Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes

Yangyang Wang; Fei Fan; Alexander L. Agapov; Tomonori Saito; Jun Yang; Xiang Yu; Kunlun Hong; Jimmy Mays; Alexei P. Sokolov

doi:10.1016/j.polymer.2014.06.085

Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes

Yangyang Wang, Fei Fan, Alexander L. Agapov, Tomonori Saito, Jun Yang, Xiang Yu, Kunlun Hong, Jimmy Mays, Alexei P. Sokolov

Soft Materials and Membranes

Research output: Contribution to journal › Article › peer-review

147 Scopus citations

Abstract

Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with "superionic" conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes.

Original language	English
Pages (from-to)	4067-4076
Number of pages	10
Journal	Polymer
Volume	55
Issue number	16
DOIs	https://doi.org/10.1016/j.polymer.2014.06.085
State	Published - Aug 5 2014

Funding

The authors thank Dr. M. Nakanishi for providing the data of electrical conductivity of the lithium chloride solution. T.S., J.M. and A.P.S. acknowledge the financial support from the Division of Materials Science and Engineering, U.S. Department of Energy, Office of Basic Energy Sciences . The polymer synthesis was partly conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy . F.F. thanks the NSF Polymer Program ( DMR-1104824 ) for funding.

Funders	Funder number
Division of Materials Science and Engineering
Office of Basic Energy Sciences
Scientific User Facilities Division
National Science Foundation	DMR-1104824
U.S. Department of Energy
Oak Ridge National Laboratory

Keywords

Decoupling
Ionic transport
Polymer electrolytes

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10.1016/j.polymer.2014.06.085

Cite this

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title = "Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes",

abstract = "Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with {"}superionic{"} conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes.",

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AU - Wang, Yangyang

AU - Fan, Fei

AU - Agapov, Alexander L.

AU - Saito, Tomonori

AU - Yang, Jun

AU - Yu, Xiang

AU - Hong, Kunlun

AU - Mays, Jimmy

AU - Sokolov, Alexei P.

PY - 2014/8/5

Y1 - 2014/8/5

N2 - Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with "superionic" conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes.

AB - Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with "superionic" conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes.

KW - Decoupling

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KW - Polymer electrolytes

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Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes

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