84
6 Combinatorial Studies of Compositions Containing Layered Phases . . .
Table 6.1 The lattice parameters obtained for the single-phase corners of the three-phase regions
as well as the average values obtained in the three-phase regions and the standard deviations (σ ).
All values are in Å. The uncertainty for the average lattice parameters is calculated as σ/
√
N where
N is the number of samples
Rocksalt
Spinel
N-layered
M-layered
a
σ
a
σ
a
σ
a
σ
c
c
Quench:
single
8.284 (2)
8.187 (1)
2.909 (1)
2.8543 (6)
phase
14.32 (1)
14.291 (6)
SNM
8.1867 (9) 0.0044 2.9025 (6) 0.0033
2.8553 (2) 0.00093
(26 fits)
14.347 (2) 0.010
14.303 (2) 0.002
RSN
8.284 (3) 0.0097 8.182 (2) 0.0070 2.902 (2) 0.0053
(12 fits)
14.322 (5) 0.017
Slow
cool:
single
8.295 (2)
8.173 (1)
2.907 (1)
2.8516 (8)
phase
14.30 (1)
14.277 (8)
MRS
8.297 (2) 0.0052 8.169 (1) 0.0018
2.8502 (5) 0.0012
(6 fits)
14.280 (6) 0.013
MRN
8.294 (2) 0.0080
2.9013 (4) 0.00014 2.854 (2) 0.0072
(12 fits)
14.312 (4) 0.012
14.25 (1)
0.032
Table 6.2 The coordinates of the four corners of the three-phase regions. All points are (Li, Mn)
Rocksalt
Spinel
N-layered
M-layered
Quench:
single-phase
(0.3, 0.2)
(0.36, 0.5)
(0.4, 0.17)
(0.61, 0.31)
Lever rule
(0.29, 0.20)
(0.36, 0.5)
(0.43, 0.19)
(0.61, 0.31)
Slow cool:
single-phase
(0.22, 0.16)
a
(0.33, 0.5)
(0.4, 0.15)
(0.58, 0.34)
a This point lies midway between the 8.29 and 8.30 Å contour lines on the boundary of the ordered
rocksalt region in Fig. 5.10
Table 6.3 Rietveld results for
bulk samples synthesized at
the R, M, and N corners by
heating in oxygen for 5 h and
quenching to room
temperature. Occupations and
positions of each site are
shown, as well as lattice
parameters in Å
R (Fm3m)
N (R−3m)
M (R−3m)
a
a = 8.2829 (4)
a = 2.916 (1)
a = 2.8574 (5)
c = 14.324 (6)
c = 14.289 (4)
4a: 4.0 Mn
3a: 0.499 Li
3a: 0.708 Li
4b: 3.272 Li
1.134 Mn
1.866 Mn
0.328 Ni
1.367 Ni
3a: 0.426 Ni
0.4 P
8c: 8 O
3b: 2.105 Li
3b: 2.976 Li
24d: 6.084 Li
0.895 Ni
0.024 Ni
2.176 Mn
15.74 Ni
6c: 5.588 O
6c: 6.253 O
24e: 24 O
(0.2564,0,0)
(0.2579,0,0)
(0.2378,0,0)
R B = 1.99 %
1.86 %
2.92 %
a This ignores the superlattice peaks which can be
indexed to the C2/m space group.
6 Combinatorial Studies of Compositions Containing Layered Phases . . .
Table 6.1 The lattice parameters obtained for the single-phase corners of the three-phase regions
as well as the average values obtained in the three-phase regions and the standard deviations (σ ).
All values are in Å. The uncertainty for the average lattice parameters is calculated as σ/
√
N where
N is the number of samples
Rocksalt
Spinel
N-layered
M-layered
a
σ
a
σ
a
σ
a
σ
c
c
Quench:
single
8.284 (2)
8.187 (1)
2.909 (1)
2.8543 (6)
phase
14.32 (1)
14.291 (6)
SNM
8.1867 (9) 0.0044 2.9025 (6) 0.0033
2.8553 (2) 0.00093
(26 fits)
14.347 (2) 0.010
14.303 (2) 0.002
RSN
8.284 (3) 0.0097 8.182 (2) 0.0070 2.902 (2) 0.0053
(12 fits)
14.322 (5) 0.017
Slow
cool:
single
8.295 (2)
8.173 (1)
2.907 (1)
2.8516 (8)
phase
14.30 (1)
14.277 (8)
MRS
8.297 (2) 0.0052 8.169 (1) 0.0018
2.8502 (5) 0.0012
(6 fits)
14.280 (6) 0.013
MRN
8.294 (2) 0.0080
2.9013 (4) 0.00014 2.854 (2) 0.0072
(12 fits)
14.312 (4) 0.012
14.25 (1)
0.032
Table 6.2 The coordinates of the four corners of the three-phase regions. All points are (Li, Mn)
Rocksalt
Spinel
N-layered
M-layered
Quench:
single-phase
(0.3, 0.2)
(0.36, 0.5)
(0.4, 0.17)
(0.61, 0.31)
Lever rule
(0.29, 0.20)
(0.36, 0.5)
(0.43, 0.19)
(0.61, 0.31)
Slow cool:
single-phase
(0.22, 0.16)
a
(0.33, 0.5)
(0.4, 0.15)
(0.58, 0.34)
a This point lies midway between the 8.29 and 8.30 Å contour lines on the boundary of the ordered
rocksalt region in Fig. 5.10
Table 6.3 Rietveld results for
bulk samples synthesized at
the R, M, and N corners by
heating in oxygen for 5 h and
quenching to room
temperature. Occupations and
positions of each site are
shown, as well as lattice
parameters in Å
R (Fm3m)
N (R−3m)
M (R−3m)
a
a = 8.2829 (4)
a = 2.916 (1)
a = 2.8574 (5)
c = 14.324 (6)
c = 14.289 (4)
4a: 4.0 Mn
3a: 0.499 Li
3a: 0.708 Li
4b: 3.272 Li
1.134 Mn
1.866 Mn
0.328 Ni
1.367 Ni
3a: 0.426 Ni
0.4 P
8c: 8 O
3b: 2.105 Li
3b: 2.976 Li
24d: 6.084 Li
0.895 Ni
0.024 Ni
2.176 Mn
15.74 Ni
6c: 5.588 O
6c: 6.253 O
24e: 24 O
(0.2564,0,0)
(0.2579,0,0)
(0.2378,0,0)
R B = 1.99 %
1.86 %
2.92 %
a This ignores the superlattice peaks which can be
indexed to the C2/m space group.