Single lithium-ion conducting poly(tetrafluorostyrene sulfonate) – polyether block copolymer electrolytes

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Single lithium-ion conducting poly(tetrafluorostyrene sulfonate) – polyether block copolymer electrolytes. / Shao, Zhecheng; Jannasch, Patric.

In: Polymer Chemistry, Vol. 8, No. 4, 2017, p. 785–794.

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T1 - Single lithium-ion conducting poly(tetrafluorostyrene sulfonate) – polyether block copolymer electrolytes

AU - Shao, Zhecheng

AU - Jannasch, Patric

N1 - Received 31 Oct 2016, Accepted 12 Dec 2016 First published online 13 Dec 2016

PY - 2017

Y1 - 2017

N2 - Solid single-ion conducting polymers continue to attract a significant interest as electrolyte materials with a great potential to improve safety and performance of energy storage devices. Still, their low conductivity is a significant hurdle presently preventing their application. Here, we report on highly conductive BAB triblock copolymers with A blocks of either poly(ethylene oxide) (PEO) or poly(ethylene oxide-co-propylene oxide) (PEOPO), and B blocks of poly(lithium 2,3,5,6-tetrafluorostyrene-4-sulfonate) (PPFSLi). The copolymers were conveniently synthesised by atom transfer radical polymerisation (ATRP) of 2,3,4,5,6-pentafluorostyrene from polyether macroinitiators, followed by quantitative thiolation using NaSH and subsequent oxidation to form the sulfonate anions. The copolymers possessed high thermal stability and their ionic content was conveniently controlled by the block ratio during the ATRP. Above the polyether melting point, a PEO-based block copolymers with [O]:[Li] = [18]:[1] showed the highest conductivity, close to 1.4×10-5 S cm-1 at 60 ˚C, while at lower temperatures, a PEOPO-material reached the highest conductivity, nearly 1.5×10-6 S cm-1 at 20 ˚C. The high conductivity of the former copolymer suggests weak interactions of the lithium ions with the pentafluorosulfonate anions in combination with a degree of Li+ dissociation facilitated by PEO. The results of the present study demonstrate that well-designed block copolymers containing lithium pentafluorostyrene sulfonate units can approach the levels of conductivity required for high-temperature lithium battery applications.

AB - Solid single-ion conducting polymers continue to attract a significant interest as electrolyte materials with a great potential to improve safety and performance of energy storage devices. Still, their low conductivity is a significant hurdle presently preventing their application. Here, we report on highly conductive BAB triblock copolymers with A blocks of either poly(ethylene oxide) (PEO) or poly(ethylene oxide-co-propylene oxide) (PEOPO), and B blocks of poly(lithium 2,3,5,6-tetrafluorostyrene-4-sulfonate) (PPFSLi). The copolymers were conveniently synthesised by atom transfer radical polymerisation (ATRP) of 2,3,4,5,6-pentafluorostyrene from polyether macroinitiators, followed by quantitative thiolation using NaSH and subsequent oxidation to form the sulfonate anions. The copolymers possessed high thermal stability and their ionic content was conveniently controlled by the block ratio during the ATRP. Above the polyether melting point, a PEO-based block copolymers with [O]:[Li] = [18]:[1] showed the highest conductivity, close to 1.4×10-5 S cm-1 at 60 ˚C, while at lower temperatures, a PEOPO-material reached the highest conductivity, nearly 1.5×10-6 S cm-1 at 20 ˚C. The high conductivity of the former copolymer suggests weak interactions of the lithium ions with the pentafluorosulfonate anions in combination with a degree of Li+ dissociation facilitated by PEO. The results of the present study demonstrate that well-designed block copolymers containing lithium pentafluorostyrene sulfonate units can approach the levels of conductivity required for high-temperature lithium battery applications.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85010495325&origin=inward&txGid=E84D672523BFDA75682962CA307152F6.wsnAw8kcdt7IPYLO0V48gA%3a54

U2 - 10.1039/C6PY01910B

DO - 10.1039/C6PY01910B

M3 - Article

VL - 8

SP - 785

EP - 794

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 4

ER -