Euan Bassey

Mg-Ion Conduction in Antiperovskite Solid Electrolytes Revealed by 25Mg Ultrahigh Field NMR and First-Principles Calculations Magnesium-ion batteries hold the potential to outperform the energy density of lithium-ion batteries, given the divalent charge carried by each Mg2+ cation, but remain in an early stage of development. Here, 25Mg solid-state nuclear magnetic resonance (ssNMR) is used to gain insight into the local structure and Mg-ion dynamics of candidate Mg-ion solid electrolytes, the antiperovskites Mg3SbN and Mg3AsN. Using the highest available magnetic field (35.2 T) for high-resolution solid-state NMR, the largest 25Mg quadrupole coupling constants (CQ) yet measured of up to 22 MHz are reported and corroborated by first-principles calculations. Predicted CQ values are shown to correlate with the antiperovskite’s tolerance factor; thus, 25Mg NMR linewidths can report on lattice distortions and phase stability of these antiperovskites. Variable-temperature 25Mg NMR spectra demonstrate changes at elevated temperatures, ascribed to Mg-ion motional effects. 25Mg T1 relaxometry measurements at ultrahigh field reveal a lower activation energy for the more distorted Mg3AsN phase, matching computational predictions of a lower energy barrier for Mg2+ ion migration and suggesting that additional scrutiny of antiperovskites as Mg-ion conductors is warranted. Given the inherent challenges of 25Mg NMR, this work demonstrates the benefits of combining ultrahigh field NMR spectroscopy, advanced pulse sequences, modern signal processing, and first-principles calculations to facilitate NMR of quadrupolar nuclei as a tool to probe the local structure and ion dynamics in beyond-Li battery materials.

Congratulations to a powerhouse of JCESR alums for their paper using NMR to probe Mg motion in antiperovskite mixed anion solids. NMR nerds will admire those linewidths. And yes, Mg actually moves!

pubs.acs.org/doi/10.1021/...

Please share: We're hiring a Postdoctoral Research Associate to join the Grey Group. The project will focus on using operando optical microscopy to study solid-state ion dynamics and phase transformations in lithium- and sodium-ion battery materials.
Learn more here: www.jobs.cam.ac.uk/job/52120/

@jmaterchem.rsc.org @illneutrons.bsky.social @diamondlightsource.bsky.social
#chemsky

A fun puzzle to brighten your Tuesday - we used 7Li, 17O & 27Al NMR, in combination with diffraction and ab initio calculations, to determine the local and bulk structure of an O2-type anion redox cathode. Stay tuned for more on this soon!
#NMRchat #battchat #compchem

pubs.rsc.org/en/content/a...

The Crucial Role of Vacancy Concentration in Enabling Superatomic Diffusion in Lithium Intermetallics Anode-free solid-state Li batteries promise significant increases in energy densities compared to current commercial batteries that rely on liquid electrolytes. Major challenges persist in controlling morphological evolution during the plating and stripping of lithium metal at the anode current collector. Elemental additives that alloy with lithium have been found to modify the plating and stripping behavior of lithium. Many alloying elements form intermetallics with lithium and the mobility of Li through these intermetallics is believed to have an important effect on morphological evolution. This study shows that Li transport coefficients through intermetallics span a wide range in values, with the B32 LiAl intermetallic predicted to have a Li tracer diffusion coefficient as high as 10–6 cm2/s at room temperature, which is 8 orders of magnitude larger than that of isostructural B32 LiZn. This work demonstrates the crucial role of vacancy concentration in controlling the mobility of Li atoms through intermetallics. While the migration barriers for Li-vacancy exchanges in both LiAl and LiZn are remarkably low, the superatomic conductivity in LiAl is shown to arise from the unique electronic structure of the B32 LiAl compound, which favors high concentrations of vacancies.

If you love a bit of Li ion diffusivity, you'll love this awesome new paper from Sesha and Anton at UCSB:
doi.org/10.1021/acse...
#battchat #compchem

I'm looking to grow some connectivity for materials scientists & engineers on BlueSky - if you identify in this grouping, I'd be happy to add you to this starter pack 🧪

go.bsky.app/U5wGm7M

@pubs.acs.org

First-Principles Statistical Mechanics Study of Magnetic Fluctuations and Order–Disorder in the Spinel LiNi0.5Mn1.5O4 Cathode While significant magnetic interactions exist in lithium transition metal oxides, commonly used as Li-ion cathodes, the interplay between magnetic couplings, disorder, and redox processes remains poor...

This was a pleasure to be a part of - Elizabeth did some amazing work building not one, not two, but THREE Monte Carlo codes to model magnetism in a Li-ion spinel, based on novel cluster expansion methods. Beautiful work!! #Battchat #compchem #chemsky
doi.org/10.1021/acs....

OK folks, I have now created a google form that allows people to sign to show their support for my open letter to the President of the Royal Society. Please sign and share widely: forms.gle/miDciq35oxyw...

I'm pleased to share that I've been accepted as a Marie Skłodowska-Curie Fellow at the CRMN in Lyon, where I'll be starting in a couple of weeks. Exciting times ahead for paramagnetic NMR method development! 🧲 🔋 @nmr900.bsky.social @cnrs.bsky.social #NMRchat #EPRchat

list of banned keywords

🚨BREAKING. From a program officer at the National Science Foundation, a list of keywords that can cause a grant to be pulled. I will be sharing screenshots of these keywords along with a decision tree. Please share widely. This is a crisis for academic freedom & science.

I made a magnetic resonance starter pack!

go.bsky.app/NiqEFGm

I am sure I missed people, please ask if you would like to be included (or removed).

#NMRChat #ChemSky

Tomorrow's webinar on NMR of quadrupolar nuclei

My second post is a link to the slides for my tutorial on solid-state NMR of half-integer quadrupolar nuclei that I gave at the PANACEA summer school in Venice last summer. #nmr

www.grandinetti.org/resources/20...

And: go.bsky.app/CctG8H4

*insert other three-letter initialisms here

Loving the positivity and growth of #chemsky, #battchat and #NMRchat!
Seems apt to re-introduce myself. I'm Euan: a postdoc at UCSB, working at the interface(s) of materials, chemistry & physics. Penchant for NMR, EPR, DFT...* Looking forward to rebuilding our precious networks and community!

Helping all the solid state chemists and inorganic materials chemists connect! Thanks for the suggestion to make this @christinabirkel.bsky.social!

go.bsky.app/CKnAwGa