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Accurately decoding the three-dimensional atomic structure of surface active sites is essential yet challenging for a rational catalyst design. Here, we used comprehensive techniques combining the pair distribution function and reverse Monte Carlo simulation to reveal the surficial distribution of Pd active sites and adjacent coordination environment in palladium-copper nanoalloys. After the fine-tuning of the atomic arrangement, excellent catalytic performance with 98% ethylene selectivity at complete acetylene conversion was obtained in the Pd34Cu66 nanocatalysts, outperforming most of the reported advanced catalysts. The quantitative deciphering shows a large number of active sites with a Pd-Pd coordination number of 3 distributed on the surface of Pd34Cu66 nanoalloys, which play a decisive role in highly efficient semihydrogenation. This finding not only opens the way for guiding the precise design of bimetal nanocatalysts from atomic-level insight but also provides a method to resolve the spatial structure of active sites.
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High-voltage ultrahigh-Ni cathodes (LiNixCoyMn1-x-yO2, x ≥â¯0.9) can significantly enhance the energy density and cost-effectiveness of Li-ion batteries beyond current levels. However, severe Li-Ni antisite defects and their undetermined dynamic evolutions during high-voltage cycling limit the further development of these ultrahigh-Ni cathodes. In this study, we quantify the dynamic evolutions of the Li-Ni antisite defect using operando neutron diffraction and reveal its coupling relationship with anionic redox, another critical challenge restricting ultrahigh-Ni cathodes. We detect a clear Ni migration coupled with an unstable oxygen lattice, which accompanies the oxidation of oxygen anions at high voltages. Based on these findings, we propose that minimized Li-Ni antisite defects and controlled Ni migrations are essential for achieving stable high-voltage cycling structures in ultrahigh-Ni cathodes. This is further demonstrated by the optimized ultrahigh-Ni cathode, where reduced dynamic evolutions of the Li-Ni antisite defect effectively inhibit the anionic redox, enhancing the 4.5 V cycling stability.
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Layered Li-rich oxides (LROs) that exhibit anionic and cationic redox are extensively studied due to their high energy storage capacities. However, voltage hysteresis, which reduces the energy conversion efficiency of the battery, is a critical limitation in the commercial application of LROs. Herein, using two Li2RuO3 (LRO) model materials with C2/c and P21/m symmetries, we explored the relationship between voltage hysteresis and the electronic structure of Li2RuO3 by neutron diffraction, in situ X-ray powder diffraction, X-ray absorption spectroscopy, macro magnetic study, and electron paramagnetic resonance (EPR) spectroscopy. The charge-transfer band gap of the LRO cathode material with isolated eg electron filling decreases, reducing the oxidation potential of anion redox and thus displaying a reduced voltage hysteresis. We further synthesized Mn-based Li-rich cathode materials with practical significance and different electron spin states. Low-spin Li1.15Ni0.377Mn0.473O2 with isolated eg electron filling exhibited a reduced voltage hysteresis and high energy conversion efficiency. We rationalized this finding via density functional theory calculations. This discovery should provide critical guidance in designing and preparing high-energy layered Li-rich cathode materials for use in next-generation high-energy-density Li-ion batteries based on anion redox activity.
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Sodium-ion batteries have garnered unprecedented attention as an electrochemical energy storage technology, but it remains challenging to design high-energy-density cathode materials with low structural strain during the dynamic (de)sodiation processes. Herein, we report a P2-layered lithium dual-site-substituted Na0.7Li0.03[Mg0.15Li0.07Mn0.75]O2 (NMLMO) cathode material, in which Li ions occupy both transition-metal (TM) and alkali-metal (AM) sites. The combination of theoretical calculations and experimental characterizations reveals that LiTM creates Na-O-Li electronic configurations to boost the capacity derived from the oxygen anionic redox, while LiAM serves as LiO6 prismatic pillars to stabilize the layered structure through suppressing the detrimental phase transitions. As a result, NMLMO delivers a high specific capacity of 266 mAh g-1 and simultaneously exhibits the nearly zero-strain characteristic within a wide voltage range of 1.5-4.6 V. Our findings highlight the effective way of dual-site substitution to break the capacity-stability trade-off in cathode materials for advanced rechargeable batteries.
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Water-in-salt electrolytes (WiSEs) have attracted extensive attention as promising alternatives to organic electrolytes. The limited electrochemical stability windows (ESWs) of aqueous electrolytes are significantly widened by WiSEs. However, the actual ESWs are lower than predicted as the interphase with WiSEs is not as stable as the solid electrolyte interphase (SEI) in conventional lithium-ion batteries. Therefore, identifying the interface state in WiSEs is vital to understanding their electrochemical behavior. Here, the structure of the lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) electrolyte near the interface of the carbon electrode (Ketjen black) was evaluated by experimental methods (neutron diffraction, Raman, and nuclear magnetic resonance spectroscopy) and molecular dynamics (MD) simulations. The results reveal that the introduction of carbon electrodes increases the size of the anionic nanoclusters and enhances the microphase separation at the interface. The MD simulations show that cation-π interactions are responsible for the evolution of anionic nanoclusters at the electrode interface. Moreover, lower charge transfer resistance is achieved at carbon-based electrodes due to the specific interface state. Our findings provide a strategy for introducing cation-π interactions between electrodes and electrolytes to improve the electrochemical performance.
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Perovskites exhibit excellent high-temperature oxygen evolution reaction (OER) activities as the anodes of solid oxide electrolysis cells (SOECs). However, the relationship between ion ordering and OER performances is rarely investigated. Herein, a series of PrBaCo2-x Fex O5+δ perovskites with tailored ion orderings are constructed. Physicochemical characterizations and density functional theory calculations confirm that the oxygen bulk migration and surface transport capacities as well as the OER activities are promoted by the A-site cation ordering, but weakened by the oxygen vacancy ordering. Hence, SOEC with the A-site-ordered and oxygen-vacancy-disordered PrBaCo2 O5+δ anode exhibits the highest performance of 3.40â A cm-2 at 800 °C and 2.0â V. This work sheds light on the critical role of ion orderings in the high-temperature OER performance and paves a new way for screening novel anode materials of SOECs.
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Spin structure of a magnetic system results from the competition of various exchange couplings. Pressure-driven spin structure evolution, through altering interatomic distance, and hence, electronic structure produces baromagnetic effect (BME), which has potential applications in sensor/actuator field. Here, we report a new spin structure(CyS-AFMb) with antiferromagnetic(AFM) nature in Fe-doped Mn0.87Fe0.13NiGe. Neutron powder diffraction (NPD) under in situ hydrostatic pressure and magnetic field was conducted to reveal the spin configuration and its instabilities. We discovered that a pressure higher than 4 kbar can induce abnormal change of Mn(Fe)-Mn(Fe) distances and transform the CyS-AFMb into a conical spiral ferromagnetic(FM) configuration(45°-CoS-FMa) with easily magnetized but shortened magnetic moment by as much as 22%. The observed BME far exceeds previous reports. Our first-principles calculations provide theoretical supports for the enhanced BME. The compressed lattice by pressure favors the 45°-CoS-FMa and significantly broadened 3d bandwidth of Mn(Fe) atoms, which leads to the shortened magnetic moment and evolution of spin structure.
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The thermal instability is a major problem in high-energy nickel-rich layered cathode materials for large-scale battery application. Due to the scarce investigation of thick electrodes at the practical full-cell level, the understanding of thermal failure mechanism is still insufficient. Herein, an intrinsic origin of thermal instability in fully charged industrial pouch cells during high-temperature storage is discovered. Through the investigation from crystals to particles, and from electrodes to cells, it is shown that serious top-down heterogeneous degradation occurs along the depth direction of the thick electrode, including phase transition, cationic disordering, intergranular/intragranular cracks, and side reactions. Such degradation originates from the abundant oxygen vacancies and reduced catalytic Ni2+ at cathode surface, causing microstructural defects and directly leading to the thermal instability. Nonmagnetic elements doping and surface modification are suggested to be effective in mitigating the thermal instability through modulating cationic disordering.
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Direct conversion of methane (CH4 ) to fuels and other high value-added chemicals is an attractive technology in the chemical industry; however, practical challenges to sustainable processes remain. Herein, we report the preparation of a heterostructured Co-doped MgO-based catalyst through topological transformation of a MgCo-layered double hydroxide (LDH) calcination from 200 to 1100 °C. Remarkably, the catalyst can activate CH4 coupling to produce C2 H6 with a selectivity of 41.60 % within 3â h under full-spectrum irradiation through calcination of LDH at 800 °C. Characterization studies and catalytic results suggest that the highly dispersed active sites and large interfaces amongst the Co-doped MgO-based catalysts enable surface activation of CH4 to methyl (CH3 *), in turn promoting coupling of CH3 * to C2 H6 . This study introduces a promising pathway for photodriven CH4 coupling to give high value-added chemicals by using layered double hydroxides as a precursor.
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The discovery of the (Li1-xFexOH)FeSe superconductor has aroused significant interest in metal hydroxide-intercalated iron chalcogenides. However, all efforts made to intercalate NaOH between FeSe and FeS layers have failed so far. Here we report two NaOH-intercalated iron chalcogenides (Na1-xOH)Fe1-yX (X = Se, S) that were synthesized by a low-temperature hydrothermal ion-exchange method. Their crystal structures were solved through single-crystal X-ray diffraction and refined against powder X-ray and neutron diffraction data. Different from the (Li1-xFexOH)FeX superconductors that crystallize in a tetragonal space group P4/nmm with Z = 2, (Na1-xOH)Fe1-yX belong to an orthorhombic space group Cmma with Z = 4. The structural solution also reveals that there are vacancies in both Na and Fe sites and there are not iron ions in the (Na1-xOH) layer. This is probably why both Fe(II) and Fe(III) species exist in the title compounds, as detected by X-ray photoelectron spectroscopy. Based on magnetization and electrical resistivity measurements, the two compounds were found to be paramagnetic semiconductors. The absence of superconductivity should be closely related to the iron vacancies in the Fe1-yX layer. Theoretical calculations suggest that inducing superconductivity in (Na1-xOH)Fe1-ySe is promising due to the similarity of the electronic structures between stoichiometric (NaOH)FeSe and the (Li1-xFexOH)FeSe superconductor.
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Zn2GeO4 is a multifunctional material whose intrinsic thermal expansion properties below ambient temperature have not been explored until now. Herein, the thermal expansion of Zn2GeO4 is investigated by synchrotron X-ray diffraction, with the finding that Zn2GeO4 exhibits very low negative (αv = -2.02 × 10-6 K-1, 100-300 K) and positive (αv = +2.54 × 10-6 K-1, 300-475 K) thermal expansion below and above room temperature, respectively. A combined study of neutron powder diffraction and extended X-ray absorption fine structure spectroscopy shows that the negative thermal expansion (NTE) of Zn2GeO4 originates from the transverse vibrations of O atoms in the four- and six-membered rings with ZnO4-GeO4 tetrahedra. In addition, the results of temperature- and pressure-dependent Raman spectra identify the low-frequency phonon modes (50-150 cm-1) with negative Grüneisen parameters softening upon pressuring and stiffening upon heating during the lattice contraction, thus contributing to the NTE. This study not only reports the interesting thermal expansion behavior of Zn2GeO4 but also provides further insights into the NTE mechanism of novel structures.
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Discovery of new high-conductivity solid-state ionic conductors has been a long-lasting interest in the field of solid-state ionics for their important applications in solid-state electrochemical devices. Here, we report the mixed oxide-ion and Li-ion conductions, together with their conducting mechanisms in the Li2W2O7 material with triclinic symmetry. The process for the ionic identity is supported by several electrochemical measurements including electrochemical impedance spectroscopy, DC polarization, oxygen concentration cell, and theoretical analysis of neutron diffraction data and bond-valence-based energy landscape calculations. We show from electrochemical measurements strong evidences of the predominating oxide-ion conducting and minor Li-ion chemistry in Li2W2O7 at high temperatures, while the bond-valence-based energy landscape analysis reveals possible multidimensional ionic migration pathways for both oxide-ions and Li-ions. Thus, the presented results provide fundamental insights into new mixed ionic conduction mechanisms in low-symmetry materials and have implications for discoveries of new ionic conductors in years to come.
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It is known that few Co-based superconducting compounds have been found compared with their Fe- or Ni-based counterparts. In this study, we have found superconductivity of 4 K in the LaCoSi compound for the first time. The combined analysis of neutron and synchrotron X-ray powder diffractions reveals that LaCoSi exhibits an isostructure with the known Fe-based LiFeAs superconductor, which is the first "111" Co-based superconductor. First-principles calculation shows that LaCoSi presents a quasi-two-dimensional band structure that is also similar to that of LiFeAs. The small structural distortion may be more conducive to the emergence of superconductivity in the LaCoSi compound, which provides a direction for finding new Co-based superconducting compounds.
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It is known that as the FeAs4 tetrahedron in the Fe-based superconductor is close to the regular tetrahedron, critical temperature (Tc) can be greatly increased. Recently, a Co-based superconductor of LaCoSi (4 K) with "111" structure was found. In this work, we improve the Tc of LaCoSi through structural regulation. Tc can be increased by the chemical substitution of Co by Fe, while the superconductivity is suppressed by the Ni substitution. The combined analysis of neutron and synchrotron X-ray powder diffractions reveals that the change of the Si-Co-Si bond angles of the CoSi4 tetrahedron is possibly responsible for the determination of superconducting properties. The Fe chemical substitution is favorable for the formation of the regular tetrahedron of CoSi4. The present new Co-based superconductor of LaCoSi provides a possible method to enhance the superconductivity performance of the Co-based superconductors via controlling Co-based tetrahedra similar to those well established in the Fe-based superconductors.
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Continued improvement in the electrochemical performance of Li-Mn-O oxide cathode materials is key to achieving advanced low-cost Li-ion batteries with high energy densities. In this study, O2-type Li0.78[Li0.24Mn0.76]O2 nanowires were synthesized by a solvothermal reaction to produce P2-type Na5/6[Li1/4Mn3/4]O2 nanowires, which were then subjected to molten salt Li-ion exchange. The resulting nanowires have diameters less than 20 nm and lengths of several micrometers. The full-Mn-based nanowires cathode material delivers a reversible capacity of 275 mAh g-1 at 0.1 C and 200 mAh g-1 at a high current rate of 15 C with a capacity retention of more than 80% and the voltage decay was dramatically suppressed after 100 cycles. This excellent performance is ascribed to the highly stable oxygen redox reaction and lack of layered-to-spinel phase transition in the O2-type structure during cycling.
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A large linear negative thermal expansion (NTE) and expanded NTE temperature range (ΔTNTE) were obtained in magnetoelastic CrTe1-xSex (0 ≤ x ≤ 0.15) compounds. For CrTe compound, its thermal expansion coefficient of volume (αV) was calculated to be -28.8 ppm K-1 with the temperature ranging from 280 to 340 K. Substituting Te with Se atoms, the NTE behavior and magnetic properties can be well manipulated. With increasing Se in CrTe1-xSex (0 ≤ x ≤ 0.15) compounds, the ΔTNTE increases from 60 K (280-340 K for x = 0), to 80 K (240-320 K for x = 0.05), to 95 K (200-295 K for x = 0.1), and finally to 100 K (170-270 K for x = 0.15). Furthermore, a linear NTE remains independent of temperature for samples with x ≤ 0.1. The relationship between tunable NTE and magnetic properties was analyzed in detail, indicating that the NTE in CrTe1-xSex compounds originates from the magnetovolume effect (MVE).
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Lattice-oxygen redox (l-OR) has become an essential companion to the traditional transition-metal (TM) redox charge compensation to achieve high capacity in Li-rich cathode oxides. However, the understanding of l-OR chemistry remains elusive, and a critical question is the structural effect on the stability of l-OR reactions. Herein, the coupling between l-OR and structure dimensionality is studied. We reveal that the evolution of the oxygen-lattice structure upon l-OR in Li-rich TM oxides which have a three-dimensional (3D)-disordered cation framework is relatively stable, which is in direct contrast to the clearly distorted oxygen-lattice framework in Li-rich oxides which have a two-dimensional (2D)/3D-ordered cation structure. Our results highlight the role of structure dimensionality in stabilizing the oxygen lattice in reversible l-OR, which broadens the horizon for designing high-energy-density Li-rich cathode oxides with stable l-OR chemistry.
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A cost-effective, scalable ball milling process is employed to synthesize the InGeSiP3 compound with a cubic ZnS structure, aiming to address the sluggish reaction kinetics of Si-based anodes for Lithium-ion batteries. Experimental measurements and first-principles calculations confirm that the synthesized InGeSiP3 exhibits significantly higher electronic conductivity, larger Li-ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP3 undergoes a reversible Li-storage mechanism that involves intercalation, followed by conversion and alloy reactions, resulting in a reversible capacity of 1733 mA h g-1 with an initial Coulombic efficiency of 90%. Moreover, the InGeSiP3-based electrodes exhibit exceptional cycling stability, retaining an 1121 mA h g-1 capacity with a retention rate of ≈87% after 1500 cycles at 2000 mA g-1 and remarkable high-rate capability, achieving 882 mA h g-1 at 10 000 mA g-1. Inspired by the distinctive characteristic of high entropy, the synthesis is extended to high entropy GaCu (or Zn)InGeSiP5, CuZnInGeSiP5, GaCuZnInGeSiP6, InGeSiP2S (or Se), and InGeSiPSSe. This endeavor overcomes the immiscibility of different metals and non-metals, paving the way for the electrochemical energy storage application of high-entropy silicon-phosphides.
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Increasing the charging cutoff voltage is a viable approach to push the energy density limits of LiCoO2 and meet the requirements of the rapid development of 3C electronics. However, an irreversible oxygen redox is readily triggered by the high charging voltage, which severely restricts practical applications of high-voltage LiCoO2. In this study, we propose a modification strategy via suppressing surface ligand-to-metal charge transfer to inhibit the oxygen redox-induced structure instability. A d0 electronic structure Zr4+ is selected as the charge transfer insulator and successfully doped into the surface lattice of LiCoO2. Using a combination of theoretical calculations, ex situ X-ray absorption spectra, and in situ differential electrochemical mass spectrometry analysis, our results show that the modified LiCoO2 exhibits suppressed oxygen redox activity and stable redox electrochemistry. As a result, it demonstrates a robust long-cycle lattice structure with a practically eliminated voltage decay (0.17 mV/cycle) and an excellent capacity retention of 89.4% after 100 cycles at 4.6 V. More broadly, this work provides a new perspective on suppressing the oxygen redox activity through modulating surface ligand-to-metal charge transfer for achieving a stable high-voltage ion storage structure.
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After several decades of studies of high-temperature superconductivity, there is no compelling theory for the mechanism yet; however, the spin fluctuations have been widely believed to play a crucial role in forming the superconducting Cooper pairs. The recent discovery of high-temperature superconductivity near 80 K in the bilayer nickelate La3Ni2O7 under pressure provides a new platform to elucidate the origins of high-temperature superconductivity. We perform elastic and inelastic neutron scattering studies on a polycrystalline sample of La3Ni2O7-δ at ambient pressure. No magnetic order can be identified down to 10 K. The absence of long-range magnetic order in neutron diffraction measurements may be ascribed to the smallness of the magnetic moment. However, we observe a weak flat spin-fluctuation signal in the inelastic scattering spectra at ⼠45 meV. The observed spin excitations could be interpreted as a result of strong interlayer and weak intralayer magnetic couplings for stripe-type antiferromagnetic orders. Our results provide crucial information on the spin dynamics and are thus important for understanding the superconductivity in La3Ni2O7.