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Conditions such as the temperature and pressure experienced by lithium-ion battery components are dependent oncell geometry and can vary widely within a large cell. The resulting uneven degradation is challenging to study at thefull cell level but can be revealed upon disassembly and post mortem analysis. In this work, we report localizedlithium plating in automotive-grade, prismatic lithium-ion cells, also under cycling conditions generally consideredto be mild (e.g., 5–65 %SOC, 23 ◦C, 0.5C cycle rate). Dead lithium content is quantified using 7Li nuclear magneticresonance spectroscopy in both electrode and separator samples, corresponding to substantial capacity fade(26–46%) of the full cells. Severe lithium plating is typically initiated in regions near the positive tab, in which boththe separators and negative electrodes are ultimately deactivated. High pressure arises during cycling, and wepropose a deactivation mechanism based on high local stress due to electrode expansion and external constraint.Further, we develop a model to demonstrate that component deactivation can result in lithium plating even undermild cycling conditions. Notably, components harvested from regions with no detected lithium plating maintainedadequate electrochemical performance. QC 20230522

Advances in methodologies for real-time analysis of batteries have come a long way, especially with the development of Operando Electrochemical Mass Spectrometry (OEMS). These approaches allow for the deter-mination of side reactions during battery cycling with unprecedented selectivity and sensitivity, providing vital information necessary for determination of lifetime-limiting processes. However, the work thus far has primarily been carried out on model battery systems, where cell atmospheres are largely altered (through open flow, closed cell, and intermittent sampling approaches) and operation conditions are therefore not comparable with real-life situations. Herein, the development and validation of an intermittently closed OEMS system adapted for readily available commercial batteries is showcased. We provide a detailed description of a unique analysis design for large-format PHEV2 cells, with subsequent pressure and gassing data. A qualitative analysis of the results shows that side reactions brought on by structural transitions within both electrodes can be clearly observed. Transi-tions causing large volume changes in graphite induce H2 and C2H4 as SEI reformation products while the c lattice collapse in NMC induces CO2 evolution (through O2 release). OEMS can therefore be used for the quick and effective study of commercially available rechargeable batteries without influencing the internal battery chemistry.

Developing high specific energy Lithium-ion (Li-ion) batteries is of vital importance to boost the production of efficient electric vehicles able to meet the customers’ expectation related to the electric range of the vehicle. One possible pathway to high specific energy is to increase the operating voltage of the Li-ion cell. Cathode materials enabling operation above 4.2 V are available. The stability of the positive electrode-electrolyte interface is still the main bottleneck to develop high voltage cells. Moreover, important research efforts are devoted to the substitution of graphite anodes with Li metal: this would improve the energy density of the cell dramatically. The use of metallic lithium is prevented by the dendrite growth during charge, with consequent safety problems. To suppress the formation of dendrites solid-state electrolytes are considered the most promising approach. For these reasons the present review summarizes the most recent research efforts in the field of high voltage solid-state electrolytes for high energy density Li-ion cells.

The energy density and lifetime of lithium-ion cells for automotive applications have both substantially improved in recent years. This enables electric vehicles in both the consumer and commercial sectors that have greater range, better reliability, and longer service lives [1]. These factors all contribute to the widespread adoption of electric vehicles. However, inhomogeneities exist within cells that contribute to uneven internal degradation and, when severe, can trigger rapid failure. These inhomogeneities can be related to manufacturing tolerances or distributions of component parameters [2], as well as gradients in internal or external conditions. As such, the reality of heterogeneous aging is a complex, multivariate problem to solve. In this latest work, we cycle automotive-grade prismatic cells for several thousand cycles (until 10-30 % capacity fade) and harvest components for post mortem aging characterization and experimental parameter identification. The constituent electrodes are a Ni-rich layered oxide (approximately LiNi0.76Mn0.15Co0.09O2) and graphite. In addition to microscopy and electrochemical testing on harvested electrodes, we quantify local lithium plating on graphite with our recently developed method utilizing ex-situ, 7Li nuclear magnetic resonance spectroscopy [3]. We believe this to be the first report of spatially-resolved lithium plating quantification in commercial lithium-ion cells. Clear patterns emerge (see Figure 1), reflecting the geometry of the cell and showing reproducible heterogeneity that cannot be attributed solely to defects in manufacture. Several tests even confirm local lithium plating and unusually rapid degradation at comparatively mild cycle conditions (slow charge/discharge, low state-of-charge, and room temperature). The wound jellyroll design in contemporary prismatic cells enables very high packing efficiency and energy density, but includes inherently weak points from where lithium plating and internal stresses [4] can propagate. In some cases, cells achieve satisfactory lifetimes without accelerated aging. In others, heterogeneities cause extreme local degradation that triggers end-of-life even though other regions may remain relatively intact. We explore the causes of these patterns and question how such damage can occur, even under cycling conditions usually considered safe. References [1] P. Svens et al., IEEE Trans. Transp. Electrif., (2022), doi:10.1109/TTE.2022.3158838. [2] D. Beck et al., Energies, 14 (2022), 3276, doi:10.3390/en14113276. [3] Y. Fang et al., manuscript submitted, (2022). [4] P. Gupta and P. Gudmundson, J. Power Sources, 511 (2021), 230465, doi:10.1016/j.jpowsour.2021.230465. Figure 1

The solid-state synthesis and structural characterisation of perovskite BaSn1−xScxO3−δ (x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pmm) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. 119Sn and 45Sc solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D2O. It also indicates that the Sn4+ and Sc3+ local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x ≤ 0.2) and in the tin coordination shell at high concentrations (x ≥ 0.3). 17O NMR spectra on 17O enriched BaSn1−xScxO3−δ materials show the existence of Sn–O–Sn, Sn–O–Sc and Sc–O–Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn0.6Sc0.4O3−δ refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O–D bond distance of 0.96(1) A and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 °C with total conductivity values in the range 1.8 × 10−4 to 1.1 × 10−3 S cm−1 between 300 and 600 °C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 °C temperature region, and a suppression of the conductivity at higher temperature.

Overcurrent abuse has been performed on commercial 48 Ah primary prismatic zinc (Zn)–Air battery cells with full air supply as well as with shut-off air supply. Compared to other battery technologies, e.g., lithium-ion batteries, metal–air batteries offer the possibility to physically stop the battery operation by stopping its air supply, thus offering an additional protection against severe battery damage in the case of, e.g., an accidental short circuit. This method may also reduce the electrical hazard in a larger battery system since, by stopping the air supply, the voltage can be brought to zero while maintaining the energy capacity of the battery. Measurements of overdischarge currents and current cut-off by suffocation have been performed to assess the safety of this type of Zn–air battery. The time to get to zero battery voltage is shown to mainly be determined by the volume of air trapped in the cell.

In situ neutron diffraction experiments of 2% Ca-doped and nominally undoped lanthanum tungstate (La28-xW4+xO54+3x/2, with x = 0.85) have been carried out under controlled pD(2)O and pO(2) at elevated temperatures. All the diffraction patterns could be refined using an average cubic fluorite-related structure, in accordance with recent reports. The material exhibits disorder of the oxygen and the cation sublattices. Splitting of the oxygen sites around tungsten from the 32f to 96k Wyckoff position in the Fm (3) over barm space group improves the model and can better represent the oxygen disorder. No phase transition was detected from room temperature up to 800 degrees C under any of the studied conditions. Expansion of the unit cell constants in the presence of water at intermediate and low temperatures was correlated with the formation of protonic defects. The thermal expansion coefficient for lanthanum tungstate is rather linear under all studied conditions (similar to 11 x 10(-6) K-1). The in situ diffraction studies are correlated with dilatometry investigations and conductivity measurements.

The crystal structure, hydration and ionic conductivity of the inherently oxygen deficient La2Ce2O7 system have been investigated. On the basis of Rietveld analysis of neutron diffraction data, the material is found to adopt a cation disordered oxygen-deficient fluorite structure. Impedance spectroscopy, performed in the temperature range 1000-200 degrees C and as a function of water vapor and oxygen partial pressure, suggests that oxide ion conductivity dominates at high temperatures, while protons are the main charge carrier at temperatures below approximately 450 degrees C. Proton conductivity was confirmed by isotope shifts under H2O and D2O. The dissolution of water was measured by means of thermogravimetry (TG). A defect chemical model is developed to derive hydration thermodynamic parameters based on TG and conductivity data. The hydration enthalpy was, moreover, determined directly by simultaneous TG and differential scanning calorimetry (TG-DSC). The TG-DSC values were in good agreement with those modeled from conductivity and TG data.

The structural properties of the binary alkaline-earth halides SrCl(2), SrBr(2), BaCl(2) and BaBr(2) have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl(2) undergoes a gradual transition to a superionic phase at 900-1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr(2) undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl(2), BaCl(2) and BaBr(2) both adopt the cotunnite crystal structure under ambient conditions. BaCl(2) undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored.

In-situ neutron diffraction combined with AC impedance spectroscopy was applied successfully to investigate the correlation between crystal structure and electrical properties of the La2Mo2O9 oxide ion conducting electrolyte material. Neutron diffraction patterns were collected as a function of temperature while the AC impedance spectra were recorded simultaneously using a modified sample environment to monitor the conductivity change of the sample. A close relationship between unit cell parameters and the bulk conductivity was observed, confirming that the oxygen transport is dependent on the lattice structure. With the transition from the low temperature alpha to the high temperature beta phase, expansion of the crystal structure makes more space available for oxygen transport, leading to a dramatic increase of the ionic conductivity. The successful application of this technique provides a new method to simultaneously investigate crystal structure and electrical properties in electro-ceramics in the future.

The influence of local ordering of the anion vacancies and cation-anion vacancy interactions on the ionic conductivity of the anion-deficient fluorite Zr0.8Sc0.2-xYxO1.9 (0.0 ≥ x ≥ 0.2) system have been investigated using impedance spectroscopy, molecular dynamics (MD) simulations, and reverse Monte Carlo (RMC) analysis of neutron powder diffraction data. At 1000 K, the ionic conductivity decreases by a factor of ∼2 as x increases from 0.0 to 0.2, while the oxygen anion partial radial distribution function, gOO(r), remains similar across the entire solid solution, even though the cation-oxygen interactions change with increasing Y2O3 content. These experimental data are used to validate the MD simulations, which probe the details of the vacancy-vacancy interactions within the x = 0.0 and x = 0.2 end members. Both possess similar vacancy-vacancy ordering that favors the formation of pairs along 〈111〉 directions. Significantly, an increased proportion of the oxygen vacancies are associated with the Zr4+ cations in Zr 0.8Y0.2O1.9, while in Zr0.8Sc 0.2O1.9 they show no significant preference for being nearest neighbor to a Sc3+ or a Zr4+ cation. Thus, it is concluded that the lower ionic conductivity at x = 0.2 is predominantly a consequence of the larger size of the Y3+ cation, which induces strain in the lattice and hinders diffusion of the O2-, rather than changes in the local ordering of the anion vacancies. © 2011 American Chemical Society.

The electrical properties of nominally undoped and 4 mol% Y-doped PbZrO3 have been investigated by AC conductivity measurements and impedance spectroscopy under various p(H2)O and p(O2) at high temperatures. The results indicate that the defect structures are dominated by acceptors (Y dopant and/or Pb vacancies formed during synthesis). In dry atmosphere and at high temperatures, the acceptors are compensated by oxygen vacancies. These are hydrated and replaced by protonic defects (hydroxide ions on oxide ion sites) at higher p(H2)o and lower temperatures. In oxidizing atmospheres, a minority concentration of electron holes dominates the conductivity. At lower temperatures and in wet atmosphere, a significant protonic conductivity contribution is also observed. Based on p(O2) and p(H2)o isotherms, a model for incorporation of protonic defects has been applied, and the standard enthalpy of hydration of oxygen vacancies in undoped PbZrO3 has been determined (-1.07 +/- 0.13 eV). The measured total conductivities are influenced by high grain boundary resistance. Hence, the enthalpy is at the present stage assigned to the polycrystalline ceramic material as such. Rough estimates of bulk proton mobility in Y-doped PbZrO3 yield u(H)(0)+ = 17 cm(2)K/Vs and Delta H-m,H(+) = 0.93 eV. A complementary DFT study of the hydration thermodynamics of PbZrO3 and the alkaline earth zirconate perovskites AZrO(3) (A = Ca, Sr, Ba) is also reported. The experimental and theoretical hydration enthalpies are compared with those of other ABO(3) perovskites. Correlations between the hydration thermodynamics and other properties of the materials are discussed. (C) 2009 Elsevier B.V. All rights reserved.

The structural properties of anion deficient ceria, CeO2-delta, have been studied as a function of oxygen partial pressure, p(O-2), over the range 0 >= log(10)p(O-2) >= -18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O-2) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, delta, and the isotropic thermal vibration parameters, u(Ce) and u(O), starting at log(10)p(O-2)similar to-11. The increases are continuous, but show a distinct kink at log(10)p(O-2)similar to-14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O2- vacancies preferentially align as pairs in the cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO2-Ce2O3 system at ambient temperature and, in particular, to the nature of the long-range ordering of O2- vacancies within the crystal structure of Ce7O12. (C) 2009 Elsevier Inc. All rights reserved.

Proton motions in hydrated proton conducting perovskites BaZr(0.90)A(0.10)O(2.95) (A = Y and Sc) have been investigated using quasielastic neutron scattering. The results reveal a localized motion on the ps time scale and with an activation energy of similar to 10-30 meV, in both materials. The temperature dependence of the total mean square displacement of the protons shows an onset of this motion at a temperature of about 300 K. The low activation energy, much lower than the activation energy for the macroscopic proton conductivity, suggests that this motion is not the rate-limiting process for the long-range proton diffusion, i.e. it is not linked to the two materials significantly different proton conductivities. In fact, a comparison of the QENS results with density functional theory calculations indicates that for both materials the observed motion may be ascribed to intra-octahedral proton transfers occurring close to a dopant atom. (C) 2008 Elsevier B.V. All rights reserved.

Solid-state sintering has been used to prepare the perovskite BaZr0.9Sc0.1O3-delta. Analysis of X-ray powder diffraction data shows that an increase of the unit cell parameter, a, was observed after deuteration. Rietveld analysis of room-temperature neutron powder diffraction data confirmed cubic symmetry (space group Pm-3m). Dynamic thermogravimetric analysis indicates that the hydration process occurs below 335 degrees C and approximately 58% of the theoretical number of protonic defects can be filled. The presence of protons/deutrons is seen from the strong O-H/O-D stretch band in the infrared spectrum of the hydrated/deuterated samples. The proton conductivity of a prehydrated sample was investigated under dry and wet Ar atmospheres

In a systematic study, we investigate the effect of dopant level and hydration on the short-range structure of the proton-conducting perovskite-type oxide BaInxZr1-xO3-x/2 (x = 0 - 0.75), using infrared and Raman spectroscopy. The results show that the doping leads to significant local distortions of the average cubic structure of these materials. By increasing the In concentration from x = 0 to x = 0.75, new bands appear and grow in intensity in both the IR and the Raman spectra, showing that the local distortions become successively more and more pronounced. The structural distortions are largely uncorrelated to the presence of oxygen vacancies, but instead are mainly driven by the size and charge difference between the In3+ and Zr4+ ions, which leads to displacements of the cations and to tilting of the (In/Zr)O-6 octahedra. On the basis of our results, we suggest that there is a threshold between x = 0.10 and x = 0.25 where the structural distortions propagate throughout the whole perovskite structure. Comparison of our spectroscopic data with the proton conductivity for the same materials indicates that the presence of extended structural distortions is favorable for fast proton transport.

High-resolution neutron powder diffraction data have been collected on deuterated and dried samples of the perovskite BaZr0.5In0.5O2.75 at 5 K and room temperature, respectively. Inspection of Fourier nuclear density maps for the deuterated phase have allowed the deuteron position to be refined on a 12h (1/2, y, 0) crystallographic site, with y = 0.217(4) yielding a chemically reasonable O-D distance of 0.92(2) angstrom. Evidence for anisotropy of the deuteron position is also found consistent with a 24k crystallographic site (0.56, 0.21, 0) indicative of displacements of the ion towards neighbouring oxygen ions. The presence of static oxygen disorder in both the dried and deuterated samples is apparent from the structural analyses. Raman spectra confirm short range deviations from cubic symmetry for both dried and hydrated samples.

BaSn0.6Sc0.4O3–δ: location of the proton using neutrons with insights into its high conductivity and local environment using EIS and NMR., The solid-state synthesis and structural characterisation of perovskite BaSn1–xScxO3–δ (x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pm3m) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. 119Sn and 45Sc solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D2O. It also indicates that the Sn4+ and Sc3+ local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x ≤ 0.2) and in the tin coordination shell at high concentrations (x ≥ 0.3). 17O NMR spectra on 17O enriched BaSn1–xScxO3–δ materials show the existence of Sn–O–Sn, Sn–O–Sc and Sc–O–Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn0.6Sc0.4O3–δ refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O–D bond distance of 0.96(1) Å and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 °C with total conductivity values in the range 1.8 × 10–4 to 1.1 × 10–3 S cm–1 between 300 and 600 °C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 °C temperature region, and a suppression of the conductivity at higher temperature.

The intermediate scattering function, I(Q,t), of proton-conducting hydrated BaZr0.90Y0.10O2.95 is explored for temperatures in the range 473−650 K and momentum transfers Q = 0.15−0.3 A−1. The exponential decay of I(Q,t) suggests that the long-range self-diffusion of protons, which occurs as a series of proton transfers between neighboring oxygens and reorientational motion of the −OH group in between such transfers, is observed.

The Zr(0.5-0.5x)Y(0.5+0.25x)Nb(0.25x)O(1.75) solid solution possesses an anion-deficient fluorite structure across the entire 0≤x≤1 range. The relationship between the disorder within the crystalline lattice and the preferred anion diffusion mechanism has been studied as a function of x, using impedance spectroscopy measurements of the ionic conductivity (σ), powder neutron diffraction studies, including analysis of the 'total' scattering to probe the nature of the short-range correlations between ions using reverse Monte Carlo (RMC) modelling, and molecular dynamics (MD) simulations using potentials derived with a strong ab initio basis. The highest total ionic conductivity (σ = 2.66 × 10(-2) Ω(-1) cm(-1) at 1473 K) is measured for the Zr(2)Y(2)O(7) (x = 0) end member, with a decrease in σ with increasing x, whilst the neutron diffraction studies show an increase in lattice disorder with x. This apparent contradiction can be understood by considering the local structural distortions around the various cation species, as determined from the RMC modelling and MD simulations. The addition of Nb(5+) and its stronger Coulomb interaction generates a more disordered local structure and enhances the mobility of some anions. However, the influence of these pentavalent cations is outweighed by the effect of the additional Y(3+) cations introduced as x increases, which effectively trap many anions and reduce the overall concentration of the mobile O(2-) species.

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