Lithium　metal　batteries　represent　promising　candidates　for　high-energy-density　batteries,however,many　challenges　must　still　be　overcome,e.g.,interface　instability　and　dendrite　growth.In　this　work,nano　silica　aerogel　was　employed　to　generate　a　hybrid　film　with　high　lithium　ion　conductivity(0.6　mS　cm-1　at　room　temperature)via　an　in　situ　crosslinking　reaction.TOF-SIMS　profile　analysis　has　revealed　conversion　mechanism　of　hybrid　film　to　Li-Si　alloy/LiF　biphasic　interface　layer,suggesting　that　the　Li-Si　alloy　and　LiF-rich　interface　layer　promoted　rapid　Li+transport　and　shielded　the　Li　anodes　from　corrosive　reactions　with　electrolyte-derived　products.When　coupled　with　nickel-cobalt-man-ganese-based　cathodes,the　batteries　achieve　outstanding　capacity　retention　over　1000　cycles　at　1　C.Additionally　the　developed　film　coated　on　Li　enabled　high　coulombic　efficiency(99.5％)after　long-term　cycling　when　coupled　with　S　cathodes.Overall,the　results　presented　herein　confirm　an　effective　strategy　for　the　development　of　high-energy　batteries.