Site Occupation of Ga and Al in Stabilized Cubic Li<sub>7–3(<i>x</i>+<i>y</i>)</sub>Ga<sub><i>x</i></sub>Al<sub><i>y</i></sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> Garnets As Deduced from <sup>27</sup>Al and <sup>71</sup>Ga MAS NMR at Ultrahigh Magnetic Fields
Bibliographic record
Abstract
Li-containing garnets, which are stabilized in their cubic modification by doping with Al or Ga, show very high Li-ion conductivities. This property qualifies them to be used as solid electrolytes in advanced all-solid-state batteries. The relation between local structures and dynamic properties, however, is still not fully understood. Here, cubic mixed-doped Li 7–3( x + y ) Ga x Al y La 3 Zr 2 O 12 garnet solid solutions with different portions of Al and Ga were synthesized. It turned out that the solubility of Ga is higher than that of Al; the evaluation of 42 different doping compositions indicated an increase of the lattice parameter a 0 with increasing Ga content. 71 Ga MAS NMR spectra recorded at 21.1 T revealed two 71 Ga NMR resonances, corresponding to Ga occupying both the 24 d (243 ppm) and 96 h sites (193 ppm). This behavior, which has been observed for the first time in this study, is very similar to that of Al. The 71 Ga NMR line at 193 ppm observed here remained invisible in previous NMR studies that were carried out at lower magnetic fields. The invisibility at lower field is because of large second-order quadrupolar broadening that has a lower effect on the 71 Ga NMR spectra at higher magnetic field. Most importantly, the similarity in site preference of Al and Ga found here inevitably raises a question about the significance of a blocking effect on long-range Li-ion transport. It weakens the assumption that the site preference of dopants is responsible for the higher Li diffusivity of Ga-doped samples compared to the Al-doped analogues. Concerning Li-ion dynamics, our 7 Li NMR line shape measurements indicate that the change in lattice constant a 0 with increasing doping level seems to have a larger influence on Li-ion dynamics than the Al:Ga ratio.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.004 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.003 | 0.002 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; both teacher heads agree on what is shown here.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".