Probing Particle-Carbon/Binder Degradation Behavior in Fatigued Layered Cathode Materials through Machine Learning Aided Diffraction Tomography.

Understanding how reaction heterogeneity impacts cathode materials during Li-ion battery (LIB) electrochemical cycling is pivotal for unraveling their electrochemical performance. Yet, experimentally verifying these reactions has proven to be a challenge. To address this, we employed scanning µ-XRD computed tomography to scrutinize Ni-rich layered LiNi0.6Co0.2Mn0.2O2 (NCM622) and Li-rich layered Li[Li0.2Ni0.2Mn0.6]O2 (LLNMO). By harnessing machine learning (ML) techniques, we scrutinized an extensive dataset of µ-XRD patterns, about 100,000 patterns per slice, to unveil the spatial distribution of crystalline structure and microstrain. Our experimental findings unequivocally reveal the distinct behavior of these materials. NCM622 exhibits structural degradation and lattice strain intricately linked to the size of secondary particles. Smaller particles and the surface of larger particles in contact with the carbon/binder matrix experience intensified structural fatigue after long-term cycling. Conversely, both the surface and bulk of LLNMO particles endure severe strain-induced structural degradation during high-voltage cycling, resulting in significant voltage decay and capacity fade. This work holds the potential to fine-tune the microstructure of advanced layered materials and manipulate composite electrode construction in order to enhance the performance of LIBs and beyond.

Elucidation of Structure-Activity Relations in Proton Electroreduction at Pd Surfaces: Theoretical and Experimental Study.

The structure-activity relationship is a cornerstone topic in catalysis, which lays the foundation for the design and functionalization of catalytic materials. Of particular interest is the catalysis of the hydrogen evolution reaction (HER) by palladium (Pd), which is envisioned to play a major role in realizing a hydrogen-based economy. Interestingly, experimentalists observed excess heat generation in such systems, which became known as the debated "cold fusion" phenomenon. Despite the considerable attention on this report, more fundamental knowledge, such as the impact of the formation of bulk Pd hydrides on the nature of active sites and the HER activity, remains largely unexplored. In this work, classical electrochemical experiments performed on model Pd(hkl) surfaces, "noise" electrochemical scanning tunneling microscopy (n-EC-STM), and density functional theory are combined to elucidate the nature of active sites for the HER. Results reveal an activity trend following Pd(111) > Pd(110) > Pd(100) and that the formation of subsurface hydride layers causes morphological changes and strain, which affect the HER activity and the nature of active sites. These findings provide significant insights into the role of subsurface hydride formation on the structure-activity relations toward the design of efficient Pd-based nanocatalysts for the HER.

Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study.

Lithium iron phosphate, LiFePO4, a widely used cathode material in commercial Li-ion batteries, unveils a complex defect structure, which is still being deciphered. Using a combined computational and experimental approach comprising density functional theory (DFT)+U and molecular dynamics calculations and X-ray and neutron diffraction, we provide a comprehensive characterization of various OH point defects in LiFePO4, including their formation, dynamics, and localization in the interstitial space and at Li, Fe, and P sites. It is demonstrated that one, two, and four (five) OH groups can effectively stabilize Li, Fe, and P vacancies, respectively. The presence of D (H) at both Li and P sites for hydrothermally synthesized deuterium-enriched LiFePO4 is confirmed by joint X-ray and neutron powder diffraction structure refinement at 5 K that also reveals a strong deficiency of P of 6%. The P occupancy decrease is explained by the formation of hydrogarnet-like P/4H and P/5H defects, which have the lowest formation energies among all considered OH defects. Molecular dynamics simulation shows a rich structural diversity of these defects, with OH groups pointing both inside and outside vacant P tetrahedra creating numerous energetically close conformers, which hinders their explicit localization with diffraction-based methods solely. The discovered conformers include structural water molecules, which are only by 0.04 eV/atom H higher in energy than separate OH defects.

MnSnTeO6: A Chiral Antiferromagnet Prepared by a Two-Step Topotactic Transformation.

MnSnTeO6, a new chiral antiferromagnet, was prepared both by topotactic transformation of the metastable rosiaite-type polymorph and by direct synthesis from coprecipitated hydroxides. Its structure and its static and dynamic magnetic properties were studied comprehensively both experimentally (through X-ray and neutron powder diffraction, magnetization, specific heat, dielectric permittivity, and ESR techniques) and theoretically (by means of ab initio density functional theory (DFT) calculations within the spin-polarized generalized gradient approximation). MnSnTeO6 is isostructural with MnSb2O6 (space group P321) and does not show any structural transition between 3 and 300 K. The magnetic susceptibility and specific heat exhibit an antiferromagnetic ordering at TN ≈ 9.8 K, which is confirmed by low-temperature neutron data. At the same time, the thermodynamic parameters demonstrate an additional anomaly on the temperature dependences of magnetic susceptibility χ(T), specific heat Cp(T) and dielectric permittivity ε(T) at T* ≈ 4.9 K, which is characterized by significant temperature hysteresis. Clear enhancement of the dielectric permittivity at T* is most likely to reflect the coupling of dielectric and magnetic subsystems leading to development of electric polarization. It was established that the ground state of MnSnTeO6 is stabilized by seven exchange parameters, and neutron diffraction revealed incommensurate magnetic structure with propagation vector k = (0, 0, 0.183) analogous to that of MnSb2O6. Ab initio DFT calculations demonstrate that the strongest exchange coupling occurs between planes along diagonals. All exchange parameters are antiferromagnetic and reveal moderate frustration.

Fast Ionic Conductivity in the Most Lithium-Rich Phosphidosilicate Li14SiP6.

Solid electrolytes with superionic conductivity are required as a main component for all-solid-state batteries. Here we present a novel solid electrolyte with three-dimensional conducting pathways based on "lithium-rich" phosphidosilicates with ionic conductivity of σ > 10-3 S cm-1 at room temperature and activation energy of 30-32 kJ mol-1 expanding the recently introduced family of lithium phosphidotetrelates. Aiming toward higher lithium ion conductivities, systematic investigations of lithium phosphidosilicates gave access to the so far lithium-richest compound within this class of materials. The crystalline material (space group Fm3m), which shows reversible thermal phase transitions, can be readily obtained by ball mill synthesis from the elements followed by moderate thermal treatment of the mixture. Lithium diffusion pathways via both tetrahedral and octahedral voids are analyzed by temperature-dependent powder neutron diffraction measurements in combination with maximum entropy method and DFT calculations. Moreover, the lithium ion mobility structurally indicated by a disordered Li/Si occupancy in the tetrahedral voids plus partially filled octahedral voids is studied by temperature-dependent impedance and 7Li NMR spectroscopy.

Sr3CrN3: A New Electride with a Partially Filled d-Shell Transition Metal.

Electrides are ionic crystals in which the electrons prefer to occupy free space, serving as anions. Because the electrons prefer to be in the pockets, channels, or layers to the atomic orbitals around the nuclei, it has been challenging to find electrides with partially filled d-shell transition metals, since an unoccupied d-shell provides an energetically favorable location for the electrons to occupy. We recently predicted the existence of electrides with partially filled d-shells using high-throughput computational screening. Here, we provide experimental support using X-ray absorption spectroscopy and X-ray and neutron diffraction to show that Sr3CrN3 is indeed an electride despite its partial d-shell configuration. Our findings indicate that Sr3CrN3 is the first known electride with a partially filled d-shell transition metal, in agreement with theory, which significantly broadens the criteria for the search for new electride materials.

Electrostrain in excess of 1% in polycrystalline piezoelectrics.

Piezoelectric actuators transform electrical energy into mechanical energy, and because of their compactness, quick response time and accurate displacement, they are sought after in many applications. Polycrystalline piezoelectric ceramics are technologically more appealing than single crystals due to their simpler and less expensive processing, but have yet to display electrostrain values that exceed 1%. Here we report a material design strategy wherein the efficient switching of ferroelectric-ferroelastic domains by an electric field is exploited to achieve a high electrostrain value of 1.3% in a pseudo-ternary ferroelectric alloy system, BiFeO3-PbTiO3-LaFeO3. Detailed structural investigations reveal that this electrostrain is associated with a combination of several factors: a large spontaneous lattice strain of the piezoelectric phase, domain miniaturization, a low-symmetry ferroelectric phase and a very large reverse switching of the non-180° domains. This insight for the design of a new class of polycrystalline piezoceramics with high electrostrains may be useful to develop alternatives to costly single-crystal actuators.

Inducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li6+ xP1- xGe xS5I for All-Solid-State Batteries.

Solid-state batteries with inorganic solid electrolytes are currently being discussed as a more reliable and safer future alternative to the current lithium-ion battery technology. To compete with state-of-the-art lithium-ion batteries, solid electrolytes with higher ionic conductivities are needed, especially if thick electrode configurations are to be used. In the search for optimized ionic conductors, the lithium argyrodites have attracted a lot of interest. Here, we systematically explore the influence of aliovalent substitution in Li6+ xP1- xGe xS5I using a combination of X-ray and neutron diffraction, as well as impedance spectroscopy and nuclear magnetic resonance. With increasing Ge content, an anion site disorder is induced and the activation barrier for ionic motion drops significantly, leading to the fastest lithium argyrodite so far with 5.4 ± 0.8 mS cm-1 in a cold-pressed state and 18.4 ± 2.7 mS cm-1 upon sintering. These high ionic conductivities allow for successful implementation within a thick-electrode solid-state battery that shows negligible capacity fade over 150 cycles. The observed changes in the activation barrier and changing site disorder provide an additional approach toward designing better performing solid electrolytes.

Crystal and Magnetic Structures of the Chain Antiferromagnet CaFe4Al8.

The crystal structure of CaFe4Al8 was studied by X-ray single crystal and powder diffraction as well as high-resolution neutron powder diffraction. CaFe4Al8 crystallizes with a tetragonal CeMn4Al8-type structure, an ordered variant of the ThMn12-type (Pearson symbol tI26, space group I4/ mmm, a = 8.777(1), c = 5.077(1) Å). Similarly to the well-known A15-type superconductors, the structure of CaFe4Al8 contains one-dimensional chains of d-metal atoms, which are parallel to the crystallographic fourfold axis. CaFe4Al8 is paramagnetic at room temperature and exhibits long-range antiferromagnetic ordering at about 180 K, combined with a short-range ordered spin arrangement. The magnetic structure, determined by powder neutron diffraction at 4 K, shows that the magnetic moments on the Fe atoms form mirror-inverted chains along the c-direction and are slightly canted from the axis.

Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I).

In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochemical impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic conductivity, we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic conductivity.

Structural Stability from Crystallographic Shear in TiO2-Nb2O5 Phases: Cation Ordering and Lithiation Behavior of TiNb24O62.

The host structure and reversible lithium insertion and extraction of an intercalation compound, TiNb24O62, are described. Neutron diffraction, applied for the first time to TiNb24O62, allowed an accurate refinement of the complex block superstructure, particularly with respect to the oxygen sublattice. Analysis of the transition-metal sites revealed significant cation ordering in the mixed-metal oxide. Electrochemical analysis demonstrated highly reversible lithium intercalation with ca. 190 mA·h·g-1 after 100 cycles (C/10 rate, 3 months). The effect of the potential window on the capacity, polarization, and reversibility was carefully examined; a minimum voltage limit of 1.1-1.2 V is critical for efficient and reversible cycling. The galvanostatic intermittent titration technique revealed three solid-solution regions, with different lithium diffusivities, in addition to the two-phase plateau that was clearly observed in the V versus Q discharge/charge profile. Lithium-ion diffusion decreases by over 3 orders of magnitude from the dilute lithium limit early in the discharge to the lithium-stuffed phase Li37.5(1.0)TiNb24O62. Nevertheless, prior to lithium stuffing, TiNb24O62 possesses intrinsically rapid lithium-ion kinetics, as demonstrated by the high-rate performance in thick films of ca. 10 µm particles when interfaced with a carbon-coated aluminum foil substrate. The TiO2·Nb2O5 phase diagram is examined and electrochemical results are compared to related superstructures of crystallographically sheared blocks of octahedra in the TiO2·Nb2O5 homologous series including the H-Nb2O5 end member.

Synthesis, Structural Characterization, and Lithium Ion Conductivity of the Lithium Thiophosphate Li2P2S6.

Inspired by the ongoing search for new superionic lithium thiophosphates for use in solid-state batteries, we present the synthesis and structural characterization of Li2P2S6, a novel crystalline lithium thiophosphate. Whereas M2P2S6 with the different alkaline elements (M = Na, K, Rb, Cs) is known, the lithium counterpart has not been reported yet. Herein, we present a combination of synchrotron pair distribution function analysis and neutron powder diffraction to elucidate the crystal structure and possible Li+ diffusion pathways of Li2P2S6. Additionally, impedance spectroscopy is used to evaluate its ionic conductivity. We show that Li2P2S6 possesses P2S62- polyhedral units with edge-sharing PS4 tetrahedra and only one-dimensional diffusion pathways with localized Li-Li pairs, leading to a low ionic conductivity for lithium.

Flux Synthesis, Crystal Structures, and Magnetic Ordering of the Rare-Earth Chromium(II) Oxyselenides RE2CrSe2O2 (RE = La-Nd).

The rare-earth chromium(II) oxyselenides RE2CrSe2O2 (RE = La-Nd) were synthesized in eutectic NaI/KI fluxes, and their crystal structures were determined by single-crystal and powder X-ray diffraction (Pb2HgCl2O2-type, C2/m, Z = 2). The magnetic structure of La2CrSe2O2 was solved and refined from neutron powder diffraction data. Main building blocks are chains of edge-sharing CrSe4O2 octahedra linked together by two edge-sharing ORE3Cr tetrahedra forming infinite ribbons. The Jahn-Teller instability of divalent Cr2+ (d4) leads to structural phase transitions at 200 and 130 K in La2CrSe2O2 and Ce2CrSe2O2, respectively. RE2CrSe2O2 are Curie-Weiss paramagnetic above TN ≈ 14-17 K. Neutron powder diffraction reveals anti-ferromagnetic ordering of the Cr2+ moments in La2CrSe2O2 below TN = 12.7(3) K with an average ordered moment of 3.40(4) µB/Cr2+ at 4 K, which was confirmed by muon spin rotation experiments.

Structural and Magnetic Properties of the Trirutile-type 1D-Heisenberg Anti-Ferromagnet CuTa2O6.

We prepared trirutile-type polycrystalline samples of CuTa2O6 by low-temperature decomposition of a Cu-Ta-oxalate precursor. Diffraction studies at room temperature identified a slight monoclinic distortion of the hitherto surmised tetragonal trirutile crystal structure. Detailed high-temperature X-ray and neutron powder diffraction investigations as well as Raman scattering spectroscopy revealed a structural phase transition at 503(3) K from the monoclinic structure to the tetragonal trirutile structure. GGA+U density functional calculations of the spin-exchange parameters as well as magnetic susceptibility and isothermal magnetization measurements reveal that CuTa2O6 is a new 1D Heisenberg magnet with predominant anti-ferromagnetic nearest-neighbor intrachain spin-exchange interaction of ∼50 K. Interchain exchange is a factor of ∼5 smaller. Heat capacity and low-temperature high-intensity neutron powder diffraction studies could not detect long-range order down to 0.45 K.

Molybdenum Oxide Nitrides of the Mo2(O,N,□)5 Type: On the Way to Mo2O5.

Blue-colored molybdenum oxide nitrides of the Mo2(O,N,□)5 type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting MoVO6 units. The new materials are stable up to ∼773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb9O24.9-type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo2O5. On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo2O5, backed by electronic-structure and phonon calculations from first principles, is given.

Lithium Diffusion Pathway in Li(1.3)Al(0.3)Ti(1.7)(PO4)3 (LATP) Superionic Conductor.

The Al-substituted LiTi2(PO4)3 powders Li(1+x)Al(x)Ti(2-x)(PO4)3 (LATP) were successfully prepared by a water-based sol-gel process with subsequent calcination and sintering. The crystal structure of obtained samples was characterized at different temperatures using high-resolution synchrotron-based X-ray and neutron powder diffraction. Possible lithium diffusion pathways were initially evaluated using the difference bond-valence approach. Experimental 3D lithium diffusion pathway in LATP was extracted from the negative nuclear density maps reconstructed by the maximum entropy method. Evaluation of the energy landscape determining the lithium diffusion process in NASICON-type superionic conductor is shown for the first time.

Sc2NiMnO6: A Double-Perovskite with a Magnetodielectric Response Driven by Multiple Magnetic Orders.

Perovskite materials provide a large variety of interesting physical properties and applications. Here, we report on unique properties of a fully ordered magnetodielectric double-perovskite, Sc2NiMnO6 (space group P21/n, a = 4.99860 Å, b = 5.35281 Å, c = 7.34496 Å, and ß = 90.7915°), exhibiting sequential magnetic transitions at T1 = 35 K and T2 = 17 K. The transition at T1 corresponds to a single-k antiferromagnetic phase with propagation vector k1 = (1/2, 0, 1/2), while the second transition at T2 corresponds to a 2-k magnetic structure with propagation vectors k1 = (1/2, 0, 1/2) and k2 = (0, 1/2, 1/2). Symmetry analysis suggests that the two ordering wave vectors are independent, and calculations imply that k1 is associated with the Mn sublattice and k2 with the Ni sublattice, suggesting that Mn-Ni coupling is very small or absent. A magnetodielectric anomaly at T2 likely arises from an antiferroelectric ordering that results from the exchange-striction between the two magnetic sublattices belonging to k1 and k2. The behavior of Sc2NiMnO6 demonstrates 3d double-perovskites with small A-site cations as a promising avenue in which to search for magnetoelectric materials.

A combined metal-halide/metal flux synthetic route towards type-I clathrates: crystal structures and thermoelectric properties of A8Al8Si38 (A = K, Rb, and Cs).

Single-phase samples of the compounds K8Al8Si38 (1), Rb8Al8Si38 (2), and Cs7.9Al7.9Si38.1 (3) were obtained with high crystallinity and in good quantities by using a novel flux method with two different flux materials, such as Al and the respective alkali-metal halide salt (KBr, RbCl, and CsCl). This approach facilitates the removal of the product mixture from the container and also allows convenient extraction of the flux media due to the good solubility of the halide salts in water. The products were analyzed by means of single-crystal X-ray structure determination, powder X-ray and neutron diffraction experiments, (27)Al-MAS NMR spectroscopy measurements, quantum chemical calculations, as well as magnetic and transport measurements (thermal conductivity, electrical resistivity, and Seebeck coefficient). Due to the excellent quality of the neutron diffraction data, the difference between the nuclear scattering factors of silicon and aluminum atoms was sufficient to refine their mixed occupancy at specific sites. The role of variable-range hopping for the interpretation of the resistivity and the Seebeck coefficient is discussed.

Data-driven capacity estimation of commercial lithium-ion batteries from voltage relaxation.

Accurate capacity estimation is crucial for the reliable and safe operation of lithium-ion batteries. In particular, exploiting the relaxation voltage curve features could enable battery capacity estimation without additional cycling information. Here, we report the study of three datasets comprising 130 commercial lithium-ion cells cycled under various conditions to evaluate the capacity estimation approach. One dataset is collected for model building from batteries with LiNi0.86Co0.11Al0.03O2-based positive electrodes. The other two datasets, used for validation, are obtained from batteries with LiNi0.83Co0.11Mn0.07O2-based positive electrodes and batteries with the blend of Li(NiCoMn)O2 - Li(NiCoAl)O2 positive electrodes. Base models that use machine learning methods are employed to estimate the battery capacity using features derived from the relaxation voltage profiles. The best model achieves a root-mean-square error of 1.1% for the dataset used for the model building. A transfer learning model is then developed by adding a featured linear transformation to the base model. This extended model achieves a root-mean-square error of less than 1.7% on the datasets used for the model validation, indicating the successful applicability of the capacity estimation approach utilizing cell voltage relaxation.

Two stage magnetic ordering and spin idle behavior of the coordination polymer Co3(OH)2(C4O4)2·3H2O determined using neutron diffraction.

We report the magnetic structure of two of the magnetically ordered phases of Co(3)(OH)(2)(C(4)O(4))(2)·3H(2)O, a coordination polymer that consists of a triangular framework decorated with anisotropic Co(II) ions. The combination of neutron diffraction experiments and magnetic susceptibility data allows us to identify one phase as displaying spin idle behavior, where only a fraction of the moments order at intermediate temperatures, while at the lowest temperatures the system orders fully. This novel magnetic behavior is discussed within the framework of a simple Hamiltonian and representational analysis and rationalizes this multiphase behavior by considering the combination of frustration and anisotropy.