transition metal (TM) impurities, few studies have addressed the substitution mechanisms of TMs, such as cobalt (Co), with hausmannite and induced changes in the mineral physicochemical properties. In this study, Co-doped hausmannites with final Co/Mn molar ratios of 0.05 and 0.11 were synthesized and characterized by wet chemical analysis, powder X-ray diffraction (XRD), Fourier transformed infrared spectra (FTIR), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure spectroscopy (XAFS). Co-doped samples have larger crystallite sizes and smaller specific surface areas than those of the hausmannite without Co. The Co cations exist in a mixed-valence of +3 and + 2. Powder XRD and acid dissolution experiments indicate that Co incorporates into the mineral structures, and increases the mineral structural stability. Co K-edge extended X-ray adsorption fine structure (EXAFS) analysis demonstrates that Co likely substitutes for lattice Mn(III). After aging at room temperature for three years, 14.1 ± 1.9% of pure hausmannite is transformed to manganite while only 2.6 ± 0.7% of manganite appears in the aged Co-doped sample with an initial Co/Mn molar ratio of 0.10. Finally, these results provide new insights into the incorporation mechanisms of TMs into low valence Mn oxides, and the stability of these minerals in natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating

The effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating was studied by performing a series of tests with deposits of Na 2 SO 4 , Na 2 SO 4 -20 %K 2 SO 4 and Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 (mol.% for all) at 700 °C in air with addition of SO 2 . For elucidating the observed corrosion phenomena, various salt-oxide/NiAl powder mixtures were exposed to the same hot corrosion test conditions. Two pseudo-binary phase diagrams of the Na, K, Mg-sulphate systems were calculated using an in-house developed thermodynamic database. Addition of MgSO 4 to Na 2 SO 4 -20 %K 2 SO 4 deposit salt inhibited the hot corrosion attack during 24 h exposure, which is related to consumption of aggressive K 2 SO 4 by the formation of solid K 2 Mg 2 (SO 4 ) 3 . However, extending the exposure with Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 deposit to 100 h resulted in severe corrosion attack. The latter observation is explained by a reaction between K 2 Mg 2 (SO 4 ) 3 and NiAl causing formation of a Mg, Ni and Al containing spinel accompanied by release of the aggressive K 2 SO 4 into the liquid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Void Formation and Self-Healing in Oxide Scales on Al-containing High-Entropy Alloy

The exceptional high-temperature oxidation resistance of Al-containing high-entropy alloys (HEAs) is often attributed to the formation of a protective α-Al 2 O 3 scale. However, the dynamic, atomic-scale mechanisms governing the stability of this scale—including interfacial void formation and the often-postulated but rarely visualized “self-healing” capacity—remain poorly understood. Herein, we reveal the complex evolution of the triple-layer oxide scale on an Al 10 CoCrFeNi HEA through combined electron microscopy and diffraction study. We show that interfacial voids are an inherent consequence of the scaling process, originating from two distinct mechanisms: the Kirkendall effect at the interface between the γ-Al 2 O 3 /α-Al 2 O 3 and alloy driven by cationic diffusion imbalance and volumetric contraction due to phase transformations at the spinel/Cr 2 O 3 interface. Crucially, we provide microstructural evidence consistent with an intrinsic self-healing response. This process is driven by coupled inward diffusion of oxygen and outward diffusion of metal cations, leading to the in-situ formation of transient θ-Al 2 O 3 and spinel phases that partially fill and seal the voids. Here, these results provide atomic-scale insights into the phase evolution, defect formation, and self-repair of oxide scales in HEAs—highlighting pathways to enhance their oxidation resistance in extreme environments.

High-entropy alloy↗

Effect of crystallite size on lithium storage performance of high entropy oxide (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 nanoparticles

High-entropy oxides (HEOs), known for their high theoretical capacity and structural stability, are considered promising anode materials for next-generation lithium-ion batteries (LIBs). In this research, we synthesized a novel spinel-type HEO, (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 , using a solution combustion method. By adjusting the quantity of the combustion agent, we produced samples with varying crystallite sizes. The crystallite size of the HEOs initially enlarges with an increased combustion agent, then diminishes. The enhancement of crystallite size correlates with improved electrochemical performance for lithium storage. Notably, the (Cr 0.2 Mn 0.2 Co 0.2 Ni 0.2 Zn 0.2 ) 3 O 4 nanoparticles, with the largest crystallite size of 36.3 nm, demonstrated a reversible capacity of 343 mA h g -1 after 100 cycles at 100 mA g -1 , a capacity retention to 319 mA h g -1 after 1000 cycles at 1 A g -1 , and a commendable rate capability of 260 mA h g -1 at 2 A g -1 . Furthermore, this study underscores the pivotal role of crystallite size in LIB performance and presents a viable strategy to enhance the lithium storage capabilities of HEOs and other metal oxides.

25 ENERGY STORAGE↗

Simultaneous Single Crystal Growth and Segregation of Ni-Rich Cathode Enabled by Nanoscale Phase Separation for Advanced Lithium-Ion Batteries

Here, a novel nanoscale phase separation process has been discovered to promote the growth and segregation of single-crystal LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811). This process occurs directly during high-temperature calcination without significant agglomeration. The key lies in converting transition metal hydroxide (TM(OH) 2 ) precursors with well-controlled morphology into transition metal oxide (TMO) intermediates before reacting them with lithium salt. The nanoscale redistribution of Ni in TMO, resulting from the concurrent formation of spinel and rock salt phases, helps to deagglomerate the clusters of later-formed NMC811 crystals. The as-prepared single-crystal NMC811 is further validated in a 2Ah pouch cell, demonstrating 1,000 stable cycles. The fundamentally new reaction mechanism of single-crystal growth and segregation provides a new direction for large-scale synthesis of a broad range of single crystals for advanced energy storage.

25 ENERGY STORAGE↗

Surface Engineering Strategy to Synthesize Bicomponent Carbons for Rechargeable Zinc-Air Batteries

Atomic Fe-N x moieties and nanosized FeCo species anchored on carbons have each been demonstrated to be among the most effective active components for oxygen reduction and evolution reactions (ORR/OER), respectively in rechargeable zinc -air batteries (ZABs). However, incorporating both of these components in a single catalyst presents a great challenge due to the trade-off in formation between them during hightemperature preparation. Herein, we integrate them into a bicomponent carbon through a surface engineering strategy. In this process, K 3 [Fe(CN) 6 ] is engineered on the surface of a precursor mixture consisting of polyaniline-coated graphene oxide and ZIF-67. This is followed by pyrolysis to produce the bicomponent carbon catalyst of FeCo nanoparticles modified carbon polyhedron (for accelerating the OER), supported on atomically dispersed Fe -N -doped carbon nanosheet (for boosting the ORR). The catalyst exhibits a small potential gap of 0.69 V for OER/ORR. In situ Raman spectroscopy demonstrates that spinel FeCo oxides may be responsible for OER. The use of this catalyst in ZABs achieves high power densities of 225 mW cm -2 in aqueous electrolyte and 164 mW cm -2 in solid-state electrolyte. Additionally, a small and stable voltage gap of 0.712 V at 10 mA cm -2 is maintained after 1035 discharge -charge cycles demonstrating the great application potential in energy devices.

An, Jia-Xing↗