xxiv
List of Figures
Fig. 4.4
Stack of X-ray diffraction (XRD) patterns with fits for samples
made with 15 % excess lithium and heated to 900
◦ C before
quenching to room temperature. For clarity, the second frame
(36–38
◦ ) has scattering intensities scaled by a factor of two,
while the fourth frame (64–67
◦ ) has a different x-scale and
intensities scaled by a factor of five. This same scaling method is
used for Figs. 4.7 and 4.9 ..............................................
53
Fig. 4.5
Hexagonal lattice parameters obtained by quenching
combinatorial samples compared to literature values from
Ref. [18]. The lines are guides for the eye ...........................
54
Fig. 4.6
Calculated crystallite size obtained for samples heated at 800
◦ C
(squares/red lines), and 900
◦ C (diamonds/black lines). Open
symbols/solid lines represent samples cooled by quenching, while
closed symbols/dashed lines are for regular cooling ................
54
Fig. 4.7
Stack of X-ray diffraction (XRD) patterns, along with two-phase
fits, of samples made with 15 % excess lithium and heated to
900
◦ C before cooling at a rate of 1
◦ C/min. The red and blue
dashed lines are guides to the eye in the samples showing two
layered structures coexisting...........................................
55
Fig. 4.8
Hexagonal lattice parameters obtained by heating combinatorial
samples to 900
◦ C in air and then either quenching (open
symbols) or slow cooling (closed symbols). All slow cooled
samples were fit as two layered structures (near the endpoints,
however, one phase always had negligible intensity and so only a
single lattice parameter is included for those compositions).......
55
Fig. 4.9
X-ray diffraction (XRD) patterns obtained by regular cooling
from 900
◦ C with 15 % excess lithium. All fits were made
assuming a single layered phase ......................................
56
Fig. 4.10 Results of the Monte Carlo simulation for the transition metal
layer with x = 0.5 in Li[Li (1−x)/3 Co x Mn (2−2x)/3 ]O 2 such that 50 %
of the atoms are cobalt, 33.3 % are manganese and 16.7 % are
lithium. Results for the simulated slow cool (10000 Monte Carlo
steps at each temperature) are: a Random occupation of sites
(equivalent to β T = 0, or infinite temperature). b β T = 1. c
β T = 5. d The result of the simulated anneal at β T = 1 (100000
Monte Carlo steps)......................................................
57
Fig. 5.1
The phase diagram with red points indicating all compositions
synthesized during the combinatorial studies for regular cooled
samples heated in oxygen. Quenched samples were also made at
these compositions, with minor variations. The axes are Li, Mn,
and Ni metal molar fractions...........................................
62
Fig. 5.2
a The complete phase diagram obtained by quenching from
800
◦ C after heating in oxygen for 3 h. The red lines are
boundaries to the single-phase regions, green dashed lines are
List of Figures
Fig. 4.4
Stack of X-ray diffraction (XRD) patterns with fits for samples
made with 15 % excess lithium and heated to 900
◦ C before
quenching to room temperature. For clarity, the second frame
(36–38
◦ ) has scattering intensities scaled by a factor of two,
while the fourth frame (64–67
◦ ) has a different x-scale and
intensities scaled by a factor of five. This same scaling method is
used for Figs. 4.7 and 4.9 ..............................................
53
Fig. 4.5
Hexagonal lattice parameters obtained by quenching
combinatorial samples compared to literature values from
Ref. [18]. The lines are guides for the eye ...........................
54
Fig. 4.6
Calculated crystallite size obtained for samples heated at 800
◦ C
(squares/red lines), and 900
◦ C (diamonds/black lines). Open
symbols/solid lines represent samples cooled by quenching, while
closed symbols/dashed lines are for regular cooling ................
54
Fig. 4.7
Stack of X-ray diffraction (XRD) patterns, along with two-phase
fits, of samples made with 15 % excess lithium and heated to
900
◦ C before cooling at a rate of 1
◦ C/min. The red and blue
dashed lines are guides to the eye in the samples showing two
layered structures coexisting...........................................
55
Fig. 4.8
Hexagonal lattice parameters obtained by heating combinatorial
samples to 900
◦ C in air and then either quenching (open
symbols) or slow cooling (closed symbols). All slow cooled
samples were fit as two layered structures (near the endpoints,
however, one phase always had negligible intensity and so only a
single lattice parameter is included for those compositions).......
55
Fig. 4.9
X-ray diffraction (XRD) patterns obtained by regular cooling
from 900
◦ C with 15 % excess lithium. All fits were made
assuming a single layered phase ......................................
56
Fig. 4.10 Results of the Monte Carlo simulation for the transition metal
layer with x = 0.5 in Li[Li (1−x)/3 Co x Mn (2−2x)/3 ]O 2 such that 50 %
of the atoms are cobalt, 33.3 % are manganese and 16.7 % are
lithium. Results for the simulated slow cool (10000 Monte Carlo
steps at each temperature) are: a Random occupation of sites
(equivalent to β T = 0, or infinite temperature). b β T = 1. c
β T = 5. d The result of the simulated anneal at β T = 1 (100000
Monte Carlo steps)......................................................
57
Fig. 5.1
The phase diagram with red points indicating all compositions
synthesized during the combinatorial studies for regular cooled
samples heated in oxygen. Quenched samples were also made at
these compositions, with minor variations. The axes are Li, Mn,
and Ni metal molar fractions...........................................
62
Fig. 5.2
a The complete phase diagram obtained by quenching from
800
◦ C after heating in oxygen for 3 h. The red lines are
boundaries to the single-phase regions, green dashed lines are