The electrochemical properties of a composite solid polymer electrolyte, consisting of poly(ethylene oxide) (PEO)-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and tetraethylene glycol dimethyl ether (TEGDME) was examined as a protective layer between lithium metal and a water-stable lithium ion-conducting glass ceramic of Li 1 +x+y(Ti,Ge) 2？xAl xP 3？ySi yO 12 (LTAP). The lithium ion conductivity and salt diffusion coefficient of PEO 18LiTFSI were dramatically enhanced by the addition of TEGDME. The water-stable lithium electrode with PEO 18LiTFSI-2TEGDME, as the protective layer, exhibited a low and stable electrode resistance of 85 Ω·cm 2 at 60 °C, after 28 days, and low overpotentials of 0.3 V for lithium plating and 0.4 V for lithium stripping at 4.0 mA·cm ？2 and 60 °C. A Li/PEO 18LiTFSI-2TEGDME/LTAP/saturated LiCl aqueous solution/Pt, air cell showed excellent cyclability up to 100 cycles at 2.0 mAh·cm ？2.
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