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The synergistic engineering of chemical complexity and crystal structures has been applied to Prussian blue analogue (PBA) cathodes in this work. More precisely, the high-entropy concept has been successfully introduced into two structure types of identical composition, namely, cubic and monoclinic. Through the utilization of a variety of complementary characterization techniques, a comprehensive investigation into the electrochemical behavior of the cubic and monoclinic PBAs has been conducted, providing nuanced insights. The implementation of the high-entropy concept exhibits crucial selectivity toward the intrinsic crystal structure. Specifically, while the overall cycling stability of both cathode systems is significantly improved, the synergistic interplay of crystal structure engineering and entropy proves particularly significant. After optimization, the cubic PBA demonstrates structural advantages, showcasing good reversibility, minimal capacity loss, high thermal stability, and unparalleled endurance even under harsh conditions (high specific current and temperature).
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Bacillus licheniformis and bacitracin have a huge application market and value in the fields of medicine, chemistry, aquaculture, agricultural, and sideline products. Therefore, the selection of B. licheniformis with high production of bacitracin is of great importance. In this experimental protocol, Bacillus with a high yield of bacitracin was isolated, purified, and identified from the fresh feces of healthy pigs. The inhibitory effect of secondary metabolite bacitracin on Micrococcus luteus was also tested. Thin-layer chromatography and high-performance liquid chromatography were used for the qualitative and quantitative detection of bacitracin. The physiological and biochemical characteristics of B. licheniformis were determined by relevant kits. The phylogenetic relationships of B. licheniformis were determined and constructed using gene sequence detection. This protocol describes and introduces the standard isolation, purification, and identification process of B. licheniformis from animal fresh feces from multiple perspectives, providing a method for the large-scale utilization of B. licheniformis and bacitracin in factories.
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Bacillus licheniformis , Bacitracina , Fezes , Animais , Bacitracina/farmacologia , Fezes/microbiologia , Bacillus licheniformis/genética , Bacillus licheniformis/metabolismo , Bacillus licheniformis/isolamento & purificação , SuínosRESUMO
P2-type cobalt-free MnNi-based layered oxides are promising cathode materials for sodium-ion batteries (SIBs) due to their high reversible capacity and well chemical stability. However, the phase transformations during repeated (dis)charge steps lead to rapid capacity decay and deteriorated Na+ diffusion kinetics. Moreover, the electrode manufacturing based on polyvinylidene difluoride (PVDF) binder system has been reported with severely defluorination issue as well as the energy intensive and expensive process due to the use of toxic and volatile N-methyl-2-pyrrolidone (NMP) solvent. It calls for designing a sustainable, better performing, and cost-effective binder for positive electrode manufacturing. In this work, we investigated inorganic sodium metasilicate (SMS) as a viable binder in conjunction with P2-Na0.67Mn0.55Ni0.25Fe0.1Ti0.1O2 (NMNFT) cathode material for SIBs. The NMNFT-SMS electrode delivered a superior electrochemical performance compared to carboxy methylcellulose (CMC) and PVDF based electrodes with a reversible capacity of ~161â mAh/g and retaining ~83 % after 200 cycles. Lower cell impedance and faster Na+ diffusion was also observed in this binder system. Meanwhile, with the assistance of TEM technique, SMS is suggested to form a uniform and stable nanoscale layer over the cathode particle surface, protecting the particle from exfoliation/cracking due to electrolyte attack. It effectively maintained the electrode connectivity and suppressed early phase transitions during cycling as confirmed by operando XRD study. With these findings, SMS binder can be proposed as a powerful multifunctional binder to enable positive electrode manufacturing of SIBs and to overall reduce battery manufacturing costs.
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The development of competitive rechargeable Mg batteries is hindered by the poor mobility of divalent Mg ions in cathode host materials. In this work, we explore the dual cation co-intercalation strategy to mitigate the sluggishness of Mg2+ in model TiS2 material. The strategy involves pairing Mg2+ with Li+ or Na+ in dual-salt electrolytes in order to exploit the faster mobility of the latter with the aim to reach better electrochemical performance. A combination of experiments and theoretical calculations details the charge storage and redox mechanism of co-intercalating cationic charge carriers. Comparative evaluation reveals that the redox activity of Mg2+ can be improved significantly with the help of the dual cation co-intercalation strategy, although the ionic radius of the accompanying monovalent ion plays a critical role on the viability of the strategy. More specifically, a significantly higher Mg2+ quantity intercalates with Li+ than with Na+ in TiS2. The reason being the absence of phase transition in the former case, which enables improved Mg2+ storage. Our results highlight dual cation co-intercalation strategy as an alternative approach to improve the electrochemical performance of rechargeable Mg batteries by opening the pathway to a rich playground of advanced cathode materials for multivalent battery applications.
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The high-entropy approach is applied to monoclinic Prussian White (PW) Na-ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn-based samples with up to six metal species sharing the N-coordinated positions was synthesized. The material of composition Na1.65 Mn0.4 Fe0.12 Ni0.12 Cu0.12 Co0.12 Cd0.12 [Fe(CN)6 ]0.92 â¡0.08 â 1.09H2 O was found to exhibit superior cyclability over medium/low-entropy and conventional single-metal PWs. We also report, to our knowledge for the first time, that a high-symmetry crystal structure may be advantageous for high-entropy PWs during battery operation. Computational comparisons of the formation enthalpy demonstrate that the compositionally less complex materials are prone to phase transitions, which negatively affect cycling performance. Based on data from complementary characterization techniques, an intrinsic mechanism for the stability improvement of the disordered PW structure upon Na+ insertion/extraction is proposed, namely the dual effect of suppression of phase transitions and mitigation of gas evolution.
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Performing reliable preparation of transmission electron microscopy (TEM) samples is the necessary basis for a meaningful investigation by ex situ and even more so by in situ TEM techniques, but it is challenging using materials that are sensitive to electron beam irradiation. Focused ion beam is currently the most commonly employed technique for a targeted preparation, but the structural modifications induced during focused ion beam preparation are not fully understood for a number of materials. Here, we have investigated the impact of both the electron and the Ga+ ion beam on insulating solid-state electrolytes (lithium phosphorus oxynitride, Na-ß"-alumina solid electrolyte and Na3.4Si2.4Zr2P0.6O12 (NaSICON)) and observed significant lithium/sodium whisker growth induced by both the electron and ion beam already at fairly low dose, leading to a significant change in the chemical composition. The metal whisker growth is presumably mainly due to surface charging, which can be reduced by coating with a gold layer or preparation under cryogenic conditions as efficient approaches to stabilize the solid electrolyte for scanning electron microscopy imaging and TEM sample preparation. Details on the different preparation approaches, the acceleration voltage dependence and the induced chemical and morphological changes are reported.
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Calcium (Ca) batteries represent an attractive option for electrochemical energy storage due to physicochemical and economic reasons. The standard reduction potential of Ca (-2.87 V) is close to Li and promises a wide voltage window for Ca full batteries, while the high abundance of Ca in the earth's crust implicates low material costs. However, the development of Ca batteries is currently hindered by technical issues such as the lack of compatible electrolytes for reversible Ca2+ plating/stripping and high-capacity cathodes with fast kinetics. Herein, we employed FeS2 as a conversion cathode material and combined it with a Li+/Ca2+ hybrid electrolyte for Ca batteries. We demonstrate that Li+ ions ensured reversible Ca2+ plating/stripping on the Ca metal anode with a small overpotential. At the same time, they enable the conversion of FeS2, offering high discharge capacity. As a result, the Ca/FeS2 cell demonstrated an excellent long-term cycling performance with a high discharge capacity of 303 mAh g-1 over 200 cycles. Even though the practical application of such an approach is questionable due to the high quantity of electrolytes, we believe that our scientific findings still provide new directions for studying Ca batteries with long-term cycling.
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Bulk-type solid-state batteries (SSBs) composed of lithium thiophosphate superionic solid electrolytes (SEs) and high-capacity cathode active materials (CAMs) have recently attracted much attention for their potential application in next-generation electrochemical energy storage. However, compatibility issues between the key components in this kind of battery system are difficult to overcome. Here, we report on a protective cathode coating that strongly reduces the prevalence of detrimental side reactions between CAM and SE during battery operation. This is demonstrated using preformed HfO2 nanoparticles as a secondary particle coating for a layered Ni-rich oxide CAM, LiNi0.85Co0.1Mn0.05O2 (NCM85). The preparation of a stable dispersion of the HfO2 nanoparticles enabled the deposition of a uniform coating of thickness ≤11 nm. When incorporated into Li6PS5Cl-based, pellet-stack SSBs, the coated NCM85 showed superior performance in terms of reversibility, cell capacity, longevity, and rate capability over its uncoated counterpart. The effectiveness of the protective coating in mitigating electro-chemo-mechanical degradation was investigated using a suite of physical and electrochemical characterization techniques. In addition, the adaptability to wet processing of the coated NCM85 is demonstrated in slurry-cast SSBs and liquid-electrolyte-based Li-ion cells.
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Electron tomography (ET) has gained increasing attention for the 3D characterization of nanoparticles. However, the missing wedge problem due to a limited tilt angle range is still the main challenge for accurate reconstruction in most experimental TEM setups. Advanced algorithms could in-paint or compensate to some extent the missing wedge artifacts, but cannot recover the missing structural information completely. 360° ET provides an option to solve this problem by tilting a needle-shaped specimen over the full tilt range and thus filling the missing information. However, sample preparation especially for fine powders to perform full-range ET is still challenging, thus limiting its application. In this work, we propose a new universal sample preparation method that enables the transfer of selected individual nanoparticle or a few separated nanoparticles by cutting a piece of carbon film supporting the specimen particles and mounting them onto the full-range tomography holder tip with the help of an easily prepared sharp tungsten tip. This method is demonstrated by 360° ET of Pt@TiO2 hollow cage catalyst showing high quality reconstruction without missing wedge.
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Efficient Lewis-acid-catalyzed direct conversion of aldehydes to 1,2-diketones in the liquid phase was enabled by using newly designed and developed ceria-zirconia-based high-entropy oxides (HEOs) as the actual catalysts. The synergistic effect of various cations incorporated in the same oxide structure (framework) was partially responsible for the efficiency of multicationic materials compared to the corresponding single-cation oxide forms. Furthermore, a clear, linear relationship between the Lewis acidity and the catalytic activity of the HEOs was observed. Due to the developed strategy, exclusively diketone-selective, recyclable, versatile heterogeneous catalytic transformation of aldehydes can be realized under mild reaction conditions.
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Solid-electrolyte interface (SEI) is "the most important but least understood (component) in rechargeable Li-ion batteries". The ideal SEI requires high elastic strength and can resist the penetration of a Li dendrite mechanically, which is vital for inhibiting the dendrite growth in lithium batteries. Even though Li2CO3 and Li2O are identified as the major components of SEI, their mechanical properties are not well understood. Herein, SEI-related materials such as Li2CO3 and Li2O were electrochemically deposited using an environmental transmission electron microscopy (ETEM), and their mechanical properties were assessed by in situ atomic force microscopy (AFM) and inverse finite element simulations. Both Li2CO3 and Li2O exhibit nanocrystalline structures and good plasticity. The ultimate strength of Li2CO3 ranges from 192 to 330 MPa, while that of Li2O is less than 100 MPa. These results provide a new understanding of the SEI and its related dendritic problems in lithium batteries.
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In nonaqueous Mg batteries, inactive adsorbed species and the passivation layer formed from the reactive Mg with impurities in the electrolyte seriously affect the Mg metal/electrolyte interface. These adlayers can impede the passage of Mg2+ ions, leading to a high Mg plating/stripping overpotential. Herein, we report the properties of a new additive, bismuth triflate (Bi(OTf)3), for synthesizing a chlorine-free Mg electrolyte to enhance Mg plating/stripping from initial cycles. The beneficial effect of Bi(OTf)3 can be ascribed to Bi/Mg3Bi2 formed in situ on the Mg metal surface, which increases the charge transfer during the on-off transition by reducing the adsorption of inactive species on the Mg surface and enhancing the resistance of the reactive surface to passivation. This simple method provides a new avenue to improve the compatibility between the Cl-free Mg electrolyte and the Mg metal anode.
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Lithium metal is considered the ultimate anode material for future rechargeable batteries1,2, but the development of Li metal-based rechargeable batteries has achieved only limited success due to uncontrollable Li dendrite growth3-7. In a broad class of all-solid-state Li batteries, one approach to suppress Li dendrite growth has been the use of mechanically stiff solid electrolytes8,9. However, Li dendrites still grow through them10,11. Resolving this issue requires a fundamental understanding of the growth and associated electro-chemo-mechanical behaviour of Li dendrites. Here, we report in situ growth observation and stress measurement of individual Li whiskers, the primary Li dendrite morphologies12. We combine an atomic force microscope with an environmental transmission electron microscope in a novel experimental set-up. At room temperature, a submicrometre whisker grows under an applied voltage (overpotential) against the atomic force microscope tip, generating a growth stress up to 130 MPa; this value is substantially higher than the stresses previously reported for bulk13 and micrometre-sized Li14. The measured yield strength of Li whiskers under pure mechanical loading reaches as high as 244 MPa. Our results provide quantitative benchmarks for the design of Li dendrite growth suppression strategies in all-solid-state batteries.
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Using α-manganese dioxide (α-MnO2) nanowires as the air electrode, a K-O2 nanobattery is assembled in an aberration corrected environmental transmission electron microscope. It is found that the α-MnO2 nanowires are reduced into Mn3O4 and MnO during discharge; meanwhile, KO2 is formed on the surface of the α-MnO2 nanowires.
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The development of silicon-based anode materials is important for improving the energy density of current lithium ion batteries. However, there are still strong demands for these materials with better cycle stability and higher reversible capacity. Here, a kind of dual bond restricted MXene-Si-CNT composite anode materials with enhanced electrochemical performance is reported. These dual bonds have been clearly revealed by an X-ray photoelectron spectroscopy technique and also proven by theoretical calculations with spontaneous reaction energy values (-0.190 and -0.429 eV/atom for Ti-Si and C-Si bonds, respectively). The cycle stability of the composites, prepared by a facile ball-milling synthetic method, can obviously be improved because of the existence of these dual bonds and the multidimensional constructed architecture. The MXene-Si-CNT composite with 60 wt % silicon possesses the best overall performance, with â¼80% capacity retention after 200 cycles, and achieves 841 mAh g-1 at 2 A g-1. This approach demonstrates a promising strategy to exploit high-performance anode materials and lessens the immanent negative effect of silicon-based materials. Furthermore, it is significant to extend this method to other anode materials with serious volumetric change problems during the cycling process.
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Investigating lightweight electromagnetic microwave absorption materials is still urgent because of the issue related to the electromagnetic pollution or military defense. Our findings indicate that core-shell MnO@carbon nanowires (MnO@C NWs) achieve substantially enhanced microwave absorption, suggesting the suitable impedance matching induced by the synergetic effect between MnO and carbon. Furthermore, the peapod-like MnO@C NWs with internal void space can be facially synthesized by partial etching of core-shell MnO@C NWs. The peapod-like MnO@C NWs with internal voids/cavities exhibit dramatically enhanced electromagnetic microwave absorption property when the carbon content is about 64 wt %, a minimum reflection loss (RL) of -55 dB at 10 wt % loading was observed at 13.6 GHz, and the bandwidth of RL less than -10 dB (90% absorption) covers 6.2 GHz at the thickness of 2 mm. The excellent electromagnetic microwave absorption performance is superior to the most of MnO x/C composites in the literatures, which probably benefits from the dielectric polarization among conductive network structure between MnO and carbon, as well as the multiple reflection and absorption induced by internal void space. Our work is expected to pave an effective way to extend the electromagnetic microwave absorption performance of MnO/C composites through partial etching to create a void space.
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Ceramics possess high temperature resistance, extreme hardness, high chemical inertness and a lower density compared to metals, but there is currently no technology that can produce satisfactory joints in ceramic parts and preserve the excellent properties of the material. The lack of suitable joining techniques for ceramics is thus a major road block for their wider applications. Herein we report a technology to weld ceramic nanowires, with the mechanical strength of the weld stronger than that of the pristine nanowires. Using an advanced aberration-corrected environmental transmission electron microscope (ETEM) under a CO2 environment, we achieved ceramic nanowelding through the chemical reaction MgO + CO2 â MgCO3 by using porous MgO as the solder. We conducted not only nanowelding on MgO, CuO, and V2O5 nanowires and successfully tested them in tension, but also macroscopic welding on a ceramic material such as SiO2, indicating the application potential of this technology in bottom-up ceramic tools and devices.
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Boron nitride nanosheets (BNNS) hold the similar two-dimensional structure as graphene and unique properties complementary to graphene, which makes it attractive in application ranging from electronics to energy storage. The exfoliation of boron nitride (BN) still remains challenge and hinders the applications of BNNS. In this work, the preparation of BNNS has been realized by a shear-assisted supercritical CO2 exfoliation process, during which supercritical CO2 intercalates and diffuses between boron nitride layers, and then the exfoliation of BN layers is obtained in the rapid depressurization process by overcoming the van der Waals forces. Our results indicate that the bulk boron nitride has been successfully exfoliated into thin nanosheets with an average 6 layers. It is found that the produced BNNS is well-dispersed in isopropyl alcohol (IPA) with a higher extinction coefficient compared with the bulk BN. Moreover, the BNNS/epoxy composite used as thermal interface materials has been prepared. The introduction of BNNS results in a 313% enhancement in thermal conductivity. Our results demonstrate that BNNS produced by supercritical CO2 exfoliation show great potential applications for heat dissipation of high efficiency electronics.
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TiO2 modified Co3O4 acicular nanotube arrays (ANTAs) have been fabricated in this study, showing a good performance in glucose detection. In the experiment, the precursor Co(CO3)0.5(OH)·0.11H2O acicular nanowire arrays (ANWAs) was first grown on the fluorine doped tin oxide (FTO) substrate by a hydrothermal method. Thereafter, the uniform pink precursor Co(CO3)0.5(OH)·0.11H2O ANWAs was completely converted to the black Co3O4 ANTAs thin film by alkaline treatment. After the decoration of TiO2, the TiO2/Co3O4 ANTAs electrode exhibits a much higher current response to glucose compared with the Co3O4 ANTAs. Importantly, this neotype composite structure of Co3O4 enhances the glucose sensing performance by increasing specific surface area, additional reactive sites and synergistic effect, which make the TiO2/Co3O4 glucose sensor show a high sensitivity of 2008.82 µA mM(-1) cm(-2), a fast response time (less than 5s) and a detection limit as low as 0.3396 µM (S/N=3). The TiO2/Co3O4 ANTAs modified electrode exhibits a high selectivity for glucose in human serum, against ascorbic acid and uric acid.
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Técnicas Biossensoriais , Glicemia/isolamento & purificação , Nanotubos/química , Ácido Ascórbico/química , Cobalto/química , Humanos , Limite de Detecção , Óxidos/química , Titânio/química , Ácido Úrico/químicaRESUMO
Undisturbed natural wetlands are important carbon sinks due to their low soil respiration. When compared with inland alpine wetlands, estuarine wetlands in densely populated areas are subjected to great pressure associated with environmental pollution. However, the effects of water pollution and eutrophication on soil respiration of estuarine and their mechanism have still not been thoroughly investigated. In this study, two representative zones of a tidal wetland located in the upstream and downstream were investigated to determine the effects of water organic pollution and eutrophication on soil respiration of estuarine wetlands and its mechanism. The results showed that eutrophication, which is a result of there being an excess of nutrients including nitrogen and phosphorus, and organic pollutants in the water near Shang shoal located upstream were higher than in downstream Xia shoal. Due to the absorption and interception function of shoals, there to be more nitrogen, phosphorus and organic matter in Shang shoal soil than in Xia shoal. Abundant nitrogen, phosphorus and organic carbon input to soil of Shang shoal promoted reproduction and growth of some highly heterotrophic metabolic microorganisms such as ß-Proteobacteria, γ-Proteobacteria and Acidobacteria which is not conducive to carbon sequestration. These results imply that the performance of pollutant interception and purification function of estuarine wetlands may weaken their carbon sequestration function to some extent.