High resolution solid-state NMR on the desktop.

High-resolution low-field nuclear magnetic resonance (NMR) spectroscopy has found wide application for characterization of liquid compounds because of the low maintenance cost of modern permanent magnets. Solid-state NMR so far is limited to low-resolution measurements of static powders, because of the limited space available in this type of magnet. Magic-angle sample spinning and low-magnetic fields are an attractive combination to achieve high spectral resolution especially for paramagnetic solids. Here we show that magic angle spinning modules can be miniaturized using 3D printing techniques so that high-resolution solid-state NMR in permanent magnets becomes possible. The suggested conical rotor design was developed using finite element calculations and provides sample spinning frequencies higher than 20 kHz. The setup was tested on various diamagnetic and paramagnetic compounds including paramagnetic battery materials. The only comparable experiments in low-cost magnets known so far, had been done in the early times of magic angle spinning using electromagnets at much lower sample spinning frequency. Our results demonstrate that high-resolution low-field magic-angle-spinning NMR does not require expensive superconducting magnets and that high-resolution solid-state NMR spectra of paramagnetic compounds are feasible. Generally, this could introduce low-field solid-state NMR for abundant nuclei standard as a routine analytical tool.

Unraveling the Reaction Mechanisms of SiO Anodes for Li-Ion Batteries by Combining in Situ 7Li and ex Situ 7Li/29Si Solid-State NMR Spectroscopy.

Silicon monoxide is a promising alternative anode material due to its much higher capacity than graphite, and improved cyclability over other Si anodes. An in-depth analysis of the lithium silicide (Li xSi) phases that form during lithiation/delithiation of SiO is presented here and the results are compared with pure-Si anodes. A series of anode materials is first prepared by heating amorphous silicon monoxide (a-SiO) at different temperatures, X-ray diffraction and 29Si NMR analysis revealing that they comprise small Si domains that are surrounded by amorphous SiO2, the domain size and crystallinity growing with heat treatment. In and ex situ 7Li and 29Si solid-state NMR combined with detailed electrochemical analysis reveals that a characteristic metallic Li xSi phase is formed on lithiating a-SiO with a relatively high Li concentration of x = 3.4-3.5, which is formed/decomposed through a continuous structural evolution involving amorphous phases differing in their degree of Si-Si connectivity. This structural evolution differs from that of pure-Si electrodes where the end member, crystalline Li15Si4, is formed/decomposed through a two-phase reaction. The reaction pathway of SiO depends, however, on the size of the ordered Si domains within the pristine material. When crystalline domains of >3 nm within a SiO2 matrix are present, a phase resembling Li15Si4 forms, albeit at a higher overpotential. The continuous formation/decomposition of amorphous Li xSi phases without the hysteresis and phase change associated with the formation of c-Li15Si4, along with a partially electrochemically active SiO2/lithium silicate buffer layer, are paramount for the good cyclability of a-SiO.

Investigating Sodium Storage Mechanisms in Tin Anodes: A Combined Pair Distribution Function Analysis, Density Functional Theory, and Solid-State NMR Approach.

The alloying mechanism of high-capacity tin anodes for sodium-ion batteries is investigated using a combined theoretical and experimental approach. Ab initio random structure searching (AIRSS) and high-throughput screening using a species-swap method provide insights into a range of possible sodium-tin structures. These structures are linked to experiments using both average and local structure probes in the form of operando pair distribution function analysis, X-ray diffraction, and 23Na solid-state nuclear magnetic resonance (ssNMR), along with ex situ 119Sn ssNMR. Through this approach, we propose structures for the previously unidentified crystalline and amorphous intermediates. The first electrochemical process of sodium insertion into tin results in the conversion of crystalline tin into a layered structure consisting of mixed Na/Sn occupancy sites intercalated between planar hexagonal layers of Sn atoms (approximate stoichiometry NaSn3). Following this, NaSn2, which is predicted to be thermodynamically stable by AIRSS, forms; this contains hexagonal layers closely related to NaSn3, but has no tin atoms between the layers. NaSn2 is broken down into an amorphous phase of approximate composition Na1.2Sn. Reverse Monte Carlo refinements of an ab initio molecular dynamics model of this phase show that the predominant tin connectivity is chains. Further reaction with sodium results in the formation of structures containing Sn-Sn dumbbells, which interconvert through a solid-solution mechanism. These structures are based upon Na5-xSn2, with increasing occupancy of one of its sodium sites commensurate with the amount of sodium added. ssNMR results indicate that the final product, Na15Sn4, can store additional sodium atoms as an off-stoichiometry compound (Na15+xSn4) in a manner similar to Li15Si4.

Unravelling Local Atomic Order of the Anionic Sublattice in M(Al1-x Gax )4 with M=Sr and Ba by Using NMR Spectroscopy and Quantum Mechanical Modelling.

The quasibinary section of the intermetallic phases MAl4 and MGa4 with M=Sr and Ba have been characterised by means of X-ray diffraction (XRD) studies and differential thermal analysis. The binary phases show complete miscibility and form solid solutions M(Al1-x Gax )4 with M=Sr and Ba. These structures crystallise in the BaAl4 structure type with four- and five-bonded Al and/or Ga atoms (denoted as Al(4b), Al(5b), Ga(4b), and Ga(5b), respectively) that form a polyanionic Al/Ga sublattice. Solid state 27 Al NMR spectroscopic analysis and quantum mechanical (QM) calculations were applied to study the bonding of the Al centres and the influence of Al/Ga substitution, especially in the regimes with low degrees of substitution. M(Al1-x Gax )4 with M=Sr and Ba and 0.925≤x≤0.975 can be described as a matrix of the binary majority compound in which a low amount of the Ga atoms has been substituted by Al atoms. In good agreement with the QM calculations, 27 Al NMR investigations and single crystal XRD studies prove a preferred occupancy of Al(4b) for these substitution regimes. Furthermore, two different local Al environments were found, namely isolated Al(4b1) atoms and Al(4b2), due to the formation of Al(4b)-Al(4b) pairs besides isolated Al(4b) atoms within the polyanionic sublattice. QM calculations of the electric field gradient (EFG) using superlattice structures under periodic boundary conditions are in good agreement with the NMR spectroscopic results.

[Ge2](4-) Dumbbells with Very Short Ge-Ge Distances in the Zintl Phase Li3NaGe2: A Solid-State Equivalent to Molecular O2.

The novel ternary Zintl phase Li3NaGe2 comprises alkali-metal cations and [Ge2](4-) dumbbells. The diatomic [Ge2](4-) unit is characterized by the shortest Ge-Ge distance (2.390(1) Å) ever observed in a Zintl phase and thus represents the first Ge=Ge double bond under such conditions, as also suggested by the (8-N) rule. Raman measurements support these findings. The multiple-bond character is confirmed by electronic-structure calculations, and an upfield (6)Li NMR shift of -10.0 ppm, which was assigned to the Li cations surrounded by the π systems of three Ge dumbbells, further underlines this interpretation. For the unperturbed, ligand-free dumbbell in Li3NaGe2, the π- bonding py and pz orbitals are degenerate as in molecular oxygen, which has singly occupied orbitals. The partially filled π-type bands of the neat solid Li3NaGe2 cross the Fermi level, resulting in metallic properties. Li3NaGe2 was synthesized from the elements as well as from binary reactants and subsequently characterized crystallographically.

Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li4SiO4-Li3PO4 Solid Electrolytes.

Solid electrolytes that are chemically stable and have a high ionic conductivity would dramatically enhance the safety and operating lifespan of rechargeable lithium batteries. Here, we apply a multi-technique approach to the Li-ion conducting system (1-z)Li4SiO4-(z)Li3PO4 with the aim of developing a solid electrolyte with enhanced ionic conductivity. Previously unidentified superstructure and immiscibility features in high-purity samples are characterized by X-ray and neutron diffraction across a range of compositions (z = 0.0-1.0). Ionic conductivities from AC impedance measurements and large-scale molecular dynamics (MD) simulations are in good agreement, showing very low values in the parent phases (Li4SiO4 and Li3PO4) but orders of magnitude higher conductivities (10(-3) S/cm at 573 K) in the mixed compositions. The MD simulations reveal new mechanistic insights into the mixed Si/P compositions in which Li-ion conduction occurs through 3D pathways and a cooperative interstitial mechanism; such correlated motion is a key factor in promoting high ionic conductivity. Solid-state (6)Li, (7)Li, and (31)P NMR experiments reveal enhanced local Li-ion dynamics and atomic disorder in the solid solutions, which are correlated to the ionic diffusivity. These unique insights will be valuable in developing strategies to optimize the ionic conductivity in this system and to identify next-generation solid electrolytes.

The Solid Solution Sr(1-x)Ba(x)Ga2: Substitutional Disorder and Chemical Bonding Visited by NMR Spectroscopy and Quantum Mechanical Calculations.

Complete miscibility of the intermetallic phases (IPs) SrGa2 and BaGa2 forming the solid solution Sr(1-x)Ba(x)Ga2 is shown by means of X-ray diffraction, thermoanalytical and metallographic studies. Regarding the distances of Sr/Ba sites versus substitution degree, a model of isolated substitution centres (ISC) for up to 10% cation substitution is explored to study the influence on the Ga bonding situation. A combined application of NMR spectroscopy and quantum mechanical (QM) calculations proves the electric field gradient (EFG) to be a sensitive measure of different bonding situations. The experimental resolution is boosted by orientation-dependent NMR on magnetically aligned powder samples, revealing in first approximation two different Ga species in the ISC regimes. EFG calculations using superlattice structures within periodic boundary conditions are in fair agreement with the NMR spectroscopy data and are discussed in detail regarding their application on disordered IPs.

NMR spectroscopy of intermetallic compounds: an experimental and theoretical approach to local atomic arrangements in binary gallides.

The results of the investigation of MGa(2) with M = Ca, Sr, Ba and of MGa(4) with M = Na, Ca, Sr, Ba by a combined application of NMR spectroscopy and quantum mechanical calculations are comprehensively evaluated. The electric-field gradient (EFG) was identified as the most reliable measure to study intermetallic compounds, since it is accessible with high precision by quantum mechanical calculations and, for nuclear spin I>1/2, by NMR spectroscopy. The EFG values obtained by NMR spectroscopy and quantum mechanical calculations agree very well for both series of investigated compounds. A deconvolution of the calculated EFGs into their contributions reveals its sensitivity to the local environment of the atoms. The EFGs of the investigated di- and tetragallides are dominated by the population of the p(x)-, p(y)-, and p(z)-like states of the Ga atoms. A general combined approach for the investigation of disordered intermetallic compounds by application of diffraction methods, NMR spectroscopy, and quantum mechanical calculations is suggested. This scheme can also be applied to other classes of crystalline disordered inorganic materials.

Stable magic angle spinning with Low-Cost 3D-Printed parts.

A 3D-printed double-bearing magic angle spinning (MAS) system was developed with a home-built 4.0 mm MAS nuclear magnetic resonance (NMR) probe at 7 T. Various fused deposition modelling 3D printers were used to produce spinning modules of ignorable materials costs for rotors with a diameter of 7.0, 4.0, and 3.5 mm. High-performance MAS experiments on the 4.0 mm-diameter model using a pencil-type ceramic rotor and 3D-printed drive cap resulted in a high-resolution 1H NMR signal of silicone grease. The 3.5 mm-diameter MAS system reached a spinning frequency of 23 kHz. Furthermore, 3D-printed inserts were designed for various rotor sizes which can isolate the sample from humidity for a duration of more than a week. Single crystal inserts for MAS rotors of commercial probes can readily be printed using two-color printers. Those developments enable customized low-cost MAS NMR for both adapting existing and manufacturing new probes, respectively.

Atomistic characterisation of Li+ mobility and conductivity in Li(7-x)PS(6-x)Ix argyrodites from molecular dynamics simulations, solid-state NMR, and impedance spectroscopy.

The atomistic mechanisms of Li(+) ion mobility/conductivity in Li(7-x)PS(6-x)I(x) argyrodites are explored from both experimental and theoretical viewpoints. Ionic conductivity in the title compound is associated with a solid-solid phase transition, which was characterised by low-temperature differential scanning calorimetry, (7)Li and (127)I NMR investigations, impedance measurements and molecular dynamics simulations. The NMR signals of both isotopes are dominated by anisotropic interactions at low temperatures. A significant narrowing of the NMR signal indicates a motional averaging of the anisotropic interactions above 177+/-2 K. The activation energy to ionic conductivity was assessed from both impedance spectroscopy and molecular dynamics simulations. The latter revealed that a series of interstitial sites become accessible to the Li(+) ions, whilst the remaining ions stay at their respective sites in the argyrodite lattice. The interstitial positions each correspond to the centres of tetrahedra of S/I atoms, and differ only in terms of their common corners, edges, or faces with adjacent PS(4) tetrahedra. From connectivity analyses and free-energy rankings, a specific tetrahedron is identified as the key restriction to ionic conductivity, and is clearly differentiated from local mobility, which follows a different mechanism with much lower activation energy. Interpolation of the lattice parameters as derived from X-ray diffraction experiments indicates a homogeneity range for Li(7-x)PS(6-x)I(x) with 0.97 < or = x < or = 1.00. Within this range, molecular dynamics simulations predict Li(+) conductivity at ambient conditions to vary considerably.

Electronic structure, chemical bonding, and solid-state NMR spectroscopy of the digallides of Ca, Sr, and Ba.

Combined application of (69,71)Ga NMR spectroscopy and quantum mechanical calculations reveals the chemical bonding in the digallides of Ca, Sr, and Ba. An analysis of the electron localization function (ELF) shows honeycomb-like 6(3) nets of the Ga atoms as the most prominent structural features in SrGa(2) and BaGa(2). For CaGa(2) a description of a 3+1-coordinated Ga atom is revealed by the ELF and by an analysis of interatomic distances. The NMR spectroscopic signal shift is mainly due to the Knight shift and is almost equal for the investigated digallides, whereas the anisotropy of the signal shift decreases with the radius of the alkaline-earth metals. Calculated and observed values of the electric field gradient (EFG) are in good agreement for CaGa(2) and BaGa(2) but differ by about 21 % for SrGa(2) indicating structural instability. Better agreement is achieved by considering a puckering of the Ga layers. For BaGa(2) an instability of the structure is indicated by a peak in the density of states at the Fermi level, which is shifted to lower energies when taking puckering of the Ga layers into account. Both structural modifications are confirmed by crystallographic information. The Fermi velocity of the electrons is strongly anisotropic and is largest in the (001) plane of the crystal structure. This results in an alignment of the crystallites with the [001] axis perpendicular to the magnetic field as observed in (69,71)Ga NMR spectroscopy and magnetic susceptibility experiments. The electron transport is predominantly mediated by the Ga-Ga p(x)- and p(y)-like electrons in the (001) plane. The specific heat capacity of BaGa(2) was determined and indicated the absence of phase transitions between 1.8 and 320 K.

Towards an atomistic understanding of disordered carbon electrode materials.

Disordered nanoporous and "hard" carbons are widely used in batteries and supercapacitors, but their atomic structures are poorly determined. Here, we combine machine learning and DFT to obtain new atomistic insight into carbonaceous energy materials. We study structural models of porous and graphitic carbons, and Na intercalation as relevant for sodium-ion batteries.

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

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 122MHz, 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 La2NiO4+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 (1-25MHz) 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.

Automatic Tuning Matching Cycler (ATMC) in situ NMR spectroscopy as a novel approach for real-time investigations of Li- and Na-ion batteries.

We have developed and explored the use of a new Automatic Tuning Matching Cycler (ATMC) in situ NMR probe system to track the formation of intermediate phases and investigate electrolyte decomposition during electrochemical cycling of Li- and Na-ion batteries (LIBs and NIBs). The new approach addresses many of the issues arising during in situ NMR, e.g., significantly different shifts of the multi-component samples, changing sample conditions (such as the magnetic susceptibility and conductivity) during cycling, signal broadening due to paramagnetism as well as interferences between the NMR and external cycler circuit that might impair the experiments. We provide practical insight into how to conduct ATMC in situ NMR experiments and discuss applications of the methodology to LiFePO4 (LFP) and Na3V2(PO4)2F3 cathodes as well as Na metal anodes. Automatic frequency sweep (7)Li in situ NMR reveals significant changes of the strongly paramagnetic broadened LFP line shape in agreement with the structural changes due to delithiation. Additionally, (31)P in situ NMR shows a full separation of the electrolyte and cathode NMR signals and is a key feature for a deeper understanding of the processes occurring during charge/discharge on the local atomic scale of NMR. (31)P in situ NMR with "on-the-fly" re-calibrated, varying carrier frequencies on Na3V2(PO4)2F3 as a cathode in a NIB enabled the detection of different P signals within a huge frequency range of 4000 ppm. The experiments show a significant shift and changes in the number as well as intensities of (31)P signals during desodiation/sodiation of the cathode. The in situ experiments reveal changes of local P environments that in part have not been seen in ex situ NMR investigations. Furthermore, we applied ATMC (23)Na in situ NMR on symmetrical Na-Na cells during galvanostatic plating. An automatic adjustment of the NMR carrier frequency during the in situ experiment ensured on-resonance conditions for the Na metal and electrolyte peak, respectively. Thus, interleaved measurements with different optimal NMR set-ups for the metal and electrolyte, respectively, became possible. This allowed the formation of different Na metal species as well as a quantification of electrolyte consumption during the electrochemical experiment to be monitored. The new approach is likely to benefit a further understanding of Na-ion battery chemistries.

Mechanistic insights into sodium storage in hard carbon anodes using local structure probes.

Operando23Na solid-state NMR and pair distribution function analysis experiments provide insights into the structure of hard carbon anodes in sodium-ion batteries. Capacity results from "diamagnetic" sodium ions first adsorbing onto pore surfaces, defects and between expanded layers, before pooling into larger quasi-metallic clusters/expanded carbon sheets at lower voltages.