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Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO<jats:sub>2<\/jats:sub>(-ACl)-A<jats:sub>2<\/jats:sub>ZrCl<jats:sub>6<\/jats:sub> (A\u2009=\u2009Li or Na) that demonstrate improved ionic conductivities at 30\u2009\u00b0C, from 0.40 to 1.3\u2009mS cm<jats:sup>\u22121<\/jats:sup> and from 0.011 to 0.11\u2009mS cm<jats:sup>\u22121<\/jats:sup> for Li<jats:sup>+<\/jats:sup> and Na<jats:sup>+<\/jats:sup>, respectively, compared to A<jats:sub>2<\/jats:sub>ZrCl<jats:sub>6<\/jats:sub>, and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li<jats:sub>2<\/jats:sub>O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and <jats:sup>6<\/jats:sup>Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li<jats:sub>2<\/jats:sub>ZrCl<jats:sub>6<\/jats:sub>, the fluorinated ZrO<jats:sub>2<\/jats:sub>\u22122Li<jats:sub>2<\/jats:sub>ZrCl<jats:sub>5<\/jats:sub>F HNSE shows improved high-voltage stability and interfacial compatibility with Li<jats:sub>6<\/jats:sub>PS<jats:sub>5<\/jats:sub>Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li<jats:sup>+<\/jats:sup> conductivity. We also report the assembly and testing of a Li-In||LiNi<jats:sub>0.88<\/jats:sub>Co<jats:sub>0.11<\/jats:sub>Mn<jats:sub>0.01<\/jats:sub>O<jats:sub>2<\/jats:sub> all-solid-state lab-scale cell operating at 30\u2009\u00b0C and 70\u2009MPa and capable of delivering a specific discharge of 115\u2009mAh g<jats:sup>\u22121<\/jats:sup> after almost 2000 cycles at 400\u2009mA\u2009g<jats:sup>\u22121<\/jats:sup>.<\/jats:p>","DOI":"10.1038\/s41467-023-38037-z","type":"journal-article","created":{"date-parts":[[2023,4,28]],"date-time":"2023-04-28T15:02:04Z","timestamp":1682694124000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":222,"title":["Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries"],"prefix":"10.1038","volume":"14","author":[{"given":"Hiram","family":"Kwak","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jae-Seung","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daseul","family":"Han","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jong Seok","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juhyoun","family":"Park","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7963-2136","authenticated-orcid":false,"given":"Gihan","family":"Kwon","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1626-5949","authenticated-orcid":false,"given":"Seong-Min","family":"Bak","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Unseon","family":"Heo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1269-7581","authenticated-orcid":false,"given":"Changhyun","family":"Park","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9074-1619","authenticated-orcid":false,"given":"Hyun-Wook","family":"Lee","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6278-6369","authenticated-orcid":false,"given":"Kyung-Wan","family":"Nam","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7200-7186","authenticated-orcid":false,"given":"Dong-Hwa","family":"Seo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0357-9508","authenticated-orcid":false,"given":"Yoon Seok","family":"Jung","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2023,4,28]]},"reference":[{"key":"38037_CR1","doi-asserted-by":"publisher","first-page":"1167","DOI":"10.1021\/ja3091438","volume":"135","author":"JB Goodenough","year":"2013","unstructured":"Goodenough, J. 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