Solid polymer electrolytes based on poly(lithium carboxylate) salts

The ionic conductivity, lithium ion transference number, electrochemical stability, and thermal property of solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and poly(lithium carboxylate)s, (poly(lithium acrylate) (Poly(Li-A)) or poly(lithium fumarate) (Poly(Li-F)), with and without BF₃·OEt₂ were investigated. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF₃·OEt₂ because the dissociation of lithium ion and carboxylate anion was promoted by the complexation with BF₃. The lithium ion transference number in the solid polymer electrolytes based on poly(lithium carboxylate)s showed relatively high values of 0.41–0.70, due to the suppression of the transport of counter anion by the use of a polymeric anion. The solid polymer electrolytes with addition of BF₃·OEt₂ showed good electrochemical stability.     

Di-urethanesil hybrid electrolytes doped with Mg(CF3SO3)2

Two siloxane-based di-urethanesil frameworks incorporating poly(oxyethylene) (POE) chains have been synthesized by the sol–gel process and doped with magnesium triflate (Mg(CF₃SO₃)₂) with the goal of developing electrolytes for the fabrication of solid-state rechargeable magnesium batteries. In these matrices, short POE chains are covalently bonded to the siloxane network via urethane linkages. The xerogels have been represented by the notation d-Ut(Y) _n Mg(CF₃SO₃)₂, where Y?=?300 and 600 represents the average molecular weight of the POE chains and n stands for salt composition (molar ratio of OCH₂CH₂ units per Mg²⁺). Xerogels with compositions ranging from 2?≤?n?<?∞ were prepared. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed in the d-Ut(300) _n Mg(CF₃SO₃)₂ materials with n?≤?6 and in the d-Ut(600) _n Mg(CF₃SO₃)₂ materials with n?≤?5. The organically modified silicate electrolytes with the highest conductivity of the d-Ut(300) _n Mg(CF₃SO₃)₂ and d-Ut(600) _n Mg(CF₃SO₃)₂ series are the samples with n?=?6 (3.9?×?10^?8 S cm^?1 at 26 °C and 8.7?×?10^?5 S cm^?1 at 97 °C) and n?=?100 (2.63?×?10^?7 S cm^?1 at 20 °C and 1.4?×?10^?5 S cm^?1 at 85 °C), respectively. Since the electrolytes for Mg batteries that have been proposed up to now have many intrinsic problems and although the room temperature conductivity values exhibited by the systems developed in the present study are still low in view of practical application, this work opens new directions for the development of solid-state Mg ion electrolytes.     

Infrared spectroscopic and conductivity studies of poly(N-methylpropylenimine)/lithium triflate electrolytes

Poly(propylenimine), PPI, was methylated using Eschweiler-Clark conditions to produce poly(N-methylpropylenimine), PMPI. Differences may be seen in the IR spectra of the PMPI (–CH₂CH₂CH₂NCH₃–) and its homolog poly(N-methylethylenimine), PMEI, (–CH₂CH₂NCH₃–), especially in the conformation region (~ 1100 to ~ 1400 cm^− 1). The addition of lithium trifluoromethanesulfonate, (LiCF₃SO₃), sharpens the distinctions between these systems. Comparison of IR spectra of polymer:LiCF₃SO₃ complexes at compositions ranging from pure polymer to 5:1 N:Li⁺ (molar ratio) suggests significant differences in the nature of polymer salt interactions and the complex structure present in each system. These are further evidenced by differential scanning calorimetry data in which PMPI displays less variation in glass transition temperature, T_g, with the addition of salt than seen in PMEI. These observations may be interpreted in terms of local structural changes originating in cation–anion and cation–polymer interactions, particularly at mid to high salt concentrations.     

Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts

Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li⁺/PEO) in one phase and for soft cations (Cu²⁺/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li⁺, Cu²⁺) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)₂-b-PEO-b-PEI-Cu(TFSI)₂ and PEI-Cu(TFSI)₂-b-PEO-LiTFSI-b-PEI-Cu(TFSI)₂. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)₂ with N/Cu²⁺ = 20:1 (10^− 6, respectively 2 × 10^− 4 S cm^− 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.     

Ionic conductivity of electrolytes based on star-branched poly(ethylene oxide) with high concentration of lithium salts

Electrolytes based on star-branched poly(ethylene oxide) with lithium bis(trifluoromethanesulfone)imide LiTFSI and lithium iodide salts were prepared by casting from solution. The electrical properties of electrolytes subjected to various heating and cooling runs were studied by impedance spectroscopy and impedance spectroscopy simultaneous with optical microscope observation. Differential scanning calorimetry was used for additional characterization. The results indicate that in electrolytes with high content of salt, values of ionic conductivity comparable to that of dilute electrolytes can be achieved. Moreover, electrolytes with high amount of salt seem to show weaker temperature dependence of conductivity. Promising results in terms of ionic conductivity were obtained for mixture of LiTFSI and lithium iodide. A few problems which may decrease the performance of studied system as a solid electrolyte were also identified, from which changes of physical properties of samples subjected to thermal cycles and aging seem to be the most important ones.     

Vibrational spectroscopy and structure of polymer electrolytes,poly(ethylene oxide) complexes of alkali metal salts

Complexes of poly(ethylene oxide) (PEO), with various alkali metal salts are known to exhibit ionic conductivities which exceed 10^?5(Ωcm)^?1 at moderate temperatures. We have employed IR and Raman spectroseopy to study well characterized samples of the following polymer-salt complexes: PEO·NaBr, PEO·NaI, PEO·NaSCN, PEO·NaBF₄, PEO·NaCF₃SO₃, PEO·KSCN, PEO·RbSCN and PEO·CsSCN. Cation-dependent vibrational bands observed in the far IR and M-O_n symmetric stretching bands observed in the Raman support a cation-oxygen atom interaction, and indicate the polyether chain may wrap around the cations. In particular, NaX and KX complexes of PEO are believed to have a helical configuration for the polymer which differs from that of pure PEO. Some general rules are presented for polymer-salt complex formation.     

A comparative study of lithium and sodium salts in PAN-based ion conducting polymer electrolytes

The conducting polymer electrolyte films consisting of polyacrylonitrile (PAN) as the host polymer, lithium triflate (LiCF₃SO₃) and sodium triflate (NaCF₃SO₃) as inorganic salts were prepared by the solution-cast technique. The pure PAN film was prepared as a reference. The ionic conductivity for the films is characterized using impedance spectroscopy. The room temperature conductivity for the PAN + 26 wt.% LiCF₃SO₃ film and the PAN + 24 wt.% NaCF₃SO₃ film is 3.04 × 10⁻⁴ S cm⁻¹ and 7.13 × 10⁻⁴ S cm⁻¹, respectively. XRD studies show that the complexation that has occurred in the PAN containing salt films and complexes formed are amorphous. The FTIR spectra results confirmed the complexation has taken place between the salt and the polymer. These results correspond with surface morphology images obtained from SEM analysis. The conductivity–temperature dependence of the highest conducting film from PAN + LiCF₃SO₃ and PAN + NaCF₃SO₃ systems follows Arrhenius equation in the temperature range of 303 to 353 K. The PAN containing 24 wt.% LiCF₃SO₃ film has a higher ionic conductivity and lower activation energy compared to the PAN containing 26 wt.%LiCF₃SO₃ film. These results can be explained based on the Lewis acidity of the alkali ions, i.e., the interaction between Li⁺ ion and the nitrogen atom of PAN is stronger than that of Na⁺ ion.     

Vibrational and impedance spectroscopic analysis of poly(vinyl alcohol)-based solid polymer electrolytes

Solid polymer electrolytes based on poly(vinyl alcohol) (PVA) doped with NH₄Br have been prepared by the solution-casting method. The complex formation between the polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The highest conductivity at 303 K has been found to be of the order of 10⁻⁴ Scm⁻¹ for 25 mol% NH₄Br-doped PVA system. The ionic transference number of polymer electrolyte has been estimated by Wagner’s polarization method, and the results reveal that the conducting species are predominantly ions. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Ionic conductivity of lithium nitride doped with hydrogen

Lithium ionic conductivity of Li₃N single crystals is reported for temperatures from 120 K to 350 K. The intrinsic ionic conductivity is rather small (< 10^?6 Ω^?1 cm^?1 at 300 K) and shows no strong anisotropy. The activation energy is near 0,6 eV. It is shown that hydrogen is the critical impurity in the crystals grown and studied at this laboratory. The relative impurity concentration is determined from infrared transmission measurements near 3130 cm^?1. An estimate for absolute values is obtained from dielectric studies. Increases in ionic conductivity with hydrogen doping by a factor 5000 are reported for E⊥c but no significant effects are found for E6c. The proposed defect is an impurity-vacancy complex consisting of an NH^?? and a lithium vacancy.     

Ionic conductivity and interfacial resistance of electrospun poly(acrylonitrile)/poly(methyl methacrylate) fibrous membrane-based polymer electrolytes for lithium ion batteries

Electrospun poly(acrylonitrile) fibrous membrane (PAN-EFM) is prepared and enhanced by adding poly(methyl methacrylate)(PMMA) and subsequently minimizing the average diameter of the PAN/PMMA blend fibers. Electrospinning of the 50/50 wt% PAN/PMMA solution is carried out with the aim of the simultaneous presence of both polymers on the fiber surface. Their presence in exterior surface is confirmed using the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique next to the leaching of PMMA with acetone. The process parameters are optimized in four stable modes with the average diameter decreasing from 445 to 150 nm. Mechanical strength of the membrane is measured and reported. Comparing the sample electrochemical properties of the EFMs reveals that the addition of PMMA increases ionic conductivity from 1.02 to 3.31 mS cm^?1 and reduces interfacial resistance from ~1000 to ~400?Ω. It is also demonstrated that the ~300-nm reduction in average diameter of the blend fibers increases ionic conductivity from 3.31 to 5.81 mS cm^?1 and reduces interfacial resistance from ~400 to ~200?Ω.     

Design of ionic liquid-based hybrid electrolytes with additive for lithium insertion in graphite effectively and their effects on interfacial properties

To address the challenge of the IL-based electrolyte cannot be effectively intercalated in graphite anode, and especially the urgent needs for the compatibility between high performance and high security, the IL-based hybrid electrolyte systems with ethylene carbonate/propylene carbonate (EC/PC) as a co-solvent and vinylene carbonate (VC) as an additive were designed. The high dielectric constant of EC/PC significantly increased the ionic conductivity and lithium ion migration of the electrolyte system. Meanwhile, the presence of VC can form SEI preventing EC and PYR₁₄⁺ reductive decomposition on the electrode interface, and at the same moment, the SEI promotes effective Li cation insertion into the graphene interlayer. The Li/C half-cells showed high reversible capacity, cycling efficiency, and good cycle stability with the IL-based hybrid electrolyte. It is worth to highlight the better performance, in terms of the excellent thermal stability and high safety. Thus, the IL-based hybrid electrolyte combined with good electrochemical performance holds substantial promise for lithium-ion battery, and should have broad application prospects in the high energy density, especially high-security requirements, of the new lithium-ion battery.     

Photorefractive properties of potassium lithium niobate doped with copper

Potassium lithium niobate doped with copper (Cu:KLN) were grown by the Czochralski method for the first time. The structure of Cu:KLN was measured by the x-ray powder diffraction method, and its lattice constants were obtained. The position of copper ions in KLN crystal was determined. The exponential gain coefficient, response time and erasure time were measured. It was found that the exponential gain coefficient of Cu:KLN is 10.5 cm⁻¹, as two times high as that of KLN, and its response time of 1.53 s is one order of magnitude shorter than that of Cu:LiNbO₃. The type of light exciting carriers in Cu:KLN has been investigated. The result showed that the electron acts the main role in Cu:KLN.     

Electromagnetic properties of lithium zinc ferrites doped with aluminum

We present the results of the effect of Al substitution on the magnetic and electrical properties of Li_0.2Zn_0.6Fe_2.2−xAl_xO₄ ferrites (0.0≤x≤0.5) prepared by the standard ceramic technique. The characterization has been performed using XRD, SEM, magnetic and dielectric response in frequency. XRD analysis confirms that the system exhibits polycrystalline single phase cubic spinel structure only for low dopant content. Doping decreases the dielectric loss tangent and the ferrite conductivity in more than two orders of magnitude in the whole analyzed frequency range. Attenuation has a maximum intensity (86 dB) near 90 MHz for x=0.4. The wider bandwidth at 20 dB (94.6 MHz) is for x=0.3.     

Ionic conductivity studies of chitosan-based polymer electrolytes doped with adipic acid

Chitosan acetate–adipic acid film polymer electrolytes have been prepared by the solution cast technique. The highest conductivity is 1.4 × 10⁻⁹ S cm⁻¹ for 35 wt.% of adipic acid at room temperature. The sample with highest conductivity has the lowest activation energy. Calculations using the Rice and Roth model provide number of mobile ions, η. The conductivity is dependent on the diffusion coefficient and mobility.     

Electrochemical and structural comparison of zinc-cobalt doped spinels with other doped lithium manganese spinels

Doping of lithium manganese spinels by zinc and cobalt of the type (Li_1xZn_x)(Mn_2–2x Co_2x)O₄ may stabilize the delithiated spinels and may offer some indications with respect to the validity of capacity fade models. There are structural chemical arguments for this cation distribution. These and other doped lithium manganese spinels were prepared by heat treatment (in the range between 500 and 800 °C for 12 h) of solution precipitated precursors. Samples were characterised structurally and electrochemically by XRD and galvanostatic cycling. Extended cycling, storage in the charged state and storage in the discharged state were investigated. Pure phases of Zn-Co doped samples were obtained only for quenching the fired samples. Otherwise separation into a tetragonal spinel and a cubic spinel occurred. XRD results prove the occupation of tetrahedral coordinated cation positions by zinc ions, in contradiction to the results of other authors. XRD profiles show an anisotropic line broadening, which is attributed to an anisotropic microstrain, maybe induced by a non-cooperative Jahn-Teller distortion. Capacity retention was better for extended cycling and worse for both kinds of storage, compared to a purely cobalt doped spinel. Therefore, thermodynamic stabilisation of the delithiated spinels could not be confirmed. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998     

Electrical impedance and conduction mechanism analysis of biopolymer electrolytes based on methyl cellulose doped with ammonium iodide

In the present study, the potential of methyl cellulose (MC) as biopolymer electrolyte (BPE) will be studied extensively by means of conductivity and the conduction mechanism. BPE films based on MC doped with ammonium iodide (NH₄I) salt were prepared by solution-casting method. X-ray diffraction (XRD) explains that the conductivity enhancement of the electrolytes is affected by the degree of crystallinity. Field emission scanning electron microscopy (FESEM) analysis shows the difference in the electrolyte’s surface with respect to NH₄I. On addition of 40 wt.% of NH₄I, the highest room temperature conductivity of (5.08?±?0.04)?×?10^?4 S cm^?1 was achieved. The temperature dependence relationship for the salted electrolyte was found to obey the Arrhenius rule where R² ～1 from which the activation energy (E _a) was evaluated. The dielectric study analyzed using complex permittivity ε* for the sample with the highest conductivity at elevated temperature shows a non- Debye behavior. These salted electrolytes follow the correlated barrier hopping (CBH) model.     

All-solid-state lithium batteries with inorganic solid electrolytes:Review of fundamental science

The scientific basis of all-solid-state lithium batteries with inorganic solid electrolytes is reviewed briefly, touching upon solid electrolytes, electrode materials, electrolyte/electrode interface phenomena, fabrication, and evaluation. The challenges and prospects are outlined as well.     

Optical properties of doubly doped ZnO phosphors co-activated with lithium ions

Time-resolved laser-induced optical properties of didymium (a mixture of neodymium and praseodymium) doped zinc oxide phosphors have been studied using nitrogen laser as an excitation source at room as well as at liquid nitrogen temperatures. A comparison of optical properties (oscillator strength and dipole-moment) at room temperature and liquid nitrogen temperature has been done and is reported in this article. It is found that oscillator strength and dipole-moment values for doped ZnO are increasing with decreasing temperature. The increasing trend of the optical parameters obtained at liquid nitrogen temperature of the doped phosphors indicates increase in efficiency.     

Vibrational spectroscopic study of lithium intercalation into LiTi2(PO4)3

Ex situ vibrational spectra are recorded during the first discharge of LiTi₂(PO₄)₃. Spectral changes are consistent with a two-phase model for the electrochemical insertion of Li⁺ ions. Differences in the frequencies and relative intensities of the LiTi₂(PO₄)₃ and Li₃Ti₂(PO₄)₃ bands are due to changes in the effective force constants, dipole moment derivatives, and polarizability derivatives as Li⁺ is inserted into LiTi₂(PO₄)₃. The intramolecular PO₄³⁻ bending modes (ν₂ and ν₄) are found to be more sensitive to Li⁺ insertion than the intramolecular PO₄³⁻ stretching modes (ν₁ and ν₃). This is because ν₂ and ν₄ are less localized than ν₁ or ν₃ and are more susceptible to small structural changes in the unit cell. Furthermore, a band at 487 cm^− 1 appears in the infrared spectrum of Li₃Ti₂(PO₄)₃. This band is assigned as a Li⁺ ion cage mode and is due to Li⁺ ions that occupy the M(3) and M′(3) sites in the Li₃Ti₂(PO₄)₃ structure. A small degree of band broadening is also detected in the vibrational spectra when Li⁺ ions are inserted, which might indicate some disordering in the cathode material.