Ethylene carbonate—propylene carbonate mixed electrolytes for lithium batteries

Electrolytic characteristics of propylene carbonate (PC)ethylene carbonate (EC) mixed electrolytes were studied, compared with those in PC electrolytes. Conductivity and Li charge—discharge efficiency values increased with EC contents increasing. For example, 1 M LiClO₄ECPC (EC mixing molar ratio; [EC]/[PC] = 4) showed the conductivity of 8.5 ohm^?1 cm^?1, which value was 40% higher than that in PC. Also, 1 M LiClO₄ECPC([EC]/[PC] = 5) showed the Li charge—discharge efficiency of 90.5% at 0.5 mA cm^?2, 0.6 C cm^?2, which value was ca. 25% higher than that in PC. ECPC mixed electrolytes were considered to be practically available for ambient lithium batteries in regard to the high Li⁺ ion conductivity and also high Li charge—discharge efficiency.     

Dimethyl sulfoxide-based electrolytes for rechargeable lithium batteries

Mixed solutions of dimethyl sulfoxide (DMSO) and low viscosity solvents have been examined as a solvent of the electrolyte for rechargeable lithium (Li) batteries. The electrolytic conductivities of LiClO₄. LiBF₄ and LiPF₆ were measured as a function of the solvent composition. Maximum conductivities were observed in the DMSO concentration ranges of 60–80 mol% for LiClO₄ and LiBF₄, and 20–60 mol% for LiPF₆. The highest conductivity of all examined systems was 1.6 × 10⁻² S cm⁻¹ in the solution containing 1,2-dimethoxyethane (DME) and LiPF₆ as the co-solvent and the electrolyte, respectively. Polarization behavior and charge-discharge characteristics of the lithium electrode were investigated in the DMSO-based solutions. The cycling efficiency was markedly dependent not only on the co-solvent but also the Li salt. The highest efficiency on the nickel substrate was observed in LiPF₆ (1 mol dm⁻³)/DMSO-DME (1:1 by volume). High rechargeability of Li was also expected in the solution containing LiClO₄ or LiBF₄ when aluminum was used as the substrate.     

Review on composite polymer electrolytes for lithium batteries

This paper reviews the state of the art of composite polymer electrolytes (CPE) in view of their electrochemical and physical properties for the applications in lithium batteries. This review mainly encompasses on composite polymer electrolyte hosts namely poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVdF) studied so far. Also the ionic conductivity, transference number, compatibility and the cycling behavior of poly(vinylidene fluoride-hexafluoro propylene) (PVdF-HFP)-[AlO(OH)]_n-LiPF₆/LiClO₄ composite electrolytes have been studied and the results are discussed.     

Charge-discharge characteristics of the lithium electrode in mixed ether electrolytes

Mixed ether solutions of 1,2-dialkoxyethanes with 1,3-dioxolane or tetrahydrofuran containing some lithium salts have been examined as electrolytes for ambient temperature, rechargeable lithium (Li) batteries. The electrolytic conductivity and the charge-discharge behaviour of the Li electrode were investigated in the alkoxyethane-based electrolytes. The solutions containing LiPF₆ showed high conductance. The polarization behavoiur and the charge-discharge efficiency of the Li electrode were markedly affected by the size of an alkoxy group of ether. The cycling efficiency also depended on the electrolytic salt and the blended co-solvent. The highest efficiency was observed in the mixed system of 1,2-dimethoxyethane-tetrahydrofuran containing LiPF₆.     

Ternary and quaternary mixed electrolytes for lithium cells

This paper reports the influence of composition of mixed solvent electrolyte composition on the discharge capacity and charge–discharge cycle life of lithium metal/amorphous V2O5–P2O5 (95:5 in molar ratio) cells. The solvents used were ethylene carbonate (EC), propylene carbonate (PC), 2-methyltetrahydrofuran (2MeTHF) and THF. LiAsF6 was used as the solute. The electrolyte solutions examined here contain ternary and quaternary mixed systems. The purpose of this work is to obtain an electrolyte solution which realizes a higher rate capability and/or a longer cycle life than the previously studied EC:PC:2MeTHF (15:70:15) ternary mixed system. Of the electrolyte systems examined here, the EC:PC:2MeTHF (30:40:30 in volume) ternary mixed solvent system showed the best cell performance. In addition, a heating test was carried out on an AA- size lithium cell with EC:PC:2MeTHF (30:40:30) as a fundamental abuse test to ensure cell safety.     

Cycling performance and safety of rechargeable lithium cells with binary and ternary mixed solvent electrolytes

The influence of electrolyte composition on the cycling performance and safety of AA rechargeable cells with a lithium metal anode, and an amorphous (a-) V₂O₅-P₂O₅ cathode was examined. The cells were cycled at a discharge current of 1000 mA and a charging current of 200 mA. The electrolytes were composed of ethylene carbonate (EC)/2-methyltetrahydrofuran (2MeTHF) binary and EC/propylene carbonate (PC)/2MeTHF ternary mixed solvents containing 40–70 vol% 2MeTHF to provide higher conductivity. The solute was 1.5mol dm^–3 LiAsF₆. The cycle life of the AA cells was evaluated by setting the end of cycle life at the cycle number where the discharge capacity fell to 50% of its maximum value. Cells with EC/2MeTHF (50:50) exhibited the longest cycle life among all the electrolytes examined here. Cells with EC/PC/2MeTHF (15:45:40) had the longest cycle life among the ternary mixed solvents systems. Fundamental abuse tests were also carried out on AA cells, which were cycled twice (fresh cells), cycled 100 times and cycled until the end of their cycle life. Neither the fresh nor the cycled cells with EC/PC/2MeTHF (15:45:40 ) smoked nor ignited in a 150 °C heating test or in an external short circuit test. However, the fresh cell with EC/2MeTHF (50:50) ignited in the 150 °C heating test. Summarizing the cycling and the abuse test results, the EC/PC/2MeTHF (15:45:40) ternary mixed systems exhibited the best performance. However, in terms of practical use, cell safety still requires further improvement.     

Electrospun PVdF-based fibrous polymer electrolytes for lithium ion polymer batteries

This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45-1.38 μm have an apparent porosity and a mean pore size (MPS) of 80-89% and 1.1-4.3 μm, respectively. They exhibited a high uptake of the electrolyte solution (320-350%) and a high ionic conductivity of above 1 × 10⁻³ s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1 M LiPF₆-EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0 V, which increased with the decrease in the AFD The interfacial resistance (R_i) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO₂) showed a very stable charge-discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60 °C.     

Benzene-based polyorganodisulfide cathode materials for secondary lithium batteries

A novel kind of benzene-based organodisulfide, 5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene (DTTA) and its homopolymer, poly(5,8-dihydro-1H,4H-2,3,6,7-tetrathia-anthracene) (PDTTA) were designed, synthesized and presented as a cathode material for high-energy secondary lithium batteries. The polyorganodisulfides were characterized by FT-IR, XPS and elemental analysis. The designed system has many advantages, such as high theoretical charge density (ca. 471 mAh/g), fast redox process and enhanced cycling stability, which are due to the intramolecular electrocatalytic effect of polyphenyl chain and the intramolecular cleavage-recombination of the SS bond, respectively. The cyclic voltammetry test results proved the effect of this kind of electrocatalysis, and the charge-discharge experimental results showed that the polymer has the specific capacity of 422 mAh/g at 2nd cycle and 170 mAh/g at the 44th cycle.     

Influence of the composition of ternary mixed solvent electrolytes on the properties of rechargeable lithium cells

A cell system consisting of an amorphous (a-)V2O5–P2O5 (95:5 in molar ratio) cathode, a lithium metal anode and an organic electrolyte by fabricating an AA-size prototype cell has been studied. The influence of the composition of ternary mixed solvent electrolytes comprising ethylene carbonate (EC), propylene carbonate (PC) and 2-methyltetrahydrofuran (2MeTHF) on the properties of AA-size Li/a-V2O5–P2O5 cells is examined. The goals are to improve the cycle life of the cell while ensuring its safety and controlling its cost. The electrolyte composition is varied by changing the solvent mixing ratio, and the lithium salt concentration, and by using different kinds of solute. The cell performance examined includes cathode utilization (cell capacity) during low temperature operation, and charge–discharge cycle life. Heating abuse tests were also carried out at 130°C on the Li/a–V2O5–P2O5 cells. The best electrolyte composition was found to be 1.15m LiAsF6–EC/PC/2MeTHF (15:70:15) from the overall results on cycle life, capacity, safety and cost.     

Improving ionic conductivity of polymer-based solid electrolytes for lithium metal batteries

Because of its superior safety and excellent processability, solid polymer electrolytes (SPEs) have attracted widespread attention. In lithium based batteries, SPEs have great prospects in replacing leaky and flammable liquid electrolytes. However, the low ionic conductivity of SPEs cannot meet the requirements of high energy density systems, which is also an important obstacle to its practical application. In this respect, escalating charge carriers (i.e. Li⁺) and Li⁺ transport paths are two major aspects of improving the ionic conductivity of SPEs. This article reviews recent advances from the two perspectives, and the underlying mechanism of these proposed strategies is discussed, including increasing the Li⁺ number and optimizing the Li⁺ transport paths through increasing the types and shortening the distance of Li⁺ transport path. It is hoped that this article can enlighten profound thinking and open up new ways to improve the ionic conductivity of SPEs.     

An electrolyte CPA equation of state for mixed solvent electrolytes

Despite great efforts over the past decades, thermodynamic modeling of electrolytes in mixed solvents is still a challenge today. The existing modeling frameworks based on activity coefficient models are data‐driven and require expert knowledge to be parameterized. It has been suggested that the predictive capabilities could be improved through the development of an electrolyte equation of state. In this work, the Cubic Plus Association (CPA) Equation of State is extended to handle mixtures containing electrolytes by including the electrostatic contributions from the Debye–Hückel and Born terms using a self‐consistent model for the static permittivity. A simple scheme for parameterization of salts with a limited number of parameters is proposed and model parameters for a range of salts are determined from experimental data of activity and osmotic coefficients as well as freezing point depression. Finally, the model is applied to predict VLE, LLE, and SLE in aqueous salt mixtures as well as in mixed solvents. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2933–2950, 2015     

安全固态锂电池室温聚合物基电解质的研究进展

目前,大多数聚合物固态电解质在室温下离子电导率较低,约为10^–8 ~10^-6 S /cm,且对温度存在着较大的依赖性,仍无法满足高性能室温固态锂电池的实际应用需要。基于此,本文先介绍了室温聚合物电解质在锂离子电池中应用的主要研究进展及其优缺点。然后,从物理调控、化学调控等多角度重点阐述了室温聚合物电解质（包括全固态聚合物电解质、准固态聚合物电解质）的制备工艺、优化与改性方法、作用机理等在电池中应用的主要研究进展和现状。最后,对锂离子电池用室温聚合物电解质存在的挑战和未来可能发展趋势进行了展望。     

Layered lithium transition metal nitrides as novel anodes for lithium secondary batteries

We report the approach to overcome the deterrents of the hexagonal Li_2.6Co_0.4N as potential insertion anode for lithium ion batteries: the rapid capacity fading upon long cycles and the fully Li-rich state before cycling. Research reveals that the appropriate amount of Co substituted by Cu can greatly improve the cycling performance of Li_2.6Co_0.4N. It is attributed to the enhanced electrochemical stability and interfacial comparability. However, doped Cu leads to a slightly decreased capacity. High energy mechanical milling (HEMM) was found to effectively improve the reversible capacity associated with the electrochemical kinetics by modifying the active hosts’ morphology characteristics. Moreover, the composite based on mesocarbon microbead (MCMB) and Li_2.6Co_0.4N was developed under HEMM. The composite demonstrates a high first cycle efficiency at 100% and a large reversible capacity of ca. 450 mAh g⁻¹, as well as a stable cycling performance. This work may contribute to a development of the lithium transition metal nitrides as novel anodes for lithium ion batteries.     

聚合物及离子液体电解质在锂二次电池中的应用

系统地介绍了锂离子二次电池电解质,特别是聚合物电解质及离子液体电解质的应用研究现状。开发具有高能量密度、稳定的充放电性能、循环寿命长、可塑性、高安全性与低成本的锂离子电池是当前的研究热点。离子液体具有较高的离子电导率、宽电化窗口,且无蒸汽压,而聚合物具有良好的机械加工性能。二者的结合将为锂离子电池电解质的研究提供了新的开发思路。     

Mechanical stability of Sn-Co alloy anodes for lithium secondary batteries

An electro-co-deposited Sn-Co alloy electrode on a copper foil was prepared to study the structure and electrochemical properties. A micro-island structure of the active material was confirmed to be self-organized during the initial cycle, and such a structural change of the active material was compared with that of other Sn-based electrodes. A key to improve the cyclability in terms of the mechanical stability of the active material is discussed.     

Ethylene carbonate/ether mixed solvents electrolyte for lithium batteries

Conductivities and Li charge—discharge efficiencies for LiClO₄ethylene carbonate (EC)/ether mixed solvents systems were studied, compared with those for propylene carbonate (PC)/ether and EC/PC/ether mixed solvents electrolytes, for use in nonaqueous lithium secondary batteries. As the ethers, tetrahydrofuran (THF), 1,2-dimethoxyethane, diethoxyethane and 1,3-dioxolane were used. Conductivities for EC/ether mixed systems were higher than those for both EC/PC/ether and PC/ether mixed systems, due to the high dielectric constant for EC and low viscosity for ethers. Conductivities showed maximum values around EC/ether mixing volume ratio = 1/1 and at about 1 M solute. For example 1 M LiClO₄EC/THF (1/1) showed approximately 40% higher conductivity, 14 × 10^?3 S cm^?1, than for PC/THF. Li charge—discharge efficiencies for EC/ether mixed systems also increased more than those for EC/PC/ether and PC/ether. This seems to be due to adsorption of less Li reactive ether and EC than PC, around deposited Li. In the same solute—solvents systems, Li cycling efficiencies for EC/eether mixed systems tended to increase Li cycling efficiency of 92%. This value was approx. 10% higher than for PC/THF.     

Electrochemical characteristics of copper silicide-coated graphite as an anode material of lithium secondary batteries

Copper silicide-coated graphite as an anode material was prepared by the sequential employments of plasma enhanced chemical vapor deposition (PECVD) and radio frequency magnetron sputtering (RFMS) method at 300 °C. The silicon-coated graphite exhibited an initial discharge capacity of 540 mAh/g with 76% coulomb efficiency, and the discharge capacity was sharply decreased down to 50% of initial capacity after 30 cycles, probably due to large volume changes during the charge-discharge cycling. Copper silicide-coated graphite, however, exhibited an initial discharge capacity of 480 mAh/g with higher retention capacity of 87% even after 30 cycles, probably due to the enhanced interfacial conductivity. The copper silicide film on the graphite surface played as the active anode material of lithium secondary batteries via the reduction of interfacial resistance and mitigation of volume changes during repeated cycles.     

Stable composite electrolytes of PVDF modified by inorganic particles for solid-state lithium batteries

Polymer electrolytes have been attracting much attention because of their flexibility and easy follow-up processing, but their Li⁺ conductivity in lithium-metal batteries (LIBs) is unsatisfactory. Stable composite electrolytes of poly (vinylidene fluoride) (PVDF) polymer with high lithium-ion conductivity have been prepared by a trigger structural modification of Li_6.5La₃Zr_1.5Nb_0.25Ta_0.25O₁₂ (LLZNTO) garnet ceramic and TiO₂ oxide. The influences of various amounts of TiO₂ and LLZNTO on electrochemical performance were systematically examined. These composite electrolytes exhibited maximal Li⁺ conductivity of 2.89 × 10⁻⁴ S cm⁻¹, which is consistent with the value of pure ceramic electrolytes. Furthermore, it possessed the stable long-term Li cycling and the wide electrochemical window, involving repeated Li plating/stripping at 0.2 mA cm⁻² over 280 h without failure. The discharge specific capacity and Coulomb efficiency for all-solid-state LIBs assembled with these membranes delivered outstanding cycling stability with high discharge capacities (117.9 mA h g⁻¹) at 0.1 C rate and Coulomb efficiency reached 99.9% after 25 cycles. The high Li⁺ conduction capability can be ascribed function of introducing TiO₂ and LLZNTO to restrain tremendously the crystalline behavior of the polymer. Furthermore, the LLZNTO can be complex with PVDF for dehydrofluorination, and it can also offer a burst transportation route for lithium ions. This system might serve as an attractive use for polymer solid electrolytes and open up new possibilities for safe all-solid-state LIBs.     

Thin films of lithium manganese oxide spinel as cathode materials for secondary lithium batteries

The miniaturization of rechargeable lithium-ion batteries requires high quality thin-film electrodes. Electrostatic spray deposition (ESD) technique was used to fabricate LiMn₂O₄ thin-film electrodes with three different morphologies: sponge-like porous, fractal-like porous, and dense structures. X-ray diffraction (XRD) and scanning electron microscopy were used to analyze the structures of the electrodes. These electrodes were made into coin cells against metallic lithium for electrochemical characterization. Galvanostatic cycling of the cells revealed different rate capability for the cells with LiMn₂O₄ electrodes of different morphologies. It is found that the cells with LiMn₂O₄ electrodes of porous, especially the sponge-like porous, morphology better rate capability than those with dense LiMn₂O₄ electrodes. Electrochemical impedance spectroscopy (EIS) study indicates that the large surface area of the porous electrodes should be attributed to the smaller interfacial resistance and better rate capability.     

Effect of purification of 2-methyltetrahydrofuran/ethylene carbonate mixed solvent electrolytes on cyclability of lithium metal anodes for rechargeable cells

The effects of the purification of LiAsF₆–2-methyl tetrahydrofuran (2MeTHF)/ethylene carbonate (EC) mixed solvent organic electrolytes on the charge–discharge cyclability of lithium metal anodes has been investigated by using an accelerated method for evaluating lithium cycling efficiency. This method involves cycle tests on coin cells with an amorphous V₂O₅–P₂O₅ (95:5 molar ratio) cathode and an anode containing a small amount of lithium. Using this method, the cycle life of the cell was determined over a short period simply from the lithium cycling efficiency. The lithium cycling efficiency in LiAsF₆–2MeTHF/EC was improved by removing both water and organic impurities such as peroxides. An electrolyte containing less than 14ppm of water and 20ppm of organic impurities had a high lithium cycling efficiency of 97.2%.