新型锂盐双乙二酸硼酸锂的制备与性能

文章综述了近年来锂离子电池豹新型锂盐一双乙二酸硼酸锂（LiBOB）研究的成果。介绍了双乙二酸硼酸锂的合成方法、组成与结构、化学和电化学性能及其与结构的关系。并重点综述了LiBOB电解液的导电性研究,对负极材料、正极材料的稳定性研究,与其他锂盐在锂离子电池中混合使用的性能研究等。总结了LiBOB的优缺点,指出了其进一步的研究方向。     

The effects of LiBOB additive for stable SEI formation of PP13TFSI-organic mixed electrolyte in lithium ion batteries

A safe electrolyte system is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13TFSI), organic electrolyte (1 mol L⁻¹ LiPF₆/EC-DEC) and lithium bis (oxalato) borate (LiBOB). The additive of LiBOB enhances the stability of interface between electrolyte and anode. The LiBOB-containing mixed electrolytes show non-flammability and good compatibility with active materials. The performance of anode for lithium ion battery is successfully improved by LiBOB-containing mixed electrolytes, which shows 200 mA h g⁻¹ reversible capacities at 0.3 C rate. The ionic conductivity and the lithium ion transference number in LiBOB-containing mixed electrolytes system also suits to application for lithium ion battery.     

Electrochemical intercalation of lithium into a natural graphite anode in quaternary ammonium-based ionic liquid electrolytes

Electrochemical intercalation of lithium into a natural graphite anode was investigated in electrolytes based on a room temperature ionic liquid consisting of trimethyl-n-hexylammonium (TMHA) cation and bis(trifluoromethanesulfone) imide (TFSI) anion. Graphite electrode was less prone to forming effective passivation film in 1 M LiTFSI/TMHA-TFSI ionic electrolyte. Reversible intercalation/de-intercalation of TMHA cations into/from the graphene interlayer was confirmed by using cyclic voltammetry, galvanostatic measurements, and ex situ X-ray diffraction technique. Addition of 20 vol% chloroethylenene carbonate (Cl-EC), ethylene carbonate (EC), vinyl carbonate (VC), or ethylene sulfite (ES) into the ionic electrolyte resulted in the formation of solid electrolyte interface (SEI) film prior to TMHA intercalation and allowed the formation of Li-C₆ graphite interlayer compound. In the ionic electrolyte containing 20 vol% Cl-EC, the natural graphite anode exhibited excellent electrochemical behavior with 352.9 mAh/g discharge capacity and 87.1% coulombic efficiency at the first cycle. A stable reversible capacity of around 360 mAh/g was obtained in the initial 20 cycles without any noticeable capacity loss. Mechanisms concerning the significant electrochemical improvement of the graphite anode were discussed. Ac impedance and SEM studies demonstrated the formation of a thin, homogenous, compact and more conductive SEI layer on the graphite electrode surface.     

Effects of electrolytes on the electrochemical performance of Si/graphite/disordered carbon composite anode for lithium-ion batteries

The influences of LiBF₄, LiClO₄, lithium bis(oxalato) borate (LiBOB), LiPF₆ with VC and without VC, and the mixed electrolytes composed of different ratios of LiBOB and LiPF₆ or LiClO₄ on the electrochemical properties of Si/graphite/disordered carbon (Si/G/DC) composite electrode were systematically investigated by constant current charge-discharge and electrochemical impedance spectra (EIS) techniques. Scanning electron microscopy (SEM) was used to observe the change of electrodes in morphology after given cycle numbers. X-ray photoelectron spectroscopy (XPS) was employed to understand the influences of different mixed electrolytes on the composition of SEI layers. The results showed that Si/G/DC composite electrode in the mixed electrolytes presented better electrochemical performance than in single electrolyte. The compactness and compositions of SEI layers intensively influenced the cycle performance of Si/G/DC composite materials. LiBOB and additive VC had a good synergistic effect on the formation of the dense SEI layers. In particular, Si/G/DC in 0.5 M LiBOB + 0.38 M LiPF₆ electrolytes containing VC exhibited a high reversible capacity and excellent cycle performance.     

锂离子电池首次充、放电时石墨负电极与电解液界面所发生的反应

采用恒电流充、放电——原位XRD法对锂离子电池（LIB）首次充、放电过程进行了研究。实验结果表明，LIB首次充电时电解液于石墨负电极的界面处发生还原反应，生成了电子不可导而锂离子可导的固体电解质中介相（SEI）薄膜。FTIR分析结果证明SEI膜系由无定形碳酸锂和烷基碳酸锂组成。恒电流充、放电实验和循环伏安实验结果表明，如果所选择的电解液（例如EC基电解液）在石墨负电极表面的还原反应很缓和，反应中所产生气体的量和速率很小，则在石墨负电极表面将形成薄而致密的SEI膜。薄而致密的SEI膜所消耗的Li^＋量小，可以降低首次充电时的不可逆容量，同时减小Li^＋对石墨进行插层和脱层时的阻力，增大LIB的充、放电容量，提高充、放电效率。     

Optimizing the compatibility between dimethyl methylphosphonate (DMMP)-based electrolytes and carbonaceous anodes

The poor compatibility between dimethyl methylphosphonate (DMMP)-based electrolytes and carbonaceous anodes was improved by optimizing the compositions of the electrolyte and the electrode. In the electrolyte, the contents of DMMP and ethylene carbonate had significant effects on both the safety characteristic and the compatibility with carbonaceous anode. For the spherical mesocarbon microbeads, a conductive composite system containing the flake graphite and the carbon nanoparticles was beneficial to the highest reversible capacity (330 mAh g⁻¹). In the common graphite anode, the water-soluble binder was the better choice than poly(vinylidene fluoride) to suppress the reductive decomposition of DMMP. In brief, the optimized compatibility indicated an extensive prospect of the flame-retarded electrolyte in the battery industry.     

Influence of manganese(II), cobalt(II), and nickel(II) additives in electrolyte on performance of graphite anode for lithium-ion batteries

Manganese dissolution into an electrolyte from the spinel LiMn₂O₄ in the lithium-ion cell has been recently investigated. In order to study the influence of the dissolved manganese species on the lithium intercalation/deintercalation into a natural graphite electrode, the electrochemical behavior of graphite was investigated in 1 mol dm⁻³ LiClO₄ electrolyte solution containing a small amount of Mn(II) by the addition of manganese(II) perchlorate. During the charging process, Mn(II) ions were firstly electroreduced on the electrode around 1.0 V versus Li/Li⁺ followed by irreversible decomposition of the electrolyte and lithium intercalation into the graphite. By microscopic observation of the graphite surface, manganese deposition was confirmed after the charge/discharge test. Due to the manganese deposition, the reversible capacity of the graphite electrode was drastically decreased. Furthermore, the cyclability of the anode was degraded with the amount of the manganese additive increasing. We compared these results with those of the cobalt(II) and nickel(II) additives by dissolving the corresponding perchlorates. Furthermore, we discussed the influence in practical cells based on the consideration of electrochemistry of the deposited metals.     

Recent advances toward high voltage,EC-free electrolytes for graphite-based Li-ion battery

Lithium-ion batteries are a key technology in today’s world and improving their performances requires, in many cases, the use of cathodes operating above the anodic stability of state-of-the-art electrolytes based on ethylene carbonate (EC) mixtures. EC, however, is a crucial component of electrolytes, due to its excellent ability to allow graphite anode operation–also required for high energy density batteries–by stabilizing the electrode/electrolyte interface. In the last years, many alternative electrolytes, aiming at allowing high voltage battery operation, have been proposed. However, often, graphite electrode operation is not well demonstrated in these electrolytes. Thus, we review here the high voltage, EC-free alternative electrolytes, focusing on those allowing the steady operation of graphite anodes. This review covers electrolyte compositions, with the widespread use of additives, the change in main lithium salt, the effect of anion (or Li salt) concentration, but also reports on graphite protection strategies, by coatings or artificial solid electrolyte interphase (SEI) or by use of water-soluble binder for electrode processing as these can also enable the use of graphite in electrolytes with suboptimal intrinsic SEI formation ability.     

Stabilisation of lithiated graphite in an electrolyte based on ionic liquids: an electrochemical and scanning electron microscopy study

1-Ethyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (EMI-TFSI) is shown to reversibly permit lithium intercalation into standard TIMREX^® SFG44 graphite when vinylene carbonate (VC) is used in small amounts as additive. The best performance was obtained when 5% of VC was added to a 1 M solution of LiPF₆ in EMI-TFSI. Intercalation of lithium in the SFG44 graphite host was demonstrated over 100 cycles without noticeable capacity fading. The reversible charge capacity was around 350 mA h g⁻¹ and an only small irreversible capacity loss per cycle could be observed. Li₄Ti₅O₁₂ was used as counter electrode material. Scanning electron microscopy indicates the reduction of the electrolyte without graphite exfoliation in the neat electrolyte and the formation of a passivation film in the case of a VC-containing electrolyte. Other additives that were tested comprise ethylene sulphite and acrylonitrile which show also a positive effect, but a smaller one than vinylene carbonate. LiCoO₂ positive electrodes were cycled in a 1 M solution of LiPF₆ in EMI-TFSI with good charge capacity retention over more than 300 cycles, when Li₄Ti₅O₁₂ was used as counter electrode. The formation of a passivation film is proven on the LiCoO₂-electrodes, when the electrolyte contained VC, but not in the neat ionic liquid. Finally, the stable cycling of a full cell configuration is proven in this electrolyte system. An ammonium-containing ionic liquid (methyltrioctylammonium-bis(trifluoromethylsulfonyl)-imide, MTO-TFSI) is shown to permit the cycling of both, graphite and lithium cobalt oxide when VC is used as additive in small amounts, but at slightly elevated temperatures.     

Mechanism of self-discharge in graphite-lithium anode

In order to evaluate the anode contribution to the lithium-ion battery self-discharge, three electrode coin cells composed of metallic lithium as reference and counter electrode, organic liquid electrolyte and graphite composite working electrode were constructed as test cells. They were first cycled for a dozen cycles and then stored in the full lithiated state of graphite, at 70 °C for periods from 1 to 8 days. The capacity loss was determined during the first delithiation following storage. The latter was found composed of two terms, a reversible and an irreversible one, where the relative amounts are storage time dependants. Electrochemical impedance spectroscopy (EIS) was used to investigate the changes in the cell interfacial characteristics. A model involving the formation of an absorbed electron-ion-electrolyte complex on the graphite surface is proposed as the mechanism of the reversible and irreversible capacity losses. It is also suggested that precipitation/dissolution reactions are taking place at the solid electrolyte interphase (SEI). Precipitation occurs with insoluble inorganic species such as, LiF and Li₂CO₃, whereas dissolution may concern the organic and/or polymer part of the SEI. The continuous growth of the inorganic (and most resistive) part of the SEI with the subsequent electrode isolation is proposed as the major mechanism of the electrode end of life.     

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.     

Fundamental study of the anodic and cathodic reactions during the electrolysis of a lithium carbonate-lithium chloride melt using a carbon anode

Cyclic voltammetry, in conjunction with the chromatographic analysis of the anode product, has been used to elucidate the reactions occurring during the electrolysis of lithium carbonate-lithium chloride melts. At a carbonate ion concentration of 0.033 mole fraction the peak anodic current densities were 3100 A m^–2 on vitreous carbon and 6900 A m^–2 on graphite with the product being carbon dioxide. The cathodic reduction of carbonate at low concentrations was found to occur at –1.0 V to –1.2 V vs a Ag/Ag(I) reference electrode which is 1.2 V less negative than the potential at which lithium ions were reduced. Voltammetric studies of the reduction of the carbonate ion indicated that the reaction mechanism involved an irreversible charge transfer.     

Ionic conductivity and lithium electrode stability in Hydrin: LiBF4 elastomers

Three commercial elastomers, Hydrin C, Hydrin H and Hydrin T, which contain ethylene oxide and epichlorohydrin repeat units, have been investigated as polymer electrolytes in contact with lithium electrode. The influence of polyethylene glycol and fine particles of zeolite on ionic conductivity of Hydrin-LiBF₄ electrolytes and the exchange current density of the lithium electrode reaction has been studied by using impedance spectroscopy and cyclic voltammetry. The specific conductivity of the elastomeric electrolyte is about 10^–5 S cm^–1 at room temperature when polyethylene glycol is present. But the mechanical stability of the film is less. The addition of zeolite particles to the elastomers also improves the specific conductivity. When present in low concentrations, the zeolite particles show catalytic effect on the electrochemical reaction at lithium electrode at ambient temperature. The lithium electrode reaction is reversible and the electrolyte possesses good electrochemical stability.     

Novel SEI formation of maleimide-based additives and its improvement of capability and cyclicability in lithium ion batteries

This investigation elucidates three maleimide (MI)-based aromatic molecules as additives in electrolyte that is used in lithium ion batteries. The 1.1 M LiPF₆ in ethylene carbonate (EC):propylene carbonate (PC):diethylene carbonate (DEC) (3:2:5 in volume) containing MI-based additives can prompt the formation of a solid electrolyte interface (SEI); and inhibit the entering into the irreversible state during lithium intercalation and co-intercalation. The reduction potential is 0.71-0.98 V versus Li/Li⁺ as determined by cyclic voltammetry (CV). The morphology and element analysis of the positive and negative electrode after the 100th charge-discharge cycle are examined by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). Moreover, the MI was used in lithium ion batteries and provided 4.9% capacity increase and 16.7% capacity retention increase when cycled at 1C/1C. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries. MI is decomposed electrochemically to form a long winding narrow SEI strip on the graphite surface. This novel SEI strip not only prevents exfoliation on the graphite electrode but also stabilizes the electrolyte. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries.     

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.     

Solid Composite Polymer Electrolytes with High Cation Transference Number

This work presents the electrochemical and structural study of the dual modified composite LiBOB-based polymer electrolyte. Modification has been carried out by calix[6]pyrrole (CP) anion trap and nanosize silica filler. The main advantage of the use of LiBOB salt is the high ionic conductivity at near-ambient temperatures and low solid-electrolyte interphase (SEI) resistance. The conductivity of LiBOB:PEO₂₀:CP_0.125 with SiO₂ is slightly lower than 10⁻⁵ Scm⁻¹ at 30 °C, a value higher by about two orders of magnitude than that of the semi-crystalline LiCF₃SO₃ (LiTf)-PEO system. At 75 to 90 °C the bulk ionic conductivity of modified LiBOB polymer electrolyte approaches 1 mScm⁻¹. The transference number of dual-modified LiBOB-polymer electrolyte is about 0.8 at 75 °C. Cyclic voltammetry tests showed a wide electrochemical stability window of the composite polymer electrolyte. The peak power of Li/MoO^xS_y cell with the polymer electrolyte film containing CP and SiO₂ reaches 2.2 mW/cm ² and 3.0 mW/cm ² at 90 and 110 °C, respectively.     

Effects of solvents and salts on the thermal stability of LiC6

Accelerating rate calorimetry (ARC) was used to study the thermal stability of Li_0.81C₆ in dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), and an EC/DEC mixture as well as in LiPF₆- and LiBOB-based electrolytes. ARC results show that linear carbonates like DMC or DEC react strongly with Li_0.81C₆ and that robust passivating layers do not form. By contrast, the cyclic carbonate, EC, creates a robust passivating film that limits the rate of reaction between Li_0.81C₆ and EC as the temperature increases. X-ray diffraction shows that the addition of LiPF₆ to EC/DEC changes the surface film that forms on Li_0.81C₆ at elevated temperature to one dominated by LiF instead of lithium-alkyl carbonate or lithium carbonate. This increases the thermal stability of Li_0.81C₆ in LiPF₆ electrolyte compared to pure EC/DEC solvent. By an apparently similar mechanism, the addition of only 0.2 M LiBOB to EC/DEC greatly improves the thermal stability of Li_0.81C₆. ARC results for Li_0.81C₆ in pure and mixed salt LiPF₆ and LiBOB EC/DEC electrolytes of various molarities shed light on the reasons for the beneficial effect of the salts.     

Comparative studies of three redox shuttle molecule classes for overcharge protection of LiFePO4-based Li-ion cells

Three classes of molecules have been shown to be successful for protecting lithium-ion cells during overcharge. These three classes are, the molecule 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB), molecules based on a phenothiazine core, such as 10-methylphenothiazine (MPT) and molecules based on a 2,2,6,6-tetramethylpiperidinyl-oxide (TEMPO) core, such as TEMPO and 4-cyano-TEMPO. These molecules were examined using Li-ion coin cells, three-electrode cyclic voltammetry and four-electrode cyclic voltammetry. Three-electrode cyclic voltammetry was used to measure the diffusion coefficients and the stability of the shuttle molecules at high and low potentials. The transport of electrons through the solid-electrolyte interface on the negative electrode to the oxidized shuttle molecule was studied using the four-electrode cell for electrolytes containing both LiPF₆ and lithium bis(oxalato)borate salts. The rate of charge transfer to the oxidized TEMPO and MPT molecules is significantly reduced on glassy carbon below 1.7 V (versus Li/Li⁺) in electrolytes containing LiBOB, but not in electrolytes containing LiPF₆. Charge transfer to oxidized DDB seems facile at all potentials above 0.2 V in both LiPF₆ and LiBOB electrolytes.     

Compatibility of quaternary ammonium-based ionic liquid electrolytes with electrodes in lithium ion batteries

Electrochemical intercalation/deintercalation behavior of lithium into/from electrodes of lithium ion batteries was comparatively investigated in 1 mol/L LiClO₄ ethylene carbonate-diethyl carbonate (EC-DEC) electrolyte and a quaternary ammonium-based ionic liquid electrolyte. The natural graphite anode exhibited satisfactory electrochemical performance in the ionic liquid electrolyte containing 20 vol.% chloroethylenene carbonate (Cl-EC). This is attributed to the mild reduction of solvated Cl-EC molecules at the graphite/ionic electrolyte interface resulting in the formation of a thin and homogenous SEI on the graphite surface. However, rate capability of the graphite anode is poor due to the higher interfacial resistance than that obtained in 1 mol/L LiClO₄/EC-DEC organic electrolyte. Spinel LiMn₂O₄ cathode was also electrochemically cycled in the ionic electrolyte showing satisfactory capacity and reversibility. The ionic electrolyte system is thus promising for 4 V lithium ion batteries based on the concept of “greenness and safety”.     

Surface layer formation on Sn anode: ATR FTIR spectroscopic characterization

Surface layer formed on Sn thin film electrode in 1 M LiPF₆/EC:DMC electrolyte was characterized using ex situ FTIR spectroscopy with the attenuated total reflection technique. IR spectral analyses showed that the immersion of Sn film in the electrolyte resulted in a chemical interfacial reaction leading to the passivation of Sn surface with primarily PF-containing inorganic surface species and small amount of organics. When constant current cycling was conducted with lithium cells with Sn film electrode at 0.1-1.0 V vs. Li/Li⁺, the interfacial reaction between Sn and electrolyte appeared significantly intensified that the features of PF-containing species became enhanced and new IR features of organic species (e.g. alkyl carbonate/carboxylate metal salts and ester functionalities) were observed. The surface layer continued to form with cycling, partly due to non-effective surface passivation as well as particle pulverization accompanied by enlargement of active surface area. Comparative IR spectral analyses indicated that the interfacial reaction between Sn and PF₆⁻ anion played a leading role in forming the surface layer, which is different from lithiated graphite that had mainly organic surface species. The data contribute to a better understanding of the interfacial processes occurring on Sn-based anode materials in lithium-ion batteries.