Polymer-Based Lithium Rechargeable Batteries
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POLYMER-BASED MARINA MASTRAGOSTINO Dipartimento di Bologna, via Selmi 2,
LITHIUM
RECHARGEABLE
BATTERIES
chimica "G.Ciamician", 40126 Bologna (Italy)
Universita'
di
ABSTRACT Solid-state based positive electrolyte investigated.
lithium rechargeable batteries with polypyrroleelectrode materials together with a new polymer designed for room temperature applications are The cyclability and stability data are reported.
INTRODUCTION Polymer electrolytes as well as heterocyclic polymers can easily be prepared in the form of thin films, an attractive feature in advancing the development of new types of flexible plastic-like Li batteries. We first investigated lithium solid-state rechargeable batteries with polybithiophene (pBT) positive electrode at 0 70 C with the PEO2OLiCIO4 "classical" polymer electrolyte [1]. 0 We then tested Li/pBT battery at 25 C with a new polymer electrolyte (PEO-SEO)2eLiClO, [2]. It is based on a complex of PEO and a styrenic macromonomer of PEO (called SEO) with lithium perchlorate, and designed for room temperature
applications
[31.
It is, however, well known that the kinetics of chargedischarge processes of these polymer electrodes are controlled by the ionic movement into the polymer matrix. This is an intrinsec limitation of these electrode materials, especially in the solid state-battery configuration. The cyclability performance of polypyrrole (pPy) electrodes is very different in liquid and s in solid-state configuration [41 [,]although_ the difference isnot so marked with pBT electrodes[] In order to improve the performance of pyrrole-based polymer electrodes in solid-state batteries with PEO-based polymer electrolytes we electrosynthesized "tailor made" substituted polypyrroles with polyether groups [5] . Because of their known cation coordinating properties these groups were expected to enhance the ionic movement into the polymer. In addition the compatibility of ether groups of these polymers with PEObased electrolytes was expected to improve the electrode-electrolyte interface. We then electrosynthesized two substituted polymers, polyN(3-oxabutyl)pyrrole (pNOPy) and polyN- (3, 6-dioxaheptyl) pyrrole
(pNDPy)
.
Electrosynthesis
conditions
and
electrochemical
characterization of these polymer electrode materials, as well as preliminary cyclability and stability data of solidstate Li/pNDPy battery with (PEO-SEO)zoLiClO4 polymer 0 electrolyte at 36 C and at room temperature, are reported and discussed.
Mat. Res. Soc. Symp. Proc. Vol. 210. @1991 Materials Research Society
192
EXPERIMENTAL The synthesis of the monomers N-(3-oxabutyl)pyrrole (NOPy) and N-(3,6-dioxaheptyl)pyrrole (NDPy) are described in ref.6 and the preparation of (PEO-SEO)2oLiClO4 in ref.2. The solidstate batteries were assembled in dry box by sandwiching a Li polymer disk (excess capacity), a thin layer of dried electrolyte (100 um) and a dried film of pyrrole-based polymer. The electrochemical tests were run on a computer-interfaced AMEL instrumentation. RESULTS AND DISCUSSION The pNOPy and PNDPy poly
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