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Increasing trends of viscosities can be observed with the rising charge densities of POMs due to the increasing confinement strength on PEG substrate from POMs. Fractional Walden rule is further applied to analyze the viscosity and proton conductivity correlations, and microscopic mechanisms of proton conduction for PEG\u2010POM nanocomposites are revealed: 1) ion transport is highly associated with polymer chain dynamic for POMs concentrations ranging from 10 to 30 % wt.; 2) ionic conduction is largely decoupled from chain dynamic of polymer matrix for concentrations ranging from 40 to 60 % wt. with Walden plots shifted to the superionic regime. The decoupling of proton transport from polymer segment dynamics allows the simultaneous enhancements of the nanocomposites\u2019 mechanical properties and proton conductions, providing guidelines for the rational design of anhydrous proton conductors with integrated functionalities.<\/jats:p>","DOI":"10.1002\/marc.202200227","type":"journal-article","created":{"date-parts":[[2022,6,1]],"date-time":"2022-06-01T10:59:27Z","timestamp":1654081167000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["Decoupling Segmental Dynamics and Ionic Transport for Superionic Anhydrous Proton Conductors of Polyoxometalate\u2010poly(ethylene glycol) Nanocomposites"],"prefix":"10.1002","volume":"44","author":[{"given":"Zhao","family":"Zheng","sequence":"first","affiliation":[{"name":"South China Advanced Institute for Soft Matter Science and Technology &amp; State Key Laboratory of Luminescent Materials and Devices South China 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