List of Figures
xxi
Fig. 1.14 A partial Li–Mn–Ni–O diagram showing the spinel and layered
phases known prior to this work (solid lines). The red dashed
lines indicate tie-lines one might expect assuming a two-phase
region exists. These tie-lines are refined considerably during this
study and are used here only for illustration .........................
16
Fig. 2.1
The PixSis solution-dispensing robot used to make all
combinatorial samples in this thesis. The three ceramic tips are
pulling solutions from the vials in preparation for a dispense onto
the partially filled alumina plate.......................................
20
Fig. 2.2
a The PixSis solution-dispensing robot making samples with
lithium and nickel. Spinel samples at various stages of synthesis.
b After drying overnight. c After heating to 300
◦ C. d After
heating to 800
◦ C in oxygen ...........................................
20
Fig. 2.3
The Li–Mn–Ni oxide triangle illustrating how samples are
synthesized over entire composition range in a ternary system....
22
Fig. 2.4
a The X-Ray diffraction (XRD) image obtained after stitching
three frames together for a spinel sample. b The result of
integrating along the arcs while the vertical lines correspond to
LiNi 0.5 Mn 1.5 O 4 spinel (JCPDS #80-2162)...........................
24
Fig. 2.5
Williamson–Hall plot for corundum obtained with the Bruker
XRD machine with a beam spot of 0.5 mm. The solid line is a
linear fit and is used to define the machine broadening. Dashed
lines are obtained assuming peaks are Gaussian and using the
Scherrer equation to describe the size broadening. The
dotted–dashed line is obtained similarly, assuming an infinite
crystallite with a strain of 1.0x10
−3 ...................................
27
Fig. 2.6
The fit obtained for a combinatorial sample of LiNiO 2 . This
reflects the quality of fit typically obtained for XRD scans of the
combinatorial samples taken with the Bruker diffractometer. For
clarity, only every third data point is included as closed circles
while the result of the fit is shown as a solid line and the
difference plot is shown below ........................................
27
Fig. 2.7
a A section of the Li–Ni–Mn–O phase diagram showing
previously known single-phase regions. Red dashed lines
represent proposed tie-lines. b An illustration of how lattice
parameter values can be used to determine the direction of
tie-lines in two-phase regions. c A schematic of using the lever
rule in a two-phase region to determine the location of a point B
on the boundary of the single-phase region (e.g. if a is correct,
point B should be Li 2 MnO 3 )...........................................
28
Fig. 2.8
A schematic of the components used in making a typical coin cell
for electrochemical testing .............................................
30
xxi
Fig. 1.14 A partial Li–Mn–Ni–O diagram showing the spinel and layered
phases known prior to this work (solid lines). The red dashed
lines indicate tie-lines one might expect assuming a two-phase
region exists. These tie-lines are refined considerably during this
study and are used here only for illustration .........................
16
Fig. 2.1
The PixSis solution-dispensing robot used to make all
combinatorial samples in this thesis. The three ceramic tips are
pulling solutions from the vials in preparation for a dispense onto
the partially filled alumina plate.......................................
20
Fig. 2.2
a The PixSis solution-dispensing robot making samples with
lithium and nickel. Spinel samples at various stages of synthesis.
b After drying overnight. c After heating to 300
◦ C. d After
heating to 800
◦ C in oxygen ...........................................
20
Fig. 2.3
The Li–Mn–Ni oxide triangle illustrating how samples are
synthesized over entire composition range in a ternary system....
22
Fig. 2.4
a The X-Ray diffraction (XRD) image obtained after stitching
three frames together for a spinel sample. b The result of
integrating along the arcs while the vertical lines correspond to
LiNi 0.5 Mn 1.5 O 4 spinel (JCPDS #80-2162)...........................
24
Fig. 2.5
Williamson–Hall plot for corundum obtained with the Bruker
XRD machine with a beam spot of 0.5 mm. The solid line is a
linear fit and is used to define the machine broadening. Dashed
lines are obtained assuming peaks are Gaussian and using the
Scherrer equation to describe the size broadening. The
dotted–dashed line is obtained similarly, assuming an infinite
crystallite with a strain of 1.0x10
−3 ...................................
27
Fig. 2.6
The fit obtained for a combinatorial sample of LiNiO 2 . This
reflects the quality of fit typically obtained for XRD scans of the
combinatorial samples taken with the Bruker diffractometer. For
clarity, only every third data point is included as closed circles
while the result of the fit is shown as a solid line and the
difference plot is shown below ........................................
27
Fig. 2.7
a A section of the Li–Ni–Mn–O phase diagram showing
previously known single-phase regions. Red dashed lines
represent proposed tie-lines. b An illustration of how lattice
parameter values can be used to determine the direction of
tie-lines in two-phase regions. c A schematic of using the lever
rule in a two-phase region to determine the location of a point B
on the boundary of the single-phase region (e.g. if a is correct,
point B should be Li 2 MnO 3 )...........................................
28
Fig. 2.8
A schematic of the components used in making a typical coin cell
for electrochemical testing .............................................
30