Vinyl ethylene carbonate as an additive to ionic liquid electrolyte for lithium ion batteries

In this research, we investigated the potential application of vinyl ethylene carbonate (VEC) and ethylene carbonate (EC) as solid electrolyte interface (SEI) film-forming additive in 1-ethyl-3-methylimidazolium (EMI)-bis(trifluoromethyl-sulfonyl) imide (TFSI)-LiTFSI ionic liquid electrolyte (IL). The electrochemical performance of natural graphite (NG7) was studied in LiTFSI/EMI-TFSI containing different weight percent of EC/VEC via cyclic voltammetry (CV), electrochemical impedance spectrum (EIS), and galvanostatic charge/discharge cycles. Temperature effect on the discharge/charge performance of NG7 electrode in the researched IL electrolyte was also discussed.     

Polyterthiophene/CNT composite as a cathode material for lithium batteries employing an ionic liquid electrolyte

A polyterthiophene (PTTh)/multi-walled carbon nanotube (CNT) composite was synthesised by in situ chemical polymerisation and used as an active cathode material in lithium cells assembled with an ionic liquid (IL) or conventional liquid electrolyte, LiBF₄/EC-DMC-DEC. The IL electrolyte consisted of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) containing LiBF₄ and a small amount of vinylene carbonate (VC). The lithium cells were characterised by cyclic voltammetry (CV) and galvanostatic charge/discharge cycling. The specific capacity of the cells with IL and conventional liquid electrolytes after the 1st cycle was 50 and 47 mAh g⁻¹ (based on PTTh weight), respectively at the C/5 rate. The capacity retention after the 100th cycle was 78% and 53%, respectively. The lithium cell assembled with a PTTh/CNT composite cathode and a non-flammable IL electrolyte exhibited a mean discharge voltage of 3.8 V vs Li⁺/Li and is a promising candidate for high-voltage power sources with enhanced safety.     

Electrosynthesis of novel photochemically active inherently conducting polymers using an ionic liquid electrolyte

Use of an ionic liquid as a solvent enabled the successful preparation of films composed of polyterthiophene doped with an anionic dye. Photoelectrochemical cells constructed using these films showed significant improvements in photovoltaic properties when the films were first reduced in the presence of a cationic dye. Absorption spectroscopic studies provided evidence for retention of both dyes in the films, while photocurrent action spectra showed that the increase in photovoltaic performance was due largely to improvements in light harvesting by the polymer.     

Self-discharge characteristics of lithium/sulfur batteries using TEGDME liquid electrolyte

We investigated self-discharge characteristics of Li/S batteries using tetra ethylene glycol dimethylether (TEGDME) electrolyte. The open circuit voltages (OCV) and discharge curves were measured as a function of storage time. The self-discharge of the Li/S battery depended on current collectors. Li/TEGDME/S batteries with stainless steel (SUS) current collector showed the highest self-discharge rate of 59% per month. The self-discharge rate of Li/TEGDME/S battery using Al current collector is 34% during initial 80 days, but only 36% after 360 days storage. The discharge capacity decreases only 2% from 80 to 360 days. The self-discharge of Li/S battery using Al current collector is severe during initial 80 days, but is not an important factor after 80 days. Average self-discharge rate of Li/TEGDME/S battery using Al current collector is 3% per month for 1 year.     

Sulfur-mesoporous carbon composites in conjunction with a novel ionic liquid electrolyte for lithium rechargeable batteries

Sulfur coated mesoporous carbon (S-C) composites have been synthesized and physically characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. Firstly, the electrochemical properties of the S-C composite cathode materials were tested in a conventional electrolyte consisting of 1 mol/L lithium bistrifluoromethanesulfonimidate in poly(ethylene glycol) dimethyl ether to compare them with pure sulfur electrode. The capacity and cyclic stability of the S-C composite were improved. Then the S-C composites were tested in a novel ionic liquid electrolyte consisting of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide and lithium bistrifluoromethanesulfonimidate. The capacity and cyclic stability of the S-C composite using the ionic liquid electrolyte were much better than for the sample tested in a conventional organic solvent electrolyte.     

Improving electrochemical properties of room temperature ionic liquid (RTIL) based electrolyte for Li-ion batteries

Room temperature ionic liquids (RTILs) with high safety characteristic usually have high viscosity and melting point, which is adverse for the application of RTIL-based electrolytes in Li-ion batteries. In this investigation, a promising RTIL, i.e. PP13TFSI consisting of N-methyl-N-propylpiperidinium (PP13) cation and bis(trifluoromethanesulfonyl)imide (TFSI) anion is synthesized. The effect of the content of Li salt in the electrolytes containing PP13TFSI and LiTFSI on the ionic conductivity and cell performance is investigated. The electrolyte of 0.3 mol kg⁻¹ LiTFSI/PP13TFSI is recommended for its higher lithium transference number and discharge capacity in the LiCoO₂/Li cell than other electrolytes. In addition, it is found that, by introducing 20% diethyl carbonate (DEC) as a co-solvent into pure RTIL electrolyte, the rate capability and low-temperature performance of the LiCoO₂/Li cells are improved obviously, without sacrificing its safety characteristics. It suggests that a component with low viscosity and melting point, i.e. DEC, is necessary to effectively overcome the shortcomings of RTIL for the application in Li-ion batteries.     

Mathematical modelling of ionic transport in the electrolyte of Li-ion batteries

The ionic conductivity of the organic electrolyte in Li-ion batteries has been modelled. The classical one-dimensional Nernst-Planck approach results in a system of two non-linear parabolic second-order partial differential equations. It is shown that under electro-neutrality conditions this complex system of equations can be reduced to simple diffusion equations with modified diffusion coefficient, facilitating the efficient use of numerical methods. As a result, detailed information about transient and steady-state behaviour of the electrolyte is revealed, including potential gradients and the diffusion and migration fluxes for both Li⁺ and ions. Furthermore, an extension of the basic model is presented, taking into account salt dissociation in the electrolyte. The most characteristics of ionic transportation are illustrated with realistic examples of constant-current (dis)charging Li-ion batteries. Some of the numerical simulations are compared with recently reported experimental results.     

Mixtures of ionic liquid and organic carbonate as electrolyte with improved safety and performance for rechargeable lithium batteries

In this paper we report the results of physical–chemical and electrochemical investigations performed on ternary mixtures of the room temperature ionic liquid (IL) N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₄TFSI), propylene carbonate (PC), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as electrolyte for lithium-ion batteries. The thermal stability, ionic conductivity, viscosity and electrochemical stability windows of all considered mixtures were investigated and compared with those of electrolytes based on the pure PYR₁₄TFSI and PC. The mixtures were also used as electrolyte in combination with LiFePO₄-based electrodes. The specific capacity and cycling stability of these systems were investigated at different C-rates, both at room temperature and 60 °C.     

Kinetic analysis of Li|Li+ interphase in an ionic liquid electrolyte

Kinetic analysis of the Li|Li⁺ interphase in an electrolyte based on N-metyl-N-propylpyrrolidinium bis(trifluoromethanesulfon)imide ionic liquid (MPPyrrTFSI) and lithium bis(trifluoromethanesulfon)imide salt (LiTFSI) was performed. Li|electrolyte|Li and LiC₆|electrolyte|Li cells were galvanostatically charged/discharged in order to form solid electrolyte interphase (SEI) protecting layer. SEM images showed that the surface of both Li and LiC₆ anodes was covered with small particles. The fitting procedure of electrochemical impedance data taken at different temperatures gave three resistances (R _el, R _SEI, R _ct) and hence, three lnR = f(T ^?1) straight lines of different slopes. Specific conductivity and activation energy of the conduction process of the liquid electrolyte, were ca. σ = 2.5 mS cm^?1 (at T = 25.0 °C) and $ E_{\text{el}}^{\# } $  = 15 kJ mol^?1. Activation energy for the conduction process in the SEI layer was ca. 56 kJ mol^?1 in the case of the metallic lithium and 62 kJ mol^?1 for the graphite anode. Activation energy of the charge transfer process, $ E_{\text{ct}}^{\# } $ , for Li and LiC₆ anodes was 71 and 65 kJ mol^?1, respectively. Analysis of literature data for different electrolytes suggests that the $ E_{\text{ct}}^{\# } $ value for Li⁺ reduction may be approximated by 57 ± 5 kJ mol^?1. Activation energy for the diffusion processes in the graphite electrode, detected from the Warburg coefficient, was ca 74 kJ mol^?1.     

A novel strategy of lithium recycling from spent lithium-ion batteries using imidazolium ionic liquid

In light of the increasing demand for environmental protection and energy conservation,the recovery of highly valuable metals,such as Li,Co,and Ni,from spent lithium-ion batteries (LIBs) has attracted wide-spread attention.Most conventional recycling strategies,however,suffer from a lack of lithium recycling,although they display high efficiency in the recovery of Co and Ni.In this work,we report an efficient extraction process of lithium from the spent LIBs by using a functional imidazolium ionic liquid.The extraction efficiency can be reached to 92.5％ after a three-stage extraction,while the extraction effi-ciency of Ni-Co-Mn is less than 4.0％.The new process shows a high selectivity of lithium ion.FTIR spec-troscopy and ultraviolet are utilized to characterize the variations in the functional groups during extraction to reveal that the possible extraction mechanism is cation exchange.The results of this work provide an effective and sustainable strategy of lithium recycling from spent LIBs.     

Predicting capacity of hard carbon anodes in sodium-ion batteries using porosity measurements

We report an inverse relationship between measurable porosity values and reversible capacity from sucrose-derived hard carbon as an anode for sodium-ion batteries (SIBs). Materials with low measureable pore volumes and surface areas obtained through N₂ sorption yield higher reversible capacities. Conversely, increasing measurable porosity and specific surface area leads to sharp decreases in reversible capacity. Utilizing a low porosity material, we thus are able to obtain a reversible capacity of 335 mAh g⁻¹. These findings suggest that sodium-ion storage is highly dependent on the absence of pores detectable through N₂ sorption in sucrose-derived carbon.     

Cyclic wet drying of an epoxy coating using an ionic liquid

The barrier protection of an organic coating for a metallic substrate is compromised by the transport of water, oxygen and ions from the environment to the metal/coating interface. Metallic outdoor structures are exposed to the weather and undergo cyclic wetting and drying conditions. In the absence of holidays, the transport of water is diffusion limited. The diffusion coefficients associated with water ingress D_in and egress D_out are indicators of the wetting and drying rates, respectively, of the coating. Gravimetric and capacitance methods are used for the measurement of D_in whereas D_out measurement has been limited to the gravimetric method. The objective of this paper is to demonstrate the application of a recently reported method that employed a hydrophilic room temperature ionic liquid to monitor the capacitance changes associated with the egress of water from which D_out was calculated. Experimental results associated with cyclic dilute NaCl wetting and ionic liquid drying are presented for an epoxy coating on an AA 2024-T3 substrate that was subjected to 50 cycles. The D_in and D_out values were calculated using a short-time approximate solution and a series solution to Fick's second law. Presented electrochemical impedance spectra associated with the ends of wet and dry stages of the cycles were analyzed using an equivalent circuit model that separated the bulk coating and metal/coating characteristics.     

Synthesis of a cardanol-amine derivative using an ionic liquid catalyst

Cardanol is a biobased raw material derived from cashew nut shell liquid. In order to extend its utility, new derivatives and additional applications are useful. In this work cardanol was first epoxidized, and a novel aniline derivative prepared from it under mild reaction conditions with the help of an ionic liquid catalyst. The reaction chemistry was studied by using nuclear magnetic resonance. The resulting aminohydrin adduct showed antioxidant property and should also be a useful synthon for further reactions. As an example, the aminohydrin was shown to undergo a condensation reaction with formaldehyde to form a prepolymer, which could be further reacted to form thermosetting resins.

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Imidazolium‐functionalized norbornene ionic liquid block copolymer and silica composite electrolyte membranes for lithium‐ion batteries

Imidazolium‐functionalized norbornene and benzene‐functionalized norbornene were synthesized and copolymerized via ring‐opening metathesis polymerization to afford a polymeric ionic liquid (PIL) block copolymers {5‐norbornene‐2‐methyl benzoate‐block ‐5‐norbornene‐2‐carboxylate‐1‐hexyl‐3‐methyl imidazolium bis[(trifluoromethyl)sulfonyl]amide [P(NPh‐b ‐NIm‐TFSI)]} with good thermal stability. On this basis, the solid electrolyte, P(NPh‐b ‐NIm‐TFSI)–lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), through blending with LiTFSI, and the nanosilica composite electrolyte, P(NPh‐b ‐NIm‐TFSI)–LiTFSI–SiO₂, through blending with LiTFSI and nanosilica, were prepared. The effects of the PILs and silica compositions on the properties, morphology, and ionic conductivity were investigated. The ionic conductivity was enhanced by an order of magnitude compared to that of polyelectrolytes with lower PIL compositions. In addition, the ionic conductivity of the nanosilica composite polyelectrolyte was obviously improved compared with that of the P(NPh‐b ‐NIm‐TFSI)–LiTFSI polyelectrolyte and increased progressively up to a maximum with increasing silica content when SiO₂ was 10 wt % or lower. The best conductivity of the P(NPh‐b ‐NIm‐TFSI)–20 wt % LiTFSI–10 wt % SiO₂ composite electrolyte with 7.7 × 10^?5 S/cm at 25 °C and 1.3 × 10^?3 S/cm at 100 °C were obtained, respectively. All of the polyelectrolytes exhibited suitable electrochemical stability windows. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44884.     

钠离子电池正极材料研究进展

钠离子电池与锂离子电池工作原理相似,却有着更低的成本和更高的安全性。在钠离子电池中,正极材料的研究尤为重要。本文对现有的钠离子电池正极材料进行了系统性的归纳,首先介绍了各类正极材料的结构和电化学特性,基于此分析目前钠离子电池正极材料面临的两个主要制约因素：一是钠离子半径大,充放电过程中对材料结构的影响大,导致容量衰减迅速;二是动力学过程慢,导致其倍率性能差。在此基础上归纳了现有的各类钠离子电池正极材料的改性方法如掺杂、包覆等。总结了材料改性及改善材料电化学性能的方法以及应用在现有材料中时所获得的效果,基于此为未来的钠离子电池正极材料及其改性研究提供了基础。     

Synergistic effect of ionic liquid and organo-functional silane on the preparation of silica based hybrid ionogels as solid-state electrolyte for Li-ion batteries

Having excellent safety and potentially high energy density, solid-state electrolytes can be used in large-scale energy storage applications instead of flammable and volatile organic solvent-based electrolytes. Aerogels are notable candidates for solid-state electrolytes due to their low density, high porosity, high specific surface area, stable thermal behavior, and ultralow dielectric constant. In this work, Li-doped silica ionogels were synthesized by the two-step sol-gel method by using trifunctional organosilane Methyltrimethoxysilane (MTMS), as silica co-precursor along with conventional precursor TEOS. In addition, 1,3-Butylmethylimidazolium bis(trifluorosulfonyl)imide (BMIMTFSI) was selected as an ionic liquid to provide ion mobility throughout the solid skeleton. The synthesized hybrid ionogels were characterized by FTIR, SEM, BET, and TGA analyzes. It was observed that the specific surface areas of the obtained ionogels varied between 685 and 725 m²/g. To examine the effect of Li⁺ ion concentration on ion conductivity, electrolyte solutions have prepared in different concentrations (0.5 ~ 2 M). The Li⁺ ion conductivity of the ionogel prepared with 2 M of Li⁺ ion solution (M-IGE-2) was determined as 4.06 × 10⁻⁴ S/cm by Potentiostatic EIS measurement and it possessed 3.3V of electrochemical stability.     

A novel nickel-based mixed rare-earth oxide/activated carbon supercapacitor using room temperature ionic liquid electrolyte

Mesopore nickel-based mixed rare-earth oxide (NMRO) and activated carbon (AC) with rich oxygen-contained groups were prepared as electrode materials in a supercapacitor using room temperature ionic liquid (RTIL) electrolyte. These electrode materials were characterized by XPS, XRD, N₂ adsorption, SEM as well as various electrochemical techniques, and showed good properties and operated well with RTIL electrolyte. A 3 V asymmetrical supercapacitor was fabricated, which delivered a real power density of 458 W kg⁻¹ as well as a real energy density of 50 Wh kg⁻¹, and during a 500-cycle galvanostatic charge/discharge measurement, no capacity decay was visible. Such promising energy-storage performance was to a large extent ascribed to nonvolatile RTIL electrolyte with wide electrochemical windows and high stable abilities worked with both electrode materials.     

离子液体催化合成丙交酯

丙交酯是合成可降解材料聚乳酸的重要中间体。以D、L-乳酸为原料,在离子液体催化剂存在下脱水环化合成丙交酯,研究了反应过程中离子液体的种类及用量等因素对丙交酯产率的影响,粗产品经重结晶纯化得到高纯度D、L-丙交酯,通过熔点、红外光谱和紫外光谱对产品进行了表征;实验表明,以离子液体为催化剂制备丙交酯具有可行性,体系粘度降低,反应条件温和,有利于丙交酯的生成;确定了[NH(C₂H₅)₃][HSO₄]为催化剂时的适宜工艺条件为催化剂用量5 wt%,缩聚温度110～140℃,解聚温度190～250℃。