Sw. Kim et Si. Pyun, Thermodynamic and kinetic approaches to lithium intercalation into a Li1-delta Mn2O4 electrode using Monte Carlo simulation, ELECTR ACT, 46(7), 2001, pp. 987-997
The thermodynamics and kinetics of electrochemical intercalation of lithium
into a Li1 - deltaMn2O4 electrode have been investigated theoretically by
a statistical thermodynamics concept using a Monte Carlo simulation based u
pon the lattice gas model. From the fluctuations in the internal energy and
the number of lithium ions in the grand canonical ensemble, the partial mo
lar internal energy and entropy of lithium ions were obtained theoretically
at a fixed chemical potential. Both theoretical and experimental partial m
olar quantities alike showed a negative deviation from those quantities of
the ideal solution below (1 - delta) = 0.5 and a positive deviation above (
1 - delta) = 0.5. The component diffusivity of lithium ions was calculated
with the aid of a random walk algorithm in the canonical ensemble. From the
combination of the thermodynamic enhancement factor and the component diff
usivity of lithium ions calculated theoretically by introducing the irrever
sible lithium trap sites into the Li1 - deltaMn2O4 electrode, the chemical
diffusivity of lithium ions was determined and compared with that measured
using the galvanostatic intermittent titration technique. From the good coi
ncidence between the chemical diffusivities calculated theoretically and de
termined experimentally, it was inferred that the lithium ions trapped irre
versibly near structural defects disturb locally the ordering of lithium io
ns and hence the chemical diffusion of lithium ions in the ordered phase is
strongly enhanced. (C) 2001 Elsevier Science Ltd. All rights reserved.