Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot

Highlights

• New external automatic tuning/matching (eATM) robot system.

• Enables “on-the-fly” recalibration of the resonance circuit during NMR experiments.

• Enhanced efficiency of variable offset cumulative spectra (VOCS) and other broadband measurements.

• Various applications to paramagnetic, quadrupolar, and/or multinuclear systems.

• Automated acquisition during variable temperature, static, and/or MAS NMR experiments.

Abstract

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated “on-the-fly” re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g. ⁷Li and ³¹P at 117 and 122 MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic ⁷Li and ³¹P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO₄; (2) paramagnetic ¹⁷O VT-NMR of the solid oxide fuel cell cathode material La₂NiO_4+δ; (3) broadband ⁹³Nb static NMR of the Li-ion battery material BNb₂O₅; and (4) broadband static ¹²⁷I NMR of a potential Li–air battery product LiIO₃. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1–25 MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems.