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Despite the emergence of sulphide, oxide, and halide\u2010based solid electrolytes for all\u2010solid\u2010state batteries, their utilization is hampered by issues, including the evolution of H<jats:sub>2<\/jats:sub>S gas, the need for expensive elements, and poor contact. Here, we first introduce Prussian Blue analogue (PBA) open\u2010framework structures as a solid electrolyte that demonstrates appreciable Na<jats:sup>+<\/jats:sup> conductivity (&gt;10<jats:sup>\u22122<\/jats:sup>mS\u2009cm<jats:sup>\u22121<\/jats:sup>). We delve into the relationship between Na<jats:sup>+<\/jats:sup> conductivity and the lattice parameter of N\u2010coordinated transition metal, which is attributed to the reduced interaction between Na<jats:sup>+<\/jats:sup> and the framework, corroborated by the distribution of relaxation times and density functional theory calculations. Among the five PBAs studied, Mn\u2010PBA have exhibited the highest Na<jats:sup>+<\/jats:sup> conductivity of 9.1\u00d710<jats:sup>\u22122<\/jats:sup>mS\u2009cm<jats:sup>\u22121<\/jats:sup>. Feasibility tests have revealed that Mn\u2010PBA have maintained a cycle retention of 95.1\u2009% after 80cycles at 30\u2009\u00b0C and a C\u2010rate of 0.2C. Our investigation into the underlying mechanisms that play a significant role in governing the conductivity and kinetics of these materials contributes valuable insights for the development of alternative strategies to realize all\u2010solid\u2010state batteries.<\/jats:p>","DOI":"10.1002\/ange.202309852","type":"journal-article","created":{"date-parts":[[2023,8,28]],"date-time":"2023-08-28T08:11:24Z","timestamp":1693210284000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Prussian Blue\u2010Type Sodium\u2010ion Conducting Solid Electrolytes for All Solid\u2010State Batteries"],"prefix":"10.1002","volume":"135","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1023-5826","authenticated-orcid":false,"given":"Taewon","family":"Kim","sequence":"first","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sang","family":"Hyeok Ahn","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"You\u2010Yeob","family":"Song","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Korea Advanced Institute of Science and Technology (KAIST)  Daejeon 34141 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Beom","family":"Jin Park","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chanhee","family":"Lee","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ahreum","family":"Choi","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Min\u2010Ho","family":"Kim","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dong\u2010Hwa","family":"Seo","sequence":"additional","affiliation":[{"name":"Department of Materials Science and Engineering Korea Advanced Institute of Science and Technology (KAIST)  Daejeon 34141 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sung\u2010Kyun","family":"Jung","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9074-1619","authenticated-orcid":false,"given":"Hyun\u2010Wook","family":"Lee","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering Ulsan National Institute of Science and Technology (UNIST)  Ulsan 44919 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,9,7]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/nenergy.2016.71"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1038\/35104644"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500192f"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201200026"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0TA07358J"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.0c03022"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2TA00329E"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41560-017-0033-8"},{"key":"e_1_2_7_9_1","doi-asserted-by":"crossref","unstructured":"K. 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