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     

CO2/ SOx-sensors with different β“-aluminas as solid electrolytes

Sensors with solid electrolytes provide the possibility of correct and fast measurements of partial pressures of various gases. By modification of the solid electrolyte, sensors with specific performances may be manufactured. Layers of Na⁺-, Li⁺-, Ca²⁺- and Sr²⁺-β“-alumina on top of polycrystalline α-alumina substrates were produced by an in-situ formation process and were used as solid electrolytes for CO₂ and SO_x sensors. Carbonates and sulphates were applied as measuring electrodes and oxidic mixtures of SiO₂ and silicates were used as reference electrodes. The different performance of these sensors was investigated over a wide temperature range and the results were compared with theoretical data. Different solid electrolyte / electrode combinations were applied, which all showed different characteristic cross sensitivities against water and organic components. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Structure property correlation in lithium borophosphate glasses

To investigate the influence of cation mobility variation due to the mixed glass former effect, 0.45Li₂O-(0.55 − x) P₂O₅−x B₂O₃ glasses (0 ≤; x ≤ 0.55) are studied keeping the molar ratio of Li₂O/(P₂O₅ + B₂O₃) constant. Addition of B₂O₃ into lithium phosphate glasses increases the glass transition temperature (T _g) and number density, decreases the molar volume, and generally renders the glasses more fragile. The glass system has been characterised experimentally by XRD, XPS and impedance studies and studied computationally by constant volume molecular dynamics (MD) simulations and bond valence (BV) method to identify the structural variation with increasing the B₂O₃ content, its consequence for Li⁺ ion mobility, as well as the distribution of bridging and non-bridging oxygen atoms. These studies indicate the increase of P-O-B bonds (up to Y = [B₂O₃]/([B₂O₃] + [P₂O₅]) ≈ 0.5 and B-O-B bonds, as well as the decrease of P-O-P bonds and non-bridging oxygens (NBOs) with rising B₂O₃ content. The system with Y ≈ 0.5 exhibits maximum ionic conductivity, 1.0 × 10⁻⁷ S cm⁻¹, with activation energy 0.63 V. Findings are rationalised by a model of structure evolution with varying B₂O₃ content Y and an empirical model quantifying the effect of the various structural building blocks on the ionic conductivity in this mixed glass former system.     

Preparation and characterization of spherical La-doped Li4Ti5O12 anode material for lithium ion batteries

The lithium secondary batteries with high power density need the electrode materials with both high specific capacity and high tap density. An “outer gel” method by TiCl₄ as the raw material has been developed to prepare spherical precursor. High tap density spherical Li₄Ti₅O₁₂ is synthesized by sintering the mixture of precursor and Li₂CO₃. La-doped Li₄Ti₅O₁₂ is also prepared by this method. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, tap density testing, and the determination of the electrochemical properties show that the Li₄Ti₅O₁₂ powders prepared by this method are spherical and exhibits high tap density. La³⁺ dopant improved the electrochemical performance over the pristine Li₄Ti₅O₁₂. It is tested that the tap density of the pristine and La³⁺-doped products is as high as 1.80 and 1.78 g•cm⁻³, respectively. Between 1.0 and 3.0 V versus Li, the initial discharge capacity of the La³⁺ dopant is as high as 161.5 mAh•g⁻¹ at 0.1C rate. After 50 cycles, the reversible capacity is still 135.4 mAh•g⁻¹.     

Optical and IR study of Li2O–CuO–P2O5 glasses

Infrared (IR) and UV spectra of ternary Li₂O–CuO–P₂O₅ glasses in two series Li₂O(65−X)%–CuO(X%)–P₂O₅(35%), X = 20, 30, 40 and Li₂O(55−X)%–CuO(X%)–P₂O₅(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm⁻¹ for P₂O₅(35%) and P₂O₅(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm⁻¹ which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm⁻¹ which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.     

Lithium ion conductive glass and its application to solid state batteries

Three kinds of coin-type battery, In-Li_x / Li_1−xCoO₂, Li_4/3+xTi_5/3O₄ / Li_1−xCoO₂, and Li_2+xFeS₂ / Li_1−xCoO₂, were fabricated with a Li⁺ ion conductive glass as an electrolyte, and their properties were investigated. They show excellent performance thanks to the solid electrolyte. Iron sulfide is found to be an excellent electrode material in solid state rechargeable batteries. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Ion transport studies in zinc/cadmium halide doped silver phosphate glasses

A number of samples of silver phosphate glasses Ag₂O−P₂O₅−Zn/CdX₂ (X=Cl, Br or I) with 1, 5, 10 and 20 mol-% zinc or cadmium halides have been prepared. Control samples of undoped silver phosphate glasses were also prepared. These glasses were characterized by elemental analysis, X-ray diffraction, IR spectra, differential scanning calorimetry, transference number measurements and electrical conductivity studies. These glasses were found to be essentially ionic conductors. The undoped silver phosphate glass (Ag₂O−P₂O₅) has a low σ value in comparison to the doped ones. The conductivity (σ) in the doped glasses increases substantially with increasing concentration of dopant salts Zn/or CdX₂ and as the anions of the dopants are changed from Cl⁻ to I⁻. It is found that the σ values of the ZnX₂ doped glasses are slightly greater than those of the CdX₂ doped ones, and the silver phosphate glasses doped with (20 mol-%) Zn/CdI₂ yielded maximum conductivity. The results have been discussed and explained on the basis of changes in the structure of the glass matrix by the addition of dopant ions of different sizes, IR spectra and thermal studies.     

Structural and electrochemical study on Li(Li1/3Ti5/3)O4 anode material for lithium ion batteries

Chemical and electrochemical studies have shown that various titanium oxides can incorporate lithium in different ratios. Other compounds with a spinel-type structure and corresponding to the spinel oxides LiTi₂O₄ and Li₄Ti₅O₁₂ have been evaluated in rechargeable lithium cells with promising features. The spinel Li[Li_1/3Ti_5/3]O₄ [1–5] compound is a very appealing electrode material for lithium ion batteries. The lithium insertion-deinsertion process occurs with a minimal variation of the cubic unit cell and this assures high stability which may reflect into long cyclability. In addition, the diffusion coefficient of lithium is of the order of 10⁻⁸ cm²s⁻¹ [5] and this suggests fast kinetics which may reflect in high power capabilities. In this work we report a study on the kinetics and the structural properties of the Li[Li_1/3Ti_5/3]O₄ intercalation electrode carried out by: cyclic voltammetry, galvanostatic cycling and in-situ X-ray diffraction. The electrochemical characterization shows that the Li[Li_1/3Ti_5/3]O₄ electrode cycles around 1.56 V vs. Li with a capacity of the order of 130 mAhg⁻¹ which approaches the maximum value of 175 mAhg⁻¹ corresponding to the insertion of 1 equivalent per formula unit. The delivered capacity remains constant for hundred cycles confirming the stability of the host structure upon the repeated Li insertion-deinsertion process. This high structural stability has been confirmed by in situ Energy Dispersion X-ray analysis. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

EPR and Optical Studies of Mo<Superscript>5+</Superscript> Ions in Lithium Molybdoborate Glasses

Electron paramagnetic resonance (EPR) and optical absorption studies of Li₂O–MoO₃–B₂O₃ with varying concentrations of Li₂O, MoO₃ and B₂O₃ have been carried out at room temperature. Two series of glasses, one with constant MoO₃ (CM) and another with constant borate (CB), have been investigated. Characteristic EPR spectra of Mo⁵⁺ have been observed centered around g ≅ 2.00, which are attributed to Mo⁵⁺ ion in an octahedral coordination sphere with an axial distortion. The spectra also show strong dependence on the concentration of Li₂O and B₂O₃. Spin concentrations (N) and magnetic susceptibilities (χ) have been calculated. In the CM series, the N values decrease with increasing Li₂O content up to 30 mol%, while in the CB series variation of N is found to increase initially up to 20 mol%, and with further increase in the Li₂O content the N values tend to decrease. The variation of magnetic susceptibilities is almost similar to that observed with the variation of N. From the optical absorption spectra, an absorption edge (α) has been evaluated. In the CM series, the values of α show a blueshift. On the other hand, in the CB series a redshift is observed. The observed variations in spectral parameters are explained by considering the molybdoborate network. Addition of Li₂O to the CM and CB series results in modification of [MoO_6/2]⁰ → [MoOO_5/2]⁻ and [BO_3/2]⁰ → [BO_4/2]⁻ → [BOO_2/2]⁻ groups, respectively, leading to creation of nonbridging oxygens. The optical basicity of the glasses has been evaluated in both the CM and the CB glasses. The optical basicity can be used to classify the covalent-to-ionic ratios of the glass, since an increasing optical basicity indicates decreasing covalency. It is observed that the covalency between Mo⁵⁺ ions and oxygen ligands increases in the CB series, whereas in the CM series the covalency between Mo⁵⁺ ions and oxygen ligands decreases. Authors' address: R. P. Sreekanth Chakradhar, Glass Technology Laboratory, Central Glass and Ceramic Research Institute, Kolkata 700032, India     

Li4Ti2.5Cr2.5O12 as anode material for lithium battery

Chromium-substituted Li₄Ti₅O₁₂ has been investigated as a negative electrode for future lithium batteries. It has been synthesized by a solid-state method followed by quenching leading to a micron-sized material. The minimum formation temperature of Li₄Ti_2.5Cr_2.5O₁₂ was found to be around 600 °C using thermogravimetric and differential thermal analysis. X-ray diffraction, scanning electron microscopy, cyclic voltammetry (CV), impedance spectroscopy, and charge–discharge cycling were used to evaluate the synthesized Li₄Ti_2.5Cr_2.5O₁₂. The particle size of the powder was around 2–4 μm. CV studies reveal a shift in the deintercalation potential by about 40 mV, i.e., from 1.54 V for Li₄Ti₅O₁₂ to 1.5 V for Li₄Ti_2.5Cr_2.5O₁₂. High-rate cyclability was exhibited by Li₄Ti_2.5Cr_2.5O₁₂ (up to 5  C) compared to the parent compound. The conduction mechanism of the compound was examined in terms of the dielectric constant and dissipation factor. The relaxation time has been evaluated and was found to be 0.07 ms. The mobility was found to be 5.133 × 10⁻⁶ cm² V⁻¹ s⁻¹.     

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     

Pool-Frenkel effect and high frequency dielectric constant determination of semiconducting P2O5-Li2MoO4-Li2O and P2O5-Na2MoO4-Na2O bulk glasses

The ternary 70P₂O₅-10Li₂MoO₄-20Li₂O and 70P₂O₅-10Na₂MoO₄-20Na₂O glasses, prepared by the press-melt quenching technique, were studied at temperatures between 298 and 418 K for their high dc electric field properties. For the above purpose, the effect of a strong electric field on the dc conduction of these amorphous bulk samples was investigated using the gap-type electrode configuration. At low electric fields, the current-voltage (I — V) characteristics have a linear shape, while at high electric fields (> 10³ V/cm), bulk samples show nonlinear effects (nonohmic conduction). Current-voltage curves show increasing departure from Ohm’s law with increasing current density, leading to critical phenomena at a maximum voltage (threshold voltage), known as switching (switch from a low-conduction state to a higher-conduction state at threshold voltage). The Pool-Frenkel high-field effect was observed at electrical fields of about 10³–10⁴ V/cm; then the lowering factor of the potential barrier, the high frequency dielectric constant, and the refractive index of these glasses were determined.      

Structure of zinc-borate low-melting glasses derived from IR spectroscopy data

The IR spectra of glasses of the ZnO—SrO—B₂O₃ system with constant additions of PbO, Al₂O₃, and Li₂O (20 mol. % in sum) were studied. It is established that on replacement of B₂O₃ by ZnO, the structure of the glasses is characterized by the presence of groupings with the bridge bonds B^III— O—B^III, B^III—O—B^IV, B^IV—O—B^IV and end groups B^III— O⁻; ZnO practically exerts no influence on the coordination transition [BO₃] → [BO₄]. At a high content of ZnO, zinc ions are present in both a six-and a four-coordinated state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 778–781, November–December, 2005.     

Investigation of thin film all-solid-state lithium ion battery materials

All-solid-state thin film batteries are feasible by employing Al as anode and LiPON as electrolyte which are subsequently deposited by sputtering. The lithium ion conductivity of ∼ 10⁻⁶ S/cm for the thin film LiPON is in agreement with data reported for bulk material. The high voltage cathode Li₂CoMn₃O₈ could be prepared by forming the compound by the combustion method andsubsequent e-beam evaporation of this material with the addition of 20 wt.-% LiNO₃ at an oxygen partial pressure of 10⁻⁵ mbar. The thin film cells could be operated between 3 and 5 V vs. Al, LiAl. The chemical diffusion coefficient was found to be in the range from 10⁻¹³ to 10⁻¹² cm²/s at room temperature by employing the GIT-technique for the composition x of Li_2-xCoMn₃O₈ in the range from 0.1 to 1.6. Impedance studies of the complete battery system revealed a charge transfer resistance of 290 Θ, a double layer capacity of ∼ 45–70 μF for an electrode area of 6.7 cm² and a rate determining chemical diffusion coefficient in the range from 10⁻¹² to 10⁻¹¹ cm²/s. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002.     

Lithium intercalation in α′-NayV2O5 synthesized via the hydrothermal route

Vanadium bronzes Na_yV₂O₅ are synthesized via the hydrothermal route from a mixture of V₂O₅ and NaOH in the presence of a reducing agent. Fine crystalline powders made of needle-like particles are obtained that exhibit the layered structure typical of the α′-Na_yV₂O₅ phase (y≈1). Electron delocalization arises from a hopping process of unpaired electrons between V⁴⁺ and V⁵⁺. Alkaline cations are intercalated between the oxide layers and discharge curves show that up to one Li⁺ ion per vanadium can be reversibly inserted between the [V₂O₅] layers in the 3.3–0.5 V range. Chemical diffusion coefficient of Li ions in Li_xNaV₂O₅ is found to be dependent on the degree of intercalation. D⁺ varies from 1×10⁻¹⁰ up to 5×10⁻¹⁰ cm²/s for 0≤×≤2. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

Effect of V5+ in the complex Li3xLa2/3−xTiO3-LaPO4 system

Lithium fast ion conductors of the composition Li_0.3La_2/3Ti_0.7P_0.3−xV_xO_3.3 (LTV) based on mixtures of Li_3xLa_2/3−xTiO₃ and LaPO₄ were prepared by solid state reaction at high temperature (≈ 1300 °C). AC impedance measurements indicate total conductivities of about 1 × 10⁻⁴ Scm⁻¹ for compositions of x=0∼0.3 at room temperature with an activation energy of ≈18 kJ·mol⁻¹ in the temperature range from 30 to 400 °C. X-ray powder diffraction patterns showed that the LTV system is composed of Li_3xLa_2/3−xTiO₃ perovskite solid solution and LaP_1−xV_xO₄ solid solution.     

Layered lithium chromium manganese oxide compounds for high capacity electrode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ cathode materials were prepared by the sol-gel process. The structural characterization was carried out by fitting the XRD data by the Rietveld method. The results of X-ray diffraction show that the crystal structure is similar to that of thelayered lithium transition metal oxides (R3-m space group). The particle morphology and size were observed by SEM, and the elemental content was determined by ICP. The electrochemical performance of the cathode was evaluated in the voltage range of 2.0 ∼ 4.9 V with a current density of 7.947 mA/g. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of around 280 mAh/g in cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ was found to be a promising cathode material. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

3D Array of Bi2S3 Nanorods Supported on Ni Foam as a Highly Efficient Integrated Oxygen Electrode for the Lithium‐Oxygen Battery

Bismuth sulfide nanorod array is directly grown on nickel foam (R‐Bi₂S₃/NF) to serve as a completely carbon and binder‐free 3D porous oxygen electrode material for lithium‐oxygen (Li‐O₂) batteries. The synergistic effect of the fast kinetics of electron transport and gas and electrolyte diffusion provided by the continuous free‐standing network structure and the excellent electrocatalytic activity of the bismuth sulfide nanorod array enables outstanding performance of the oxygen electrode. Li‐O₂ battery with the free‐standing R‐Bi₂S₃/NF oxygen electrode exhibits high energy efficiency (78.7%), good rate capability (4464 mA h g⁻¹ at 1500 mA g⁻¹), as well as excellent cyclability (146 cycles) while maintaining a moderate specific capacity of 1000 mA h g⁻¹. The effect of cathodes with different reactant (O₂) and intermediate (LiO₂) adsorbability on the product (Li₂O₂) growth model is studied by first‐principle calculations. The strong O₂ adsorption and weak LiO₂ adsorption on Bi₂S₃ drives the growth of large‐size Li₂O₂ particles via solution growth model. Remarkably, the large‐area pouch‐type Li‐O₂ battery delivers an energy density of 330 Wh kg⁻¹. The present results open up a promising avenue toward developing novel electrode architecture for high‐performance Li‐O₂ batteries through controlling morphology and functionality of porous electrodes.     

Fast ionic conduction in cubic hafnium garnet Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Hf<Subscript>2</Subscript>O<Subscript>12</Subscript>

A new member of the family of garnets with fast lithium ion conduction has been found with the composition Li₇La₃Hf₂O₁₂. The anion arrangement corresponds to the oxygen framework in garnets, e.g., in Ca₃Fe₂Si₃O₁₂. Hafnium is coordinated octahedrally while the lanthanum environment can be described as a distorted cube. Lithium occupies a large number of positions with tetrahedral, trigonal planar, and metaprismatic coordination. Li₇La₃Hf₂O₁₂ shows a lithium bulk ion conductivity of 2.4 × 10⁻⁴ Ω⁻¹ cm⁻¹ at room temperature with an activation energy of 0.29 eV.