Analysis of SEI formed with cyano-containing imidazolium-based ionic liquid electrolyte in lithium secondary batteries

Two kinds of cyano-containing imidazolium-based ionic liquid, 1-cyanopropyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CpMI-TFSI) and 1-cyanomethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (CmMI-TFSI), each of which contained 20 wt% dissolved LiTFSI, were used as electrolytes for lithium secondary batteries. Compared with 1-ethyl-3-methylimidazolium-bis(trifluoromethane-sulfonyl)imide (EMI-TFSI) electrolyte, a reversible lithium deposition/dissolution on a stainless-steel working electrode was observed during CV measurements in these cyano-containing electrolytes, which indicated that a passivation layer (solid electrolyte interphase, SEI) was formed during potential scanning. The morphology of the working electrode with each electrolyte system was studied by SEM. Different dentrite forms were found on the electrodes with each electrolyte. The SEI that formed in CpMI-TFSI electrolyte showed the best passivating effect, while the deposited film formed in EMI-TFSI electrolyte showed no passivating effect. The chemical characteristics of the deposited films on the working electrodes were compared by XPS measurements. A component with a cyano group was found in SEIs in CpMI-TFSI and CmMI-TFSI electrolytes. The introduction of a cyano functional group suppressed the decomposition of electrolyte and improved the cathodic stability of the imidazolium-based ionic liquid. The reduction reaction route of imidazolium-based ionic liquid was considered to be different depending on whether or not the molecular structure contained a cyano functional group.     

Functionalized imidazolium ionic liquids as electrolyte components of lithium batteries

Some basic properties and compatibility toward lithium electrode for electrolytes based on substituted imidazolium ionic liquid have been investigated. The ionic liquids having imidazolium cation substituted by methylcarboxyl or cyano group suffers from low conductivity. However, reversible lithium deposition–dissolution process was observed in electrolytes based on these electrolytes. In particular, lithium salt solution in cyanomethyl-substituted imidazolium ionic liquid provided similar cycle efficiency to conventional organic solvent electrolyte at constant-current condition. The mixed ionic liquid electrolyte containing the cyanomethyl-substituted ionic liquid also provided good cycle performance despite of containing large amount of 1-ethyl-3-methyl imidazolium (EMI)-based ionic liquid. Such mixed electrolyte system serves both the stability of lithium electrode process and valid conductivity for practical use.     

LiTFSI-BEPyTFSI as an improved ionic liquid electrolyte for rechargeable lithium batteries

We report an electrochemical study of solutions of lithium bis(trifluoromethanesulfonyl)imide, LiTFSI, in a N-n-butyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)imide, BEPyTFSI. We show that these ionic liquid solutions have stability towards lithium metal electrode which allows various electrochemical tests, including impedance spectroscopy and voltammetry. The ionic conductivity and lithium transference number, of the order of 10⁻³ S cm⁻¹ and 0.4, respectively, make these solutions suitable for application as electrolytes in advanced lithium batteries. A prototype of these batteries, having lithium iron phosphate as the cathode, showed good performance in terms of charge–discharge efficiency and rate capability. The results reported in this work, although preliminary, are encouraging in supporting the practical interest of this LiTFSI-BEPyTFSI class of lithium conducting ionic liquids.     

Limiting current density in bis(trifluoromethylsulfonyl)amide-based ionic liquid for lithium batteries

The physicochemical and electrochemical properties of the binary ionic liquid (IL), lithium bis(trifluoromethylsulfonyl)amide (LiTFSA) dissolved in N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)amide (DEMETFSA), were investigated. The ionic conductivity of the binary IL decreased with an increase in LiTFSA concentration. The self-diffusion coefficients of Li⁺, DEME⁺, and TFSA⁻ dissolved in the IL were measured by using the pulsed-field-gradient spin-echo (PGSE) NMR method. The self-diffusion coefficient of each ionic species was also found to decrease with increasing concentration of LiTFSA. The limiting current density in the IL electrolyte was evaluated by chronoamperometry using symmetric Li|IL|Li cell. The results suggest that the diffusion process of Li(I) in the IL dominates the limiting current density in the cell. The highest limiting current density is achieved at a concentration of 0.64 mol dm⁻³ of LiTFSA.     

UV-cured polymer electrolytes encompassing hydrophobic room temperature ionic liquid for lithium batteries

We demonstrate herewith the application of in situ one-shot free radical photo-polymerisation (UV-curing) process to incorporate room temperature ionic liquids (RTILs) into polymer membranes which can be used as electrolytes for lithium-based batteries. The reactive formulation for the preparation of the polymer membranes was based on a dimethacrylic oligomer (BEMA). The polymer electrolyte membranes were synthesized by UV radiating a mixture of BEMA and a proper radical photo-initiator with different compositions of 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide [EMIPFSI] and, additionally, LiTFSI as lithium source.Stable and flexible polymer films with good mechanical integrity can easily be produced with varying the EMIPFSI content by using this method. Remarkable values of ionic conductivity were obtained even at ambient temperature. Galvanostatic charge/discharge cyclability tests were performed on the polymer electrolyte membranes by constructing a cell using LiFePO₄ as cathode and Li metal as anode. The preliminary results are interesting, exhibiting good reversibility and cyclability.     

One ether-functionalized guanidinium ionic liquid as new electrolyte for lithium battery

One ether-functionalized guanidinium ionic liquid is used as new electrolytes for lithium battery. Viscosity, conductivity, behavior of lithium redox, chemical stability against lithium metal, and charge-discharge characteristics of lithium batteries, are investigated for the IL electrolytes with different concentrations of lithium salt. Though the cathodic limiting potential of the IL are 0.7 V vs. Li/Li⁺, the lithium plating and striping on Ni electrode can be observed in the IL electrolytes, and the IL electrolytes show good chemical stability against lithium metal. Li/LiCoO₂ cells using the IL electrolytes without additives have good capacity and cycle property at the current rate of 0.2 C when the LiTFSI concentration is higher than 0.3 mol kg⁻¹, and the cell using the IL electrolyte with 0.75 mol kg⁻¹ LiTFSI owns good rate property. The activation energies of the LiCoO₂ electrode for lithium intercalation are estimated, and help to analyze the factors determining the rate property.     

Polymer electrolytes containing guanidinium-based polymeric ionic liquids for rechargeable lithium batteries

The electrochemical properties of solvent-free, quaternary polymer electrolytes based on a novel polymeric ionic liquid (PIL) as polymer host and incorporating 1g13TFSI ionic liquid, LiTFSI salt and nano-scale silica are reported. The PIL-LiTFSI-1g13TFSI-SiO₂ electrolyte membranes are found to be chemically stable even at 80 °C in contact with lithium anode and thermally stable up to 320 °C. Particularly, the quaternary polymer electrolytes exhibit high lithium ion conductivity at high temperature, wide electrochemical stability window, time-stable interfacial resistance values and good lithium stripping/plating performance. Batteries assembled with the quaternary polymer electrolyte at 80 °C are capable to deliver 140 mAh g⁻¹ at 0.1C rates with very good capacity retention.     

Electrospun polymer membrane activated with room temperature ionic liquid: Novel polymer electrolytes for lithium batteries

A new class of polymer electrolytes (PEs) based on an electrospun polymer membrane incorporating a room-temperature ionic liquid (RTIL) has been prepared and evaluated for suitability in lithium cells. The electrospun poly(vinylidene fluoride-co-hexafluoropropylene) P(VdF-HFP) membrane is activated with a 0.5 M solution of LiTFSI in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) or a 0.5 M solution of LiBF₄ in 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄). The resulting PEs have an ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 25 °C and anodic stability at >4.5 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. A Li/LiFePO₄ cell with a PE based on BMITFSI delivers high discharge capacities when evaluated at 25 °C at the 0.1C rate (149 mAh g⁻¹) and the 0.5C rate (132 mAh g⁻¹). A very stable cycle performance is also exhibited at these low current densities. The properties decrease at the higher, 1C rate, when operated at 25 °C. Nevertheless, improved properties are obtained at a moderately elevated temperature of operation, i.e. 40 °C. This is attributed to enhanced conductivity of the electrolyte and faster reaction kinetics at higher temperatures. At 40 °C, a reversible capacity of 140 mAh g⁻¹ is obtained at the 1C rate.     

Novel ionic plastic crystal-polymeric ionic liquid all-solid-state electrolytes for lithium ion batteries

离子塑性晶体作为一类新型的固态电解质材料,近年来受到研究人员的极大关注。本文合成了一种新型离子塑性晶体：N,N-二甲基吡咯双氟磺酰亚胺（P₁₁FSI）,并将其与吡咯阳离子离子液体聚合物-聚二甲基二烯丙基铵双氟磺酰亚胺（PILFSI）和锂盐（LiFSI）复合制备了P₁₁FSI-PILFSI-LiFSI全固态电解质。采用差示扫描量热法、热重分析、阻抗测试、线性扫描伏安法及对称锂电池测试等一系列表征技术对全固态电解质的热性能和电化学性能进行了系统研究。所制备的电解质膜具有好的柔韧性和热稳定性,高的离子电导率和电化学稳定性,以及与金属锂良好的界面相容性。将全固态电解质应用于Li/LiFePO₄电池中,在50℃、0.2 C充放电倍率时,电池放电比容量在60次循环后仍可达151.1 mA·h/g,容量保持率为96.8%;且在0.5 C、1.0 C倍率下放电比容量仍然高达138.1 mA·h/g和128.1 mA·h/g,展现出高的放电比容量,好的循环性能和倍率性能,有望应用于全固态锂离子电池中。     

Progress of inorganic solid electrolyte for lithium ion batteries

目前,商品化的锂离子电池电解液主要以碳酸乙烯酯、碳酸二甲酯和碳酸甲乙酯等有机溶剂为溶剂,在电池使用过程中,存在电解液分解、锂枝晶生成和漏液等问题,从而影响电池的稳定性和安全性。无机固态锂电池电解质具有热稳定性高、电化学性能稳定、与高电压正极材料相容性好、安全性高及环境友好等优点,是目前储能领域研究的一个热点。研究和开发具有高离子电导率的无机固态电解质是促进其在电池中应用的关键和难点,本文综述了几类目前研究较多的LiPON型、钙钛矿型、石榴石型、LISICON型电解质,重点关注了其在离子电导率方面的研究及应用进展。     

Ionic liquid doped PEO-based solid polymer electrolytes for lithium-ion polymer batteries

The influence of adding the room-temperature ionic liquid 1-ethyl-3-methyllimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) to poly(ethylene oxide) (PEO)–lithium difluoro(oxalato)borate (LiDFOB) solid polymer electrolyte and the use of these electrolytes in solid-state Li/LiFePO₄ batteries has been investigated. Different structural, thermal, electrical and electrochemical studies exhibit promising characteristics of these polymer electrolyte membranes, suitable as electrolytes in rechargeable lithium-ion batteries. The crystallinity decreased significantly due to the incorporation of ionic liquid, investigated by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The ion–polymer interaction, particularly the interaction of cations in LiDFOB and ionic liquid with ether oxygen atom of PEO chains, has been evidenced by FT-IR studies. The polymer electrolyte with ～40 wt% of ionic liquid offers a maximum ionic conductivity of ～1.85 × 10^?4 S/cm at 30 °C with improved electrochemical stabilities. The Li/PEO-LiDFOB-40 wt% EMImTFSI/LiFePO₄ coin-typed cell cycled at 0.1 C shows the 1st discharge capacity about 155 mAh g^?1, and remains 134.2 mAh g^?1 on the 50th cycle. The addition of the ionic liquid to PEO₂₀-LiDFOB polymer electrolyte has resulted in a very promising improvement in performance of the lithium polymer batteries.     

Solid polymer electrolytes with sulfur based ionic liquid for lithium batteries

The electrochemical properties of a solid hybrid polymer electrolyte for lithium batteries based upon tri-ethyl sulfonium bis(trifluorosulfonyl) imide (S₂TFSI), lithium TFSI, and poly(ethylene oxide) (PEO) is presented. We have synthesized homogenous freestanding films that possess low temperature ionic conductivity and wide electrochemical stability. The hybrid electrolyte has demonstrated ionic conductivity of 0.117 mS cm⁻¹ at 0 °C, and 1.20 mS cm⁻¹ at 25 °C. At slightly elevated temperature ionic conductivity is on the order of 10 mS cm⁻¹. The hybrid electrolyte has demonstrated reversible stability against metallic lithium at the anodic interface and >4.5 V vs. Li/Li⁺ at the cathodic interface.     

A binary ionic liquid system composed of N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide and lithium bis(trifluoromethanesulfonyl)imide: A new promising electrolyte for lithium batteries

Room temperature ionic liquids are nowadays the most appealing research target in the field of liquid electrolytes for lithium batteries, due to their high thermal stability, ionic conductivity and wide electrochemical windows. The cation structure of such solvents strictly influences their physical and chemical properties, in particular the viscosity and conductivity.In this paper we report on the preparation and characterization of a complete series of solutions between lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the promising N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (PY_1,2O1) ionic liquid. A wide molality range has been explored in order to identify the optimal compositions in terms of conductivity and electrochemical stability. Our thermal results show that the solutions are amorphous independently on the LiTFSI content. Up to salt concentration of 0.4 mol kg⁻¹ the solutions have a very low viscosity (η ∼ 36 cP), a high ionic conductivity, even at temperatures below 0 °C, and a good electrochemical stability. Cations transport numbers ranging between 0.05 and 0.39 have been determined as a function of LiTFSI content. The combination of these properties makes the PY_1,2O1-based solutions potentially attractive liquid electrolytes for lithium batteries.     

Lithium electrolytes based on modified imidazolium ionic liquids

In this study, new electrolytes for Li-ion batteries in the form of lithium salt solutions in room temperature imidazolium ionic liquids (RTIL) are reported. The ionic liquids applied, for higher reduction potential stability, were substituted at position C2 with oligooxyethylene groups of various length ([Im nEO]⁺X⁻; where: n = 0, 3, 7, 20 and X = Cl, BF₄, N(CF₃SO₂)₂). It was found that they are good solvents for lithium salts (LiBF₄, LiN(CF₃SO₂)₂, {[CH₃(OCH₂CH₂)₃O]₃BC₄H₉}Li) forming liquid solutions of low glass transition temperature (T_g in the −70 to −40 °C range). Ionic conductivity depends on the length of oxyethylene substituent in Im nEO and on the concentration of the salt applied, for 10 mol%, σ_RT is of the order of 10⁻⁴ S cm⁻¹. On the basis of polarization measurements by the variable-current method, the proportion of lithium cations in electric charge transfer (t₊) has been determined. The values obtained (typical for ionic liquids) are low and depend on n and lithium salt concentration but do not exceed a dozen or so percent.     

Novel composite polymer electrolyte for lithium air batteries

Hydrophobic ionic liquid–silica–PVdF-HFP polymer composite electrolyte is synthesized and employed in lithium air batteries for the first time. Discharge performance of lithium air battery using this composite electrolyte membrane in ambient atmosphere shows a higher capacity of 2800 mAh g⁻¹ of carbon in the absence of O₂ catalyst, whereas, the cell with pure ionic liquid as electrolyte delivers much lower discharge capacity of 1500 mAh g⁻¹. When catalyzed by α-MnO₂, the initial discharge capacity of the cell with composite electrolyte can be extended to 4080 mAh g⁻¹ of carbon, which can be calculated as 2040 mAh g⁻¹ associated with the total mass of the cathode. The flat discharge plateau and large discharge capacity indicate that the hydrophobic ionic liquid–silica–PVdF-HFP polymer composite electrolyte membrane can effectively protect lithium from moisture invasion.     

Lithium ion conduction in ionic liquid-based gel polymer electrolyte

The conduction mechanism of gel electrolyte system consisting of poly(ethylene oxide) branched poly(methyl methacrylate) (PEO-PMA) matrix and ionic liquid containing lithium salt has been investigated. The kinetics of ion conduction and the mobility of lithium ion are different by the kind of ionic liquid; 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfone)imide (EMITFSI) or hexyltrimethylammonium bis(trifluoromethane sulfone)imide (HTMATFSI). Lithium ion exhibits a significant contribution for ion conduction in the gel electrolyte containing HTMATFSI. In contrast, the mobility of lithium ion is not obvious in the gel electrolyte containing EMITFSI. Such difference is considered to originate from the difference in ‘miscibility’ of polymer component in ionic liquid.     

All solid state lithium ion rechargeable batteries using NASICON structured electrolyte

Abstract

NASICON (Sodium super ionic conductor) structured Li_1·5Al_0·5Ge_1·5(PO₄)₃ (LAGP) solid electrolyte is synthesized through a solid state reaction. The total conductivity of the LAGP electrolyte is 7×10^?5 S cm^?1 with a potential window larger than 6 V. All solid state lithium batteries are fabricated using LiMn₂O₄ as a cathode, LAGP as an electrolyte and lithium metal as an anode. The LiMn₂O₄/LAGP/Li cell can deliver a capacity of about 80 mAh g^?1 in the first discharge cycle and increases gradually with charge/discharge cycles, indicating that LAGP can be used as a promising electrolyte for lithium rechargeable batteries.     

Novel polymer electrolytes based on thermoplastic polyurethane and ionic liquid/lithium bis(trifluoromethanesulfonyl)imide/propylene carbonate salt system

Polymer electrolytes were prepared from thermoplastic polyurethane with addition of mixture of ionic liquid N-ethyl(methylether)-N-methylpyrrolidinium trifluoromethanesulfonimmide (PYRA_12O1TFSI), lithium bis(trifluoromethanesulfoneimide) salt and propylene carbonate. The electrolytes characterization was performed by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The electrical properties were investigated in detail by impedance spectroscopy with the aid of equivalent circuit fitting of the impedance spectra. A model describing temperature evolution of ionic conductivity and the properties of electrolyte/blocking electrode interface was developed. The electrochemical stability of the electrolytes was studied by linear voltammetry. Our results indicate that the studied electrolytes have good self-standing characteristics, and also a sufficient level of thermal stability and a fairly good electrochemical window. The ionic conductivity increases with increasing amount of mixture, and the character of temperature dependence of conductivity indicates decoupling of ion transport from polymer matrix. For studied system, the highest value of ionic conductivity measured at room temperature was 10⁻⁴ S cm⁻¹.     

Possible use of non-flammable phosphonate ethers as pure electrolyte solvent for lithium batteries

Dimethyl methyl phosphonate (DMMP) was selected and tested as a non-flammable solvent for primary and secondary lithium batteries, because of its non-flammability, good solvency of lithium salts and appropriate liquidus properties. Experimental results demonstrated that DMMP can solvate considerable amount of commonly used lithium salts to form non-flammable and Li⁺-conducting electrolyte, which has very wide electrochemical window (>5 V vs. Li) and excellent electrochemical compatibility with metallic lithium anode and oxide cathodes. Primary Li–MnO₂ cells using DMMP-based electrolyte showed almost the same discharge performances as those using organic carbonate electrolytes, and also, Li–LiMn₂O₄ cells using DMMP electrolyte exhibited greatly improved cycleability and dischargeability, suggesting a feasible application of this new electrolyte for constructing high performance and non-flammable lithium batteries.     

Electrochemical performance of gel polymer electrolyte with ionic liquid and PUA/PMMA prepared by ultraviolet curing technology for lithium-ion battery

A series of diethylethyletherylmethanamine bis(trifluoromethanesulfonyl)imide (DEEYTFSI) ionic liquid gel polymer electrolyte based polyurethane acrylate (PUA)/poly(methyl methacryltae) (PMMA) matrix with different contents of DEEYTFSI, PUA and LiTFSI were prepared via ultraviolet (UV) curing system. Electrochemical performances of the gel polymer were studied by electrochemical station and charge–discharge system. The gel polymer electrolyte with 19 wt.% DEEYTFSI obtained a maximum conductivity σ of 2.76 × 10^?4 S cm^?1 and the transference number t_Li+ of ～0.22 at room temperature. 19 wt.% DEEYTFSI caused the easier transferring of lithium ions due to less apparent activation energy E_a of 21.1 kJ mol^?1. The DEEYTFSI/LiTFSI/PUA/PMMA electrolyte had good compatibility with LiFePO₄ cathode. The DEEYTFSI/LiTFSI/PUA/PMMA electrolyte with the electrochemical window of 4.70 V was enough stability for being the electrolyte material of lithium battery. The Li/19 wt.% DEEYTFSI–LiTFSI–PUA–PMMA/LiFePO₄ coin-typed cell cycled at 0.1 C presented 95% efficiency on the 50th cycle.