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2009-EEPS Secondary batteries-lithium rechangeable systems Electrolytes Overview
Electrolytes: OverviewFi
of
w
re
elK Xu, U.S. Army Research Laboratory, Adelphi, MD, USA
Published by ElsevierIntroduction
Electrochemistry is the science of controlled redox re-
actions proceeding at various electrolyte–electrode inter-
faces. In electrochemical power sources, these interfaces
are responsible for the sustainable operation of the devices
not only by preventing parasitic reactions between the
electrolyte components and the strongly oxidative or re-
ductive electrodes but also by exerting critical controls on
the reaction kinetics, especially at high rates or low tem-
peratures. Focusing on the cell chemistries based on lith-
ium, this article describes how the selection of electrolyte
components (salts, solvents, and additives) dictates the
formation chemistry, and consequently affects the physi-
cochemical properties of these interfaces on both negative
and positive electrode materials. Approaches to tailor the
surface chemistries are also summarized.Zn Zn2+
Site and direction of
electron exchange
(a) (b
gure 1 The difference between a chemical and an electrochemica
Daniell’s cell is used as an example eCu2tSO42 t ZnZn2tSO4
here chaotic collision between reactants is accompanied by disorder
actants localizes the electron exchange sites to the two electrolyte
ectrons through an external circuit.What Is Electrolyte?
In electrochemistry, redox reactions are forced to pro-
ceed in such a manner that there are no direct electron
exchanges between the reactants amid their chaotic col-
lisions (Figure 1(a)). Instead, the oxidant (positive elec-
trode or cathode) and reductant (negative electrode or
anode) are physically separated by an electronic barrier,
so that, during the reaction, the interfaces between the
barrier and the two electrodes are the only locations
where electron exchanges can occur, thus producing a
steady orientation flow of electrons via an external circuit
(Figure 1(b)). An electrochemical cell is a reactor for
such controlled redox re
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