List of Figures
Fig. 1.1
The Li–Co–Mn–Ni–O pseudo-quaternary system of extreme
interest for potential positive electrode materials. The blue lines
indicate the axes, while the red dots represent a few of the
single-phase materials known prior to the current study. The
single-phase regions along the Li–Co–Mn and Li–Mn–Ni faces
are shown and are the results of this project for samples quenched
from 800
◦ C and the red lines bound three-phase regions ..........
3
Fig. 1.2
Structure of a layered lithium metal oxide along the 001
projection (a) and the 110 projection (b). c Structure of a cubic
spinel along the 110 projection showing the lithium atoms in the
tunnels. The bonds between transition metal atoms and oxygen
atoms are shown as well as the edges of the unit cell. The
octahedra shown in c have a transition metal atom at the center
and six oxygen atoms at the corners ..................................
4
Fig. 1.3
The Li–Co–Mn–O pseudo-ternary system with single-phase
materials known prior to the combinatorial studies discussed
here. The red symbols indicate layered oxides while the green
and blue are cubic and tetragonal spinels, respectively, and the
black circle represents bixbyite Mn 2 O 3 . The lithium corner is
labeled as Li as no stable solid phases are seen here as lithium is
gradually lost during synthesis ........................................
6
Fig. 1.4
Stack of XRD patterns for various values of x along the line from
Li 2 MnO 3 (x = 0) to LiCoO 2 (x = 1). Vertical offsets are applied
for clarity, as is the practice throughout this thesis. (Reprinted
from Ref. [18] with permission from Elsevier)......................
7
Fig. 1.5
a A hexagonal array of atoms as seen in layered Li–Mn–Ni
oxides as would be obtained for a disordered transition metal
layer where every site is randomly occupied by Ni, Mn, and/or
Li. The red dashed lines indicate the unit cell. b A transition
metal layer showing ordering where one third of the sites are red
(e.g., lithium in Li 2 MnO 3 ) and the other two thirds are blue (e.g.,
manganese in Li 2 MnO 3 ). The red dashed lines show the
monoclinic unit cell necessary to describe the structure............
7
xix
Fig. 1.1
The Li–Co–Mn–Ni–O pseudo-quaternary system of extreme
interest for potential positive electrode materials. The blue lines
indicate the axes, while the red dots represent a few of the
single-phase materials known prior to the current study. The
single-phase regions along the Li–Co–Mn and Li–Mn–Ni faces
are shown and are the results of this project for samples quenched
from 800
◦ C and the red lines bound three-phase regions ..........
3
Fig. 1.2
Structure of a layered lithium metal oxide along the 001
projection (a) and the 110 projection (b). c Structure of a cubic
spinel along the 110 projection showing the lithium atoms in the
tunnels. The bonds between transition metal atoms and oxygen
atoms are shown as well as the edges of the unit cell. The
octahedra shown in c have a transition metal atom at the center
and six oxygen atoms at the corners ..................................
4
Fig. 1.3
The Li–Co–Mn–O pseudo-ternary system with single-phase
materials known prior to the combinatorial studies discussed
here. The red symbols indicate layered oxides while the green
and blue are cubic and tetragonal spinels, respectively, and the
black circle represents bixbyite Mn 2 O 3 . The lithium corner is
labeled as Li as no stable solid phases are seen here as lithium is
gradually lost during synthesis ........................................
6
Fig. 1.4
Stack of XRD patterns for various values of x along the line from
Li 2 MnO 3 (x = 0) to LiCoO 2 (x = 1). Vertical offsets are applied
for clarity, as is the practice throughout this thesis. (Reprinted
from Ref. [18] with permission from Elsevier)......................
7
Fig. 1.5
a A hexagonal array of atoms as seen in layered Li–Mn–Ni
oxides as would be obtained for a disordered transition metal
layer where every site is randomly occupied by Ni, Mn, and/or
Li. The red dashed lines indicate the unit cell. b A transition
metal layer showing ordering where one third of the sites are red
(e.g., lithium in Li 2 MnO 3 ) and the other two thirds are blue (e.g.,
manganese in Li 2 MnO 3 ). The red dashed lines show the
monoclinic unit cell necessary to describe the structure............
7
xix