Local Structure and Dynamics in Methylammonium, Formamidinium, and Cesium Tin(II) Mixed-Halide Perovskites from 119Sn Solid-State NMR.

Organic-inorganic tin(II) halide perovskites have emerged as promising alternatives to lead halide perovskites in optoelectronic applications. While they suffer from considerably poorer performance and stability in comparison to their lead analogues, their performance improvements have so far largely been driven by trial and error efforts due to a critical lack of methods to probe their atomic-level microstructure. Here, we identify the challenges and devise a 119Sn solid-state NMR protocol for the determination of the local structure of mixed-cation and mixed-halide tin(II) halide perovskites as well as their degradation products and related phases. We establish that the longitudinal relaxation of 119Sn can span 6 orders of magnitude in this class of compounds, which makes judicious choice of experimental NMR parameters essential for the reliable detection of various phases. We show that Cl/Br and I/Br mixed-halide perovskites form solid alloys in any ratio, while only limited mixing is possible for I/Cl compositions. We elucidate the degradation pathways of Cs-, MA-, and FA-based tin(II) halides and show that degradation leads to highly disordered, qualitatively similar products, regardless of the A-site cation and halide. We detect the presence of metallic tin among the degradation products, which we suggest could contribute to the previously reported high conductivities in tin(II) halide perovskites. 119Sn NMR chemical shifts are a sensitive probe of the halide coordination environment as well as of the A-site cation composition. Finally, we use variable-temperature multifield relaxation measurements to quantify ion dynamics in MASnBr3 and establish activation energies for motion and show that this motion leads to spontaneous halide homogenization at room temperature whenever two different pure-halide perovskites are put in physical contact.

Local atomic and electronic structure in the LiVPO4 (F,O) tavorite-type materials from solid-state NMR combined with DFT calculations.

7 Li, 31 P, and 19 F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4 F1-y Oy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7 Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X-VO4 -X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4 X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIV O vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain.

On the measurement of intermolecular heteronuclear cross relaxation rates in ionic liquids.

The HOESY (Heteronuclear Overhauser Effect SpectroscopY) NMR experiment is commonly used to study interactions and structuring in ionic liquids (ILs) via the measurement of the cross relaxation rate σ between two spins. In the intermolecular case, σ is proportional to r-n, where r is the internuclear distance and n can vary between 1 and 6 depending on the frequency of the nuclei and their dynamics, thus σ can potentially provide detailed information on the liquid phase structure. However, in HOESY studies of ILs only relative values for σ are typically reported, making comparisons between different samples difficult. Herein we discuss the quantitative measurement of intermolecular cross relaxation rates based on the normalisation of HOESY signal intensities to the nuclear Boltzmann polarisation, demonstrated for 7Li-1H spin pairs in a lithium-containing pyrrolidinum-based ionic liquid electrolyte. We also use a simple model based on diffusing hard spheres for interpreting these quantities in terms of a distance of closest approach.

Electrochemical behavior of Bi4B2O9 towards lithium-reversible conversion reactions without nanosizing.

Conversion type materials, in particular metal fluorides, have emerged as attractive candidates for positive electrodes in next generation Li-ion batteries (LIBs). However, their practical use is being hindered by issues related to reversibility and large polarization. To minimize these issues, a few approaches enlisting the anionic network have been considered. We herein report the electrochemical properties of bismuth oxyborate Bi4B2O9 and show that this compound reacts with lithium via a conversion reaction leading to a sustained capacity of 140 mA h g-1 when cycled between 1.7 and 3.5 V vs. Li+/Li0 while having a surprisingly small polarization (∼300 mV) in the presence of solely 5% in weight of a carbon additive. These observations are rationalized in terms of charge transfer kinetics via complementary XRD, HRTEM and NMR measurements. This finding demonstrates that borate based conversion type materials display rapid charge transfer with limited carbon additives, hence offering a new strategy to improve their overall cycling efficiency.

Powder crystallography of pharmaceutical materials by combined crystal structure prediction and solid-state 1H NMR spectroscopy.

A protocol for the ab initio crystal structure determination of powdered solids at natural isotopic abundance by combining solid-state NMR spectroscopy, crystal structure prediction, and DFT chemical shift calculations was evaluated to determine the crystal structures of four small drug molecules: cocaine, flutamide, flufenamic acid, and theophylline. For cocaine, flutamide and flufenamic acid, we find that the assigned (1)H isotropic chemical shifts provide sufficient discrimination to determine the correct structures from a set of predicted structures using the root-mean-square deviation (rmsd) between experimentally determined and calculated chemical shifts. In most cases unassigned shifts could not be used to determine the structures. This method requires no prior knowledge of the crystal structure, and was used to determine the correct crystal structure to within an atomic rmsd of less than 0.12 Å with respect to the known reference structure. For theophylline, the NMR spectra are too simple to allow for unambiguous structure selection.

Operando nuclear magnetic resonance spectroscopy: Detection of the onset of metallic lithium deposition on graphite at low temperature and fast charge in a full Li-ion battery.

Lithium-ion batteries are at the core of the democratisation of electric transportation and portative electronic devices. However, fast and/or low temperature charge induce performance loss, mainly through lithium plating, a degrading mechanism. In this report, 7Li operando Nuclear Magnetic Resonance spectroscopy is used to detect the onset of metastable lithium deposits in an NMC622/graphite cell at 0 °C and fast charge. An operando setup, compatible with low temperatures, was developed with special attention to the pressure applied on the electrodes/separator stack and noise reduction to enable early detection and good time-resolution. Direct detection of metallic lithium enables drawing correlations between lithium plating and electrochemical data.

Resolving the different silicon clusters in Li12Si7 by 29Si and (6,7)Li solid-state NMR spectroscopy.

Structural signatures: The analysis of Si-Si and Si-Li connectivities by solid-state NMR spectroscopy allows the different types of silicon clusters to be discriminated in the model lithium silicide compound Li(12)Si(7) (see picture, Si clusters red and blue, Li ions gray). The results provide new NMR spectroscopic strategies with which to differentiate and study the structures formed in silicon-based electrode materials.

Monitoring metallic sub-micrometric lithium structures in Li-ion batteries by in situ electron paramagnetic resonance correlated spectroscopy and imaging.

Monitoring the formation of dendrites or filaments of lithium is of paramount importance for Li-based battery technologies, hence the intense activities in designing in situ techniques to visualize their growth. Herein we report the benefit of correlating in situ electron paramagnetic resonance (EPR) spectroscopy and EPR imaging to analyze the morphology and location of metallic lithium in a symmetric Li/LiPF6/Li electrochemical cell during polarization. We exploit the variations in shape, resonance field and amplitude of the EPR spectra to follow, operando, the nucleation of sub-micrometric Li particles (narrow and symmetrical signal) that conjointly occurs with the fragmentation of bulk Li on the opposite electrode (asymmetrical signal). Moreover, in situ EPR correlated spectroscopy and imaging (spectral-spatial EPR imaging) allows the identification (spectral) and localization (spatial) of the sub-micrometric Li particles created by plating (deposition) or stripping (altered bulk Li surface). We finally demonstrate the possibility to visualize, via in situ EPR imaging, dendrites formed through the separator in the whole cell. Such a technique could be of great help in mastering the Li-electrolyte interface issues that plague the development of solid-state batteries.

Activation of anionic redox in d0 transition metal chalcogenides by anion doping.

Expanding the chemical space for designing novel anionic redox materials from oxides to sulfides has enabled to better apprehend fundamental aspects dealing with cationic-anionic relative band positioning. Pursuing with chalcogenides, but deviating from cationic substitution, we here present another twist to our band positioning strategy that relies on mixed ligands with the synthesis of the Li2TiS3-xSex solid solution series. Through the series the electrochemical activity displays a bell shape variation that peaks at 260 mAh/g for the composition x = 0.6 with barely no capacity for the x = 0 and x = 3 end members. We show that this capacity results from cumulated anionic (Se2-/Sen-) and (S2-/Sn-) and cationic Ti3+/Ti4+ redox processes and provide evidence for a metal-ligand charge transfer by temperature-driven electron localization. Moreover, DFT calculations reveal that an anionic redox process cannot take place without the dynamic involvement of the transition metal electronic states. These insights can guide the rational synthesis of other Li-rich chalcogenides that are of interest for the development of solid-state batteries.

Powder crystallography by combined crystal structure prediction and high-resolution 1H solid-state NMR spectroscopy.

A fast method for crystal structure determination using crystal structure prediction and solid-state (1)H NMR is presented. This technique does not need any prior knowledge except the chemical formula; resonance assignment is not necessary. Starting from an ensemble of predicted crystal structures for powdered thymol, comparison between experimental and calculated (1)H solid-state isotropic NMR chemical shifts is sufficient to determine which predicted structure corresponds to the powder under study. The same approach using proton-proton spin-diffusion data is successful and can be used for cross-validation.

A general strategy for obtaining 19F-19F and 13C-19F residual dipolar couplings in perfluorocarbons from the NMR spectroscopy of liquid crystalline samples.

A two-dimensional Fluorine Detected Local Field (FDLF) NMR experiment is demonstrated on a sample of perfluoropropyl iodide dissolved in the nematic solvent ZLI1132. In analogy to the proton detected local field (PDLF) technique, for each resolved site of the carbon spectrum, a simple map of the heteronuclear coupling network is obtained in the indirect dimension. A full analysis of the FDLF spectrum was achieved with the aid of two-dimensional (19)F-(13)C HETCOR and (13)C, D-resolved spectra (with D representing the anisotropic spin-spin coupling). A one-dimensional (19)F spectrum was recorded on the same sample at intermediate resolution, and values of the residual spin-spin couplings T(CF) and T(FF) obtained from both experiments were combined and used to provide starting parameters for the analysis of a very high resolution (19)F spectrum, including the weak satellite lines from single-(13)C isotopomers. The high-precision, residual, anisotropic couplings were used to explore whether they have an appreciable contribution from the anisotropic electron-mediated spin-spin couplings.

Ab initio simulation of proton spin diffusion.

The many-body nature of the ubiquitous spin diffusion phenomenon makes it difficult to predict accurately from first principles. We show how the use of reduced Liouville spaces makes it possible to reproduce experimental proton spin diffusion measurements directly from crystalline geometry for powdered solids under magic-angle spinning.

Computation and NMR crystallography of terbutaline sulfate.

This article addresses, by means of computation and advanced experiments, one of the key challenges of NMR crystallography, namely the assignment of individual resonances to specific sites in a crystal structure. Moreover, it shows how NMR can be used for crystal structure validation. The case examined is form B of terbutaline sulfate. CPMAS (13)C and fast MAS (1)H spectra have been recorded and the peaks assigned as far as possible. Comparison of (13)C chemical shifts computed using the CASTEP program (incorporating the Gauge Including Projector Augmented Wave principle) with those obtained experimentally enable the accuracy of the two distinct single-crystal evaluations of the structure to be compared and an error in one of these is located. The computations have substantially aided in the assignments of both (13)C and (1)H resonances, as has a series of two-dimensional (2D) spectra (HETCOR, DQ-CRAMPS and proton-proton spin diffusion). The 2D spectra have enabled many of the proton chemical shifts to be pinpointed. The relationships of the NMR shifts to the specific nuclear sites in the crystal structure have therefore been established for most (13)C peaks and for some (1)H signals. Emphasis is placed on the effects of hydrogen bonding on the proton chemical shifts.

In Situ Magnetic Resonance Imaging of a Complete Supercapacitor Giving Additional Insight on the Role of Nanopores.

Nuclear magnetic resonance is one of the rare techniques able to probe selectively the ions inside the nanoporous network in supercapacitor devices. With a magnetic resonance imaging method able to detect all ions (adsorbed and nonadsorbed), we record one-dimensional concentration profiles of the active ions in supercapacitors with an electrode configuration close to that used in industry. Larger anionic concentration changes are probed upon charge and discharge in a carbide-derived carbon (CDC) with micropores smaller than 1 nm compared to a conventional nanoporous carbon (CC) with a larger distribution of pore sizes, up to 2 nm. They highlight the increased interaction of the anions with CDC and provide a better understanding of the enhanced capacitance in CDC-based supercapacitors.

The Fate of Water at the Electrochemical Interfaces: Electrochemical Behavior of Free Water Versus Coordinating Water.

The water reduction that produces hydrogen is one key reaction for electrochemical energy storage. While it has been widely studied in traditional aqueous electrolytes for water splitting (electrolyzers), it also plays an important role for batteries. Indeed, the reduction of water at relatively high potential prevents the practical realization of high-voltage aqueous batteries, while water contamination is detrimental for organic battery electrolytes. Nevertheless, recent studies pointed toward the positive effect of traces of water for Li-air batteries as well as for the formation of solid-electrolyte interphase. Herein, we provide a detailed understanding of the role of the solvation on water reduction reaction in organic electrolytes. Using electrochemistry, classical molecular dynamics simulations, and nuclear magnetic resonance spectroscopy, we were able to demonstrate that (1) the hydrophilicity/hydrophobicity of the species inside the electrochemical double layer directly controls the reduction of water and (2) water-coordinating strong Lewis acids such as Li+ cation are more reactive than free water (or noncoordinating) water molecules.

Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging.

Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 µm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

A scaling factor theorem for homonuclear dipolar decoupling in solid-state NMR spectroscopy.

A relationship between the dipolar and the chemical-shift scaling factors of cyclic radio-frequency irradiation schemes is introduced. This scaling factor theorem is derived analytically using Average Hamiltonian Theory, and its validity is illustrated numerically with homonuclear dipolar decoupling sequences generated randomly, and with the analysis of existing sequences. While derived for a static sample, the theorem provides insight into homonuclear dipolar decoupling schemes that combine radio-frequency irradiation with fast rotation of the sample at the magic-angle with respect to the static magnetic field.

Powder NMR crystallography of thymol.

A protocol for the structure determination of powdered solids at natural abundance by NMR is presented and illustrated for the case of the small drug molecule thymol. The procedure uses proton spin-diffusion data from two-dimensional NMR experiments in combination with periodic DFT refinements incorporating (1)H and (13)C NMR chemical shifts. For thymol, the method yields a crystal structure for the powdered sample, which differs by an atomic root-mean-square-deviation (all atoms except methyl group protons) of only 0.07 A from the single crystal X-ray diffraction structure with DFT-optimized proton positions.