The seminal research by Wright et al. on polyethylene oxide (PEO) solid polymer electrolyte (SPE) generated intense interest in all solid-state rechargeable lithium batteries. Following this a number of researchers have studied the physical, electrical and transport properties of thin film PEO electrolyte containing Li salt. These studies have clearly identified the limitations of the PEO electrolyte. Chief among the limitations are a low cation transport number (t(+)), high crystallinity and segmental motion of the polymer chain, which carries the cation through the bulk electrolyte. While low t(+) leads to cell polarization and increase in cell resistance high T-g reduces conductivity at and around room temperatures. For example, the conductivity of PEO electrolyte containing lithium salt is < 10(-7) S cm(-1) at room temperature. Although modified PEO electrolytes with lower T-g exhibited higher conductivity (similar to 10(-5) S cm(-1) at RT) the t(+) is still very low similar to 0.25 for lithium ion. Numerous other attempts to improving t(+) have met with limited success. The latest approach involves integrating nano domains of inorganic moieties, such as silcate, alumosilicate, etc. within the polymer component. This approach yields an inorganic-organic component (OIC) based polymer electrolyte with higher conductivity and t(+) for Li+. This paper describes the improved electrical and electrochemical properties of OIC-based polymer electrolyte and cells containing Li anode with either a TiS2 cathode or Mag-10 carbon electrode. Several solid polymer electrolytes derived from silicate OIC and salt-in-polymer constituent based on Li triflate (LiTf) and PEO are studied. A typical composition of the SPE investigated in this work consists of 600 kDa PEO, lithium triflate (LiTf, LiSO3CF3) and 55% of silicate based on (3-glycidoxypropyl)trimethoxysilane and tetramethoxysilane at molar ratio 4:1 and 0.65 mol% of aluminum(tri-sec-butoxide) (GTMOS-A11-900k-55%). Several pouch cells consisting of Li/OIC-based-SPE/cathode containing OIC-based-SPE-LiTf binder were fabricated and tested, these cells are called modified cells. The charge/discharge and impedance characteristics of the new cells (also called modified cells) are compared with that of the pouch cells containing the conventional PEO-LiTf electrolyte as the cathode binder, these cells are called non-modified cells. The new cells can be charged and discharged at 70 degrees C at higher currents. However, the old cells can be charged and discharged only at 80 degrees C or above and at lower currents. The cell impedance for the new cells is much lower than that for the old cells. (c) 2005 Elsevier B.V. All rights reserved.