Functional binders for reversible lithium intercalation into graphite in propylene carbonate and ionic liquid media

Poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), and poly(vinyl alcohol) (PVA), which have oxygen species as functional groups, were utilized as a binder for graphite electrodes, and the electrochemical reversibility of lithium intercalation was examined in PC medium and ionic liquid electrolyte, lithium bis(trifluoromethanesulfonyl)amide dissolved in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (BMP-TFSA). Columbic efficiency of 75–80% with more than 300 mAh g^?1 was achieved upon first reduction/oxidation cycle in both electrolytes using these binding polymers, which were significantly improved in comparison to a conventional PVdF binder (less than 45% of columbic efficiency for the first cycle). For the graphite-PVdF electrode, co-intercalation and/or decomposition of PC molecules solvating to Li ions were observed by the electrochemical reduction, resulting in the cracking of graphite particles. In contrast, the co-intercalation and decomposition of PC molecules and BMP cations for the first reduction process were completely suppressed for the graphite electrodes prepared with the polymers containing oxygen atoms. It was proposed that the selective permeability of lithium ions was attained by the uniform coating of the graphite particles with PAA, PMA, and PVA polymers, because the electrostatic interaction between the positively charged lithium ions and negatively charged oxygen atom in the polymer should modulate the desolvation process of lithium ions during the lithium intercalation into graphite, showing the similar functions like artificial solid-electrolyte interphase.     

LiBOB-based gel electrolyte Li-ion battery for high temperature operation

In this work, we evaluated the chemical compatibility of 1.0m (molality) lithium bis(oxalate)borate (LiBOB) 1:1 (w/w) propylene carbonate (PC)/ethylene carbonate (EC) liquid electrolyte with lithium metal and spinel LiMn₂O₄ cathode using storage and cycling tests at high temperatures. Impedance analyses show that LiBOB and lithium are very compatible due to the formation of a stable passivation layer on the surface of lithium. Cycling tests of Li/Cu and Li/LiMn₂O₄ cells, respectively, show that lithium can be plated and stripped in LiBOB-based electrolyte with more than 80% cycling efficiency, and that this electrolyte can support LiMn₂O₄ cycling reversibly up to 60 °C without visible capacity loss. Using LiBOB-based liquid electrolyte and porous Kynar^® membrane, microporous gel electrolyte (MGE) Li-ion cells were assembled and evaluated. Results show that the MGE cell presents an improved cycling performance compared with a liquid cell, especially at elevated temperatures. It is confirmed that the LiBOB-based gel electrolyte Li-ion batteries can be operated at 60 °C with good capacity retention.     

Observation of electrodeposited lithium by optical microscope in room temperature ionic liquid-based electrolyte

Room temperature ionic liquids (RTILs) were applied to a lithium (Li) metal battery system, and the behavior of Li electrodeposition on nickel electrodes in RTILs was investigated using in situ optical microscopy with/without an organic additive, vinylene carbonate (VC), in the RTILs. Two RTILs, PP13[TFSA] (N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)amide) and EMI[FSA] (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide), were chosen as the base electrolytes. Dendritic particles were obtained in the case of EMI[FSA] with and without VC, and PP13[TFSA] without VC, while non-dendritic fine particles were obtained in the case of PP13[TFSA] with VC.     

Solid-state Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 °C

The cycle behaviour and rate performance of solid-state Li/LiFePO₄ polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR₁₃TFSI) room temperature ionic liquid (IL) into the P(EO)₂₀LiTFSI electrolyte and the cathode have been investigated at 40 °C. The ionic conductivity of the P(EO)₂₀LiTFSI + PYR₁₃TFSI polymer electrolyte was about 6 × 10⁻⁴ S cm⁻¹ at 40 °C for a PYR₁₃⁺/Li⁺ mole ratio of 1.73. Li/LiFePO₄ batteries retained about 86% of their initial discharge capacity (127 mAh g⁻¹) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO₄ batteries exhibited some discharge capability at high currents up to 1.52 mA cm⁻² (2 C) at 40 °C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.     

Crosslinkable fumed silica-based nanocomposite electrolytes for rechargeable lithium batteries

Electrochemical and rheological properties are reported of composite polymer electrolytes (CPEs) consisting of dual-functionalized fumed silica with methacrylate and octyl groups + low-molecular weight poly(ethylene glycol) dimethyl ether (PEGdm) + lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, lithium imide) + butyl methacrylate (BMA). The role of butyl methacrylate, which aids in formation of a crosslinked network by tethering adjacent fumed silica particles, on rheology and electrochemistry is examined together with the effects of fumed silica surface group, fumed silica weight percent, salt concentration, and solvent molecular weight. Chemical crosslinking of the fumed silica with 20% BMA shows a substantial increase in the elastic modulus of the system and a transition from a liquid-like/flocculated state to an elastic network. In contrast, no change in lithium transference number and only a modest decrease (factor of 2) on conductivity of the CPE are observed, indicating that a crosslinked silica network has minimal effect on the mechanism of ionic transport. These trends suggest that the chemical crosslinks occur on a microscopic scale, as opposed to a molecular scale, between adjacent silica particles and therefore do not impede the segmental mobility of the PEGdm. The relative proportion of the methacrylate and octyl groups on the silica surface displays a nominal effect on both rheology and conductivity following crosslinking although the pre-cure rheology is a function of the surface groups. Chemical crosslinked nanocomposite polymer electrolytes offer significant higher elastic modulus and yield stress than the physical nanocomposite counterpart with a small/negligible penalty of transport properties. The crosslinked CPEs exhibit good interfacial stability with lithium metal at open circuit, however, they perform poorly in cycling of lithium–lithium cells.     

Imidazolium-organic solvent mixtures as electrolytes for lithium batteries

γ-Butyrolactone (BL) has been mixed to the room temperature ionic liquid (RTIL) 1-butyl 3-methyl-imidazolium tetrafluoroborate (BMIBF₄) (ratio: 3/2, v/v) in the presence of lithium tetrafluoroborate (LiBF₄) for use as electrolyte in lithium-ion batteries. This mixture exhibits a larger thermal stability than the reference electrolyte EC/DEC/DMC (2/2/1) + LiPF₆ (1 M) and can be considered as a new RTIL as no free BL molecules are present in the liquid phase. The cycling ability of this electrolyte has been investigated at a graphite, a titanate oxide (Li₄Ti₅O₁₂) and a cobalt oxide (Li_xCoO₂) electrodes. The ionic liquid is strongly reduced at the graphite electrode near 1 V and leads to the formation of a blocking film, which prevents any further cycling. The titanate oxide electrode can be cycled with a high capacity without any significant fading. Cycling of the positive cobalt oxide electrode was unsuccessfully owing to an oxidation reaction at the electrode surface, which prevents the intercalation or de-intercalation of Li ions in and from the host material. Less reactive cathode material than cobalt oxide must be employed with this RTIL.     

Electrochemical characterization of blend polymer electrolytes based on poly(oligo[oxyethylene]oxyterephthaloyl) for rechargeable lithium metal polymer batteries

Solid polymer electrolytes composed of poly(ethylene oxide)(PEO), poly(oligo[oxyethylene]oxyterephthaloyl) and lithium perchlorate have been prepared and characterized. Addition of poly(oligo[oxyethylene]oxyterephthaloyl) to PEO/LiClO₄ reduced the degree of crystallinity and improved the ambient temperature ionic conductivity. The blend polymer electrolyte containing 40 wt.% of poly(oligo[oxyethylene]oxyterephthaloyl) showed an ionic conductivity of 2.0 × 10⁻⁵ S cm⁻¹ at room temperature and a sufficient electrochemical stability to allow application in the lithium batteries. By using the blend polymer electrolytes, the lithium metal polymer cells composed of lithium anode and LiCoO₂ cathode were assembled and their cycling performances were evaluated at 40 °C.     

Effect of an electrolyte salt dissolving in polysiloxane-based electrolyte on passive film formation on a graphite electrode

Electrochemical impedance spectroscopy (EIS) was performed during the first charge of a graphite/lithium metal test cell to determine the effect of an electrolyte salt on passive film formation in a polysiloxane-based electrolyte. The graphite electrode was separated from the lithium metal electrode by a porous polyethylene membrane immersed in a polysiloxane-based electrolyte with the dissolved lithium bis(oxalato) borate (LiBOB) or lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). In case of LiTFSI, the conductivity of system decreased at 1.2 V. In contrast, for the case of LiBOB, the conductivity decreased at 1.7 V. The magnitudes of charge transfer resistance and film resistance for LiTFSI were smaller than that for LiBOB. Passive films on highly oriented pyrolytic graphite (HOPG) after charging (lithiating) in polysiloxane-based electrolyte were inspected microscopically. Gel-like film and island-like films were observed for LiBOB [H. Nakahara, A. Masias, S.Y. Yoon, T. Koike, K. Takeya, Proceedings of the 41st Power Sources Conference, vol. 165, Philadelphia, June 14–17, 2004; H. Nakahara, S.Y. Yoon, T. Piao, S. Nutt, F. Mansfeld, J. Power Sources, in press; H. Nakahara, S.Y. Yoon, S. Nutt, J. Power Sources, in press]. However, for LiTFSI, there was sludge accumulation on the HOPG surface. Compositional analysis revealed the presence of silicon on both HOPG specimens with LiBOB and with LiTFSI. The electrolyte salt dissolved in the polysiloxane-based electrolyte changed the electrochemical and morphological nature of passive films on graphite electrode.     

Nonflammable gel electrolyte containing alkyl phosphate for rechargeable lithium batteries

A nonflammable polymeric gel electrolyte has been developed for rechargeable lithium battery systems. The gel film consists of poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP) swollen with lithium hexafluorophosphate (LiPF₆) solution in ternary solvent containing trimethyl phosphate (TMP). High ionic conductivity of 6.2 mS cm⁻¹ at 20 °C was obtained for the gel electrolyte consisting of 0.8 M LiPF₆/EC + DEC + TMP (55:25:20) with PVdF-HFP, which is comparable to that of the liquid electrolyte containing the same electrolytic salt. Addition of a small amount of vinylene carbonate (VC) in the gel electrolyte improved the rechargeability of a graphite electrode. The rechargeable capacity of the graphite in the gel containing VC was ca. 300 mAh g⁻¹, which is almost the same as that in a conventional liquid electrolyte system.     

An imidazolium based ionic liquid electrolyte for lithium batteries

An electrolyte for lithium batteries based on the ionic liquid 3-methy-1-propylimidazolium bis(trifluoromethysulfony)imide (PMIMTFSI) complexed with lithium bis(trifluoromethysulfony)imide (LiTFSI) at a molar ratio of 1:1 has been investigated. The electrolyte shows a high ionic conductivity (∼1.2 × 10⁻³ S cm⁻¹) at room temperature. Over the whole investigated temperature range the ionic conductivity is more than one order of magnitude higher than for an analogue electrolyte based on N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py₁₄TFSI) complexed with LiTFSI and used here as a benchmark. Raman results indicate furthermore that the degree of lithium coordinated TFSI is slightly lower in the electrolyte based on PMIMTFSI and thus that the Li⁺ charge carriers should be higher than in electrolytes based on Py₁₄TFSI. An ionic liquid gel electrolyte membrane was obtained by soaking a fibrous fully interconnected membrane, made of electrospun P(VdF-HFP), in the electrolyte. The gel electrolyte was cycled in Li/ionic liquid polymer electrolyte/Li cells over 15 days and in Li/LiFePO₄ cells demonstrating good interfacial stability and highly stable discharge capacities with a retention of >96% after 50 cycles (∼146 mAh g⁻¹).     

Cycling and rate performance of Li-LiFePO4 cells in mixed FSI-TFSI room temperature ionic liquids

A study is conducted of the performance of lithium iron(II) phosphate, LiFePO₄, as a cathode material in a lithium secondary battery that features an ionic liquid electrolyte solution and a metallic lithium anode. The electrolyte solution comprises an ionic liquid of a N-methyl-N-alkyl-pyrrolidinium (alkyl = n-propyl or n-butyl) cation and either the bis(fluorosulfonyl)imide [(FSO₂)₂N⁻] or bis(trifluoromethanesulfonyl)imide [(F₃CSO₂)₂N⁻] anion, together with 0.5 mol kg⁻¹ of lithium bis(trifluoromethanesulfonyl)imide salt. For N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide, coin cells discharging at rates of C/10 and 4C yield specific capacities of 153 and 110 mAh g⁻¹, respectively, at an average coulombic efficiency of 99.8%. This performance is maintained for over 400 cycles at 50 °C and therefore indicates that these electrolyte solutions support long-term cycling of both LiFePO₄ and metallic lithium while, due to the negligible volatility of ionic liquids, surrounding the lithium in an inherently safe, non-flammable medium.     

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

A micro-porous polymer electrolyte based on PVA was obtained from PVA–PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301–351 K. It is observed that a 2 M LiClO₄ solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10⁻³ S cm⁻¹ at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn₂O₄ cell to reveal the compatibility and electrochemical stability between electrode materials.     

Application of electrolyte using novel ionic liquid to Si thick film anode of Li-ion battery

An applicability of a novel ionic liquid, consisting of 1-methoxyethoxymethyl(tri-n-butyl)phosphonium cation and bis(trifluoromethanesulfonyl)amide anion, was investigated as an electrolyte of Li-ion battery using a thick film electrode of Si prepared by a gas-deposition method. The electrochemical properties in the novel ionic liquid were compared to those in a commercial ionic liquid and a typical organic solvent of propylene carbonate. The initial discharge capacity of 3450 mAh g⁻¹ and excellent cycling performance were achieved in the novel ionic liquid. The novel ionic liquid was confirmed to effectively suppress a collapse and an electrical isolation of the Si thick film induced by pulverization during charge-discharge cycling. The excellent performance is possibly attributed to more effective desolvation of Li ions from the anions due to its lower dielectric constant compared with the propylene carbonate solvent.     

P(DMS-co-EO)/P(EPI-co-EO) blend as a polymeric electrolyte

A new polymer electrolyte comprising the blend of poly(dimethylsiloxane-co-ethylene oxide) (P(DMS-co-EO)), and poly(epichlorohydrin-co-ethylene oxide) (P(EPI-co-EO)), with different concentrations of LiClO₄ is described. The polymer electrolyte was prepared by a solution-cast technique. The electrochemical properties were studied by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry techniques. The maximum ionic conductivity (σ=1.2×10⁻⁴ S cm⁻¹) was obtained for the P(DMS-co-EO)/P(EPI-co-EO) 15/85 and 20/80 blends with 6 wt.% LiClO₄. These same films had a wide electrochemical stability, higher than 5 V at room temperature. A stable passive layer at the interface between the polymer electrolyte and lithium metal was formed within the first few days and maintained during the follow storage period. UV-Vis absorption spectra of the blends showed a transparent polymer electrolyte in the visible region.     

Application of bis(fluorosulfonyl)imide-based ionic liquid electrolyte to silicon-nickel-carbon composite anode for lithium-ion batteries

An ionic liquid electrolyte containing bis(fluorosulfonyl)imide (FSI) anion without any solvent is applied to a silicon-nickel-carbon (Si-Ni-carbon) composite anode for rechargeable lithium (Li)-ion batteries. The FSI-based ionic liquid electrolyte successfully provides a stable, reversible capacity for the Si-Ni-carbon anode, which is comparable to the performance observed in a typical commercialized solvent-based electrolyte, while a common ionic liquid electrolyte containing bis(trifluoromethanesulfonyl)imide (TFSI) anion without FSI presents no reversible capacity to the anode at all. Ac impedance analysis reveals that the FSI-based electrolyte provides very low interfacial and charge-transfer resistances at the Si-based composite anode, even when compared to the corresponding resistances observed in a typical solvent-based electrolyte. Galvanostatic cycling of the Si-based composite anode in the FSI-based electrolyte with a charge limitation of 800 mAh g⁻¹ is stable and provides a discharge capacity of 790 mAh g⁻¹ at the 50th cycle, corresponding to a cycle efficiency of 98.8%.     

Carbon anode for dry-polymer electrolyte lithium batteries

A spherical carbon material of meso-carbon microbead (MCMB) was examined as an anode in a polyethylene oxide (PEO) based polymer electrolyte lithium battery. The electrochemical performance of the carbon electrode with the polymer electrolyte depended on the electrode thickness and the particle size of MCMB. The 30 μm-thick electrode of MCMB with the particle size of 20–30 μm showed a reversible capacity comparable with that in a liquid electrolyte, but the 100 μm-thick electrode showed a half of the 30 μm-thick electrode. The smaller particle size of 5–8 μm exhibited a high irreversible capacity at the first charge–discharge cycle. The reaction heat between MCMB and the polymer electrolyte was 0.5 J mAh^?1, which was much lower compared to those between lithium metal and the polymer electrolyte, 1.2 J mAh^?1, and MCMB and conventional liquid electrolyte, 4.3 J mAh^?1.     

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.     

Tin and tin-based intermetallics as new anode materials for lithium-ion cells

The galvanostatic cycling behaviour of Sn/SnSb composite electrodes has been studied in 1 mol l⁻¹ LiClO₄/propylene carbonate (PC), 1 mol l⁻¹ LiPF₆/ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1), and 1 mol l⁻¹ LiClO₄/PC saturated with trans-decalin (t-Dec). Capacities between 500 and 600 mA h g⁻¹ (with respect to the mass of active material) were obtained. Reasons for the irreversible capacities are given and film formation on lithium storage metals and alloys is discussed. The observed coulombic efficiencies were slightly higher for the EC-containing electrolyte than for the PC-based one. Alternatively, improved efficiencies and stand-time behaviour were obtained when the PC electrolyte was saturated with t-Dec, which acts as a surfactant.     

Ionic liquid–polymer gel electrolytes based on morpholinium salt and PVdF(HFP) copolymer

New ionic liquid–polymer gel electrolytes (IPGEs) are prepared from N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (Mor_1,2TFSI) and poly(vinylidene fluoride)-hexafluoropropylene copolymer (PVdF(HFP)). To investigate the effect of propylene carbonate (PC) on the ionic conductivity of the IPGEs, the preparation methods are roughly divided into two groups according to the presence or absence of PC. The ionic conductivity for each IPGE is measured with increasing temperature and changing weight ratio of Mor_1,2TFSI. The results show that the ionic conductivity increases as the temperature and weight ratio of the Mor_1,2TFSI increase, and that the added PC improves the ionic conductivity of the IPGEs. In addition, thermogravimetric analysis and the data from infrared spectroscopy demonstrate the thermal stability of each IPGE and the presence of PC in the polymer network. Although the IPGEs that contain PC display high conductivity (∼1.1 × 10⁻² S cm⁻¹) at 60 °C, they are thermally unstable.