Electrolytic characteristics of mixed solvent electrolytes for lithium secondary batteries

Measurements on conductivity and Li charge-discharge efficiency in various propylene carbonate (PC)-based electrolytes were carried out to obtain electrolytes for Li secondary batteries. Among the electrolytes examined, 2 M LiClO₄—PC—THF (PC/THF volume ratio = $\text{4}\text{6}$) showed 1.6 times higher conductivity of 9.8 × 10^?3 Ω^?1 cm^?1 and also ca. 10% higher Li charge-discharge efficiency of 81.3% at 5 mA cm^?2 (0.3 C cm^?2) than those in 1 M LiClO₄—PC. Generally, Li cycling efficiency increases with increase in electrolyte conductivity. From the analysis made on electrolytic parameters, such as transport number of Li⁺ ion, it was concluded that conductivity and Li cycling efficiency increases were caused by the total effects of lower chemical reactivity of THF to Li and smaller practical Li⁺ ion radius based on Li⁺—THF complex formation.     

Effects of quinoneimine dyes on lithium cycling efficiency for LiClO4-propylene carbonate

Additive effects of quinoneimine dyes (QIDs) on Li cycling efficiency (E _ff) were examined in 1 M LiClO₄-propylene carbonate (PC). TheE _ff values were measured galvanostatically on a Pt working electrode. TheE _ff values for solutions with QID addition were higher than those for PC alone and theE _k values depended on cycling current density and on the amounts of QID added. For example, 1 M LiClO₄-PC with added methylene blue (MB) (10^–3 M addition) showedE _ff values exceeding 90% at 0.5mA cm^–2, 0.6 C cm^–2, while theE _ff values for PC alone were approximately 65%. From observation with a scanning electron microscope the morphology for the deposited Li in solution with MB added was found to be smoother than that in PC alone. TheE _ff values for solutions with QID added tended to increase with an increase in the reduction potential for QID vs Li-Li₊. The enhancement of the Li cycling efficiency by QID addition seems to be caused by Li₊ ion-conductive film formation on the deposited Li surface, resulting from the reaction between QID and the deposited Li, that suppresses the reaction between PC and the deposited Li. This film formation was strongly suggested by the measurement of the resistance on the Li surface.     

Ethylene carbonate—propylene carbonate mixed electrolytes for lithium batteries

Electrolytic characteristics of propylene carbonate (PC)ethylene carbonate (EC) mixed electrolytes were studied, compared with those in PC electrolytes. Conductivity and Li charge—discharge efficiency values increased with EC contents increasing. For example, 1 M LiClO₄ECPC (EC mixing molar ratio; [EC]/[PC] = 4) showed the conductivity of 8.5 ohm^?1 cm^?1, which value was 40% higher than that in PC. Also, 1 M LiClO₄ECPC([EC]/[PC] = 5) showed the Li charge—discharge efficiency of 90.5% at 0.5 mA cm^?2, 0.6 C cm^?2, which value was ca. 25% higher than that in PC. ECPC mixed electrolytes were considered to be practically available for ambient lithium batteries in regard to the high Li⁺ ion conductivity and also high Li charge—discharge efficiency.     

The cycling behavior of the lithium electrode in LiAsF6/methyl acetate solutions

The cycling behavior of the Li electrode in LiAsF₆ and LiClO₄/methyl acetate electrolytes has been investigated. Coulometric cycling results, both with and without the additive SO₂, show that the highest efficiencies ( > 90%) are obtained using 1.0 M LiAsF₆/MA as the electrolyte. Among the substrates tested Ni > Cu Al. Current density has little effect in the range 1-100mA/cm². Stripping at low cds (0.5mA/cm²) gives lower Li recovery. Charge retention data for the Li electrode over 26 days indicate that the LiAsF₆/MA electrolyte is superior to any other reported so far. The major problem encountered with the Li electrode during cycling in LiAsF₆/MA was the extremely limited cycle life. For 0.8C/cm₂ deposits, only about 12 cycles could be obtained before the efficiency fell from over 93% to below 50%. A discussion of the related problems of limited cycle life and dendrite formation is presented.     

Surface layer formation on Li1 + xMn2O4 − δ thin film electrodes during electrochemical cycling

A surface layer formation on positive Li_{1 + x}Mn₂O_{4 − δ} thin film model electrodes as a result of electrochemical cycling procedures has been detected and characterized by scanning electron microscopy and X-ray photoemission spectroscopy. These thin film spinel electrodes, prepared by pulsed laser deposition, were cycled in 1 M LiClO₄ in propylene carbonate between 3.5 and 4.4 V vs. Li/Li⁺ at 40 °C and stopped at defined potentials and cycle numbers. The observed surface layers show, depending on the cycling conditions, a spotty and/or layered appearance and the fraction of this layer covering the cycled electrode depends on the charge potential and the number of electrochemical cycles.     

Study of ionic conductivity and microstructure of a cross-linked polyurethane acrylate electrolyte

A cross-linked polyurethane acrylate (PUA) was synthesized by end capping 4,4′-methylene bis(cyclohexyl isocyanate), H₁₂MDI/poly-(ethylene glycol), PEG based prepolymer with hydroxy ethyl acrylate (HEA). Significant interactions of the Li⁺ ions with the soft and hard segments of the host polymer have been observed for the PUA complexed with lithium perchlorate (LiClO₄) by means of differential scanning calorimetry (DSC), Fourier transform infra-red (FTIR) spectroscopy, ⁷Li magic angle spinning (MAS) NMR measurements and thermogravimetric analysis (TGA). The ⁷Li MAS NMR investigation of the PUA indicates the presence of at least three distinct Li⁺ sites at lower temperature, which merge to a single one at higher temperature in similar line with uncross-linked polyurethane. The results of TGA, DSC and FTIR spectroscopy support the formation of different types of complexes by the interaction of the Li⁺ ions with different coordination sites of PUA. No detectable interactions could be observed between Li⁺ ions and groups in HEA. The DSC data indicates the formation of transient cross-links with the ether oxygens of the soft segment and mixing of soft and hard phases induced by the Li⁺ ions. In addition, a Vogel-Tamman-Fulcher (VTF) like temperature dependence of ionic conductivity implies coupling of the ion movement with the segmental motion of the polymer chains in the cross-linked environment. Predominant formation of contact ion pairs of LiClO₄ has been consistently observed through AC conductivity, DSC and NMR spectroscopic results. Swelling measurements of PUA with plasticizers reveal the improved dimensional stability for these cross-linked PUA in comparison with uncross-linked polyurethane.     

Morphology,crystallinity, and electrochemical properties of in situ formed poly(ethylene oxide)/TiO2 nanocomposite polymer electrolytes

A method to produce nanocomposite polymer electrolytes consisting of poly(ethylene oxide) (PEO) as the polymer matrix, lithium tetrafluoroborate (LiBF₄) as the lithium salt, and TiO₂ as the inert ceramic filler is described. The ceramic filler, TiO₂, was synthesized in situ by a sol–gel process. The morphology and crystallinity of the nanocomposite polymer electrolytes were examined by scanning electron microscopy and differential scanning calorimetry, respectively. The electrochemical properties of interest to battery applications, such as ionic conductivity, Li⁺ transference number, and stability window were investigated. The room‐temperature ionic conductivity of these polymer electrolytes was an order of magnitude higher than that of the TiO₂ free sample. A high Li⁺ transference number of 0.51 was recorded, and the nanocomposite electrolyte was found to be electrochemically stable up to 4.5 V versus Li⁺/Li. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2815–2822, 2003     

Physical and electrochemical properties of low molecular weight poly(ethylene glycol)‐bridged polysilsesquioxane organic–inorganic composite electrolytes via sol–gel process

A new class of ionic conducting organic/inorganic hybrid composite electrolyte with high conductivity, better electrochemical stability and mechanical behavior was prepared through the sol–gel processing between ethylene‐bridged polysilsesquioxane and poly(ethylene glycol) (PEG). The composite electrolyte with 0.05 LiClO₄ per PEG repeat unit has the best conductivity up to 10^?4 S/cm at room temperature with the transference number up to 0.48 and an electrochemical stability window as high as 5.5 V versus Li/Li⁺. Moreover, the effect of the PEG chain length on the properties of the composite electrolyte has also been studied. The interactions between ions and polymer have also been investigated for the composite electrolyte in the presence of LiClO₄ by means of FTIR, DSC, and TGA. The results indicated the interaction of Li⁺ ions with the ether oxygen of the PEG, and the formation of transient crosslinking with LiClO₄, resulting in an increase of the T_g of the composite electrolyte. The VTF‐type behavior of the ionic conductivity implied that the diffusion of the charge carriers was assisted by the segmental motions of the polymer chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2752–2758, 2007     

Anodic oxidation of dimethyl sulfoxide based electrolyte solutions: Anin situ FTIR study

Anodic oxidation of dimethyl sulfoxide (DMSO) based electrolyte solutions, containing LiClO₄, LiBF₄ and KPF₆, on platinum (Pt), glassy carbon (GC) andn-TiO₂ (anatase), electrodes was studied usingin situ Fourier transform infrared spectroscopy (FTIR). All solutions contained small amounts of H₂O. Regardless of the supporting electrolyte all systems were unstable at potentials above 1.0 V vs SCE. The major oxidation product is dimethyl sulfone, formation of which is initiated by the trace water breakdown. In contrast to acetonitrile based solutions there is no evidence of electrolyte involvement in the breakdown process. Photoanodic decomposition of dimethyl sulfoxide based solutions proceeds in the same way as the anodic oxidation in the dark. In the presence of nucleophilic agent (iodides) the prevailing redox process is iodide oxidation. Small amounts of, probably, methylsulfinyliodide are also formed. The irreversible consumption of charge mediator significantly restricts the possible practical use of DMSO in photoelectrochemical devices.     

Analysis of the interaction using FTIR within the components of OREC composite GPE based on the synthesized copolymer matrix of P(MMA-MAh)

Poly(methyl methacrylate-maleic anhydride) (P(MMA-MAh)) has been synthesized from methyl methacrylate (MMA) and maleic anhydride (MAh) monomers. The molar ratio of monomers was found to be 1MAh:8MMA. The molecular weight of copolymer was determined in the order 10⁴ (g/mol).Rectorite modified with dodecyl benzyl dimethyl ammonium chloride (OREC) was used as a filler additive to modify gel polymer electrolytes (GPEs) which consisted of P(MMA-MAh) used as polymer matrix, propylene carbonate (PC) as a plasticizer and LiClO₄ as lithium ion producer. Characterization of interaction of CO in PC and copolymer with Li⁺ and OH group on OREC surface has been thoroughly examined using FTIR. The quantitative analysis of FTIR shows that the absorptivity coefficient a of copolymer/LiClO₄, PC/LiClO₄, PC/OREC and copolymer/OREC is 0.756, 0.113, 0.430 and 0.602, respectively, which means that the Li⁺ or OH bonded CO is more sensitive than free CO in FTIR spectra. The limit value of bonded CO equivalent fraction of copolymer/LiClO₄, PC/LiClO₄, PC/OREC and copolymer/OREC is 55, 94, 57 and 26%, respectively, which implies that all the interaction within the components is reversible and the intensity of interaction is ordered as PC/LiClO₄, PC/OREC, copolymer/OREC and copolymer/LiClO₄.     

The effect of desiccants on the cycling efficiency of the lithium electrode in propylene carbonate-based electrolytes

Cycling efficiencies of the Li electrode ,in propylene carbonate (PC) 1 M in either LiClO₄ or LiAsF₆ were assessed as a function of electrolyte purification procedure. The use of neutral alumina and galvanostatic pre-electrolysis resulted in the highest efficiency values to date. While cyclic voltammograms at Pt or vitreous C were insensitive to electrolyte impurities, voltammograms on Ni about the Li potential were very informative. Thus, the repeated deposition and subsequent removal of thin (2 mC/cm²) Li plates revealed enhanced nucleation but diminished rate of growth of the nuclei as cycling progresses. A model of Li encapsulation is proposed to account for the eventual failure of the Li electrode.     

A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries

Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO₄ in EC/PC and showed a high ionic conductivity about 1.6 mS cm⁻¹ at room temperature. The electrochemical stability is at 5.0 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Blending poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) as composite polymer electrolyte

A blend of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (PSAN) has been evaluated as a composite polymer electrolyte by means of differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, ac impedance measurements, and linear sweep voltammetry (LSV). The blends show an interaction with the Li⁺ ions when complexed with lithium perchlorate (LiClO₄), which results in an increase in the glass‐transition temperature (T_g) of the blends. The purpose of using PSAN as another component of the blend is to improve the poor mechanical properties of PMMA‐based plasticized electrolytes. The mechanical property is further improved by introducing fumed silica as inert filler, and hence the liquid electrolyte uptake and ionic conductivity of the composite systems are increased. Room‐temperature conductivity of the order of 10^?4 S/cm has been achieved for one of the composite electrolytes made from a 1/1 blend of PSAN and PMMA containing 120% liquid electrolyte [1M LiClO₄/propylene carbonate (PC)] and 10% fumed silica. These systems also showed good compatibility with Li electrodes and sufficient electrochemical stability for safe operation in Li batteries. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1319–1328, 2001     

In situ sulfur K-edge X-ray absorption near edge structure of an embedded pyrite particle electrode in a non-aqueous Li-based electrolyte solution

Changes in the composition of embedded pyrite (FeS₂) particle electrodes in 1 M LiClO₄ propylene carbonate solutions as a function of the applied potential have been examined in situ by S K-edge fluorescence X-ray absorption near edge structure (XANES), using a specially designed cell that minimizes attenuation of low energy X-rays. Pyrite electrodes that had been scanned from 3.0 V versus Li/Li⁺, i.e. close to the open circuit voltage, down to 1.0 V (fully discharged state, i.e. 4e⁻-reduction) and then half recharged (2e⁻-reoxidation) by scanning the potential in the positive direction up to 2.2 V versus Li/Li⁺, revealed features consistent with the presence of Li₂FeS₂, in agreement with in situ Fe K-edge results reported earlier by this research group. Moreover, only subtle changes were discerned between the in situ S K-edge XANES of the half-, and fully-recharged electrodes. This close resemblance may reflect similarities between the spectral signatures of Li₂FeS₂ and Fe_1−xS (pyrrhotite), which is the main product of the discharge reaction. Evidence for the formation of elemental sulfur and Li₂S, which are believed to be minor products of the reaction, was obtained from analysis of the first differential S XANES and selected difference spectra. The compositional variations of the embedded pyrite particles throughout the course of the electrochemical processes occur in the presence of a persistent sulfate coating.     

Comparative kinetic studies of polypyrrole electrogeneration from acetonitrile solutions

The formation and growth of polypyrrole films on platinum electrodes from acetonitrile media has been followed by microgravimetricex situ determination of the polymer grafted on the electrode. Kinetic parameters were also obtained from the charge consumed during polymerization. The electrogenerated polymer films were checked in the background electrolyte by voltammetry and chronoamperometry. Assuming a constant oxidation or reduction charge per unit of polymer weight, these charges were used to obtain the reaction order during the polymerization processes. The kinetics were found to be dependent on [pyrrole]^0.5 [LiClO₄]^0.5 from gravimetric determination; [pyrrole]^0.4 [LiClO₄]^0.5 from the polymerization charge; [pyrrole]^0.4 [LiClO₄]^0.5 from the anodic charge of the control voltammograms and [pyrrole]^0.4 [LiClO₄]^0.4 from the anodic and cathodic charge of the control chronoamperograms. Good agreement was found between the different methods. The good agreement between order dependence was due to the low water content.     

A polymeric solid electrolyte based on a binary blend of poly(ethylene oxide), poly(methyl vinyl ether-maleic acid) and LiClO4

A new polymeric solid electrolyte based on a PEO/PMVE-MAc blend, complexed with LiClO₄, was obtained and characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), polarized light optical microscopy, electrochemical impedance and cyclic voltammetry. DSC traces indicated miscibility for all the PSE samples. Crystallinity was suppressed for samples with LiClO₄ concentrations higher than 2.5 wt%. FTIR associated with DSC studies indicated that there is a preferential formation of complexes PEO/Li⁺/PMVE-MAc in all PSE samples studied here. The ionic conductivity of PSE reaches a maximum of about 10⁻⁵ S/cm at ambient temperature and 7.5 wt% LiClO₄. The electrochemical stability window is 4.5 V and associated with the other characteristics, make the PSE studied here suitable for applications in ‘smart-windows’, batteries, sensors, etc.     

Behaviour of highly crystalline graphitic materials in lithium-ion cells with propylene carbonate containing electrolytes: An in situ Raman and SEM study

The microcrystalline flaked graphites SFG6 and SFG44 were evaluated with regard to their compatibility with propylene carbonate (PC) by in situ Raman microscopy and postmortem scanning electron microscopy (SEM) study. PC is employed as electrolyte component in lithium-ion batteries. However, when used with certain types of graphitic materials, exfoliation occurs. To compare the effects of exfoliation, the first lithium insertion properties of these graphitic materials were measured with in situ Raman microscopy. Lithium half-cells containing either 1 M LiClO₄ 1:1 (w/w) ethylene carbonate (EC):dimethyl carbonate (DMC) or 1:1 (w/w) EC:PC were investigated. The commencement of the exfoliation process was detected in SFG44 EC:PC by the appearance of a shoulder band at 1597 cm⁻¹ on the G-band (1584 cm⁻¹) below 0.9 V versus Li/Li⁺. The band (assigned as the exfoliation or E-band) at higher wavenumbers (1597 cm⁻¹) corresponded to solvated lithium ions intercalated into graphite. The in situ Raman spectra of SFG6 in EC:DMC or EC:PC and SFG44 in EC:DMC did not show the E-band and instead displayed regular lithium intercalation spectra.In situ Raman microscopy and SEM were further employed to study the exfoliation process observed for SFG44 in 1:1 (w/w) EC:PC, when the potential was held under steady-state conditions at 0.8, 0.6 and 0.3 V, respectively. A blue-shift in the E-band from 1597 to 1607 cm⁻¹ was observed as the potential was lowered. SEM images showed dissimilar degrees of exfoliation at these three potentials.     

Dimethyl sulfoxide-based electrolytes for rechargeable lithium batteries

Mixed solutions of dimethyl sulfoxide (DMSO) and low viscosity solvents have been examined as a solvent of the electrolyte for rechargeable lithium (Li) batteries. The electrolytic conductivities of LiClO₄. LiBF₄ and LiPF₆ were measured as a function of the solvent composition. Maximum conductivities were observed in the DMSO concentration ranges of 60–80 mol% for LiClO₄ and LiBF₄, and 20–60 mol% for LiPF₆. The highest conductivity of all examined systems was 1.6 × 10⁻² S cm⁻¹ in the solution containing 1,2-dimethoxyethane (DME) and LiPF₆ as the co-solvent and the electrolyte, respectively. Polarization behavior and charge-discharge characteristics of the lithium electrode were investigated in the DMSO-based solutions. The cycling efficiency was markedly dependent not only on the co-solvent but also the Li salt. The highest efficiency on the nickel substrate was observed in LiPF₆ (1 mol dm⁻³)/DMSO-DME (1:1 by volume). High rechargeability of Li was also expected in the solution containing LiClO₄ or LiBF₄ when aluminum was used as the substrate.     

Polyterthiophene/CNT composite as a cathode material for lithium batteries employing an ionic liquid electrolyte

A polyterthiophene (PTTh)/multi-walled carbon nanotube (CNT) composite was synthesised by in situ chemical polymerisation and used as an active cathode material in lithium cells assembled with an ionic liquid (IL) or conventional liquid electrolyte, LiBF₄/EC-DMC-DEC. The IL electrolyte consisted of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) containing LiBF₄ and a small amount of vinylene carbonate (VC). The lithium cells were characterised by cyclic voltammetry (CV) and galvanostatic charge/discharge cycling. The specific capacity of the cells with IL and conventional liquid electrolytes after the 1st cycle was 50 and 47 mAh g⁻¹ (based on PTTh weight), respectively at the C/5 rate. The capacity retention after the 100th cycle was 78% and 53%, respectively. The lithium cell assembled with a PTTh/CNT composite cathode and a non-flammable IL electrolyte exhibited a mean discharge voltage of 3.8 V vs Li⁺/Li and is a promising candidate for high-voltage power sources with enhanced safety.     

Effect of additives in PEO/PAA/PMAA composite solid polymer electrolytes on the ionic conductivity and Li ion battery performance

Polyethylene oxide (PEO) based-solid polymer electrolytes were prepared with low weight polymers bearing carboxylic acid groups added onto the polymer backbone, and the variation of the conductivity and performance of the resulting Li ion battery system was examined. The composite solid polymer electrolytes (CSPEs) were composed of PEO, LiClO_4, PAA (polyacrylic acid), PMAA (polymethacrylic acid), and Al₂O₃. The addition of additives to the PEO matrix enhanced the ionic conductivities of the electrolyte. The composite electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 exhibited a low polarization resistance of 881.5 ohms in its impedance spectra, while the PEO:LiClO₄ film showed a high value of 4,592 ohms. The highest ionic conductivity of 9.87 × 10⁻⁴ S cm⁻¹ was attained for the electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 at 20 °C. The cyclic voltammogram of Li⁺ recorded for the cell consisting of the PEO:LiClO₄:PAA/PMAA/Li_0.3:Al₂O₃ composite electrolyte exhibited the same diffusion process as that obtained with an ultra-microelectrode. Based on this electrolyte, the applicability of the solid polymer electrolytes to lithium batteries was examined for an Li/SPE/LiNi_0.5Co_0.5O₂ cell.