Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study

We report here on comparative measurements of cationic transference numbers of some lithium battery related electrolytes including lithium tetrafluoroborate in propylene carbonate, lithium hexafluorophosphate in blends of ethylene carbonate/diethyl carbonate and ethylene carbonate/propylene carbonate/dimethyl carbonate, as well as lithium difluoromono (oxalate) borate in an ethylene carbonate/diethyl carbonate blend via four different methods. Whereas three electrochemical methods yield transference numbers decreasing with concentration in accordance with electrostatic theories, valid for low to intermediate concentrations of the electrolyte, nuclear magnetic resonance spectroscopy measurements show increasing transference numbers with increasing concentration. The discrepancy is attributed to effects of ion–ion and ion–solvent interaction.     

Determination of lithium transference number in PEO-DME-LiClO4 modified with alumina powders of various surface acidity

The effect of alumina additives bearing various surface groups on conductivity and lithium cation transference numbers in poly(ethylene oxide) dimethyl ether (PEO-DME)-LiClO₄ electrolytes is examined. It is demonstrated that an increase in the conductivity and lithium transference number in composite electrolytes compared to pure PEO-DME-LiClO₄ electrolyte is observed in the limited salt concentration range. Both quantities seem to depend mostly on ionic species mobility. Also, their salt concentration dependence resembles that of viscosity of electrolytes studied. The conduction mechanism is discussed on the basis of conductivity, transference numbers and ionic association studies.     

Electrochemical behaviour of the cell Pb/PEO40. Pb(ClO4)2/Pb

The electrochemical behaviour of the polymer-based cell Pb/(PEO)₄₀. Pb(ClO₄)₂/Pb has been investigated over the temperature range 20–160°C by means of impedance spectroscopy and dc polarization methods. The bulk resistance and the charge transfer resistance display a linear trend in an Arrhenius plot. The transference numbers have been evaluated by an electrochemical method, and compared with those obtained from a preliminary experiment with Tubandt's method. These measurements indicate that both cations and anions are mobile, with a transference number for Pb²⁺ lower than 0.1 between 70 and 130°C.     

Effect of the silica precursor on the conductivity of hectorite-derived polymer nanocomposites

New hectorite and organo-hectorite clays have been prepared using different silica sol sources, in order to examine the importance of sol particle size, pH, and surface chemistry on the final matrix. Polymer-clay nanocomposites (PCN) are prepared by intercalating polyethylene oxide in the clay layers of lithium hectorites. The resulting films are physically and electrochemically evaluated. Conductivity values, activation energies, and lithium transference numbers indicate that the PCNs are single ion conductors with transference numbers close to unity. The activation energies are in the range of 0.02 V, two orders of magnitude lower than the conventional polymer electrolytes.     

Electrochemical and NMR characterizations of mixed polymer electrolytes based on oligoether sulfate and imide salts

Polymer electrolytes based on mixtures of lithium trifluoromethylsulfonylimide, LiTFSI and lithium oligoether sulfates dissolved in poly(oxyethylene) were studied. The properties of these mixed electrolytes i.e. thermal stability, ionic conductivities, transference numbers, diffusion coefficients and electrochemical stabilities were established in a wide range of compositions. A satisfactory compromise was found between high cationic transference numbers and high conductivities, while markedly decreasing the total amount of LiTFSI used. Since lithium oligoether sulfates should be considerably less expensive than LiTFSI and easy to recycle, these mixed polymer electrolytes seem to be promising.     

Novel composite polymer electrolyte comprising poly(ethylene oxide) and triblock copolymer/mesostructured silica hybrid used for lithium polymer battery

Ordered mesoporous materials, due to its potential applications in catalysis, separation technologies, and nano-science have attracted much attention in the past few years. In this work, a novel PEO-based composite polymer electrolyte by using organic-inorganic hybrid EO₂₀PO₇₀EO₂₀ @ mesoporous silica (P123 @ SBA-15) as the filler has been developed. The interactions between P123 @ SBA-15 hybrid and PEO chains are studied by X-ray diffraction (XRD), differential scanning calorimeter (DSC), and FT-IR techniques. The effects of P123 @ SBA-15 on the electrochemical properties of the PEO-based electrolyte, such as ionic conductivity, lithium ion transference number are studied by electrochemical ac impedance spectroscopy and steady-state current method. The experiment results show that P123 @ SBA-15 can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolyte, which are induced by the special topology structure of P123 in P123 @ SBA-15 hybrid, at the same time. The excellent lithium transport properties and broad electrochemical stability window suggesting that PEO-LiClO₄/P123 @ SBA-15 composite polymer electrolyte can be used as candidate electrolyte materials for lithium polymer batteries.     

Poly(oxyethylene) electrolytes based on lithium pentafluorobenzene sulfonate

Lithium pentafluorobenzene sulfonate was synthesized by a protocol whereby pollution by aromatic nucleophilic substitutions on the perfluorinated ring was avoided. Its poly(oxyethylene) complexes, although less conductive than lithium imide complexes, provided cationic transference numbers higher than 0.5. Surprisingly, even at fairly low concentrations, this salt markedly increased the mechanical properties of the polymer electrolyte. This effect was attributed to telechelic interactions of the ion pairs with distinct polyether chains and is in agreement with the high cationic transference numbers.     

Lithium transference number measurements and complex abilities in anion trapping triphenyloborane-poly(ethylene oxide) dimethyl ether-lithium trifluoromethanesulfonate composite electrolyte

In this paper we report the combined, positive effect of triphenyloborane (BPh₃) additive on conductivity and lithium cation transference numbers in poly(ethylene oxide) dimethyl ether (PEODME)-lithium trifluoromethanesulfonate (LiCF₃SO₃, LiTf) electrolytes. The transport mechanism is discussed on the basis of impedance measurements, restricted diffusion t⁺ measurements, ionic association semi-empirical quantitative estimation and spectroscopic studies. A substantial increase in the lithium transference number values in triphenylborane enriched composite electrolytes was observed in comparison with the pure PEODME-LiCF₃SO₃ electrolyte. This effect is assisted by ionic conductivity enhancement.     

Effect of surface modified porous inorganic-organic hybrid polyphosphazene nanotubes on the properties of polyethylene oxide based solid polymer electrolytes

2-(2-methyloxyethoxy)ethanol modified poly (cyclotriphosphazene-co-4,4′-sufonyldiphenol) (PZS) nanotubes were synthesized and solid composite polymer electrolytes based on the surface modified polyphosphazene nanotubes added to PEO/LiClO₄ model system were prepared. Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to investigate the characteristics of the composite polymer electrolytes (CPE). The ionic conductivity, lithium ion transference number and electrochemical stability window can be enhanced after the addition of surface modified PZS nanotubes. The electrochemical investigation shows that the solid composite polymer electrolytes incorporated with PZS nanotubes have higher ionic conductivity and lithium ion transference number than the filler SiO₂. Maximum ionic conductivity values of 4.95 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.64 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt % content of surface modified PZS nanotubes were obtained and the lithium ion transference number was 0.41. The good chemical properties of the solid state composite polymer electrolytes suggested that the inorganic-organic hybrid polyphosphazene nanotubes had a promising use as fillers in solid composite polymer electrolytes and the PEO₁₀-LiClO₄-PZS nanotubes solid composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.     

Ionic conductivity and interfacial properties of polymer electrolytes based on PEO and boroxine ring polymer

Blended polymer electrolytes based on poly(ethylene oxide) (PEO) and boroxine ring polymer (BP) solvated with lithium triflate were formulated and evaluated. Compared to PEO–salt polymer electrolyte, ionic conductivities of blended polymer electrolytes were two orders of magnitude higher in a low‐temperature range; as well, lithium transference numbers were increased to ～ 0.4. These were due to the increased mobility and anion trapping of boroxine rings. BP also exhibited the stabilizing effect on lithium–polymer electrolyte interface, and a reduced interfacial resistance between lithium metal and the polymer electrolyte was found with increasing of BP content. Polymer electrolytes based on PEO and BP are suitable for use in lithium secondary battery. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 17–21, 2002; DOI 10.1002/app.10090     

Lithium ion transport through nonaqueous perfluoroionomeric membranes

The transport properties of lithiated perfluorinated ionomers imbibed with nonaqueous solvents and solvent mixtures were studied. Polymeric ion‐exchange membranes have potential use in the next generation single‐ion secondary lithium polymer batteries, where the lithiated form of the membrane is used as a polymer electrolyte. The novelty of the approach for lithium battery applications lies in the advantage offered by a transference number of unity, no additional salt (e.g., LiPF₆) is needed, and the excellent physical and chemical stability of the fluoropolymers. Ion‐exchange membranes were converted to the Li⁺ salt form and analyzed for total conversion using FT‐IR. Nonaqueous solvents and solvent mixtures were imbibed into the membranes in a glove box, and the uptake was measured over time. A four‐point probe was used to determine the ionic conductivity based on impedance measurements performed over a frequency range of 10 to 35,000 Hz. Conductivities exceeding 10^?4 S/cm with transference numbers of unity were achieved making these ionomeric membranes potentially useful in rechargeable lithium polymer batteries.     

EFFECT OF IMPELLER AND VESSEL SIZE ON IMPELLER POWER NUMBER IN CLOSED VESSELS FOR REYNOLDS NUMBERS BETWEEN 40 AND 65000

Impeller power numbers in closed square vessels with/or without baffles and in closed cylindrical vessels with baffles were studied for impeller Reynolds numbers in the range between 40 and 65000. Flat vertical blade disk style, vertical blade open style and 45° pitched blade open style impellers were used. It was found that the impeller power number is affected by the vessel and impeller size and the system scale up     

Cationic conduction in oligoether salt–comblike polyether complex

Polymeric solid electrolytes, with excellent cationic conductivity, were prepared from the complexation of lithium methoxyoligo(oxyethylene) sulfate and lithium methoxyoligo(oxyethylene) sulfonate with poly[methoxyoligo(oxyethylene)methacrylate-co-acrylamide]. The electrolytes exhibit low glass transition temperature and have almost no crystal. Their ionic conductivities at 25°C are over 10^?5 S/cm. The carrier number in the complex decreases while ionic mobility increases considerably with increasing considerably with increasing temperature. The polarization reversing method confirms that the cationic transference numbers are all over 0.9. The electrolytes have single ion conduction characteristics in DC polarization. © 1995 John Wiley & Sons, Inc.     

Electrochemical investigation of polymer electrolytes based on lithium 2-(phenylsulfanyl)-1,1,2,2-tetrafluoro-ethansulfonate

The salt PhSCF₂CF₂SO₃Li appears promising for lithium-polymer batteries. Its poly(oxyethylene) complexes, although less conductive than lithium imide complexes, provided cationic transference numbers ranging between 0.45 and 0.5, enabling high cationic conductivities to be obtained. Thanks to its double substitution by aryl and perfluorinated moieties, the thioether function is stable enough to be used with positive electrodes, such as vanadium oxide and perhaps cobalt oxide.     

TURBULENT RANGE IMPELLER POWER NUMBERS IN CLOSED CYLINDRICAL AND SQUARE VESSELS

Impeller power numbers in closed square vessels with/or without baffles and in closed cylindrical vessels with baffles were studied for impeller Reynolds numbers in the range between 75000 and 300000. A flat vertical blade disk style, a vertical blade open style and a 45° pitched blade open style impellers were used. A substantial reduction of power number is observed for all three impellers inside the square vessels without baffles in comparison with baffled cylindrical and square ones reaching up to 61 %.     

Use of amalgam concentration cells for determination of transference numbers in solid electrolytes—I. Electronic transference numbers of β-aluminas

The determination of transference numbers for different doped as well as undoped sodium-β-aluminas has been carried out by means of a method based on emf measurements of amalgam concentration cells of the type Na_x2Hg_1−x2/sodium-β-alumina/Na_x1Hg_1−x1 at 25°C. The details of this method, whose validity extends also to cationic conducting solids other than β-aluminas, are described and discussed for comparison with the results of previous investigations.     

New polymer electrolytes based on ether sulfate anions for lithium polymer batteries: Part II: Conductivity and transport properties of blended and cross-linked ionomers

Multifunctional ionomers based on poly(oxyethylene)-co-poly(epichlorohydrin) random copolymers were blended with poly(oxyethylene) or cross-linked through urethane curing. Their conductivities, transference numbers and electrochemical stability were investigated. The cross-linked materials exhibited good mechanical properties. Gelled by liquid organic electrolytes they provided conductivities very close to that of the liquid electrolyte. A thorough comparative investigation of the cationic transference numbers of cross-linked and uncross-linked ionomers was performed. From these data it may be assumed that the cell electrical polarization is enough to induce chain disentanglements, which result in a significant anionic transference number.     

Ion transport phenomena in polymeric electrolytes

The aim of the present work is to generalize an ion transport phenomena observed in composite polymeric electrolytes using the previously developed models as well as design a new approach which would be helpful in describing changes in conductivity and lithium ion transference numbers occurring upon addition of fillers to polymeric electrolytes. The concept is based on the observation of changes in ionic associations in the polymeric electrolytes studied in a wide salt concentration range. The idea is illustrated by the results coming from a variety of electrochemical and structural data obtained for composite electrolytes containing specially designed inorganic and organic fillers.     

Electron-hole transport in (La0.9Sr0.1)0.98Ga0.8Mg0.2O3−δ electrolyte: effects of ceramic microstructure

The oxygen ion transference numbers of a series of (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3−δ (LSGM) ceramics with different microstructures, prepared by sintering at 1673 K for 0.5-120 h, were determined at 973-1223 K by a modified Faradaic efficiency technique, taking electrode polarization into account. In air, the transference numbers vary in the range 0.984-0.998, decreasing when temperature or oxygen partial pressure increases. Longer sintering times lead to grain growth and to the dissolution of Sr-rich secondary phases and magnesium oxide, present in trace amounts at the grain boundaries, into the major perovskite phase. This is accompanied with a slight decrease of the total grain-interior resistivity and thermal expansion, while the boundary resistance evaluated from impedance spectroscopy data decreases 3-7 times. The electron-hole transport in LSGM ceramics was found to decrease when the sintering time increases from 0.5 to 40 h, probably indicating a considerable contribution of acceptor-enriched boundaries in the hole conduction. Due to reducing boundary area in single-phase materials, further sintering leads to higher p-type conductivity. The results show that, as for ionic conductivity, electronic transport in solid electrolytes significantly depends on ceramic microstructure.     

A comparison of the electro-osmotic properties of charged polymer membranes and those predicted from binary electrolyte solution models Part I. Univalent forms of sulphonate membranes and chloride electrolyte models

By changing from the usual solvent-fixed frame of reference for flows to one based upon a fixed anion, electro-osmotic transference numbers are defined for any electrolyte, for which transport numbers are known. For sulphonate membranes, chloride electrolyte analogues were chosen. Agreement between observed transference numbers and those of the model electrolytes are shown to be excellent for both polystyrene based and perfluoro-sulphonic acid membranes.From irreversible thermodynamics it is shown that the transference number for any membrane will have a maximum value equal to the molar ratio of water to fixed charge in the membrane and independent of ionic form. The observed value is in addition, proportional to the fraction of the total water friction, which is due to water interaction with counterion. It is the latter which is estimated successfully from model electrolytes. The ionic forms used were Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and H⁺ at 25°C in membranes in which electrolyte exclusion was almost complete.