Development of rechargeable lithium metal battery (LMB) remains a challenge because of uneven lithium deposition during repeated cycles of charge and discharge. Ionic liquids have received intensive scientific interest as electrolytes because of their exceptional thermal and electrochemical stabilities. Ionic liquid and ionic‐liquid–nanoparticle hybrid electrolytes based on 1‐methy‐3‐propylimidazolium (IM) and 1‐methy‐3‐propylpiperidinium (PP) have been synthesized and their ionic conductivity, electrochemical stability, mechanical properties, and ability to promote stable Li electrodeposition investigated. PP‐based electrolytes were found to be more conductive and substantially more efficient in suppressing dendrite formation on cycled lithium anodes; as little as 11 wt % PP‐IL in a PC‐LiTFSI host produces more than a ten‐fold increase in cell lifetime. Both PP‐ and IM‐based nanoparticle hybrid electrolytes provide up to 10 000‐fold improvements in cell lifetime than anticipated based on their mechanical modulus alone. Galvanostatic cycling measurements in Li/Li4Ti5O12 half cells using IL–nanoparticle hybrid electrolytes reveal more than 500 cycles of trouble‐free operation and enhanced rate capability. 相似文献
A novel single lithium‐ion (Li‐ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4‐styrenesulfonyl)(trifluoromethyl(S‐trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI?), and high‐molecular‐weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass‐transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li‐ion transference number (tLi+=0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li‐ion conductivity as high as 1.35×10?4 S cm?1 at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries. 相似文献
Smart self‐protection is essential for addressing safety issues of energy‐storage devices. However, conventional strategies based on sol‐gel transition electrolytes often suffer from unstable self‐recovery performance. Herein, smart separators based on thermal‐gated poly(N‐isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc‐ion batteries (ZIBs). Such PNIPAM‐based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self‐protection of ZIBs at high temperatures. Furthermore, the thermal‐gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature‐dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal‐responsive energy‐storage devices with safe and controlled energy delivery. 相似文献
Down to the wire : A simple and effective method to synthesize silver nanowires through an ionic‐liquid‐assisted polyol process is developed (see scheme; scale bar=5 nm). The ionic liquids are tuned to provide the anisotropic growth of silver nanoparticles into nanowires.
Smart self-protection is essential for addressing safety issues of energy-storage devices. However, conventional strategies based on sol-gel transition electrolytes often suffer from unstable self-recovery performance. Herein, smart separators based on thermal-gated poly(N-isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc-ion batteries (ZIBs). Such PNIPAM-based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self-protection of ZIBs at high temperatures. Furthermore, the thermal-gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature-dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal-responsive energy-storage devices with safe and controlled energy delivery. 相似文献
Further enhancement in the energy densities of rechargeable lithium batteries calls for novel cell chemistry with advanced electrode materials that are compatible with suitable electrolytes without compromising the overall performance and safety, especially when considering high‐voltage applications. Significant advancements in cell chemistry based on traditional organic carbonate‐based electrolytes may be successfully achieved by introducing fluorine into the salt, solvent/cosolvent, or functional additive structure. The combination of the benefits from different constituents enables optimization of the electrolyte and battery chemistry toward specific, targeted applications. This Review aims to highlight key research activities and technical developments of fluorine‐based materials for aprotic non‐aqueous solvent‐based electrolytes and their components along with the related ongoing scientific challenges and limitations. Ionic liquid‐based electrolytes containing fluorine will not be considered in this Review. 相似文献
A new type of water‐soluble ionic cellulose was obtained by means of the dissolution of cellulose in dimethylimidazolium methylphosphite at elevated temperatures over 120 °C. FTIR spectroscopy, 1H and 13C NMR spectroscopy, and elemental analysis results revealed that the repeating unit of the water‐soluble cellulose consists of a dialkylimidazolium cation and a phosphite anion bonded to cellulose. The degree of phosphorylation on the cellulose chain was between 0.4 and 1.3 depending on the reaction temperature and time. With an increasing degree of phosphorylation, water solubility was increased. Scanning electron microscopy and X‐ray diffraction analyses revealed that the cellulose crystalline phase in the parent crystalline cellulose changed to an amorphous phase upon transformation into ionic cellulose. Thermogravimetric analysis showed the prepared phosphorylated cellulose was stable over 250 °C and a substantial amount of residue remained at 500 °C. 相似文献
To assess the potential of ionic liquids (ILs) as a solubilizing media that facilitates proton‐transfer reactions, acridine prototropism is investigated using UV/Vis molecular absorbance as well as steady‐state and time‐resolved fluorescence with different ILs in the presence of a small amount of dilute acid or base. It is found that protonation and deprotonation of acridine, when dissolved in different ILs, can be triggered by the addition of a small amount of dilute aqueous HCl and NaOH, respectively, in both the ground and excited states, irrespective of the identity of the IL. However, the amount of dilute acid/base needed to protonate/deprotonate acridine dissolved in different ILs is found to vary from one IL to another. Steady‐state fluorescence measurements also imply the presence of interactions between the acidic proton(s) of IL cation and excited acridine. The interconversion of neutral and protonated acridine, as well as the presence of a weakly fluorescent complex between excited acridine and the acidic proton(s) of the IL cation, is further corroborated by the parameters recovered from the fitting of the excited‐state intensity‐decay data. It is established that ILs as solubilizing media readily support facile proton transfer in both ground and excited states. 相似文献
It is a very urgent and important task to improve the safety and high‐temperature performance of lithium/lithium‐ion batteries (LIBs). Here, a novel ionic liquid, 1‐(2‐ethoxyethyl)‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR1(2o2)TFSI), was designed and synthesized, and then mixed with dimethyl carbonate (DMC) as appropriate solvent and LiTFSI lithium salt to produce an electrolyte with high ionic conductivity for safe LIBs. Various characterizations and tests show that the highly flexible ether group could markedly reduce the viscosity and provide coordination sites for Li‐ion, and the DMC could reduce the viscosity and effectively enhance the Li‐ion transport rate and transference number. The electrolyte exhibits excellent electrochemical performance in Li/LiFeO4 cells at room temperature as well as at a high temperature of 60 °C. More importantly, with the addition of DMC, the IL‐based electrolyte remains nonflammable and appropriate DMC can effectively inhibit the growth of lithium dendrites. Our present work may provide an attractive and promising strategy for high performance and safety of both lithium and lithium‐ion batteries. 相似文献
Adaptive biasing force molecular dynamics simulations and density functional theory calculations were performed to understand the interaction of Li+ with pure carbonates and ethylene carbonate (EC)‐based binary mixtures. The most favorable Li carbonate cluster configurations obtained from molecular dynamics simulations were subjected to detailed structural and thermochemistry calculations on the basis of the M06‐2X/6‐311++G(d,p) level of theory. We report the ranking of these electrolytes on the basis of the free energies of Li‐ion solvation in carbonates and EC‐based mixtures. A strong local tetrahedral order involving four carbonates around the Li+ was seen in the first solvation shell. Thermochemistry calculations revealed that the enthalpy of solvation and the Gibbs free energy of solvation of the Li+ ion with carbonates are negative and suggested the ion–carbonate complexation process to be exothermic and spontaneous. Natural bond orbital analysis indicated that Li+ interacts with the lone pairs of electrons on the carbonyl oxygen atom in the primary solvation sphere. These interactions lead to an increase in the carbonyl (C=O) bond lengths, as evidenced by a redshift in the vibrational frequencies [ν(C=O)] and a decrease in the electron density values at the C=O bond critical points in the primary solvation sphere. Quantum theory of atoms in molecules, localized molecular orbital energy decomposition analysis (LMO‐EDA), and noncovalent interaction plots revealed the electrostatic nature of the Li+ ion interactions with the carbonyl oxygen atoms in these complexes. On the basis of LMO‐EDA, the strongest attractive interaction in these complexes was found to be the electrostatic interaction followed by polarization, dispersion, and exchange interactions. Overall, our calculations predicted EC and a binary mixture of EC/dimethyl carbonate to be appropriate electrolytes for Li‐ion batteries, which complies with experiments and other theoretical results. 相似文献
Electrochemical devices, especially energy storage, have been around for many decades. Liquid electrolytes (LEs), which are known for their volatility and flammability, are mostly used in the fabrication of the devices. Dye-sensitized solar cells (DSSCs) and quantum dot sensitized solar cells (QDSSCs) are also using electrochemical reaction to operate. Following the demand for green and safer energy sources to replace fossil energy, this has raised the research interest in solid-state electrochemical devices. Solid polymer electrolytes (SPEs) are among the candidates to replace the LEs. Hence, understanding the mechanism of ions’ transport in SPEs is crucial to achieve similar, if not better, performance to that of LEs. In this paper, the development of SPE from basic construction to electrolyte optimization, which includes polymer blending and adding various types of additives, such as plasticizers and fillers, is discussed. 相似文献
Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite‐free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg?1) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx. Herein, we demonstrate the first reversible Al/S battery in ionic‐liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid‐state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid‐state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system. 相似文献
A random copolymer of ethylene oxide with CO2, namely, poly(ethylene carbonate/ethylene oxide) (P(EC/EO)), has been synthesized as a novel candidate for polymer electrolytes. Electrolyte composed of P(EC/EO) and lithium bis(fluorosulfonyl)imide has an ionic conductivity of 0.48 mS cm−1 and a Li transference number (t +) of 0.66 at 60 °C. To study ion‐conductive behavior of P(EC/EO)‐based electrolytes, the Fourier transform infrared (FT‐IR) technique is used to analyze the interactions between Li+ and functional groups of the copolymer. The carbonate groups may interact preferentially with Li+ rather than the ether groups in P(EC/EO). This study suggests that copolymerization of carbonate and flexible ether units can realize both high conductivity and t + for polymer electrolytes. High‐performance P(EC/EO) electrolyte is expected to be a candidate material for use in all‐solid‐state batteries.