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Published June 2013 | public
Journal Article

First-Order Disordered-to-Lamellar Phase Transition in Lithium Salt-Doped Block Copolymers


We study the microphase separation of block copolymer electrolytes containing lithium salts. Taking poly(ethylene oxide)-b-polystyrene (PEO-b-PS) as an example, we show that in the presence of lithium salts the disordered-to-lamellar phase transition becomes first-order even at the level of mean-field theory, with a moderate range of temperature in which both the disordered and lamellar phases coexist, and different salt concentration in the coexisting phases. The coexistence arises from the different partitioning of the salt ions between the disordered phase and the lamellar phase, driven primarily by the solvation energy of anions. A striking consequence of the coexistence is that heating a lamellar phase into the coexistence region leads to increased order in the remaining lamellar phase.

Additional Information

© 2013 American Chemical Society. Received: March 22, 2013; Accepted: May 13, 2013; Published: May 16, 2013. This research has been supported by the National Science Foundation, Grants No. CBET-0965812 and No. CHE-1040558.

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