44 research outputs found
Concentrated Ionic-Liquid-Based Electrolytes for High-Voltage Lithium Batteries with Improved Performance at Room Temperature
Ionic liquids (ILs) have been widely explored as alternative electrolytes to combat the safety issues associated with conventional organic electrolytes. However, hindered by their relatively high viscosity, the electrochemical performances of ILâbased cells are generally assessed at mediumâtoâhigh temperature and limited cycling rate. A suitable combination of alkoxyâfunctionalized cations with asymmetric imide anions can effectively lower the lattice energy and improve the fluidity of the IL material. The Li/LiNiMnO cell employing NâNâdiethylâNâmethylâNâ(2âmethoxyethyl)ammonium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (DEMEFTFSI)âbased electrolyte delivered an initial capacity of 153â
mAhâg within the voltage range of 2.5â4.6â
V, with a capacity retention of 65.5â% after 500â
cycles and stable coulombic efficiencies exceeding 99.5â%. Moreover, preliminary battery tests demonstrated that the drawbacks in terms of rate capability could be improved by using Liâconcentrated ILâbased electrolytes. The improved roomâtemperature rate performance of these electrolytes was likely owing to the formation of Liâcontaining aggregate species, changing the concentrationâdependent Liâion transport mechanism
Highly Concentrated KTFSIâ:âGlyme Electrolytes for K/BilayeredâVâOâ Batteries
Highly concentrated glymeâbased electrolytes are friendly to a series of negative electrodes for potassiumâbased batteries, including potassium metal. However, their compatibility with positive electrodes has been rarely explored. In this work, the influence of the molar fraction of potassium bis(trifluoromethanesulfonyl)imide dissolved in glyme on the cycling ability of K/bilayeredâV2O5 batteries has been investigated. At high salt concentration, the interaction between K+ ions with the glyme is strengthened, leading to a limited number of free glyme molecules. Therefore, the anodic decomposition of the electrolyte solvent, as well as the dissolution of the Al current collectors, is effectively suppressed, resulting in the improved cycling ability of the K/bilayeredâV2O5 cells. In these cells, the positive electrode active material exhibits reversible capacities of 93 and 57â
mAhâgâ1 at specific current densities of 50 and 1000â
mAâgâ1, respectively. After 200 chargeâdischarge cycles at 500â
mAâgâ1, the cell retains 94â% of the initial capacity. The promising rate performance and capacity retention demonstrate the importance of proper electrolyte engineering for the K/bilayeredâV2O5 batteries, and the good compatibility of highly concentrated glymeâbased electrolytes with positive electrode materials for potassium batteries
Highly concentrated KTFSI: Glyme electrolytes for K/bilayered-V2O5 batteries
Highly concentrated glyme-based electrolytes are friendly to a series of negative electrodes for potassium-based batteries, including potassium metal. However, their compatibility with positive electrodes has been rarely explored. In this work, the influence of the molar fraction of potassium bis(trifluoromethanesulfonyl)imide dissolved in glyme on the cycling ability of K/bilayered-V2O5 batteries has been investigated. At high salt concentration, the interaction between K+ ions with the glyme is strengthened, leading to a limited number of free glyme molecules. Therefore, the anodic decomposition of the electrolyte solvent, as well as the dissolution of the Al current collectors, is effectively suppressed, resulting in the improved cycling ability of the K/bilayered-V2O5 cells. In these cells, the positive electrode active material exhibits reversible capacities of 93 and 57 mAh gâ1 at specific current densities of 50 and 1000 mA gâ1, respectively. After 200 charge-discharge cycles at 500 mA gâ1, the cell retains 94 % of the initial capacity. The promising rate performance and capacity retention demonstrate the importance of proper electrolyte engineering for the K/bilayered-V2O5 batteries, and the good compatibility of highly concentrated glyme-based electrolytes with positive electrode materials for potassium batteries. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA
Operando pH Measurements Decipher Hâș/ZnÂČâș Intercalation Chemistry in High-Performance Aqueous Zn/ÎŽ-VâOâ Batteries
Vanadium oxides have been recognized to be among the most promising positive electrode materials for aqueous zinc metal batteries (AZMBs). However, their underlying intercalation mechanisms are still vigorously debated. To shed light on the intercalation mechanisms, high-performance ÎŽ-V2O5 is investigated as a model compound. Its structural and electrochemical behaviors in the designed cells with three different electrolytes, i.e., 3 m Zn(CF3SO3)2/water, 0.01 M H2SO4/water, and 1 M Zn(CF3SO3)2/acetonitrile, demonstrate that the conventional structural and elemental characterization methods cannot adequately clarify the separate roles of H+ and Zn2+ intercalations in the Zn(CF3SO3)2/water electrolyte. Thus, an operando pH determination method is developed and used toward Zn/ÎŽ-V2O5 AZMBs. This method indicates the intercalation of both H+ and Zn2+ into ÎŽ-V2O5 and uncovers an unusual H+/Zn2+-exchange intercalationâdeintercalation mechanism. Density functional theory calculations further reveal that the H+/Zn2+ intercalation chemistry is a consequence of the variation of the electrochemical potential of Zn2+ and H+ during the electrochemical intercalation/release
Dual-anion ionic liquid electrolyte enables stable Ni-rich cathodes in lithium-metal batteries
High-energy-density lithium-metal batteries face the challenge of developing functional electrolytes enabling both the stabilization of the lithium-metal negative electrode and high-voltage positive electrodes (> 4 V versus Li+/Li). Herein, a low-volatility and non-flammable ionic liquid electrolyte (ILE) incorporating two anions, bis(fluorosulfonyl) imide (FSI) and bis(trifluoromethanesulfonyl)imide (TFSI), is successfully applied to overcome this challenge, employing the high-energy, low-Co, and Ni-rich positive-electrode material, LiNi0.88Co0.09Mn0.03O2 (NCM88), in Li-metal batteries. With this specific electrolyte, the cathode exhibits remarkable electrochemical performance, achieving an initial specific capacity of 214 mAh gâ1 and outstanding capacity retention of 88% over 1,000 cycles. More importantly, this electrolyte enables an average Coulombic efficiency of 99.94%. The excellent compatibility of the dual-anion ILE with both the lithium metal (50 ÎŒm) and the high-voltage positive-electrode material enables the realization of Li-metal cells achieving specific energies of more than 560 Wh kgâ1 based on their combined active material masses. © 2021 The Author
Enhancing the Interfacial Stability of HighâEnergy Si/Graphite || LiNiCoMnO Batteries Employing a DualâAnion Ionic Liquidâbased Electrolyte
The poorly flammable room-temperature ionic liquid-based electrolyte composed of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PyrFSI) with fluoroethylene carbonate (FEC) as an additive is investigated towards its compatibility with the LiNiCoMnO (NCM88) cathode and a high-capacity Si/graphite (SiG) anode, revealing a remarkably stable performance in lithium-ion cells. Interestingly, this dual-anion electrolyte with FEC additive forms a stable electrode-electrolyte interphase on both sides, which suppresses the morphological degradation of the electrode materials and continuous electrolyte decomposition. Consequently, lithium-ion cells using such dual-anion ionic liquid-based electrolyte display significantly improved cycling stability compared to conventional carbonate ester-based electrolyte, achieving a high specific energy of 385 Wh kg (based on both cathode and anode active materials weight) with a capacity retention of 74% after 200 cycles at 0.2 C, demonstrating the possibility to realize safe and high energy density LIBs
Enhanced Li+ Transport in Ionic Liquid-Based Electrolytes Aided by Fluorinated Ethers for Highly Efficient Lithium Metal Batteries with Improved Rate Capability
FSI-based ionic liquids (ILs) are promising electrolyte candidates for long-life and safe lithium metal batteries (LMBs). However, their practical application is hindered by sluggish Li transport at room temperature. Herein, it is shown that additions of bis(2,2,2-trifluoroethyl) ether (BTFE) to LiFSI-PyrFSI ILs can effectively mitigate this shortcoming, while maintaining ILsâČ high compatibility with lithium metal. Raman spectroscopy and small-angle X-ray scattering indicate that the promoted Li+ transport in the optimized electrolyte, [LiFSI][PyrFSI][BTFE] (LiPyBT), originates from the reduced solution viscosity and increased formation of Li-FSI complexes, which are associated with the low viscosity and non-coordinating character of BTFE. As a result, Li/LiFePO (LFP) cells using LiPyBT electrolyte reach 150 mAh g at 1 C rate (1 mA cm) and a capacity retention of 94.6% after 400 cycles, revealing better characteristics with respect to the cells employing the LiFSI-PyrFSI (operate only a few cycles) and commercial carbonate (80% retention after only 218 cycles) electrolytes. A wide operating temperature (from â10 to 40 °C) of the Li/LiPyBT/LFP cells and a good compatibility of LiPyBT with LiNiMnCoO (NMC532) are demonstrated also. The insight into the enhanced Li transport and solid electrolyte interphase characteristics suggests valuable information to develop IL-based electrolytes for LMBs
The unseen evidence of reduced Ionicity. The elephant in (the) room temperature ionic liquids
The unambiguous quantification of the proton transfer in Protic Ionic Liquids (PILs) and its differentiation from the concept of ionicity are still unsolved questions. Albeit researchers awfully quickly treat them as synonyms, the two concepts are intrinsically different and imply a dramatic modification in the expected chemical and physical properties of a PIL. Some attempts have been made to shed light on this discrimination, but single-technique-based approaches fail in giving a clear answer. Aiming at definitively figuring out the differentiation between proton transfer and ionicity, we performed a multi-technique analysis (NMR, Raman, IR, thermal and electrochemical analyses, among others). Indeed, thermal and spectroscopic analyses are employed to determine the acid strength's role in ions' complete formation. To overcome the ambiguity between ionicity and formation degree, we introduce a new paradigm where Reduced Ionicity accounts for both the quantities mentioned above. The reduced ionicity directly affects the thermal stability, the phase behavior, and the spectroscopic observations, resulting in particular features in NMR and vibrational spectra. The combination of physical-chemical analyses and Pulsed-Gradient Spin-Echo (PGSE) NMR allows determining the reduced ionicity (and not the ionicity, as reported so far) of the investigated systems. In this context, being the proton transfer not quantitatively accessible directly, the reduced ionicity of a reference series of triethylamine-based PILs is investigated through transport properties as a function of temperature. Our findings point towards a substantial dependence of the reduced ionicity by the acid strength and the anion's coordination power. Furthermore, some interesting insights about the proton transfer are obtained, combining all the findings collected
Cuff-Method Thigh Arterial Occlusion Counteracts Cerebral Hypoperfusion Against the PushâPull Effect in Humans
Exposure to acute transition from negative (âGz) to positive (+ Gz) gravity significantly impairs cerebral perfusion in pilots of high-performance aircraft during pushâpull maneuver. This pushâpull effect may raise the risk for loss of vision or consciousness. The aim of the present study was to explore effective countermeasures against cerebral hypoperfusion induced by the pushâpull effect. Twenty healthy young volunteers (male, 21 ± 1 year old) were tested during the simulated pushâpull maneuver by tilting. A thigh cuff (TC) pressure of 200 mmHg was applied before and during simulated pushâpull maneuver (â0.87 to + 1.00 Gz). Beat-to-beat cerebral and systemic hemodynamics were measured continuously. During rapid âGz to + Gz transition, mean cerebral blood flow velocity (CBFV) was decreased, but to a lesser extent, in the TC bout compared with the control bout (â3.1 ± 4.9 vs. â7.8 ± 4.4 cm/s, P < 0.001). Similarly, brain-level mean blood pressure showed smaller reduction in the TC bout than in the control bout (â46 ± 12 vs. â61 ± 13 mmHg, P < 0.001). The systolic CBFV was lower but diastolic CBFV was higher in the TC bout. The systemic blood pressure response was blunted in the TC bout, along with similar heart rate increase, smaller decrease, and earlier recovery of total peripheral resistance index than control during the gravitational transition. These data demonstrated that restricting thigh blood flow can effectively mitigate the transient cerebral hypoperfusion induced by rapid shift from âGz to + Gz, characterized by remarkable improvement of cerebral diastolic flow