The fact base

The fact base: 12 materials

Every structural, compositional and electrochemical number the thesis gives for each material, transcribed from Tables II.3–II.10, III.1–III.2 and Chapter IV of the revised manuscript, with the quantities derived here: c/a and volume recomputed, lithium per formula unit from the ICP, and the Ni\(^{2}\)⁺ that charge balance requires. The source is data/compositions.yml, written by analysis/facts.py.

c/a recomputed from a and c; V as printed, flagged where a and c give another value. Li/Ni: refined antisite disorder, given for two materials only. Li (ICP): Li per transition metal from Table II.4. Ni\(^{2}\)⁺: per formula unit, required by charge balance with Co\(^{3}\)⁺, Mn\(^{4}\)⁺, Al\(^{3}\)⁺, Fe\(^{3}\)⁺, Sb\(^{5}\)⁺, Mg\(^{2}\)⁺, Y\(^{3}\)⁺, La\(^{3}\)⁺, Sc\(^{3}\)⁺, Na⁺. Q₁: initial discharge capacity (mAh g\(^{-1}\), 0.1 C, 2.5–4.5 V); ICE: initial Coulombic efficiency; retention after 200 cycles (Tables III.1–III.2, §III.6).

Material	Nominal formula	a (Å)	c (Å)	c/a	V (Å³)	Table	I(003)/I(104)	Li/Ni (%)	Li (ICP)	Ni\(^{2}\)⁺ (charge)	Q₁ · ICE · retention
Pristine NCA Co reduction (II.6.1)	LiNi0.8Co0.15Al0.05O2	2.8815	14.2229	4.936	102.27	II.3, II.5	1.05	—	0.932	0	128 · 63 % · 87.9 %
5 % Mn–NCA Co reduction (II.6.1)	LiNi0.8Co0.1Mn0.05Al0.05O2	2.8817	14.2232	4.936	102.29	II.3	—	—	0.924	0.05	—
10 % Mn–NCA Co reduction (II.6.1)	LiNi0.8Co0.05Mn0.1Al0.05O2	2.899	14.3274	4.942	104.28	II.3	—	—	0.917	0.1	—
Pristine NMA Co reduction (II.6.1) · reference of II.6.3–II.6.5	LiNi0.8Mn0.15Al0.05O2	2.9042	14.3489	4.941	104.58 ≠ 104.81	II.3	1.2	3.5	0.908	0.15	147 · 98 % · 76.53 %
		2.86	14.3	5.000	101.3	II.7, II.9
		2.86	14.3	5.000	102.6 ≠ 101.3	II.8
Fe/Sb–NCA Fe/Sb co-doping (II.6.2)	LiNi0.8Co0.05Fe0.05Sb0.05Al0.05O2	2.882	14.2485	4.944	102.49	II.5	1.3	—	—	0.1	143.5 · 88.31 % · 87.11 %
Mg–NMA Multi-cation substitution (II.6.3)	LiNi0.8Mn0.12Mg0.03Al0.05O2	2.852	14.31	5.018	100.83	II.7	1.28	—	—	0.09	138 · 81.56 % · 71.01 %
Y–NMA Multi-cation substitution (II.6.3)	LiNi0.8Mn0.12Y0.03Al0.05O2	2.86	14.35	5.018	101.65	II.7	1.35	—	—	0.12	182 · 94.15 % · 92.86 %
La–NMA Multi-cation substitution (II.6.3)	LiNi0.8Mn0.12La0.03Al0.05O2	2.892	14.52	5.021	105.17	II.7	1.4	2.2	—	0.12	153 · 81.32 % · 96.34 %
Sc–NMA Single-site doping (II.6.4)	LiNi0.8Mn0.12Sc0.03Al0.05O2	2.872	14.42	5.021	103.5 ≠ 103.01	II.8	1.32	—	—	0.12	—
Na–NMA Single-site doping (II.6.4)	Li0.97Na0.03Ni0.8Mn0.15Al0.05O2	2.868	14.58	5.084	104.3 ≠ 103.86	II.8	1.45	—	—	0.15	—
Fe/Sb–NMA Fe/Sb co-doping (II.6.5)	LiNi0.8Mn0.15Sb0.05Fe0.05Al0.05O2	2.91	14.37	4.938	105.38	II.9	1.35	—	—	0.55 TM 1.1	153 · 80.85 % · 96.71 %
LiNbO₃-coated NMA All-solid-state (IV.2–IV.3)	LiNi0.8Mn0.15Al0.05O2 + ≈1 wt% LiNbO3	no diffraction reported					—	—	—	0.15	Li6PS5Cl electrolyte, Li–In anode; 73.8 % of capacity after 50 cycles against 60.1 % for pristine NMA (§IV.3.2)

What the numbers say, material by material

5 % Mn–NCA: Table II.3 prints the formula with Co0.15 (sum 1.05); the text and the ICP give Co0.10.
Pristine NMA: Two incompatible cells for one powder: a = 2.9042 Å (Table II.3) and 2.860 Å (Tables II.7–II.9); Table II.8 also gives V = 102.6 Å³ where a and c give 101.3 Å³. \(\chi^2\) 2.3 (II.7, II.8) and 3.40 (II.9).
Fe/Sb–NCA: The text says c/a decreases from 4.944 to 4.9359; Table II.5 shows it increasing (NCA 4.9359 → Fe/Sb–NCA 4.944). Sb\(^{5}\)⁺ is asserted, not measured. I(003)/I(104) of pristine NCA is 1.05, below the 1.2 threshold the text says it exceeds.
La–NMA: La\(^{3}\)⁺ (1.03 Å) on the octahedral TM site of a layered oxide is unusual; La-rich second phases are the usual alternative. The 1.1 % expansion of a is read as incorporation.
Sc–NMA: Sc assumed on the TM (Mn) site. No electrochemistry reported.
Na–NMA: Na assumed on the Li site; c expands by 2 % (\(14.30 \to 14.58\) Å). No electrochemistry reported.
Fe/Sb–NMA: The formula of §II.4.4 has 1.10 metals per formula unit; Table II.10's own theoretical wt% correspond to about Ni0.76Mn0.08Fe0.05Sb0.05Al0.06. Against the pristine row of Table II.9, a grows by 1.7 % and V by 4.0 %, while the text says the volume stays nearly unchanged.
LiNbO₃-coated NMA: No diffraction of the coated powder or of the composite is reported: coating thickness, crystallinity and Nb diffusion into the lattice are not determined.

How to read it

Ni\(^{2}\)⁺ by charge balance assumes the usual valences (Co\(^{3}\)⁺, Mn\(^{4}\)⁺, Al\(^{3}\)⁺, Fe\(^{3}\)⁺, Sb\(^{5}\)⁺, Mg\(^{2}\)⁺, the trivalent dopants, Li⁺ and Na⁺) and full oxygen. It rises from 0 in NCA to 0.15 per formula unit in NMA; it is the nickel that can mix into the lithium layer, and the Ni K edge (P4) measures it.
Lithium from the ICP: Table II.4 gives wt% of the metals and lithium; converted, 0.91–0.93 Li per transition metal. Part may be surface LiOH and \(\mathrm{Li_{2}CO_{3}}\), which would make the bulk deficit larger.
Two cells for pristine NMA: the material that is the reference of three of the four lines has a = 2.9042 Å in Table II.3 and 2.860 Å in Tables II.7–II.9. Compare cells within a table, not across.
Where the beam time will add columns: Ni and Mn on the Li layer, Li occupancy, z(O), the Ni valence, the site of each dopant, phase content, cells with esd, all for the same powders.