Triethyl orthoformate as a new film-forming electrolytes solvent for lithium-ion batteries with graphite anodes

Triethyl orthoformate (TEOF) as a new solvent used in propylene carbonate (PC)-based electrolytes together with graphitic anodes in lithium-ion batteries has been investigated. It can be observed that TEOF was capable of suppressing the co-intercalation of PC solvated lithium-ions into the graphite layer during the first lithiation process and the irreversible discharge capacity of the first cycle is the smallest when using 1.0 M LiPF₆ in PC and TEOF at solvent ratio of 1:1 as the electrolytes. The CV, FTIR, EIS, SEM results show that the PC-based electrolytes containing the solvent TEOF can generate an effective solid electrolytes interphase (SEI) film during the first cycling process, and the film is probably mainly composed of ROCO₂Li, ROLi, Li₂CO₃, etc. The formation of a stable passivating film on the graphite surface is believed to be the reason for the improved cell performance. All these results show that TEOF possesses a promising performance for use as an effective film-forming electrolytes solvent in lithium-ion batteries with graphitic anodes.     

Supercritical carbon dioxide extraction of lithium-ion battery electrolytes

Two different separator materials (polyethylene fleece – Freudenberg 2190 and porous glass fiber – Whatman^® GF/D) and two different lithium-ion battery electrolytes have been investigated regarding their behavior in an autoclave extraction with supercritical helium head pressure carbon dioxide (sc HHPCO₂). Mixtures of dimethyl carbonate (DMC)/ethylene carbonate (EC) and ethylmethyl carbonate (EMC)/EC, each with 1 mol/L LiPF₆ were used.In addition to these proof of principle experiments, the developed extraction method was further applied to real battery samples. Commercial 18650 cells (after formation and aging) were opened and the jelly roll was extracted with sc HHPCO₂. Extracts were analyzed with gas and ion chromatography (GC, IC). Recovery rates and extract compositions strongly depend on the material of which the electrolyte is extracted. Further structure determination of electrolyte aging products was performed with different ionization modes in GC–mass spectrometry (GC–MS) experiments. Diethyl carbonate (DEC), dimethyl-2,5-dioxahexane dicarboxylate (DMDOHC), ethylmethyl-2,5-dioxahexane dicarboxylate (EMDOHC) and diethyl-2,5-dioxahexane dicarboxylate (DEDOHC) are aging products of electrolyte degradation which were successfully extracted and identified. Their concentrations correlate with solid electrolyte interphase (SEI) growth on the negative electrode which was investigated with scanning electron microscopy (SEM).     

基于LiPF6的锂离子电池电解液的发展现状

近年来随着社会的发展和科技的进步,锂离子电池已成为重要的主流动力电池之一。分别从溶剂和添加剂2个方面综述了基于LiPF6的锂离子电池电解液的发展现状,详细介绍了适用于锂离子电池电解液的溶剂和添加剂,应用于锂离子电池电解液的常用有机溶剂有碳酸酯类、醚类和羧酸酯类有机溶剂,添加剂以其作用目的区分,可分为SEI成膜添加剂、导电添加剂、稳定添加剂、控制水分和游离酸添加剂、抗过充添加剂、阻燃添加剂及浸润性添加剂等;展望了锂离子电池电解液的研究方向。     

Gel electrolyte for lithium-ion batteries

The electrochemical performance of gel electrolytes based on crosslinked poly[ethyleneoxide-co-2-(2-methoxyethyoxy)ethyl glycidyl ether-co-allyl glycidyl ether] was investigated using graphite/Li_1.1[Ni_1/3Mn_1/3Co_1/3]_0.9O₂ lithium-ion cells. It was found that the conductivity of the crosslinked gel electrolytes was as high as 5.9 mS/cm at room temperature, which is very similar to that of the conventional organic carbonate liquid electrolytes. Moreover, the capacity retention of lithium-ion cells comprising gel electrolytes was also similar to that of cells with conventional electrolytes. Despite of the high conductivity of the gel electrolytes, the rate capability of lithium-ion cells comprising gel electrolytes is inferior to that of the conventional cells. The difference was believed to be caused by the poor wettability of gel electrolytes on the electrode surfaces.     

Morphology and electrochemical and mechanical properties of polyethylene‐oxide‐based nanofibrous electrolytes applicable in lithium ion batteries

We report the synthesis of all‐solid‐state polymeric electrolytes based on electrospun nanofibers. These nanofibers are composed of polyethylene oxide (PEO) as the matrix, lithium perchlorate (LiClO₄) as the lithium salt and propylene carbonate (PC) as the plasticizer. The effects of the PEO, LiClO₄ and PC ratios on the morphological, mechanical and electrochemical characteristics were investigated using the response surface method (RSM) and analysis of variance test. The prepared nanofibrous electrolytes were characterized using SEM, Fourier transform infrared, XRD and DSC analyses. Conductivity measurements and tensile tests were conducted on the prepared electrolytes. The results show that the average diameter of the nanofibers decreased on reduction of the PEO concentration and addition of PC and LiClO₄. Fourier transport infrared analysis confirmed the complexation between PEO and the additives. The highest conductivity was 0.05 mS cm^?1 at room temperature for the nanofibrous electrolyte with the lowest PEO concentration and the highest ratio of LiClO₄. The optimum nanofibrous electrolyte showed stable cycling over 30 cycles. The conductivity of a polymer film electrolyte was 29 times lower than that of the prepared nanofibrous electrolyte with similar chemical composition. Furthermore, significant fading in mechanical properties was observed on addition of the PC plasticizer. The results obtained imply that further optimization might lead to practical uses of nanofibrous electrolytes in lithium ion batteries. © 2019 Society of Chemical Industry     

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.     

硅烷添加剂在锂离子电池电解液中的应用

硅烷添加剂因具有高热稳定性、低可燃性、无毒性、高电导率和高分解电压等优点,近年来成为了锂离子电池电解液新型添加剂的研究热点。本文重点介绍了在硅烷电解液添加剂中Si—O结构、Si—N结构所发挥的作用以及机理,最后对硅烷添加剂的进一步研究趋势和应用前景进行了展望。     

Ternary polymer electrolytes with 1-methylimidazole based ionic liquids and aprotic solvents

New polymer gel electrolytes containing ionic liquids were developed for modern chemical power sources—supercapacitors and lithium-ion batteries. Ternary systems polymer-ionic liquid-aprotic solvent as well as materials containing also lithium salts (LiClO₄ or LiPF₆) were prepared by direct, thermally initiated polymerisation. Poly(2-ethoxyethyl methacrylate) PEOEMA was combined with various ionic liquids based on 1-methylimidazole. Only 1-butyl-3-methylimidazolium hexafluorophosphate BMIPF₆ formed a homogenous and slightly translucent polymer electrolyte, where aprotic solvents—propylene carbonate and ethylene carbonates were used as plasticisers. Materials were studied using the electrochemical and thermogravimetric methods and exhibit high ionic conductivity up to 0.94 mS cm⁻¹ at 25 °C together with high electrochemical stability: the accessible potential window on the glassy carbon was found ca. 4.3 V. Prepared non-volatile materials are long-term and thermally stable up to 150 °C.     

Application of Film-forming Additives for Ionic Liquid Based Electrolyte

N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide was synthesized for the application in ionic liquid based electrolytes in lithium ion battery, 10% vinylene carbonate (VC) and 10% 1,3-propane sultone (PS) were added to the electrolyte system respectively as additives to improve the property of solid electrolyte interface and cyclic performance. The results of cyclic voltammetry showed that homogenous and compact solid electrolyte interface film formed on graphite electrode which was detected by observing the morphology of cycled graphite anode. Charging and discharging performance of LiFePO4/Li half cell was tested in the electrolyte with or without additives. The initial specific discharging capacities were increased to 129.4 and 123.0 mA×h/g by the addition of VC and PS, respectively, compared with that of additive-free electrolyte. The discharging retentions were 88.9% and 84.6% in electrolyte containing VC and PS after 10 cycles.     

含LiDFOB的FEC/PC/DMC基电解液的高电压电化学性能

利用氟代碳酸乙烯酯(FEC)和二氟草酸硼酸锂(LiDFOB)优良的成膜性、稳定性和耐高压性,研究了在1 mol/L LiPF6 FEC/碳酸丙烯酯(PC)/碳酸二甲酯(DMC)中加入LiDFOB和三(三甲基硅烷)硼酸酯(TMSB)对高电压材料LiNi0.5Mn1.5O4电化学性能的影响,利用循环伏安法和扫描电镜分析了两种电解液中电化学性能的差异. 结果表明,在FEC基电解液中加入LiDFOB和添加剂TMSB使电解液的分解电位提高至5.5 V(vs. Li/Li+)以上,对铝箔有良好的钝化作用. Li/LiNi0.5Mn1.5O4半电池在含LiDFOB和TMSB的电解液中的初始放电比容量达126.8 mA?h/g,库伦效率为99%,充放电200次后比容量仍为108.2 mA?h/g,容量保持率为85.3%. 而在不含LiDFOB和TMSB的电解液中,电池容量迅速衰减,85次充放电循环后容量保持率仅为60.7%.     

Recent progress on garnet-type oxide electrolytes for all-solid-state lithium-ion batteries

Currently, the safety of lithium-ion batteries has attracted much attention. All-solid-state batteries (ASSBs) are promising replacements for liquid-electrolyte lithium-ion batteries due to their high energy density and excellent safety. The choice of electrolyte is the most critical part of ASSBs. Li₇La₃Zr₂O₁₂ (LLZO)-based solid-state electrolytes (SSEs) render high energy density, wide electrochemical window and high lithium-ion mobility. However, their low lithium-ion conductivity compared with liquid organic electrolytes and rigid interfacial contact at electrode/electrolyte interface mainly hinder the development of LLZO-based ASSBs. Herein, we review recent progress in the area of LLZO-based SSEs by discussing the structure and transport mechanism of lithium (Li)-ions of LLZO. Also, we summarize bottleneck problems and corresponding solutions, providing theoretical basis and technical support for the development of LLZO-based ASSBs. Finally, future prospects of LLZO-based ASSBs are discussed in next-generation energy storage systems.     

Comparison between cyclic voltammetry and chronoamperometry when coupled with EQCM for the study of the SEI on a carbon film electrode

Cyclic voltammetry (CV) and chronoamperometry have been conducted with the electrochemical quartz crystal microbalance (EQCM) to characterize electron-beam deposited carbon film electrodes in LiClO₄-containing mixed electrolytes of ethylene carbonate (EC) and dimethyl carbonate (DMC). For a system whose electrolyte viscosity changes in the course of experiments, such as the above combination of electrode and electrolyte, the mass change per mole of electrons transferred (MPE) of the species on quartz crystals depends on the potential scan rate of CV. Chronoamperometry with a short period is more desirable for the estimation of the MPE of the solid electrolyte interphase (SEI) because the viscosity-induced frequency change, which hinders the correct MPE estimation, constitutes a small portion of the measured frequency change under this experimental condition.     

Controlling Gas Generation of Li-Ion Battery through Divinyl Sulfone Electrolyte Additive

The focus of mainstream lithium-ion battery (LIB) research is on increasing the battery’s capacity and performance; however, more effort should be invested in LIB safety for widespread use. One aspect of major concern for LIB cells is the gas generation phenomenon. Following conventional battery engineering practices with electrolyte additives, we examined the potential usage of electrolyte additives to address this specific issue and found a feasible candidate in divinyl sulfone (DVSF). We manufactured four identical battery cells and employed an electrolyte mixture with four different DVSF concentrations (0%, 0.5%, 1.0%, and 2.0%). By measuring the generated gas volume from each battery cell, we demonstrated the potential of DVSF additives as an effective approach for reducing the gas generation in LIB cells. We found that a DVSF concentration of only 1% was necessary to reduce the gas generation by approximately 50% while simultaneously experiencing a negligible impact on the cycle life. To better understand this effect on a molecular level, we examined possible electrochemical reactions through ab initio molecular dynamics (AIMD) based on the density functional theory (DFT). From the electrolyte mixture’s exposure to either an electrochemically reductive or an oxidative environment, we determined the reaction pathways for the generation of CO₂ gas and the mechanism by which DVSF additives effectively blocked the gas’s generation. The key reaction was merging DVSF with cyclic carbonates, such as FEC. Therefore, we concluded that DVSF additives could offer a relatively simplistic and effective approach for controlling the gas generation in lithium-ion batteries.     

Study of the formation of a solid electrolyte interphase (SEI) in ionically crosslinked polyampholytic gel electrolytes

An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate with acrylic acid. A novel ionically crosslinked polyampholytic gel electrolyte was prepared through the free radical copolymerization of the ionic complex and acrylamide in a solvent mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (1:1:1, v/v) containing 1 mol/L of LiPF₆. The impedance analysis indicated that the ionic conductivity of the polyampholytic gel electrolyte was rather close to that of solution electrolytes in the absence of a polymer at the same temperature. The temperature dependence of the conductivity was found to be well in accord with the Arrhenius behavior. The formation processes of the solid electrolyte interphase (SEI) formed in both gel and solution electrolytes during the cycles of charge-discharge were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry curves show a strong peak at a potential of 0.68 V and an increase of the interfacial resistance from 17.2 Ω to 35.8 Ω after the first cycle of charge-discharge. The results indicate that the formation process of SEI formed in both gel and solution electrolytes was similar which could effectively prevent the organic electrolyte from further decomposition and inserting into the graphite electrode. The morphologies of SEI formed in both gel and solution electrolytes were analyzed by field emission scanning electron microscopy. The results indicate that the SEI formed in the gel electrolyte showed a rough surface consisting of smaller solid depositions. Moreover, the SEI formed in the gel electrolyte became more compact and thicker as the cycling increased.     

1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery

Several 1-alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids (alkyl-DMimTFSI) were prepared by changing carbon chain lengths and configuration of the alkyl group, and their electrochemical properties and compatibility with Li/LiFePO₄ battery electrodes were investigated in detail. Experiments indicated the type of ionic liquid has a wide electrochemical window (−0.16 to 5.2 V vs. Li⁺/Li) and are theoretically feasible as an electrolyte for batteries with metallic lithium as anode. Addition of vinylene carbonate (VC) improves the compatibility of alkyl-DMimTFSI-based electrolytes towards lithium anode and LiFePO₄ cathode, and enhanced the formation of solid electrolyte interface to protect lithium anodes from corrosion. The electrochemical properties of the ionic liquids obviously depend on carbon chain length and configuration of the alkyl, including ionic conductivity, viscosity, and charge/discharge capacity etc. Among five alkyl-DMimTFSI-LiTFSI-VC electrolytes, Li/LiFePO₄ battery with the electrolyte-based on amyl-DMimTFSI shows best charge/discharge capacity and reversibility due to relatively high conductivity and low viscosity, its initial discharge capacity is about 152.6 mAh g⁻¹, which the value is near to theoretical specific capacity (170 mAh g⁻¹). Although the battery with electrolyte-based isooctyl-DMimTFSI has lowest initial discharge capacity (8.1 mAh g⁻¹) due to relatively poor conductivity and high viscosity, the value will be dramatically added to 129.6 mAh g⁻¹ when 10% propylene carbonate was introduced into the ternary electrolyte as diluent. These results clearly indicates this type of ionic liquids have fine application prospect for lithium batteries as highly safety electrolytes in the future.     

Electrochemical oxidation of multi-wall carbon nanotubes

The electrochemical modification of carbon nanotube films (buckypapers) in three different electrolytes consisting of two acids and a basic solvent at very low concentrations was studied. The electrolysis was performed at 1 A up to a maximum of 12 h. Four different characterization techniques have been employed for assessing the effectiveness of the proposed process. The results presented are very encouraging for the development of electrochemical oxidation as the main surface modification method for carbon nanotubes. It was found that the use of nitric acid electrolyte leads to scalable and controllable oxidation as compared to the basic electrolyte which was also effective but appeared to damage the graphitic structure of nanotubes during longer treatments.     

Electrolyte additives for enhanced thermal stability of the graphite anode interface in a Li-ion battery

The influence of electrolyte additives on the thermal stability of graphite anodes in a Li-ion battery has been investigated. The selected additives are: ethyltriacetoxysilane, 1,3-benzoldioxole, tetra(ethylene glycol)dimethylether and vinylene carbonate. These compounds were added in 4% to an electrolyte consisting of 1M LiBF₄ ethylene carbonate (EC)/diethyl carbonate (DEC) solvent mixture. Differential scanning calorimetry (DSC) was used to investigate the thermal stability. The electrochemical performance was investigated by galvanostatic cycling and the formed solid electrolyte interphase (SEI) was characterised by photoelectron spectroscopy (PES) using Al Kα and synchrotron radiation (SR). The onset temperature for the thermally activated reactions was found to increase for all electrodes cycled with additives compared to electrodes cycled without additives. The onset temperature increased in the order: no additive < tetra(ethylene glycol)dimethyl ether < 1,3-benzoldioxole < ethyl-triacetoxysilane < vinylene carbonate. Features in the PES spectra found to be associated with high onset temperatures for thermally activated reactions are: (i) no discernible graphite peak, (ii) small amount of salt species of the type LiF and Li_xBF_yO_z and (iii) larger amounts of organic compounds preferably with a high oxygen content.     

Electrochemical activation of carbon dioxide for synthesis of dimethyl carbonate in an ionic liquid

The direct synthesis of dimethyl carbonate from methanol and carbon dioxide is challenging due to the thermodynamic stability and kinetic inertness of CO₂. Electrochemical technique can overcome this challenge by providing a method for preliminary activation of CO₂. Electrocatalytic activation and conversion of carbon dioxide to dimethyl carbonate with platinum electrodes in a dialkylimidazolium ionic liquids-basic compounds-methanol system was conducted under ambient conditions. Among the basic compounds and ionic liquids, CH₃OK acts as a co-catalyst and 1-butyl-3-methylimidazolium bromide (bmimBr) acts as an electrolyte. In the bmimBr-CH₃OK-methanol system, the absence of CH₃I and/or any other organic additives allows dimethyl carbonate to be effectively synthesized. The reaction mechanism proposed here is different from those previously reported.     

密度泛函理论在高电压电解液设计中的应用

基于密度泛函理论的量子化学计算为高电压电解液的配方设计提供了理论基础。运用Gaussian软件可以有效模拟电解液中某一成分的分子构型和溶剂化状态,计算出化合物的分解路径与分解产物,进而大幅缩短电解液研发周期。本文回顾了近年来该计算方法在锂离子电池电解液研究中的相关进展,并以高电压电解液为例,介绍了该理论在溶剂氧化电位计算方面的应用,结合分子模型的优化,实现了计算值与实验值的基本统一。此外,详细阐述了砜类、氟类、离子液体等几种新型高电压溶剂和磷酸酯类、硼类、腈类等几种成膜添加剂的应用。相信今后随着动力学理论的完善和计算机技术的优化,该方法在高浓度电解液、固液界面作用机理等当前难以实现的理论模拟问题方面的应用指日可待。     

LiPF6/LiBOB blend salt electrolyte for high-power lithium-ion batteries

LiPF₆/LiBOB blend salt-based electrolytes were investigated as potential candidates for high-power lithium-ion batteries, especially for transportation applications. It was demonstrated that both the power capability and the cycling performance of the lithium-ion cells could be attenuated by controlling the concentration of LiBOB in blend salt electrolytes. The power capability of the lithium-ion cells decreases with the concentration of LiBOB, while the capacity retention of the cells at 55 °C increases with the LiBOB concentration. When electrolytes with no more than 0.1 M LiBOB was used, the MCMB/LiMn_1/3Ni_1/3Co_1/3O₂ cells have excellent capacity retention at 55 °C, while their impedance meets the requirement set by the FreedomCar Partnership. The similar performance improvement on the MCMB/LiMn₂O₄ cells was also observed with the blend salt electrolyte.