A 7Li and 19F NMR relaxation study of LiCF3SO3 in plasticised solid polyether electrolytes

⁷Li and ¹⁹F NMR relaxation time (T₁, T₂, T_1ρ) measurements have been used to probe the dynamics of LiCF₃SO₃ dissolved in an amorphous co-polymer poly(ethylene oxide-co-propylene oxide), and in particular the influence of the plasticising agents propylene carbonate and dimethyl formamide. The changes in relaxation behaviour of ¹⁹F and ⁷Li with increasing plasticiser concentration are very different, as is the effect of each plasticiser. These differences can be explained qualitatively in terms of the interaction between the plasticiser and the ions. Preliminary ⁷Li T_1ρ measurements reveal two components at low temperatures.

NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH₂CH(CN)]_n), and the salt LiCF₃SO3 . From NMR studies of the temperature and concentration dependencies of ⁷Li- and ^lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li⁺–PAN interaction. The characteristic δ_s(CF₃) mode of the CF₃SO₃⁻ anion at _~750–780 cm^−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li_~60–10:1). A strong Li⁺–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at _~2244 cm^−l in pure PAN, to _~2275 cm^−l for Li⁺-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF3 SO₃, the glass transition occurs at progressively lower temperatures.

Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes

Measurements of the glass transition temperature (T_g) and free volume behaviour of poly(acrylonitrile) (PAN) and PAN/lithium triflate (LiTf), with varying salt composition from 10 to 66 wt% LiTf, were made by positron annihilation lifetime spectroscopy (PALS). Addition of salt from 10 to 45 wt% LiTf resulted in an increase in the mean free volume cavity size at room temperature (r.t.) as measured by the orthoPositronium (oPs) pickoff lifetime, τ₃, with little change in relative concentration of free volume sites as measured by oPs pickoff intensity, I₃. The region from 45 to 66 wt% salt displayed no variation in relative free volume cavity size and concentration. This salt concentration range (45 wt%<[LiTf]<66 wt%) corresponds to a region of high ionic conductivity of order 10⁻⁵ to 10⁻⁶ S cm⁻¹ at T_g as measured by PALS. A percolation phenomenon is postulated to describe conduction in this composition region. Salt addition was shown to lower the T_g as measured by PALS; T_g was 115°C for PAN and 85°C for PAN/66 wt% LiTf. The T_g and free volume behaviour of this polymer-in-salt electrolyte (PISE) was compared to a poly(ether urethane)/LiClO₄ where the polymer is the major component, i.e. traditional solid polymer electrolyte (SPE). In contrast to the PISE, the T_g of the SPE was shown to increase with increasing salt concentration from 5.3 to 15.9 wt%. The relative free volume cavity size and concentration at r.t. were shown to decrease with increasing salt concentration. Ionic conductivity in this SPE was of order 10⁻⁵ S cm⁻¹ at r.t., which is over 60°C above T_g, 10⁻⁸ S cm⁻¹ at 25°C above T_g, and conductivity was not measurable at T_g.

Properties of a nanocomposite polymer electrolyte from an amorphous comb-branch polymer and nanoparticles

Three fully amorphous comb-branch polymers based on poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether of different molecular weights as side chains were synthesized. SiO2 nanoparticles of various contents and the salt LiCF3SO3 were added to these comb-branch polymers to obtain nanocomposite polymer electrolytes. The thermal and transport properties of the samples have been characterized. The maximum conductivity of 2.8x10(-4) S cm(-1) is obtained at 28 degreesC. In the system the longer side chain of the comb-branch polymer electrolyte increases in ionic conductivity after the addition of nanoparticles. To account for the role of the ceramic fillers in the nanocomposite polymer electrolyte, a model based on a fully amorphous comb-branch polymer matrix in enhancing transport properties of Li+ ions is proposed.

A new solid-state electrolyte: Rubbery 'polymer-in-salt' containing LiN(CF3SO2)(2)

A new class of rubbery 'polymer-in-salt' electrolytes for application in solid-state lithium batteries has been explored by differential scanning calorimetry and a.c. impedance analysis. Simple phase diagrams of LiN(CF3SO2)(2)+LiClO4 and LiC(CF3SO2)(3)+LiN(CF3SO2)(2) have been drawn, which are very important to determine polymer-in-salt electrolyte materials. The conductivities obtained by a.c. impedance measurement are smaller for the electrolyte that contains acetate LiOAc salt than for the electrolyte without this salt.

Comb polymer electrolytes - Ionic conductivity and cation-polymer interaction

Three comb polymers(CP) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were prepared from methyl vinyl ether/maleic anhydride alternating copolymer. Homogeneous amorphous polymer electrolytes were made from CP and LiCF3SO3 or LiClO4 by solvent-casting method, and their conductivities were measured as a function of temperature and salt concentration. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation. The conductivity maximum appears at lower salt concentration when CP has longer side chains. XPS was used to study the cation-polymer interaction.

Ionic conductivity of polymer gel electrolytes based on poly(polyethylene glycol dimethacrylate)

Gel electrolytes have been prepared by thermal polymerization of poly(polyethylene glycol dimethacrylate) (P(PEGD)) in the presence of propylene carbonate (PC) and alkali metal salts, such as LiClO4, LICF(3)SO(3) and LiBF4. The conductivity was studied by means of impedance spectroscopy, and it is found that the temperature dependence of conductivities follow a Arrhenius relationship when the molar percentage of PC is higher than 75% or LiClO4 concentration is lower than 0.9 mol/l. However, when LiCF3SO3 or LiBF4 is used instead of LiClO4 as the salt, the situation is different. For LICF(3)SO(3), the Arrhenius relationship almost holds true for all the salt concentrations studied; while for LiBF4, the Arrhenius equation hardly fits for any salt concentration. The dependence of activation energy on salt concentration is also examined, both for LiClO4 and LiCF3SO3, the values of E(a) tend to reach a minimum value with increasing salt concentration. Copyright (C) 1996 Elsevier Science Ltd.

Study on a new comb polymer electrolyte(II)

A comb polymer(CP350) with oligo-oxyethlene side chains was prepared from methyl vinyl ether/maleic anhydride copolymer. Homogeneous amorphous polymer electrolyte were made from the comb polymer and LiCF3SO3 by solvent casting from acetone, and their conductivities were measured as a function of temperature and salt concentration. Maximum conductivity close I to 5.08 x 10(-5)S/cm was achieved at room temperature at [Li]/[EO] ratio of about 0.12.

Microscopic interactions in nanocomposite electrolytes

Nanocomposite electrolytes of a fully amorphous trifunctional polyether (3PEG) and poly- (methylene ethylene oxide) (PMEO) have been complexed with two lithium salts and nanoparticulate (~20 nm) fillers of TiO2 and Al2O3. Addition of the fillers to the polymer salt complexes shows a significant change in the conformational modes of both polymers, especially the D-LAM region between 200 and 400 cm-1, indicating a reduced segmental flexibility of the chain. These changes are more pronounced with the use of TiO2 than Al2O3. Incorporation of the nanoparticulate fillers to the electrolytes fails to influence the degree of ion association, suggesting that the number of charge carriers available for conduction in both polymers using both LiClO4 and LiCF3SO3 is not the source of any conductivity increase. Addition of the fillers, which was seen to increase the conductivity in PEO-based systems, generally lowers the conductivity in the present PMEO systems, while the addition of TiO2 has little or no effect except in the cases of 3PEG 1.5 and 1.25 mol/kg LiClO4. In this case, 10 wt % TiO2 provides a conductivity increase of half an order of magnitude at approximately 60 °C. We also report for the first time a Raman spectroscopy investigation into the PEO-based nanocomposite electrolytes. The present results are discussed in terms of the electrostatic interactions involving dielectric properties of the fillers, of special interest being the interactions between the polymer and the fillers and between the ionic species and the fillers, when the effect of crystallization can be ignored.