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Li-ion batteries (LIBs) for electric vehicles and aviation demand high energy density, fast charging and a wide operating temperature range, which are virtually impossible because they require electrolytes to simultaneously have high ionic conductivity, low solvation energy and low melting point and form an anion-derived inorganic interphase1-5. Here we report guidelines for designing such electrolytes by using small-sized solvents with low solvation energy. The tiny solvent in the secondary solvation sheath pulls out the Li+ in the primary solvation sheath to form a fast ion-conduction ligand channel to enhance Li+ transport, while the small-sized solvent with low solvation energy also allows the anion to enter the first Li+ solvation shell to form an inorganic-rich interphase. The electrolyte-design concept is demonstrated by using fluoroacetonitrile (FAN) solvent. The electrolyte of 1.3 M lithium bis(fluorosulfonyl)imide (LiFSI) in FAN exhibits ultrahigh ionic conductivity of 40.3 mS cm-1 at 25 °C and 11.9 mS cm-1 even at -70 °C, thus enabling 4.5-V graphite||LiNi0.8Mn0.1Co0.1O2 pouch cells (1.2 Ah, 2.85 mAh cm-2) to achieve high reversibility (0.62 Ah) when the cells are charged and discharged even at -65 °C. The electrolyte with small-sized solvents enables LIBs to simultaneously achieve high energy density, fast charging and a wide operating temperature range, which is unattainable for the current electrolyte design but is highly desired for extreme LIBs. This mechanism is generalizable and can be expanded to other metal-ion battery electrolytes.
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The temperature dependence of the dynamic contact angles (DCAs) of water on a metallic surface remains unclear, especially under elevated pressures. Here in this work, the advancing and receding contact angles (RCAs), as well as the contact angle hysteresis (CAH), of water on stainless-steel 316 (SS316) surfaces were studied using the dynamic sessile drop method for temperatures up to 300 °C and pressures up to 10 MPa. It was found that the temperature dependence of the DCAs exhibits a different pattern as compared to the piecewise linear decline of static contact angles. The advancing contact angle (ACA) remains nearly constant and does not decrease until the temperature becomes close to the saturated temperature. The decrease in ACA is attributed to evaporation, which reduces the advancement of energy barrier. The RCA linearly declines below 120 °C and remains stable above 120 °C. The increasing temperature enhances the pinning effect and changes the droplet receding mode. Under all pressures tested, the CAH demonstrates a "increase-constant-decrease" trilinear relationship with temperature. Furthermore, the mean solid surface entropy and solid-gas interfacial tension of SS316 were estimated to be 0.1152 mJ/(m2·°C) and 61.49 mJ/m2, respectively.
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Rational design of advanced electrolytes to improve the high-voltage capability has been attracting wide attention as one critical solution to enable next-generation high-energy-density batteries. However, the limited understanding of electrolyte antioxidant chemistry as well as the lack of valid quantization approaches have resulted in knowledge gap, which hinders the formulation of new electrolytes. Herein, we construct a standard curve based on representative solvation structures to quantify the oxidation stability of ether-based electrolytes, which reveals the linear correlation between the oxidation potential and the atomic charge of the least oxidation-resistant solvent. Dictated by the regularity between solvation composition and oxidation potential, a (Trifluoromethyl)cyclohexane-based localized high-concentration electrolyte dominated by anion-less solvation structures was designed to optimize the cycling performance of 4.5â V 30â µm-Li||3.8â mAh cm-2-LiCoO2 batteries, which maintained 80 % capacity retention even after 440 cycles. The consistency of experimental and computational results validates the proposed principles, offering a fundamental guideline to evaluate and design aggressive electrochemical systems.
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In situ thermal desorption (ISTD) provides an efficient solution to remediation of soil and groundwater contaminated with nonaqueous phase liquids (NAPLs). Establishing a relationship between the subsurface temperature rise and NAPL removal is significant to reduce energy consumption of ISTD. However, the co-boiling phenomenon between NAPL and water poses a great challenge in developing this relationship due to the nonequilibrium heat and mass transport effects. We performed a systematic experimental investigation into the local temperature rise patterns at different distances from a NAPL pool and under different degrees of superheat by selecting four representative NAPLs (i.e., trichloroethylene, tetrachlorethylene, n-hexane, and n-octane) according to their density and boiling point relative to water. The patterns of temperature rise indicated that the underground temperature field can be divided into three zones: the zone of local thermal equilibrium, the nonequilibrium zone affected by co-boiling, and the zone unaffected by co-boiling. We developed a pattern-recognition-based approach, which considers the effects of local heat and mass transport to establish a qualitative correlation between the temperature rise and NAPL removal. Our results give deeper insights into the understanding of subsurface temperatures in ISTD practice, which can serve as the guideline for more accurate and sustainable remediation.
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Poluentes do Solo , Tricloroetileno , Poluentes Químicos da Água , Temperatura Alta , Água , Temperatura , Poluentes Químicos da Água/análiseRESUMO
The evaporation of water droplets on a solid surface at elevated temperatures under a pressurized condition has not yet been well understood, although this phenomenon is of both theoretical and practical significance. In this work, water droplet evaporation on smooth stainless steel surfaces in nitrogen gas atmosphere at elevated pressures and temperatures (up to 2 MPa and 202.4 °C, respectively) was investigated experimentally. It was observed that the increase in pressure diminishes the proportion of the constant contact radius stage over the entire evaporation time, whereas an opposite trend was found when raising the temperature, due to the change in the surface pinning ability with pressure (and temperature). The results also suggested that the evaporation mode transition is mainly affected by temperature rather than pressure. In addition, the evaporation rate was calculated under various degrees of subcooling, revealing that the evaporation rate increases almost linearly with pressure when keeping the degree of subcooling constant. However, when fixing the test temperature, a nonlinear decrease of the evaporation rate with pressure was observed. A power law growth of the evaporation rate with temperature was also found at a constant pressure. Last, it was uncovered by a theoretical analysis that the saturated vapor concentration is the dominant factor dictating the evaporation rate.
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It is of both practical and scientific significance to understand the temperature dependence of contact angles of water on various surfaces. However, the variation trend of water wettability on a smooth hydrophobic surface with increasing temperature remains unclear. In this work, in situ characterization of the contact angle of water on Teflon (polytetrafluoroethylene) surfaces and the interfacial tension of water over a temperature spectrum from â¼25 to 160 °C under pressurized conditions (2, 3, and 5 MPa) in a nitrogen atmosphere was conducted by employing the sessile drop and pendant drop methods, respectively. A nearly invariant trend of the contact angle was observed over the entire temperature and pressure range. As expected, however, it was shown that the water-N2 interfacial tension almost linearly declines with increasing temperature and that pressure has a negative effect on the interfacial tension. Based on the theory of surface thermodynamics, the effects of temperature on the contact angles were analyzed in combination with the gas adsorption effect. Estimations on the solid-gas interfacial tension, surface entropy, and the heat of immersion were made to gain more insights into the temperature dependence of the water contact angle on a smooth hydrophobic surface.
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Seasonal storage of solar thermal energy through supercooled phase change materials (PCM) offers a promising solution for decarbonizing space and water heating in winter. Despite the high energy density and adaptability, natural PCMs often lack the necessary supercooling for stable, long-term storage. Leveraging erythritol, a sustainable mid-temperature PCM with high latent heat, we introduce a straightforward method to stabilize its supercooling by incorporating carrageenan (CG), a bio-derived food thickener. By improving the solid-liquid interfacial energy with the addition of CG the latent heat of erythritol can be effectively locked at a very low temperature. We show that the composite PCM can sustain an ultrastable supercooled state below -30 °C, which guarantees no accidental loss of the latent heat in severe cold regions on Earth. We further demonstrate that the common ultrasonication method can be used as the key to unlocking the latent heat stored in the CG-thickened erythritol, showing its great potential to serve as a high-performance, eco-friendly PCM for long-term seasonal solar energy storage.
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The water evaporation rate of 3D solar evaporator heavily relies on the water transport height of the evaporator. In this work, a 3D solar evaporator featuring a soil capillary-like structure is designed by surface coating native balsa wood using potassium hydroxide activated carbon (KAC). This KAC-coated wood evaporator can transport water up to 32 cm, surpassing that of native wood by ≈8 times. Moreover, under 1 kW m-2 solar radiation without wind, the KAC-coated wood evaporator exhibits a remarkable water evaporation rate of 25.3 kg m-2 h-1, ranking among the highest compared with other reported evaporators. The exceptional water transport capabilities of the KAC-coated wood should be attributed to the black and hydrophilic KAC film, which creates a porous network resembling a soil capillary structure to facilitate efficient water transport. In the porous network of coated KAC film, the small internal pores play a pivotal role in achieving rapid capillary condensation, while the larger interstitial channels store condensed water, further promoting water transport up more and micropore capillary condensation. Moreover, this innovative design demonstrates efficacy in retarding phenol from wastewater through absorption onto the coated KAC film, thus presenting a new avenue for high-efficiency clean water production.
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Leakage of oils and organic solvents poses a significant threat to aquatic environments. Here, low-temperature carbonized aerogels with highly porous and anisotropic structures obtained only from biomass-derived materials were proposed to absorb polymorphic oils from contaminated water. Specifically, carbonized aerogels prepared at temperatures of 300 °C and 350 °C exhibited ultra-high absorption capacities (40â125 g g-1) and oil-water separation efficiencies (> 99%) even in harsh environments, which were attributed to their exceptional properties, including high porosity, abundant macropores, excellent thermal stability, and hydrophobicity. Through citric acid crosslinking and low-temperature carbonization, the aerogels exhibited superior compression elasticity and could be cyclically utilized through simple extrusion while realizing the recovery of oils. Moreover, the outstanding photothermal conversion properties obtained through carbonization contributed to the high temperature and fluidity of the oils surrounding the aerogels, which is crucial for improving the absorption performance of high-viscosity oils. Such absorbent materials are used to separate crude oil from oil-water mixtures, which can achieve maximum absorption of 56 g g-1 and increase the absorption rate (from several days to 10 min) in a low-temperature (4 °C) seawater environment.
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Óleos , Água , Biomassa , Adsorção , Óleos/química , Solventes , Elasticidade , Água/químicaRESUMO
Elevating the charging cut-off voltage is one of the efficient approaches to boost the energy density of Li-ion batteries (LIBs). However, this method is limited by the occurrence of severe parasitic reactions at the electrolyte/electrode interfaces. Herein, to address this issue, we design a non-flammable fluorinated sulfonate electrolyte by multifunctional solvent molecule design, which enables the formation of an inorganic-rich cathode electrolyte interphase (CEI) on high-voltage cathodes and a hybrid organic/inorganic solid electrolyte interphase (SEI) on the graphite anode. The electrolyte, consisting of 1.9 M LiFSI in a 1:2 v/v mixture of 2,2,2-trifluoroethyl trifluoromethanesulfonate and 2,2,2-trifluoroethyl methanesulfonate, endows 4.55 V-charged graphite||LiCoO2 and 4.6 V-charged graphite||NCM811 batteries with capacity retentions of 89% over 5329 cycles and 85% over 2002 cycles, respectively, thus resulting in energy density increases of 33% and 16% compared to those charged to 4.3 V. This work demonstrates a practical strategy for upgrading the commercial LIBs.
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HYPOTHESIS: Pressure dependence of contact angle is expected to be influenced by temperature. Nevertheless, the correlation of water contact angle with pressure is rarely investigated at high temperatures (over 100 â). EXPERIMENTS: In this work, measurements of the contact angle and interfacial tension of water in N2 atmosphere were conducted at various pressures and temperatures (up to 17 MPa and 300 â). The experimental observations were elucidated based on the theory of surface thermodynamics. FINDINGS: It was shown that the water-N2 interfacial tension linearly decreases with increasing the pressure, and that the pressure coefficient declines as temperature rises. The pressure dependence of the water contact angle was found to be different for the low- and high-temperature regimes: the water contact angle increases below 100 â, whereas an inverse variation occurs over 100 â. According to the theoretical analysis, the pressure dependence of both the water interfacial tension and contact angle is attributed to N2 adsorption on the surfaces of water and silicon. The variations in the water contact angle with pressure, including both the sign and magnitude, are actually the consequence of the changes of water-N2 and Si-N2 interfacial tensions manipulated by pressure and temperature.
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HYPOTHESIS: In terms of the Young's equation, the temperature dependence of liquid-solid contact angle is affected by the surface material, so the wetting behavior could be tuned by both changing the temperature and surface material. However, the synergistic effects of surface material and temperature on the water contact angle remain unclear, especially at elevated temperatures. EXPERIMENTS: In this study, a systematic characterization of water contact angle against various smooth metallic and nonmetallic surfaces was conducted for temperatures up to 300 â in a high-pressure chamber at 15 MPa. The measured results were finally compared with the predictions made by the sharp-kink approximation model. FINDINGS: Not surprisingly, it was observed the temperature-dependent water contact angle is sensitive to the type of solid surface. The temperature coefficients and critical temperature points on the contact-angle-temperature curves can be manipulated by altering the surface material. However, the influence of surface material is weakened by raising temperature, thus leading to the nearly consistent temperature-dependent water contact angle over 120â. Additionally, the necessity of investigating the internal flows within the water drops was highlighted to unravel the positive temperature correlation of the water contact angle at high temperatures, in view of the presence of non-spherical-cap-shaped drops.
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Água , Temperatura , MolhabilidadeRESUMO
The independent expertise required by the preparation and application of graphene has brought a challenge to the more fluent development of graphene devices. We combine the advantages of chemical vapor deposition and micromechanical exfoliation methods of synthesizing graphene to develop a "graphene tape" for the fast utilization of graphene, which is robust, storable, and user-friendly. Prepared by pretransferring graphene to the surface of a polymer carrier film with weak interfacial adhesion, this graphene tape enables the acquisition, patterning, and layer-by-layer epitaxy of scalable graphene on a target substrate through simple cutting, pressing, and peeling off. Multiple characterizations demonstrate its comparable quality with as-synthesized graphene even after stored for over 30 days, overcoming the time and space limitations of acquiring a graphene sample. We believe that this graphene tape can bridge the current gap between graphene synthesis and applications and promote industrial progress of graphene-based devices in the post-Moore era.
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Electrolyte engineering advances Li metal batteries (LMBs) with high Coulombic efficiency (CE) by constructing LiF-rich solid electrolyte interphase (SEI). However, the low conductivity of LiF disturbs Li+ diffusion across SEI, thus inducing Li+ transfer-driven dendritic deposition. In this work, we establish a mechanistic model to decipher how the SEI affects Li plating in high-fluorine electrolytes. The presented theory depicts a linear correlation between the capacity loss and current density to identify the slope k (determined by Li+ mobility of SEI components) as an indicator for describing the homogeneity of Li+ flux across SEI, while the intercept dictates the maximum CE that electrolytes can achieve. This model inspires the design of an efficient electrolyte that generates dual-halide SEI to homogenize Li+ distribution and Li deposition. The model-driven protocol offers a promising energetic analysis to evaluate the compatibility of electrolytes to Li anode, thus guiding the design of promising electrolytes for LMBs.
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Li-ion batteries have made inroads into the electric vehicle market with high energy densities, yet they still suffer from slow kinetics limited by the graphite anode. Here, electrolytes enabling extreme fast charging (XFC) of a microsized graphite anode without Li plating are designed. Comprehensive characterization and simulations on the diffusion of Li+ in the bulk electrolyte, charge-transfer process, and the solid electrolyte interphase (SEI) demonstrate that high ionic conductivity, low desolvation energy of Li+ , and protective SEI are essential for XFC. Based on the criterion, two fast-charging electrolytes are designed: low-voltage 1.8 m LiFSI in 1,3-dioxolane (for LiFePO4 ||graphite cells) and high-voltage 1.0 m LiPF6 in a mixture of 4-fluoroethylene carbonate and acetonitrile (7:3 by vol) (for LiNi0.8 Co0.1 Mn0.1 O2 ||graphite cells). The former electrolyte enables the graphite electrode to achieve 180 mAh g-1 at 50C (1C = 370 mAh g-1 ), which is 10 times higher than that of a conventional electrolyte. The latter electrolyte enables LiNi0.8 Co0.1 Mn0.1 O2 ||graphite cells (2 mAh cm-2 , N/P ratio = 1) to provide a record-breaking reversible capacity of 170 mAh g-1 at 4C charge and 0.3C discharge. This work unveils the key mechanisms for XFC and provides instructive electrolyte design principles for practical fast-charging LIBs with graphite anodes.
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Contact angle, a quantitative measure of macroscopic surface wettability, plays an important role in understanding liquid-vapor heterogeneous phase change phenomena, e.g., boiling heat transfer. The contact angles of water at elevated temperatures are of particular interest for understanding of wettability-regulated boiling heat transfer in steam-based power generation. From a more theoretical perspective, the temperature dependence of contact angle of water is also essential to estimation of several key surface thermodynamic properties, such as the solid surface tension, the surface entropy, and the heats of immersion and adsorption. Here, a comprehensive review of historical efforts in measuring the contact angles of water over a wide temperature range on a variety of solids, not limited to metallic surfaces, is presented. As suggested by the literature data, the temperature dependence of contact angle of water may be classified into three regimes: (a) low temperatures below the saturation point (i.e., 100 °C at atmospheric pressure), (b) medium temperatures up to ~170 °C, and (c) high temperatures up to 300 °C at pressurized conditions. A slightly-decreasing or nearly-invariant trend of the contact angles of water on both non-metallic and metallic surfaces was reported for the low-temperature regime. In contrast, a steeper linear decline in water contact angle was demonstrated at temperatures above 100 °C. The few experimental data available on several metallic surfaces showed that the contact angle of water either again becomes nearly temperature-independent or further decreases with temperature above 210 °C. A theoretical understanding of the temperature dependence is given based on surface thermodynamic analysis, although the exact molecular mechanisms underlying these experimental observations remain unclear. Consequently, the theoretical model for predicting the variation of the contact angle of water with temperature is not well-developed. As the critical point of water (374 °C and 22.1 MPa) is approached, the surface tension, and hence the contact angle, should become vanishingly small. However, this theoretical expectation has not yet been verified due to the lack of experimental data at such high temperatures/pressures. Finally, future research directions are identified, including a systematic exploration of the contact angle at near-critical temperatures, the effects of surface oxidation, corrosion, and deposition on contact angle during operation of boilers and reactors, and the particular effect of irradiation on contact angle in nuclear reactor applications.
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Enhancing critical heat flux (CHF) during boiling with structured surfaces has received much attention because of its important implications for two-phase flow. The role of surface structures on bubble evolution and CHF enhancement remains unclear because of the lack of direct visualization of the liquid- and solid-vapor interfaces. Here, we use high-magnification in-liquid endoscopy to directly probe bubble behavior during boiling. We report the previously unidentified coexistence of two distinct three-phase contact lines underneath growing bubbles on structured surfaces, resulting in retention of a thin liquid film within the structures between the two contact lines due to their disparate advancing velocities. This finding sheds light on a previously unidentified mechanism governing bubble evolution on structured surfaces, which has notable implications for a variety of real systems using bubble formation, such as thermal management, microfluidics, and electrochemical reactors.
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Phase change heat transfer (e.g., boiling of water) on surfaces can be enhanced by tuning the surface wettability, which is often quantified by the contact angle and is expected to be influenced by temperature and pressure. However, the temperature (and pressure) dependence of contact angles of water on metallic surfaces remain unclear. In this study, an in situ characterization of the contact angles of water on 304 stainless steel surfaces at temperatures from room temperature to 250 °C and at pressures up to 15 MPa was performed using the sessile drop method. It was shown that three distinct regimes can be identified on the contact angle-temperature curves. A slightly-decreasing trend of the contact angles with temperature was observed below 120 °C, followed by a steeper linear decrease at higher temperatures. A further rise of the decreasing rate with temperature was observed above 210 °C. In contrast to temperature, the pressure was shown to have little effects on the contact angles. Based on the theory of surface thermodynamics, the effects of temperature (and pressure) on the contact angles were analyzed in terms of the interfacial tensions. An empirical correlation was developed to predict the contact angles as a function of temperature.
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Creating long-lived topological textured liquid crystals (LCs) in confined nonspherical space is of significance in both generations of structures and fundamental studies of topological physics. However, it remains a great challenge due to the fluid character of LCs and the unstable tensional state of transient nonspheres. Here, we realize a rich series of topological textures confined in nonspherical geometries by drop impact assembly (DIA) of graphene oxide (GO) aqueous LCs. Various highly curved nonspherical morphologies of LCs were captured by gelator bath, generating distinct out-of-equilibrium yet long-lived macroscopic topological textures in 3D confinement. Our hydrodynamic investigations on DIA processes reveal that the shear-thinning fluid behavior of LCs and the arrested GO alignments mainly contribute to the topological richness in DIA. Utilizing the shaping behavior of GO LCs compared to other conventional linear polymers such as alginate, we further extend the DIA methodology to design more complex yet highly controllable functional composites and hybrids. This work thus reveals the potential to scale production of uniform yet anisotropic materials with rich topologic textures and tailored composition.