Ionically Conducting Composite Membranes from the Li2O?Al2O3?TiO2?P2O5Glass?Ceramic (original) (raw)

Flexible Light-Weight Lithium-Ion-Conducting Inorganic–Organic Composite Electrolyte Membrane

ACS energy letters, 2017

A fast Li + ion-conducting membrane is the key component behind a successful performance of an aqueous or hybrid Li-air battery. Currently available ceramic ionic conductors are hardly scalable, difficult to seal, brittle and electrochemically unstable against the commonly used catholytes. In this work, an easily scalable high performance hybrid inorganic-organic membrane is realized that consists of NASICON-type Li 1+x Al x Ge 2-x (PO 4) 3 (LAGP) as the fast ion conducting ceramic filler within a high stability polymer blend. The as-prepared hybrid

Preparation and Characterization of Lithium Ion Conducting Glass–Polymer Composites

Chemistry Letters, 2001

Li 3 SbS 4 glass was prepared by a mechanochemical process and a glass-ceramic was prepared by heating the glass above the crystallization temperature. The glass-ceramic had a crystal structure similar to that of γ-Li 3 PS 4. As indicated by the Raman spectra, both electrolytes contained an SbS 4 unit. The conductivity of the pelletized Li 3 SbS 4 glass was 1.5 × 10 −6 S•cm −1 at 25°C, which was higher than that of its glass-ceramic. The amount of H 2 S generated from Li 3 SbS 4 glass in humid air was considerably lower than that from the Li 3 PS 4 glass.

Flexible Ion-Conducting Composite Membranes for Lithium Batteries

The use of metallic lithium anodes enables higher energy density and higher specifi c capacity Li-based batteries. However, it is essential to suppress lithium dendrite growth during electrodeposition. Li-ion-conducting ceramics (LICC) can mechanically suppress dendritic growth but are too fragile and also have low Li-ion conductivity. Here, a simple, versatile, and scalable procedure for fabricating fl exible Li-ion-conducting composite membranes composed of a single layer of LICC particles fi rmly embedded in a polymer matrix with their top and bottom surfaces exposed to allow for ionic transport is described. The membranes are thin (<100 μm) and possess high Li-ion conductance at thicknesses where LICC disks are mechanically unstable. It is demonstrated that these membranes suppress Li dendrite growth even when the shear modulus of the matrix is lower than that of lithium. It is anticipated that these membranes enable the use of metallic lithium anodes in conventional and solidstate Li-ion batteries as well as in future Li S and Li O 2 batteries.

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

Results in Physics

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li 2 O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO 2 ÁxLi 2 OÁ15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800°C followed by thermal annealing at 320°C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li 2 O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 lm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li 2 O in the electrolytes was found to generate some new crystalline phases including hexagonal Li 6 (TeO 6), monoclinic Zn 2 Te 3 O 8 and monoclinic Li 2 Te 2 O 5. The estimated crystallite size of the electrolyte was ranged from %40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li 2 O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li 2 O exhibited the optimum performance with an ionic conductivity %2.4 Â 10 À7 S cm À1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

Characteristics of lithium-ion-conducting composite polymer-glass secondary cell electrolytes

Journal of Power Sources, 2002

A family of lithium-ion-conducting composite polymer-glass electrolytes containing the glass composition 14Li 2 O-9Al 2 O 3-38TiO 2-39P 2 O 5 (abbreviated as (LiAlTiP) x O y) with high ionic conductivity, an excellent electrochemical stability range, and high compatibility with lithium insertion anodes is described. An optimized composition has a room temperature conductivity of 1:7 Â 10 À4 S cm À1 , an Li þ transference number of 0.39, and an electrochemical stability window to þ5.1 V versus Li/Li þ. It also has good interfacial stability under both open-circuit and lithium metal plating-stripping conditions and provides good shelf-life.

Hot-pressed, dry, composite, PEO-based electrolyte membranes: I. Ionic conductivity characterization

Lithium polymer composite electrolytes, formed by a blend of poly(ethylene oxide) (PEO), LiCF 3 SO 3 lithium salt and a selected, nanoparticle ceramic ®ller, were prepared by hot-pressing through a solvent-free procedure. These dry, ionically conducting membranes were characterized in terms of ionic conductivity in the 30±105 8C temperature range. The in¯uences of several parameters such as the temperature, PEO molecular mass, the EO/Li molar ratio, and the nature and the content of ceramic ®ller were carefully evaluated. #

Lithium conducting solid electrolyte Li1+xAlxGe2−x(PO4)3 membrane for aqueous lithium air battery

Solid State Ionics, 2014

We report the preparation and characterization of hybrid inorganic-organic membranes based on NASICON-type Li 1 + x Al x Ge 2 − x (PO 4) 3 (LAGP) as the fast ion conducting ceramic and fast ionic polymeric solid electrolyte PEO: PVDF:LiBF 4 for possible application as Li anode protecting membrane in lithium air batteries. The resulting membranes showed enhanced conductivity of 10 −4 S cm −1 in combination with improved mechanical flexibility when compared to the ceramic along with higher stability in aqueous solutions in comparison with pure polymer.

Solvent-Free Composite PEO-Ceramic Fiber/Mat Electrolytes for Lithium Secondary Cells

Journal of The Electrochemical Society, 2005

Solvent-free composite poly͑ethylene oxide͒ ͑PEO͒-ceramic fiber or mat electrolytes with high ionic conductivity and good interfacial stability have been developed using high-ionic-conductivity La 0.55 Li 0.35 TiO 3 fibers and mats. The conducting ceramic fibers can penetrate the cross section of the electrolyte film to provide long-range lithium-ion transfer channels, thus producing composite electrolytes with high conductivity. In this work, a maximum room-temperature conductivity of 5.0 ϫ 10 Ϫ4 S cm Ϫ1 was achieved for 20 wt % La 0.55 Li 0.35 TiO 3 fiber in a PEO-LiN͑SO 2 CF 2 CF 3) 2 mixture containing 12.5 wt % Li ϩ in PEO. The maximum transference number obtained was 0.7. The ceramic fibers in this composite electrolyte are coated by a very thin PEO layer, which is sufficient to provide good interfacial stability with lithium-ion and lithium-metal anodes.

Dispersion of Li2SO4-LiPO3 glass in LiTi2(PO4)3 matrix: Assessment of enhanced electrical transport

Journal of Alloys and Compounds, 2018

A novel mechanical milling assisted synthesis route has been used to prepare new generation Li þ ion glass-ceramic composites using (i) glassy system 60[Li 2 SO 4 ]-40[LiPO 3 ] (60LSLP) and (ii) Li þ NASICON, i.e., LiTi 2 (PO 4) 3 known as LTP. Effect of compositional alterations, sintering conditions and cooling process on electrical transport has been investigated. Preparation conditions along with compositional alterations have yielded in reporting the best conducting composition. The ionic glass content was varied in (60LSLP) y-(LTP) 100-y matrix for y ¼ 5e20 wt %. It has been observed that various parameters viz. milling time, composition, annealing temperature, time and cooling conditions have a significant impact on ionic transport. The highest in-grain (~2 Â 10 À4 U À1 cm À1) and grain boundary (~1 Â 10 À5 U À1 cm À1) Li þ ion conductivity values at 100 C have been obtained for y ¼ 20 wt%. These have been found to be significantly higher than that of the pristine LTP prepared with similar preparation conditions. Electrical response (Z 00-u) and dielectric relaxation (tan du) investigations suggest that mobile Li þ ions from glassy phase significantly contribute to conductivity. The elemental distribution investigations using Energy Dispersive X-ray Spectroscopy (EDS) mapping on fractured surface suggests homogeneous distribution of LTP and glassy phase in the composite. Cyclic Voltammetry (CV) results reveal no degradation in the electrochemical stability in 20 cycles, and that these composites are potential candidates for Li þ ion all-solid-state battery applications.