RESUMO
2D alloy-based anodes show promise in potassium-ion batteries (PIBs). Nevertheless, their low tap density and huge volume expansion cause insufficient volumetric capacity and cycling stability. Herein, a 3D highly dense encapsulated architecture of 2D-Bi nanosheets (HD-Bi@G) with conducive elastic networks and 3D compact encapsulation structure of 2D nano-sheets are developed. As expected, HD-Bi@G anode exhibits a considerable volumetric capacity of 1032.2 mAh cm-3, stable long-life span with 75% retention after 2000 cycles, superior rate capability of 271.0 mAh g-1 at 104 C, and high areal capacity of 7.94 mAh cm-2 (loading: 24.2 mg cm-2) in PIBs. The superior volumetric and areal performance mechanisms are revealed through systematic kinetic investigations, ex situ characterization techniques, and theorical calculation. The 3D high-conductivity elastic network with dense encapsulated 2D-Bi architecture effectively relieves the volume expansion and pulverization of Bi nanosheets, maintains internal 2D structure with fast kinetics, and overcome sluggish ionic/electronic diffusion obstacle of ultra-thick, dense electrodes. The uniquely encapsulated 2D-nanosheet structure greatly reduces K+ diffusion energy barrier and accelerates K+ diffusion kinetics. These findings validate a feasible approach to fabricate 3D dense encapsulated architectures of 2D-alloy nanosheets with conductive elastic networks, enabling the design of ultra-thick, dense electrodes for high-volumetric-energy-density energy storage.
RESUMO
The inferior cycling stabilities or low capacities of 2D Sb or Bi limit their applications in high-capacity and long-stability potassium/lithium-ion batteries (PIBs/LIBs). Therefore, integrating the synergy of high-capacity Sb and high-stability Bi to fabricate 2D binary alloys is an intriguing and challenging endeavor. Herein, a series of novel 2D binary SbBi alloys with different atomic ratios are fabricated using a simple one-step co-replacement method. Among these fabricated alloys, the 2D-Sb0.6 Bi0.4 anode exhibits high-capacity and ultra-stable potassium and lithium storage performance. Particularly, the 2D-Sb0.6 Bi0.4 anode has a high-stability capacity of 381.1 mAh g-1 after 500 cycles at 0.2 A g-1 (≈87.8% retention) and an ultra-long-cycling stability of 1000 cycles (0.037% decay per cycle) at 1.0 A g-1 in PIBs. Besides, the superior lithium and potassium storage mechanism is revealed by kinetic analysis, in-situ/ex-situ characterization techniques, and theoretical calculations. This mainly originates from the ultra-stable structure and synergistic interaction within the 2D-binary alloy, which significantly alleviates the volume expansion, enhances K+ adsorption energy, and decreases the K+ diffusion energy barrier compared to individual 2D-Bi or 2D-Sb. This study verifies a new scalable design strategy for creating 2D binary (even ternary) alloys, offering valuable insights into their fundamental mechanisms in rechargeable batteries.
RESUMO
AlPO4-11 and AlPO4-5 molecular sieves are ionothermally prepared without addition of water by using anhydrous starting materials, such as NH4H2PO4, pseudoboehmite (AlOOH), and NH4F. The synthesis appears to be an autocatalytic process. Water has a remarkable effect on the synthesis process. Addition of reagent quantities of water (H2O/Al = 1, molar ratio) can enhance the crystallization kinetics greatly.
RESUMO
Polymorph A-enriched beta zeolites were synthesized by employing high HF concentrations in the synthesis medium. The polymorphic compositions of the synthesized beta zeolites were determined by the complementary characterization methods (19)F NMR analysis and PXRD simulation. With a variety of SDAs, a high HF concentration (HF/SDA > 1.0) in the synthesis medium results in the A-rich feature (55-65% A) of beta zeolites, while a moderate HF concentration only results in typical beta zeolites. A systematic study on the synthesis conditions reveals the existence of a buffered system of H(+) and F(-) formed in the highly HF-concentrated medium. This buffer results in a small but continuous supply of F(-) during zeolite crystallization, in contrast to the conventional fluoride route where all F(-) are discharged all-at-once at the initial stage.
Assuntos
Alcanos/síntese química , Compostos de Alumínio/síntese química , Magnésio/química , Fosfatos/síntese química , Temperatura , Alcanos/química , Compostos de Alumínio/química , Aminas/química , Catálise , Imidazóis/química , Líquidos Iônicos/química , Espectroscopia de Ressonância Magnética/métodos , Espectroscopia de Ressonância Magnética/normas , Tamanho da Partícula , Fosfatos/química , Padrões de Referência , Propriedades de SuperfícieRESUMO
A one-step hydrotreatment of vegetable oil combining deoxygenation and isomerization to directly produce low cloud point, high quality diesel is devised. The Pt/zeolite bifunctional catalysts prepared by using SAPO-11 and ZSM-22 zeolites as supports are used in this process. Catalytic reactions are conducted in a fixed-bed reactor under a hydrogen atmosphere. Over the bifunctional catalyst, 100 % conversion of soybean oil is obtained at 357 °C, 4 MPa, and 1 h(-1), and 80 % organic liquid yield is achieved, which is close to the maximum theoretical liquid yield. In the organic products, the alkanes selectivity is 100 % with an i-alkanes selectivity above 63 %. NH(3)-temperature programmed desorption (TPD), pyridine IR spectroscopy, and other characterization techniques are used to study the effect of the support acidity on the reaction pathway. Over the Pt/zeolite bifunctional catalyst with less strong Lewis acid sites, the reaction proceeds via the decarboxylation plus decarbonylation pathway. This one-step method provides a new strategy to produce low cloud point, high quality diesel from biomass feedstock in a more economic and attractive way.
Assuntos
Alcanos/química , Biocombustíveis , Óleos de Plantas/química , Hidrogenação , Platina/química , Temperatura , Triglicerídeos/química , Zeolitas/químicaRESUMO
Cationic templating of imidazolium adjusted by the amine concentration in an ionothermal system results in products with larger channels or cage-like structures by reassembling the inorganic hosts around the changed organic guests.
RESUMO
The structure-directing effect of amine has been observed in the ionothermal synthesis of aluminophosphate molecular sieves in 1-butyl-3-methylimidazolium bromide ionic liquid. The seven different amines we tested have an influence on the crystallization dynamics and the final product, leading to the formation of pure AFI and ATV structures.