Effect of ethylene carbonate plasticizer and TiO<Subscript>2</Subscript> nanoparticles on 49% poly(methyl methacrylate) grafted natural rubber-based polymer electrolyte

The effect of plasticizer and TiO₂ nanoparticles on the conductivity, chemical interaction and surface morphology of polymer electrolyte of MG49–EC–LiClO₄–TiO₂ has been investigated. The electrolyte films were successfully prepared by solution casting technique. The ceramic filler, TiO₂, was synthesized in situ by sol-gel process and was added into the MG49–EC–LiClO₄ electrolyte system. Alternating current electrochemical impedance spectroscopy was employed to investigate the ionic conductivity of the electrolyte films at 25 °C, and the analysis showed that the addition of TiO₂ filler and ethylene carbonate (EC) plasticizer has increased the ionic conductivity of the electrolyte up to its optimum level. The highest conductivity of 1.1 × 10⁻³ Scm⁻¹ was obtained at 30 wt.% of EC. Fourier transform infrared spectroscopy measurement was employed to study the interactions between lithium ions and oxygen atoms that occurred at carbonyl (C=O) and ether (C-O-C) groups. The scanning electron microscopy micrograph shows that the electrolyte with 30 wt.% EC posses the smoothest surface for which the highest conductivity was obtained.     

New advanced in situ carbon monoxide sensor for the process application

Mixed potential solid electrolyte CO sensors with sensing electrodes based on composite with various semiconducting oxides were extensively studied in the temperature range 500–650 °C for sensitivity, stability and cross-sensitivity besides CO to other combustion components like CO₂, H₂O, O₂, and SO₂. The highest CO sensitivity was found for the CO sensor with composite electrode based on Au/Ga₂O₃ showing also good reproducibility and stability in hazardous combustion environment. CO sensor response behavior in non equilibrated oxygen containing gas mixtures is mainly determined by the catalytic activity of the measuring electrode and depends strongly on preparation and measuring conditions. Mixed oxides based on doped chromites show only a little sensitivity to CO. CO sensor based on Au/Ga₂O₃ composite electrodes was showing good CO selectivity in the presence of other combustion gas species and finally was tested in combustion environment at power plant. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

AgNbO3 dispersed Ag2SO4 composite for potentiometric SO2 gas sensor application

Composite electrolytes of Ag₂SO₄ is prepared by dispersing fine particles, average particle size <40 microns (350 mesh), of ferroelectric AgNbO₃ in varying weight fraction. Enhancement in the conductivity is observed in β-phase of host system. The effect of dispersion on the conductivity, activation energy and transition temperature is studied as a function of weight % of the dispersoid in the host. Two distinct conduction mechanisms, viz. conduction through electrolyte bulk in parallel with conduction along the inter-grain interaction layer (R _b ^‖ ‖R_∞) and perpendicular to the interface (R _b ^⊥ ) could be resolved in the frequency range of 5 Hz to 13 MHz at temperatures below 300 °C. The interface interaction is found to be nucleophilic increasing the concentration of Ag⁺ vacancies at the interface. Potentiometric SO₂ gas sensors are tested with this composite electrolyte as an auxiliary phase. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Determination of amorphous layers on thick film Nasicon in dependence on different sintering processes

In thick film gas sensors Nasicon is used as a solid electrolyte with high Na⁺ ionic conductivity. Sensors like CO₂, O₂, Pt ▮ Na₂CO₃, BaCO₃ ∥ NASICON [Pt]_glass, O₂, CO₂ are suitable to measure the CO₂-concentration over 5 orders of magnitude. To characterize the screen printed Nasicon as a main component of such sensors grazing incidence diffractometry (GID), SEM, impedance spectroscopy and dc polarization measurements are performed in order to improve the long-term stability. The sintering process of the thick film influences the chemical surface composition of Nasicon and as a consequence the response of the sensor. Nasicon films sintered at temperatures between 1070 and 1210 °C show an amorphous layer increasing up to 1.1 μm thickness on the surface. Impedance measurements show, that cells using in such a way prearated Nasicon are responsible for water vapour. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Electrochemical comparison between SnO2 and Li2SnO3 synthesized at high and low temperatures

Li₂SnO₃ has been synthesized at 1000 °C from Li₂CO₃ and SnO₂ (high temperature form - HT) and it has also been prepared from ball-milled SnO₂ and Li₂CO₃ at 650 °C (low temperature form - LT). The Li₂SnO₃ materials have been tested as a negative electrode for possible use in a Li-ion cell and their electrochemical behaviour has been compared with that of SnO₂. In theory, Li₂SnO₃ and SnO₂ should be able to cycle the same number of lithium atoms per tin atom but on the initial discharge SnO₂ has inserted more lithium than Li₂SnO₃. During the initial discharge of SnO₂ and Li₂SnO₃, a side electrochemical reaction seems to be occurring. The resultant compound apparently inserts lithium reversibly for potentials around 1 V; however, cycling from 0.02–2 V significantly degrades performance compared to 0.02–1 V. Li₂SnO₃ (HT) allows the de-insertion of more lithium than Li₂SnO₃ (LT) and SnO₂ in the first charge. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Reference electrode formation in potentiometric CO2 sensors with alkali ion conducting alumosilicate glasses as solid electrolytes

Potentiometric CO₂ gas sensors with Li conducting glasses/glass ceramics of the system Li₂O-Al₂O₃-SiO₂ (different nominal composition) as solid electrolytes have been investigated. Li₂CO₃ was used as CO₂ and O₂ sensitive auxiliary electrode. During the sensor test measurements, the CO₂ partial pressure was varied between 1×10⁻³ and 1×10⁻¹ bar at a constant O₂ partial pressure of 2.1×10⁻¹ bar whereas N₂ was used as carrier gas. Comparative measurements were accomplished with sensors comprising Na and K ion conducting glasses. A metastable reference electrode was formed at the contact zone between the Au metal electrode and the former Li glasses of definite nominal composition by crystallization processes taking place, which lead to stable, reproducible CO₂ dependent EMF signals for more than 90d. The thermodynamically expected EMF difference and the observed EMF difference agree quite well between 500 and 600 °C. At 600 °C, the drift of sensors with glasses as solid electrolytes and direct Au glass/glass ceramics contact as reference electrode amounts typically 0.32 mV/d (p(CO₂)=1×10⁻³ bar, p(O₂)=2.1×10⁻¹ bar at the measuring electrode), if a metastable multiphase equilibrium is formed. At identical partial pressures of CO₂ and O₂, the signal reproducibility of these sensors with different solid electrolyte glasses of the same nominal composition lies within 30 mV at 600 °C. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Potentiometric carbon dioxide sensor based on thin Li3PO4 electrolyte and Li2CO3 sensing electrode

Potentiometric CO₂ gas sensors with thin-film lithium phosphate (Li₃PO₄) electrolytes were developed by using radio frequency (RF) magnetron sputtering. Li₂CO₃ and a mixture of Li₂TiO₃ and TiO₂ were used as sensing and reference electrodes, respectively. By using the RF sputtering deposition process, we obtained a dense, crystalline, thin-film Li₃PO₄ electrolyte with good adhesion on the Al₂O₃ substrate. The thin-film Li₃PO₄ electrolyte had good ionic conductivity, i.e., 2.15?×?10^?6 S cm^?1 at 500 °C, and its activation energy was 0.97 eV. The thin-film Li₃PO₄ electrolyte was suitable for the miniaturization of potentiometric CO₂ sensors. The thin-film potentiometric CO₂ sensor provided relatively good sensing response for overall CO₂ concentrations (500 to 3,000 ppm and 5 to 20 %) at 500 °C. The Nernstian slope of 78.2 mV/decade obtained for CO₂ concentrations from 5 to 20 % at 500 °C was close to the theoretical value (76.6 mV/decade). Although the sensor’s reading deviated from the theoretical value at low CO₂ concentrations (500 to 3,000 ppm), the sensor provided better sensing performance than a potentiometric CO₂ sensor with a thick electrolyte. As a result, it was assumed that the thin-film sensor could be used to monitor the overall concentration of CO₂ in the environment.     

Three-dimensionally ordered composite electrode between LiMn2O4 and Li1.5Al0.5Ti1.5(PO4)3

A novel electrode system composed of three-dimensionally ordered macroporous (3DOM) Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) and LiMn₂O₄ was fabricated by the colloidal crystal templating method and sol–gel process. A LATP nanoparticle for the fabrication of 3DOM-LATP was prepared by a sol–gel process. A suspension containing polystyrene (PS) beads and the LATP nanoparticles was filtrated by using a polycarbonate filter to accumulate PS beads and LATP. The accumulated PS beads had a close-packing structure, and the void between PS beads was filled with LATP nanoparticles. 3DOM-LATP was obtained by heat treatment of the accumulated composite. Li–Mn–O sol was injected by a vacuum impregnation process into the macropores of 3DOM-LATP and then was heated to form three-dimensionally ordered composite materials consisting of LiMn₂O₄ and LATP. The formation of the composite between 3DOM-LATP and LiMn₂O₄ were confirmed with scanning electron microscopy and X-ray diffraction method. The prepared composite electrode system exhibited a good electrochemical performance. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Cu-Ce0.8Gd0.2O2−δ materials as SOFC electrolyte and anode

Co-sintering of Cu-CGO cermet anodes on CGO (Ce_0.8Gd_0.2O_2−δ) electrolyte was conducted at low temperature (1000 °C) by introducing small amounts (2 mol.%) of CuO sintering aid to the electrolytic CGO. The Cu-CGO anodes with Cu contents from 20–50 vol.% were prepared by combustion synthesis followed by sintering and reduction. Symmetrical anode/electrolyte/anode assemblies of Cu-GCO/CGO/Cu-CGO were fabricated by manually depositing the anode combustion powder on a green substrate of the 2 mol% CuO-containing CGO, followed by co-pressing and co-sintering of the assembly at 1000 °C. The low-temperature sintered CGO is submicron with 95–99% relative density. CuO addition has no significant effect on either the total or ionic conductivity of the electrolyte, but p-type conduction in the temperature range, 900–1200 °C, is 25 times higher than that of undoped CGO. Oxygen-ion transference numbers of the Cu-containing CGO lie in the range 0.89–0.99, as determined by the modified e.m.f. technique under an oxygen/air potential gradient. The activation energy for ionic conduction, 83 kJmol⁻¹, is significantly lower than that for p-type electronic transport, 140 kJmol⁻¹. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Sub-10 nm V2O5 Crystals on Carbon Nanosheets for Advanced All-Solid-State Lithium Metal Batteries

V₂O₅, as a lithium-free cathode material, has inherent defects such as sluggish kinetics and volume change and, at the same time, requires a lithium metal anode that tends to form dendrites in liquid electrolytes. Both the lithium dendrite and the flammable electrolyte solvent bring longtime safety issues. This work introduces nonflammable inorganic–organic composite solid electrolyte to inhibit the growth of the lithium dendrite and suppress the instability caused by V₂O₅ nanometerization. However, the long-term cycling and rate performances are still insufficient even when reducing V₂O₅ size to about 50 nm. As an improvement, sub-10 nm V₂O₅/C nanosheets are designed and prepared using corn stalks as precursors through simple impregnation and calcination process. The V₂O₅/C offers a much better electrode/electrolyte contact and interface stability than bulk V₂O₅ and commercial V₂O₅ in the inorganic–organic composite solid electrolyte. The discharge capacity is 228 mAh g⁻¹ at 0.1 C after 50 cycles and ≈110 mAh g⁻¹ at 2.0 C.     

IS α-Al2O3/ La0.8Sr0.2Ga0.8Mg0.2O3–δ really a new ionic conductor composite?really a new ionic conductor composite?

The recent interest in the (Sr, Mg) doped LaGaO₃ family compounds as electrolyte for Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFCs) has suggested the study of the system α-Al₂O₃/La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ as a possible new ionic conductor composite. The studies concerning the electrical and microstructural characterization of the system α-Al₂O₃/La_0.8Sr_0.2Ga_0.8Mg_0.2O_3–δ, in a wide compositions range, are reported and discussed. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Electrochemical characterization of a composite polymer electrolyte with improved lithium metal electrode interfacial properties

In the development of rechargeable lithium polymer batteries it is of paramount importance to control the passivation phenomena occurring at the lithium electrode interface. It is well estabilished that the type and the growth of the lithium passivation layer is unpredictably influenced by the presence of liquid components and/or impurities in the electrolyte. Therefore, one approach to improve the stability of the lithium interface is the use of liquid-free, highly pure electrolytes. The electrochemical properties of a composite polymer electrolyte obtained by hot pressing a mixture of polyethylene oxide (PEO), a lithium salt (lithium tetrafluoroborate, LiBF₄) and a powdered ceramic additive (γ-LiAlO₂), will be presented and discussed. The electrochemical characterization included the determination of the ionic conductivity, the anodic break-down voltage and, most importantly, the stability of the lithium metal electrode interface and the lithium stripping-plating process efficiency. The main feature of this dry, true solid-state electrolyte is a very good compatibility with the lithium metal electrode, demonstrated by a very high lithium cycling efficiency, which approaches a value of 99%. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Potentiometric CO2 - sensors with ion - conducting glasses as solid electrolytes

Alkali-ion conducting glasses/glass ceramics of the system Me₂O-A1₂O₃-SiO₂ (Me=Li, Na) were applied as solid electrolytes in potentiometric gas sensors to detect CO₂ in the presence of O₂ at increased temperatures. The corresponding Me-Carbonates were utilized as auxiliary electrodes. Sensors using the direct Au-glass contact as a kind of reference electrode (type I), as well as symmetrical sensors with carbonate phase at the reference and measuring electrode (type II - for comparative measurements) were manufactured. By applying Au as electrode metal, the theoretically expected EMF difference and the observed EMF difference of both sensor types agree quite well with the expected values according to the Nernst equation between 500 and 600 °C (over four orders of magnitude of CO₂ partial pressure (10⁻⁵ – 10⁻¹ bar) at constant O₂ partial pressure (2.1×10⁻¹ bar)). A long time stability of 120 days for sensors of type I with Li glasses has been observed, although evaporation of carbonate phase (Li₂CO₃) was detected under the conditions of sensor application. Sensors of type I (with Li₂CO₃) show thermodynamically unexpected cross-sensitivities to H₂O. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Electrochemical characterization of a lithiated mixed nickel-cobalt oxide (LiNi0.5Co0.5O2) prepared by sol-gel process

Lithiated transition metal oxides having a layered structure and general formula LiMO₂, have been extensively studied as positive electrode active materials for lithium or lithium-ion batteries. In particular, lithium nickel dioxide (LiNiO₂) and lithium cobalt dioxide (LiCoO₂) present a layered structure with high diffusion coefficients for the lithium ion. This latter property is very important in order to realize practical devices having high discharge rates. LiNiO₂, compared with LiCoO₂, has the advantage to be a cheaper material with a higher specific capacity for lithium cycling, but its stability upon cycling can be greatly influenced by the displacement of Ni ions from the Ni layers to the Li planes as the content in lithium is reduced over a certain value. Recently, solid solutions such as LiNi_xCo_1−xO₂ have been proposed to offer a compromise between stability, cost and capacity. In this work we have studied LiNi_0.5Co_0.5O₂ prepared by the Complex Sol-Gel Process (CSGP). The advantage of this procedure toward the solid-state process is the high homogeneity in composition and in particle dimension of the synthesized compounds. The samples have been characterized electrochemically using chronopotentiometric, voltammetric and impedance measurements in liquid electrolyte. The results indicates that CSGP-synthesized LiNi_0.5Co_0.5O₂ shows good cyclability (after 1000 cycles about 2/3 of the initial capacity can still be cycled) only if the anodic potential is limited to about 4.2 V. The quite low values of the specific capacity (∼70 mAh/g at C/1 charge-discharge rate) can be justified by the non-complete calcination reaction, as suggested by X-ray measurements. Kinetic properties have been evaluated by Electrochemical Impedance Spectroscopy measurements, which have shown quite high values for the lithium chemical diffusion coefficient (10⁻⁷÷10⁻⁸ cm²s⁻¹) and its unexpected decrease as deintercalation proceeds from x=0.5 in LiNi_0.5Co_0.5O₂. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Morphological investigations on the solid electrolyte Li3.6Ge0.6V0.4O4 and use in a solid state lithium battery

The development of a solid state thin film lithium battery system needs a detailed investigation of the electrolyte as well as the electrodes. The realisation of a total solid state battery includes the assumption, that the interfacial contact between the electrodes and the electrolyte is as good as possible. The interfacial resistance should be low for an easily intercalation or deintercalation of lithium at the electrodes and the ionic conductivity of the electrolyte should be high. A further critical aspect of the solid state battery is the porosity of the electrodes and the electrolyte. A homogeneous surface coverage and a high density are useful for a high contact concentration between the grains of electrolyte itself and between the electrolyte and the electrodes. As a possible electrolyte we have investigated the system Li₄GeO₄/Li₃VO₄, which we prepared in the stoichiometry Li_3.6 Ge_0.6 V_0.4 O₄. This lithium conducting system shows a high lithium conductivity of about 4 x 10⁻⁵ S/cm at room temperature and higher values at elevated temperatures. The conductivity is the result of interstitial Li cations in the solid state solution. The deposition of the inorganic thin film was done by a spray pyrolysis technique on different substrates. A variety of different substrates were investigated as a function of adhesion and modified surface conditions. The aim is to find a correlation between the substrate and the morphology of the thin film. The temperature of the deposition was varied between 400 and 600 °C. The temperature dependent cristallinity was also studied. Furthermore the change of the unit cell volume and its constants a, b and c has been investigated as a function of temperature by high temperature diffractometry. The thermal expansion coefficient of the electrolyte could be calculated, to examine stresses with various substrates. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

YSZ-cells for potentiometric nitric oxide sensors

Potentiometric sensors based on zirconia can be used for determining gaseous NO at temperatures between 400 and 480 °C. For such mixed potential sensors, NO sensitive electrode materials such as CdMn₂O₄ and V₂O₅ have been described. In order to improve the cell voltage response, composite electrode materials based on V₂O₅-γ-Al₂O₃ were investigated. Sensors employing these materials show a better voltage response and an improved adhesion to the solid electrolyte compared with pure V₂O₅. The optimal temperature was found to be 440 °C. The NO sensitivity is nearly independent on the oxygen partial pressure in the gas. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Investigation of dibutyl phthalate as plasticizer on poly(methyl methacrylate)–lithium tetraborate based polymer electrolytes

Polymer electrolyte membranes, comprising of poly(methyl methacrylate) (PMMA), lithium tetraborate (Li₂B₄O₇) as salt and dibutyl phthalate (DBP) as plasticizer were prepared using a solution casting method. The incorporation of DBP enhanced the ionic conductivity of the polymer electrolyte. The polymer electrolyte containing 70 wt.% of poly(methyl methacrylate)–lithium tetraborate and 30 wt.% of DBP presents the highest ionic conductivity of 1.58 × 10⁻⁷ S/cm. The temperature dependence of ionic conductivity study showed that these polymer electrolytes obey Vogel–Tamman–Fulcher (VTF) type behaviour. Thermogravimetric analysis (TGA) was employed to analyse the thermal stability of the polymer electrolytes. Fourier transform infrared (FTIR) studies confirmed the complexation between poly(methyl methacrylate), lithium tetraborate and DBP.     

Hydroxyl ion conduction in ytterbium-doped strontium cerate at T<580 K in H2O/air atmosphere

Open circuit voltage (OCV) measurements in H₂O/air concentration cells at T<580 K using Yb-doped SrCeO₃ electrolyte indicate that under these conditions, protons are transported through the electrolyte as -ve ions, possibly as hydroxyl (OH⁻) ions. The H⁺ ionic transport, which is generally reported, becomes the dominant mode for H₂O/air concentration cells at temperatures greater than 750 K or when H₂O/air electrodes are replaced by H₂/Ar, and the anomalous OCV sign disappears. The combination of low temperature and the presence of hydrogen and oxygen as provided by the H₂O/air system appears to be necessary for the postulated hydroxyl ion electrode reactions to take place. In addition to OCV measurements, results from impedance spectroscopy are used to provide evidence in support of the suggested hydroxyl ion mode of protonic transport under the specified conditions. These findings are directly relevant in the development of novel humidity sensors in the temperature range 450–580K and is reported in a separate paper in this conference. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

AC Conductivity,XRD and transport properties of melt quenched PbI<Subscript>2</Subscript>–Ag<Subscript>2</Subscript>O–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Composite materials used for electrode and electrolyte materials have been intensely studied in view of their advantages such as higher conductivity and better operational performance compared to their single-phase counterparts. The present work aims at studying the electrical and structural characteristics of a new composite electrolyte namely, (PbI₂) _x  − (Ag₂O–Cr₂O₃)_100−x where x = 5, 10, 15, 20, and 25 mol%, respectively, prepared by the melt quenching technique. The room temperature X-ray diffraction spectra revealed certain crystalline phases in the samples. AC conductivity analysis for all the prepared samples was carried out over the frequency range 1 MHz–20 Hz and in the temperature window 297–468 K. The room temperature conductivity values were calculated to be in the order of 10⁻⁵–10⁻³ Scm⁻¹. An Arrhenius dependence of temperature with conductivity was observed, and the activation energies calculated were found to be in the range 0.27–0.31 eV. Furthermore, the total ionic transport number (t _i) values obtained for all these indicated the ionic nature of this system. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Sol-Gel derived CeO2:TiO2 coatings for electrochromic devices

Thin films of mixed CeO₂-TiO₂ with different Ce/Ti mole ratios were prepared following an alcohol based sol-gel route via the spin coating technique using mixed inorganic-organic [CeCl₃.7H₂O and Ti(OPr)₄] precursors. Ion storage capacity for films obtained from aged sols was observed to be high. Enhanced titanium oxide content improved the insertion capacity of the corresponding films as was evident from inserted charge determined by multiple step chronoamperometric measurements. Electrochemical, optical, structural and thermal performances showed the suitability of the films in an all solid state electrochromic (transmissive) device with tungsten trioxide (WO₃) as electrochromic material and a conductive polymeric electrolyte based on lithium. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.