ICP-OES; titration of surface lithium species; TGA–MS; XPS (Ni 2p, Sb 3d); ⁵⁷Fe Mössbauer where available; laboratory XRD with an internal standard; glove box

No proposal: the groups' own means, from November 2026

K9 as stored and, where possible, re-calcined fresh under O₂ and kept under argon; electrodes of NMA, Y–, La– and Fe/Sb–NMA after 200 cycles, harvested in the glove box.

—

• Li by ICP-OES on washed and unwashed powder, with the basis of Table II.4 stated: the bulk and surface lithium separated.
• Surface LiOH and \(\mathrm{Li_{2}CO_{3}}\) by titration; TGA–MS for \(\mathrm{H_{2}O}\) and \(\mathrm{CO_{2}}\).
• XPS of Sb 3d and Ni 2p (surface valence), ⁵⁷Fe Mössbauer (bulk Fe valence and site) where an instrument is available.
• Laboratory XRD with Si (NIST 640) as internal standard: the cell of each powder with zero shift stated, the two NMA cells reconciled.

A lithium balance and a composition per material; the reference cells; the samples the facilities need.

Every occupancy refined at the facility is refined under the composition measured here.

Powders stored in air since 2025 will carry surface \(\mathrm{Li_{2}CO_{3}}\); measuring it is part of the answer (F02), and re-calcination under O₂ is the remedy.

Before mid-February 2027

D2B (λ = 1.594 Å, Δd/d \(\approx\) \(5\times10^{-4}\), 2\(\theta\) to 160°); alternative D20 in its high-resolution configuration

ILL standard proposal, College 5, with EHU proposers for the two-thirds rule; cited by and citing the garnet proposal of llzo-neutrons

K9 (2–3 g each, natural Li, 8 mm vanadium cans) and two cycled electrodes scraped and pooled (NMA, La–NMA).

\(\approx 6\) shifts: about 4 h per powder for 9 powders, the cycled electrodes, vanadium and empty can. Estimate.

• Full patterns to \(d \approx 0.81\) Å at room temperature.
• Joint refinement with the ID22 pattern of the same powder (P2) in diff-ref-struct: Li, Ni and Mn on both layers, z(O) and the O occupancy, displacement parameters; ICP composition and charge balance as constraints.

The Ni on the Li layer of each material with esd, and whether Mn shares it; the Li occupancy; z(O) and the slab thicknesses; the mixing after 200 cycles for two materials.

Only neutrons tell Ni from Mn and Co on a site (33–40 times the X-ray contrast) and see Li and O with weight (Contrast page); with X-rays fixing the cell and profile, the joint refinement removes the correlations a single radiation leaves.

Absorption: μR \(\approx 0.48\) (NMA) and 0.50 (NCA, Co absorbs 37 b) in an 8 mm can with natural Li, correctable; a 6 mm can or ⁷Li for one composition if needed.

15 February 2027 (ILL standard round)

ID22 (31–35 keV, multi-analyser, FWHM \(\approx 0.0025\)°, robot); and resonant data just below the Ni K edge (8.33 keV)

ESRF standard proposal with EHU as main proposer, or within a BAG with the garnet proposal; BM25 SpLine as the Spanish route

A12 in 0.5 mm capillaries (and thinner for the Co and Mn absorbing materials at low energy), with an internal standard; the cycled electrodes.

\(\approx 4\) shifts: 15 patterns of a few tens of minutes with the robot, plus resonant patterns at two energies below the Ni K edge for NMA, 10 % Mn–NCA and La–NMA. Estimate.

• The cell of every material with esd, on one protocol; peak shapes (strain, stacking faults).
• Phase content to \(\approx 0.1\) wt%: \(\mathrm{Li_{2}CO_{3}}\), LiOH, rock-salt NiO-like, La/Y/Sc-rich oxides, crystalline \(\mathrm{LiNbO_{3}}\).
• The site of Y and La (X-ray contrast 10–15 %); resonant diffraction at the Ni K edge to separate Ni from Mn and Co in X-rays, as a cross-check of P1.

One table of cells for the thesis; the phase content of each powder; the Y and La sites; an independent X-ray answer to the Ni-or-Mn question.

Resolution and statistics no laboratory instrument reaches, without the fluorescence that Cu Kα excites in Mn, Co and Fe.

At the Ni K edge absorption is strong: flat-plate or thin capillaries, and only a few compositions.

1 March 2027 (ESRF standard round)

ID31 (high energy, electrochemical cells) or ID15A (operando, oven to 1200 K)

ESRF standard proposal; the Grenoble Battery Hub as a route for long-term access

Coin or pouch cells of NMA, Y–NMA, La–NMA and Fe/Sb–NMA against Li; electrodes charged to 4.5 V for heating.

\(\approx 6\) shifts: four cells over the first charge and two cycles, at about one pattern a minute; four charged electrodes heated to 600 °C. Estimate.

• Operando: a and c against state of charge, the H2–H3 coexistence and the c-axis collapse above 4.1 V, for each material.
• In situ heating of the charged electrodes: the layered → spinel → rock-salt sequence and its onset temperature.

Whether the dopants with the best retention (La, Y, Fe/Sb) soften the c collapse or delay the H3 phase; the thermal onset of each charged cathode.

High energy goes through a working cell; the time resolution follows the transitions the thesis invokes but did not observe.

Cell design: the facilities' standard cells, built with their staff; rates of C/10 to C/5 to fit the shifts.

1 March 2027 (ESRF standard round)

BM23 (4.5–90 keV); BM08 LISA or BM20 for the Sc K edge (4.49 keV); BM25 SpLine as the Spanish route

ESRF standard proposal; BM25 through the Spanish committee

K9, Sc–NMA and the coated NMA, as diluted pellets; references NiO, \(\mathrm{LiNiO_{2}}\) (or NCA from a supplier), \(\mathrm{MnO_{2}}\), \(\mathrm{Li_{2}MnO_{3}}\), \(\mathrm{Fe_{2}O_{3}}\), \(\mathrm{Sb_{2}O_{3}}\), \(\mathrm{Sb_{2}O_{5}}\), \(\mathrm{Y_{2}O_{3}}\), \(\mathrm{La_{2}O_{3}}\), \(\mathrm{LiNbO_{3}}\).

\(\approx 9\) shifts: Ni K and Mn K on all, Co K on the NCA line, Fe K and Sb K (30.49 keV) on the Fe/Sb materials, Y K and La K on Y– and La–NMA, Nb K on the coated NMA; Sc K separately. Estimate.

• Ni K XANES: the mean Ni oxidation state of each material, against the charge-balance prediction.
• Mn K, Co K: Mn\(^{4}\)⁺ and Co\(^{3}\)⁺; Fe K and Sb K: valence and local environment of the co-dopants.
• Y K and La K EXAFS: the coordination of Y and La, octahedral in the layer or in a second phase.

The Ni\(^{2}\)⁺ content of each material measured; the Sb valence settled; the local site of Y, La and Sc.

Valence and local coordination are not diffraction quantities; the edges of these elements are all in BM23's range but Sc.

Mn K and Fe K edges are close (6.54, 7.11 keV); Fe K EXAFS limited in range by the Co K edge in Fe/Sb–NCA.

1 March 2027 (ESRF); March call (BM25)

ID15A (X-ray PDF, operando); BM23 (Nb K); ILL operando neutron cell for solid-state batteries (ILLBAT) on D20 or D2B

After P1–P4, September 2027 rounds; with the garnet strand of llzo-neutrons

\(\mathrm{LiNbO_{3}}\)-coated and pristine NMA, their \(\mathrm{Li_{6}PS_{5}Cl}\) composites before and after cycling.

\(\approx 3\) shifts ID15A. Estimate.

• X-ray PDF of the coating and of the composite interface; Nb K of the coated powder and of the cycled composite.
• Operando neutron diffraction of the NMA | \(\mathrm{Li_{6}PS_{5}Cl}\) cell in the ILL's solid-state cell, as published for NCM with argyrodite electrolytes.

The state of the coating and the interface phases after cycling.

It joins the cathode strand to the electrolyte strand of the joint project.

Only worth asking once P1–P4 have shown which materials carry the effects.

September 2027 rounds