Synthesis and properties of a new class of fluorine-containing dilithium salts for lithium-ion batteries

A facile synthetic route for the development of a new class of dilithium salts is described. Because of the presence of two lithium ions per molecule, these salts require lower concentrations than commonly used salts to achieve comparable ionic conductivities at ambient temperatures. An ionic conductivity of 3.55 × 10^− 3 S/cm at 30 °C was obtained using 0.5 M salt solution in 1:1 wt/wt ethylene carbonate:dimethyl carbonate. The salts exhibit excellent thermal stabilities to at least 350 °C and are electrochemically stable below 4.2 V versus lithium metal. The best salt was tested with a polymer electrolyte system. Incorporation of a polyethylene glycol-based borate ester plasticizer improved the ionic conductivity of the solid polymer electrolyte film up to 1.36 × 10^− 5 S/cm at 30 °C, which is 10 times higher than that of un-plasticized electrolyte films.     

Single ion conductors—polyphosphazenes with sulfonimide functional groups

A novel single ion conductive polymer electrolyte was developed by covalently linking an arylsulfonimide substituent to the polyphosphazene backbone. Polymeric single-ion conductors incorporate the anion of a salt either into the polymer backbone or as a pendent group linked to the polymer backbone. Immobilization of the anion could provide access to electrochemical devices that would be less vulnerable to increased resistance associated with salt concentration gradients at the interfaces during charging and discharging. In this work, an immobilized sulfonimide lithium salt is the source of lithium cations, while a cation-solvating cosubstituent, 2-(2-methoxyethoxy)ethoxy, was used to increase free volume and assist cation transport. The ionic conductivities showed a dependence on the percentage of lithiated sulfonimide substituent present. Increasing amounts of the lithium sulfonimide component increased the charge carrier concentration but decreased the ionic conductivity due to decreased macromolecular motion and possible increased shielding of the nitrogen atoms in the polyphosphazene backbone. Maximum ionic conductivity values of 2.45 × 10^− 6 S/cm at ambient temperature and 4.99 × 10^− 5 S/cm at 80 °C were obtained. Gel polymer electrolytes containing N-methyl-2-pyrrolidone gave ionic conductivities in the 10^− 3 S/cm range. The ion conduction process was investigated through model polymers that contained the non-immobilized sulfonimide — systems that had higher conductivities than their single ion counterparts.     

Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

Development of dry polymer electrolyte based on polyethylene oxide with co-bridging agent crosslinked by electron beam

Polyethylene oxide (PEO)-based electrolytes were crosslinked using electron beam (EB) irradiation. The gel contents of a polymer film were increased after irradiation doses of 0, 140, 280, and 420 kGy, with ionic conductivities of 0.831, 1.55, 6.08, and 7.95 (× 10^? 5) S cm^? 1 at 40 °C, respectively. The slight decrease in conductivity at higher temperatures after irradiation is due to the retardation of polymer motion by crosslinking. The electrolyte with higher EB dose amount exhibits higher conductivity due to stabilization of the amorphous state. The EB crosslinking with a co-bridging agent shows enhanced conductivities of 4.71, 6.59, and 7.18 (× 10^? 5) S cm^? 1 at 40 °C, after irradiation with 140, 280, and 420 kGy. Addition of the co-bridging agent is effective for developing a crosslinked structure with a smaller EB dose. Tensile strength becomes two to three times higher with irradiation compared to the non-treated polymer. Combination of the EB technique with a co-bridging agent is a simple and effective method to prepare strong dry polymer electrolyte films with improved room temperature conductivity.     

Ionic conductivity of polymer electrolyte membranes based on polyphosphazene with oligo(propylene oxide) side chains

A polyphosphazene [NP(NHR)₂]_n with oligo[propylene oxide] side chains − R = –[CH(CH₃)–CH₂O]_m–CH₃ (m = 6 – 10) was synthesized by living cationic polymerisation and polymer-analogue substitution of chlorine from the intermediate precursor [NPCl₂]_n using the corresponding primary amine RNH₂. The polymer had an average molecular weight of 3.3 × 10⁵ D. Polymer electrolytes with different concentrations of dissolved lithium triflate (LiCF₃SO₃) were prepared. Mechanically stable polymer electrolyte membranes were formed using UV radiation induced crosslinking of the polymer salt mixture in the presence of benzophenone as photoinitiator. The glass transition temperature of the parent polymer was found to be − 75 °C before cross linking. It increases after crosslinking and with increasing amounts of salt to a maximum of − 55 °C for 20 wt.% LiCF₃SO₃. The ionic conductivity was determined by impedance spectroscopy in the temperature range 0–80 °C. The highest conductivity was found for a salt concentration of 20 wt.% LiCF₃SO₃: 6.5 × 10^− 6 S·cm^− 1 at 20 °C and 2.8 × 10^− 4 S cm^− 1 at 80 °C. The temperature dependence of the conductivities was well described by the MIGRATION concept.     

Organic dopant added polyvinylidene fluoride based solid polymer electrolytes for dye-sensitized solar cells

The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I₂ electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I₂ electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I₂ and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I₂ electrolyte exhibited the ionic conductivity of 4.68×10⁻⁶ S cm⁻¹ and this value was increased to 7.43×10⁻⁵ S cm⁻¹ when PTZ was added to PVDF/KI/I₂ electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I₂ electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I₂ electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I₂ electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I₂ electrolyte was found to be optimal for DSSC applications.     

Preparation and characterization of solid polymer electrolytes based on PHEMO and PVDF-HFP

Polymer electrolyte membranes consisting of a novel hyperbranched polyether PHEMO (poly(3-{2-[2-(2-hydroxyethoxy) ethoxy] ethoxy}methyl-3′-methyloxetane)), PVDF-HFP (poly(vinylidene fluoride-hexafluoropropylene)) and LiTFSI have been prepared by solution casting technique. X-ray diffraction of the PHEMO/PVDF-HFP polymer matrix and pure PVDF-HFP revealed the difference in crystallinity between them. The effect of different amounts of PVDF-HFP and lithium salts on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared polymer electrolytes can reach 1.64 × 10^? 4 S·cm^? 1 at 30 °C and 1.75 × 10^? 3 S·cm^? 1 at 80 °C. Thermogravimetric analysis informed that the PHEMO/PVDF-HFP matrix exhibited good thermal stability with a decomposition temperature higher than 400 °C. The electrochemical experiments showed that the electrochemical window of the polymer electrolyte was around 4.2 V vs. Li⁺/Li. The PHEMO/PVDF-HFP polymer electrolyte, which has good electrochemical stability and thermal stability, could be a promising solid polymer electrolyte for polymer lithium ion batteries.     

A preliminary study on a new LiBOB/acetamide solid phase transition electrolyte

New solid electrolytes containing acetamide and lithium bioxalato borate (LiBOB) with different molar ratios have been investigated. Their melting points (T_m) are around 42 °C. The ionic conductivities and activation energies vary drastically below and above T_m, indicating a typical feature of phase transition electrolyte. The ionic conductivity of the LiBOB/acetamide electrolyte with a molar ratio of 1:8 is 5 × 10^? 8 S cm^? 1 at 25 °C but increases to 4 × 10^? 3 S cm^? 1 at 60 °C. It was found that anode materials, such as graphite and Li₄Ti₅O₁₂, could not discharge and charge properly in this electrolyte at 60 °C due to the difficulty in forming a stable passivating layer on the anodes. However, a Li/LiFePO₄ cell with this electrolyte can be charged properly after heating to 60 °C, but cannot be charged at room temperature. Although the LiBOB/acetamide electrolytes are not suitable for Li-ion batteries due to poor electrode compatibility, the current results indicate that a solid electrolyte with a slightly higher phase transition temperature than room temperature may find potential application in stationary battery for energy storage where the electrolyte is at high conductive liquid state at elevated temperature and low conductive solid state at low temperature. The interaction between acetamide and LiBOB in the electrolyte is also studied by Raman and FTIR spectroscopy.     

Effects of compositions on properties of PEO–KI–I2 salts polymer electrolytes for DSSC

The effects of compositions on properties of PEO/KI/I₂ salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10^− 5 S/cm at 303 K (ambient temperature) and 2.32 × 10^− 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I⁻] and [I₃⁻] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I₃⁻ (114 cm^− 1) and I₅⁻ (145 cm^− 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I₂ polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm², 593 mV and 2.044% respectively.     

Synthesis and ionic conductivity of polymeric ion gel containing room temperature ionic liquid and phosphotungstic acid

Composite electrolyte comprising phosphotungstic acid (PWA) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF₄) room temperature ionic liquid (RTIL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix has been prepared. The polymer matrix was formed by free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) monomers. BMImBF₄ was used as both ionic source and plasticizer, and PWA filler provided the proton conductivity in this system. The interactions and structure changes of the PHEMA-RTIL-PWA composites were investigated by Fourier transform infrared spectra, differential scanning calorimetry, and X-ray diffraction. PWA fillers maintained their Keggin structure within a limited range and enhanced the ionic conductivity of the composite electrolyte. The electrolyte with PWA at the 2 wt.% showed the highest ionic conductivity of 8 × 10^− 4 S cm^− 1 at room temperature and 96% relative humidity.     

Polyphosphazene based composite polymer electrolytes

Composite salt-in-polymer electrolyte membranes were prepared from poly[(bis(2-methoxyethyl)amino)_1−x(n-propylamino)_x-phosphazene] (BMEAP) with dissolved LiCF₃SO₃ and dispersed Al₂O₃ nanoparticles (40 nm). Membranes with good mechanical stability were obtained. Low ionic conductivities were found in particle free membranes with maximum conductivities at 10 wt.% LiCF₃SO₃ ranging from 3.1 × 10^− 7 S/cm at 30 °C to 1.8 × 10^− 5 S/cm at 90 °C. For the composite membranes, addition of 2 wt.% Al₂O₃ nanoparticles leads to a steep increase of the conductivity by almost two orders of magnitude as compared to the homogeneous membranes. The highest room temperature conductivity for the investigated BMEAP–LiCF₃SO₃–Al₂O₃ composite systems was 10^− 5 S/cm.     

Preparation of poly(vinyl phosphate-b-styrene) copolymers and its blend with PPO as proton exchange membrane for DMFC applications

Poly(vinyl phosphate-b-styrene) (poly(VPP-b-St)) block copolymers were prepared via consecutive telomerization of vinyl acetate (VAc), atom transfer radical polymerization (ATRP) with styrene, saponification, and phosphorylation with phosphorus oxychloride. The resulting block copolymers were characterized by FT-IR and pH titration. Then, the block copolymers were blended with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to prepare direct methanol fuel cell (DMFC) membrane. The performance of poly(VPP-b-St)/PPO blend membranes was measured in terms of proton conductivity, methanol permeability, thermal and hydrolytic stability. The proton conductivities were in the range of 10^− 4 to 10^− 2 S/cm (60 °C, RH = 95%); the methanol permeabilities were in the range of 4.14 × 10^− 8 to 9.62 × 10^− 8 cm²/s (25 °C), and quite lower than that of Nafion® 117. Also, the thermal stability of the blend membranes was characterized by TGA, and was stable up to 400 °C; the blend membranes had better hydrolytic stability.     

Solid electrolyte membranes from semi-interpenetrating polymer networks of PEG-grafted polymethacrylates and poly(methyl methacrylate)

Solid polymer electrolyte membranes were prepared as semi-interpenetrating networks by photo-induced polymerization of mixtures of poly(ethylene glycol) (PEG) methacrylate macromonomers in the presence of poly(methyl methacrylate) (PMMA) and lithium bis(trifluoromethanesulfonyl)imide salt. The composition of the membranes was varied with respect to the PMMA content, the degree of cross-linking, and the salt concentration. Infrared analysis of the membranes indicated that the lithium ions were coordinated by the PEG side chains. Calorimetry results showed a single glass transition for the blend membranes. However, dynamic mechanical measurements, as well as a closer analysis of the calorimetry data, revealed that the blends were heterogeneous systems. The ionic conductivity of the membranes increased with the content of PEG-grafted polymethacrylate, and was found to exceed 10^− 5 S cm^− 1 at 30 °C for membranes containing more than 85 wt.% of this component in the polymer blend.     

Study of EVOH based single ion polymer electrolyte: Composition and microstructure effects on the proton conductivity

A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C₄H₉O₂Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C₆H₁₃O₃Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n ≥ 5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10^− 3 S cm^− 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.     

Synthesis of ammonia at atmospheric pressure with Ce0.8M0.2O2−δ (M = La,Y, Gd,Sm) and their proton conduction at intermediate temperature

Ionic conduction in fluorite-type structure oxide ceramics Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) at temperature 400–800 °C was systematically studied under wet hydrogen/dry nitrogen atmosphere. On the sintered complex oxides as solid electrolyte, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in the solid states proton conducting cell reactor by electrochemical methods, which directly evidenced the protonic conduction in those oxides at intermediate temperature. The rate of evolution of ammonia in Ce_0.8M_0.2O_2−δ (M = La, Y, Gd, Sm) is up to 7.2 × 10^− 9, 7.5 × 10^− 9, 7.7 × 10^− 9, 8.2 × 10^− 9 mol s^− 1 cm^− 2, respectively.     

Electrical and dielectric properties of β-BaB2O4 (BBO) and CsLiB6O10 (CLBO) crystals

In barium borate (BBO) crystals, sodium and potassium ions, inherited due to the preparation technique, are dominant charge carriers. The conductivity between layers is higher; the conductivity activation energy and the conductivity at 350 °C being equal to 1.01±0.05 eV and (1.3±0.2)×10⁻⁸ S/cm, respectively. The conductivity activation energy and the conductivity at 350 °C along the channels are equal to 1.13±0.05 eV and to (4±0.2)×10⁻⁹ S/cm, respectively. Relative static permittivity is almost isotropic, and equal to 7.65±0.05. Upon storing of cesium–lithium borate (CLBO) crystals, pre-heating to 600 °C eliminates the influence of surface humidity. At 500 K, the ionic conductivity ranges from 4×10⁻¹² to 2×10⁻¹⁰ S/cm; the conductivity activation energy ranges from 1.01 to 1.17 eV. Relative static permittivity is equal to 7.4±0.3.     

Polymer electrolytes based on cross-linked cyclotriphosphazenes

Substituted cyclotriphosphazenes were used to prepare lithium ion conducting polymer networks. Two types of compounds were synthesized starting with the precursor hexachlorocyclotriphosphazene (HCCP): Type I (CVEEP) in which all the chlorine atoms in HCCP were replaced by vinyloxyethoxyethoxy groups (VEE = –OCH₂CH₂OCH₂CH₂OCHCH₂), and type II (CVMEEP) in which half of the chlorine was replaced by VEE and the other half by methoxyethoxyethoxy groups (MEE = –OCH₂CH₂OCH₂CH₂OCH₃). The terminal vinyl groups were used to build up a network by a thermally initiated cross-linking of lithium salt containing membranes. Polymer electrolytes with dissolved LiSO₃CF₃ and LiN(SO₂CF₃)₂ were investigated by impedance measurements. The ionic conductivity of CVMEEP with 10 wt.% LiSO₃CF₃ was 3.2 × 10^− 5 S/cm at 30 °C and 4.1 × 10^− 4 S/cm at 90 °C. Lower conductivity values in the range 10^− 8–10^− 9 S/cm were obtained at 30 °C for the highly crosslinked CVEEP. An interesting polymer electrolyte with good mechanical properties and a good conductivity of 1.3 × 10^− 5 S/cm (30 °C) was obtained from a solution of MEEP (= poly[bis(methoxy–ethoxy–ethoxy)phosphazene]) and LiSO₃CF₃ in CVEEP as an interpenetrating network.     

High mobility I− / I3− redox couple in a molecular plastic crystal: A potential new generation of electrolyte for solid-state photoelectrochemical cells

A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state “solvent” for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from − 40 to 60 °C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 × 10^− 3 S cm^− 1 at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells.     

Li3+ ion irradiation effects on ionic conduction in P(VDF–HFP)–(PC + DEC)–LiClO4 gel polymer electrolyte system

Swift heavy ion irradiation of P(VDF–HFP)–(PC + DEC)–LiClO₄ gel polymer electrolyte system with 48 MeV Li³⁺ ions having five different fluences was investigated with a view to increase the Li⁺ ion diffusivity in the electrolyte. Irradiation with swift heavy ion (SHI) shows enhancement of conductivity at lower fluences and decrease in conductivity at higher fluences with respect to unirradiated polymer electrolyte films. Maximum room temperature (303 K) ionic conductivity is found to be 2.2 × 10^− 2 S/cm after irradiation with fluence of 10¹¹ ions/cm². This interesting result could be ascribed to the fluence-dependent change in porosity and to the fact that for a particular ion beam with a given energy higher fluence provides critical activation energy for cross-linking and crystallization to occur, which results in the decrease in ionic conductivity. The XRD results show decrease in the degree of crystallinity upon ion irradiation at low fluences (≤ 10¹¹ ions/cm²) and increase in crystallinity at high fluences (> 10¹¹ ions/cm²). The scanning electron micrographs (SEM) exhibit increased porosity of the polymer electrolyte films after low fluence ion irradiation.     

Effect of amphiphilic hyperbranched-star polymer on the structure and properties of PVDF based porous polymer electrolytes

An amphiphilic hyperbranched-star polymer (HPE-g-MPEG) was synthesized by grafting methoxy poly(ethylene glycol) to the end of the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent. The synthesized amphiphilic hyperbranched-star polymer was blended with poly(vinylidene fluoride) (PVDF) to fabricate porous membranes via typical phase inversion process, and then the membranes were filled and swollen by a liquid electrolyte solution to form polymer electrolytes. The influences of HPE-g-MPEG on the morphology, crystallinity, liquid electrolyte uptake, mechanical properties of the porous membranes and the electrochemical properties of the activated membranes were investigated. It was found that the addition of HPE-g-MPEG resulted in a significant increase in porosity and a considerable reduction in crystallinity of the blend membranes, which favored the liquid electrolyte uptake and, consequently, led to a remarkable increase in ion conductivity at ambient temperature. The maximum ion conductivity observed in this study was 1.76 × 10^? 3 S/cm at 20 °C for the blend membrane with a HPE-g-MPEG/PVDF ratio of 3/10 (w/w).