Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

Montmorillonite-based ceramic membranes as novel lithium-ion battery separators

Novel montmorillonite-based ceramic membrane (CM) has been prepared with poly(vinylidene fluoride-co-hexafluoropropene) (PVdF-HFP) copolymer as binder. Physical properties such as surface morphology, porosity, liquid electrolyte uptake and thermal stability were analysed. The ceramic membrane was activated by soaking it in a non-aqueous liquid electrolyte (1.0 M LiPF₆ solution in 1/1 v/v ethylene carbonate/diethyl carbonate mixture) for 10 min. The compatibility of the membrane with lithium metal anode as a function of storage time was analysed by assembling a Li/CM/Li symmetric cell. Finally, a lab-scale cell composed of Li/CM/LiFePO₄ is assembled and its cycling performance analysed at different C-rates. Although the ceramic membrane is not flexible, it shows high thermal stability and stable interfacial properties when in contact with the lithium metal anode. A stable cycling behaviour is demonstrated even at 1C-rate with limited fade in capacity.     

Application of ionic liquid doped solid polymer electrolyte

The electrical, structural, and photoelectrochemical properties of the polymer electrolyte PEO:NaI/I₂ doped with an ionic liquid 1-ethyl 3-methylimidazolium dicyanamide (EMImDCN) have been reported. Incorporation of the ionic liquid (IL) increases the membrane homogeneity, decreased surface roughness, and enhances the short current (J _sc). Additionally, the doping of IL provides more charge carriers which enhances overall ionic conductivity (σ). The optimized σ was found at 40 wt.% IL composition. The fabricated DSSC using this new solid electrolyte showed 1.43% efficiency at 100 mW cm⁻².     

A polymer electrolyte based on poly(vinylidene fluoride-hexafluoropylene)/hydroxypropyl methyl cellulose blending for lithium-ion battery

A polymer electrolyte based on the blending of poly(vinylidene fluoride-hexafluoropylene) (PVDF-HFP) and hydroxypropyl methyl cellulose (HPMC) was prepared for the first time. The structure and performance of the gel polymer electrolyte were characterized and measured by X-ray diffraction, Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, electrochemical impedance spectroscopy, linear sweep voltammetry, and by a charge/discharge test. The results show that the gel polymer electrolyte has the best performance when PVDF-HFP/HPMC ratio (w/w) is 4:1. At room temperature, the ionic conductivity can reach 0.38?×?10^?3 S cm^?1, the electrochemical stable window is up to 5.0 V (vs. Li/Li⁺), and the half cell of Li/GPE/LiMn₂O₄ shows high-discharge-specific capacity and good cycling performance.     

Electrical studies on ionic liquid-based gel polymer electrolyte for its application in EDLCs

Ionic liquid-based gel polymer electrolyte (GPE) has been synthesized using standard solution cast technique. Different weight percent of ionic liquid, 1-Butyl-3-methylimidazolium chloride (BMIMCl) and liquid electrolyte, ethylene carbonate (EC)–propylene carbonate (PC)–tetra ethyl ammonium tetra fluoro borate (TEABF₄) was incorporated in polymer, poly(vinylidene fluoride-co-hexafluoro propylene (PVdF-HFP) to obtain mechanically stable gel polymer electrolyte film (GPE) having maximum conductivity of ~10⁻³ S cm⁻¹ at room temperature, which is acceptable from device fabrication point of view. Potential window and ionic transference number has been obtained to examine the potential limit and ionic characteristics of optimized GPE system. Temperature dependence behavior of electrical conductivity curve follows Arrhenius nature in the temperature range of 303–373 K. Pattern of dielectric constant and its loss as a function of frequency and temperature have been studied and is being explained on the basis of electrode interfacial polarization effect. Frequency-dependent conductivity spectra obey the Jonscher’s power law. Further, optimized composition of GPE has been tested successfully for its application in supercapacitor fabrication with activated charcoal as an electrode material. Maximum specific capacitance of 118.6 mF cm⁻² equivalent to single electrode specific capacitance of 61.7 F g⁻¹ have been observed for the optimized GPE film.

     

A thermal and electrochemical properties research on gel polymer electrolyte membrane of lithium ion battery

N-methyl-N-propyl-piperidin-bis(trifluoromethylsulfonyl)imide/bis(trifluoromethylsulfonyl) imide lithium base/polymethyl methacrylate(PP₁₃TFSI/LiTFSI/PMMA) gel polymer electrolyte (GPE) membrane was prepared by in situ polymerization. The physical and chemical properties were comprehensively discussed. The decomposition characteristics were emphasized by thermogravimetric (TG-DTG) method in the nitrogen atmosphere at the different heating rates of 5, 10, 15 and 20 °C min⁻¹, respectively. The activation energy was calculated with the iso-conversional methods of Ozawa and Kissinger, Friedman, respectively, and the Coats-Redfern methods were adopted to employ the detailed mechanism of the electrolyte membrane. The equation f(α)=3/2[(1−α)^1/3−1] was quite an appropriate kinetic mechanisms to describe the thermal decomposition process with an activation energy (E_α) of 184 kJ/mol and a pre-exponential factor (A) of 1.894×10¹¹ were obtained.     

A facile pyrolysis method to prepare vanadium oxides for high performance aqueous Zn-ion battery

Vanadium oxides, as one of the most promising cathode materials for zinc ion batteries, have attracted extensive attention in recent years. Different from the generally used hydrothermal and solvothermal methods to adjust the composition, structure, morphology and electrical properties of vanadium oxides, we firstly adopt a simple pyrolysis method to synthesize a series of vanadium oxides and use them as cathode materials for aqueous Zn-ion battery, whose electrochemical performances is superior to most state-of-the-art vanadium oxides. The as-obtained V₄O₇ under the calcination temperature of 700 °C exhibits excellent zinc ion storage performance with maximum specific capacity of 367.2 mAh g⁻¹ at the current density of 1 A g⁻¹, about 84.9% capacity retention after 100 cycles, excellent rate performance, high capacity. In addition, a series of structural and electrochemical characterization are used to reveal the possible mechanism of charge and discharge.     

Synthesis of LiCoPO4 as a cathode material for lithium-ion battery by a polymer method

A polymer method has been used to synthesize high operation voltage LiCoPO₄ cathode material. Thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM),galvanostatic charge–discharge test and cyclic voltammetry (CV) are used to study the LiCoPO ₄ . The results show LiCoPO₄ has a well-crystallized olivine structure with submicron size. In the range of 3.0–5.1 V, the initial discharge capacities of polymer material are 97.3, 91.5, and 86.5 mAh g^?1 at 0.1, 0.2. and 1 C, respectively. Thus, the polymer method has a great potential in preparing electrode materials for lithium-ion batteries.     

A novel method to prepare Au nanocage@SiO_2 nanoparticle

Gold （Au） nanocage@SiO2 nanoparticles are prepared by a novel approach. The silver （Ag） nanocube@SiO2 structure is synthetized firstly. Next, the method of etching a SiO2 shell by boiling water is adopted to change the penetration rate of AuCl4- through the SiO2 shell. AuCl4- can penetrate through silica shells of different thickness values to react with the Ag nanocube core by changing the incubation time. The surface plasma resonance （SPR） peak of synthetic Au nanocage@SiO2 can be easily tuned into the near-infrared region. Besides, CdTeS quantum dots （QDs） are successfully connected to the surface of Au nanocage@SiO2, which testifies that the incubation process does not change the property of silica.     

Performance enforcement of gel polymer electrolyte for lithium ion battery with co-doping silicon dioxide and zirconium dioxide nanoparticles

In this work, we report a new method to enforce the comprehensive performances of gel polymer electrolyte (GPE) for lithium ion battery. Poly(methyl methacrylate-acrylonitrile-vinyl acetate) [P(MMA-AN-VAc)] is synthesized as polymer matrix. The physical and electrochemical performances of the matrix and the corresponding GPEs, doped with nano-SiO₂ and nano-ZrO₂ particles individually or simultaneously, are investigated by scanning electron microscopy, thermogravimetry, electrochemical impedance spectroscopy, and charge/discharge test. It is found that the membrane co-doped with 5 wt.% nano-SiO₂?+?5 wt.% nano-ZrO₂ and the corresponding GPE combine the advantages of those doped individually with 10 wt.% nano-SiO₂ or 10 wt.% nano-ZrO₂. Accordingly, the comprehensive performances of the membrane and the corresponding GPE, in terms of thermal stability, ionic conductivity, and electrochemical stability on the anode and cathode of lithium ion battery, is enforced by co-doping 5 wt.% nano-SiO₂ and 5 wt.% nano-ZrO₂.     

A low-temperature electrolyte for lithium-ion batteries

In this paper, the electrochemical performance of a new low-temperature electrolyte, 0.9 mol L^?1 lithium oxalyldifluoroborate (LiODFB)/LiBF₄ (5.365:1, by mass) mixed salts in the ethylene carbonate (EC)/dimethyl sulfite (DMS)/ethyl methyl carbonate (EMC) mixed solvent (1:1:3, by volume, the same below), is studied to seek the promising candidate for advanced low-temperature lithium-ion batteries (LIBs). The results show that LIBs using this new electrolyte can be operable well at temperature below ?20 °C. This is useful to expand the application range of LIBs, especially at specific low-temperature environments, such as military and aerospace applications.     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

A piperidinium-based ionic liquid electrolyte to enhance the electrochemical properties of LiFePO<Subscript>4</Subscript> battery

A piperidinium-based ionic liquid, N-methylpiperidinium-N-acetate bis(trifluoromethylsulfonyl)imide ([MMEPip][TFSI]), was synthesized and used as an additive to the electrolyte of LiFePO₄ battery. The electrochemical performance of the electrolytes based on different contents of [MMEPip][TFSI] has been investigated. It was found that the [MMEPip][TFSI] significantly improved the high-rate performance and cyclability of the LiFePO₄ cells. In the optimized electrolyte with 3 wt% [MMEPip][TFSI], 70 % capacity can be retained with an increase in rate to 3.5 C, which was 8 % higher than that of electrolyte without [MMEPip][TFSI]. For the Li/LiFePO₄ half-cells, after 100 cycles at 0.1 C, the discharge capacity retention was 78 % in the electrolyte without ionic liquid. However, in the electrolyte with 3 wt% [MMEPip][TFSI], it displayed a high capacity retention of 91 %. The good electrochemical performances indicated that the [MMEPip][TFSI] additive would positively enhance the electrochemical performance of LiFePO₄ battery.     

Lithium ion transport and ion-polymer interaction in PEO based polymer electrolyte plasticized with ionic liquid

The polyethylene oxide (PEO) based lithium ion conducting polymer electrolytes complexed with lithium trifluoromethanesulfonate (LiCF₃SO₃ or LiTf) plasticized with an ionic liquid 1-ethyl 3-methyl imidazolium trifluoromethanesulfonate (EMITf) have been reported. Morphological, spectroscopic, thermal and electrochemical investigations demonstrate promising characteristics of the polymer films, suitable as electrolyte in various energy storage/conversion devices. Significant structural changes have been observed in the polymer electrolyte due to the ionic liquid addition, investigated by X-ray diffraction (XRD) and optical microscopy. The ion-polymer interaction, particularly the interaction of imidazolium cation with PEO chains, has been evidenced by IR and Raman spectroscopic studies. The optimized composition of the polymer electrolyte i.e. PEO_25.LiTf + 40 wt.% EMITf offer room temperature ionic conductivity of ~ 3 × 10^− 4 S cm^− 1 with wide electrochemical stability window and excellent thermal stability. The ‘σ versus 1/T’ curves show apparent Arrhenius behavior below and above melting temperature. The ionic conductivity has been observed due to Li⁺ ions, as confirmed from ⁷Li-NMR studies, though the component ions of ionic liquid and anions also contribute significantly to the overall conductivity.     

Effects of ionic liquid on the hydroxylpropylmethyl cellulose (HPMC) solid polymer electrolyte

Biodegradable solid polymer electrolyte (SPE) is prepared by solution-casting technique using low-cost cellulose derivative, hydroxypropylmethyl cellulose (HPMC) as a host polymer. Owing to the hydrophobic nature of this polymer, it is predicted to exhibit low ionic conductivity upon addition of magnesium trifluoromethanesulfonate (MgTf₂) salt. Therefore, ionic liquid (IL), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIMTf), is added in order to enhance its ionic conductivity. Based on the findings, the ionic conductivity at room temperature and the dielectric behaviors of the SPE complex improved upon incorporation of 40 wt.% IL. On top of that, addition of IL reduces the degree of crystallinity and the glass transition temperature (T _g ) of the SPE. The conductivity-temperature plot revealed that the transportation of ions in these films obey Arrhenius theory. The interaction between SPE complex, MgTf₂ salt, and BMIMTf is investigated by means of Fourier transform infrared (FTIR) spectroscopy through the change in peak intensity around 3413, 1570, and 1060 cm^?1, which are responsible for –OH stretching band, C–C and C–N bending modes of cyclic BMIM⁺, and C–O–C stretching band, respectively.     

LiPF6-EC-MPC electrolyte for LiMn2O4 cathode in lithium-ion battery

Methyl propyl carbonate (MPC) is a promising single solvent for lithium-ion battery without addition of ethylene carbonate (EC), but it is unstable upon cycling because of exposure to the spinel LiMn₂O₄ cathode. Thus, we attempted to add EC to MPC in order to form LiPF₆-EC-MPC electrolyte; the effects of solvent ratio and salt concentration on the cycling performance of LiMn₂O₄ cathode were also investigated. The experiments were characterized by conductivity measurements, charge-discharge at a constant current density and voltage–capacity curves at low temperature. To further enhance our understanding of the performance improvement of LiMn₂O₄/Li cells, the electrochemical characterization techniques (such as, LSV, EIS) were performed on these cells. The results show that the ionic conductivity of the electrolyte and the cycling performance of the spinel LiMn₂O₄ cathode have been dramatically enhanced. From the point of view of operation at low temperature (− 20 °C), 1 M LiPF₆ EC/MPC (1/3) electrolyte is highly recommended for spinel LiMn₂O₄ cathode in lithium-ion battery.     

一种求解锂离子电池单粒子模型液相扩散方程的新方法

电解液中的锂离子浓度表达是锂离子电池电化学模型求解的基本任务之一.为了平衡单粒子模型的液相动态性能和计算效率,假设反应仅发生在集电极和电解质界面上,为此,提出一种基于液相扩散方程无穷级数解析解的界面浓度求解新方法.在恒流工况下,利用数列单调收敛准则将解析解转化为一个收敛和函数.在动态工况下,将该解析解简化为输入与和函数的无限离散卷积.利用和函数随时间单调衰减并收敛至零的特性对其进行截断,从而得到有限离散卷积求解算法.对比专业有限元分析软件,该方法在恒流工况和动态工况下均能以较少的计算时间获得相当好的精度.而且,该方法仅有一个配置参数.因此,所提方法将有效减小应用于实时电池管理系统上的电化学模型计算负担.     

一种求解锂离子电池单粒子模型液相扩散方程的新方法

电解液中的锂离子浓度表达是锂离子电池电化学模型求解的基本任务之一.为了平衡单粒子模型的液相动态性能和计算效率,假设反应仅发生在集电极和电解质界面上,为此,提出一种基于液相扩散方程无穷级数解析解的界面浓度求解新方法.在恒流工况下,利用数列单调收敛准则将解析解转化为一个收敛和函数.在动态工况下,将该解析解简化为输入与和函数的无限离散卷积.利用和函数随时间单调衰减并收敛至零的特性对其进行截断,从而得到有限离散卷积求解算法.对比专业有限元分析软件,该方法在恒流工况和动态工况下均能以较少的计算时间获得相当好的精度.而且,该方法仅有一个配置参数.因此,所提方法将有效减小应用于实时电池管理系统上的电化学模型计算负担.