In this study, Synchrotron X-ray diffraction (XRD) radiography was utilized to investigate the ageing heterogeneity in 48 Ah prismatic lithium-ion cells with Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) as the positive electrode active material and graphite as the negative electrode active material after similar to 2800 cycles. The study revealed that the area closest to the positive electrode tab is most vulnerable to degradation, particularly impacting the NMC material. Application of principal component analysis allowed to differentiate and visualize part of positive electrode material that has a different degradation due to the lithium plating. A comparison of non-destructive X-ray diffraction-based methods and electrochemical characterization method which was performed on the opened cell has shown an importance of a complementary approach. Our results highlight the feasibility of employing non-destructive techniques to study large prismatic cells, thereby presenting extensive opportunities for advancements in battery research and industry.

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 determination 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. Transitions 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.

Conditions such as the temperature and pressure experienced by lithium-ion battery components are dependent on cell geometry and can vary widely within a large cell. The resulting uneven degradation is challenging to study at the full cell level but can be revealed upon disassembly and post mortem analysis. In this work, we report localized lithium plating in automotive-grade, prismatic lithium-ion cells, also under cycling conditions generally considered to be mild (e.g., 5-65 %SOC, 23 degrees C, 0.5C cycle rate). Dead lithium content is quantified using 7Li nuclear magnetic resonance 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 both the separators and negative electrodes are ultimately deactivated. High pressure arises during cycling, and we propose 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 under mild cycling conditions. Notably, components harvested from regions with no detected lithium plating maintained adequate electrochemical performance.

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

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.

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.

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!d (x1⁄4 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 Pm! 3m) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. Sn and Sc 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 Sn 4+ and Sc 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). O NMR spectra on O enriched BaSn1!xScxO3!d 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!d refines the deuteron position at the 24k crystallographic site (x, y, 0) with x 1⁄4 0.579(3) and y 1⁄4 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.

BaTi0.5SC0.5O3 - delta was prepared via solid state reaction route and final sintering at 1550 degrees C. High resolution X-ray powder diffraction on the as-prepared material reveals a cubic perovskite structure with a unit cell parameter, a = 4.1343(1) angstrom. Thermogravimetric analysis revealed the presence of significant levels of protons in the as-prepared material and 74% of the theoretically achievable protonation through filling of oxide ion vacancies was attained on exposure to a humid environment at 185 degrees C. Infrared spectroscopy revealed a broad O-H stretching band confirming the presence of OHo center dot defects. Electrical conductivity was measured with variable frequency AC impedance methods in oxygen, argon, and hydrogen under dry, hydrated (H2O) and heavy water (D2O) conditions. In the temperature range of 150-550 degrees C in a wet gas atmosphere the conductivity is significantly higher than that observed for dry conditions, indicating that protons are the dominant charge carriers. Conductivity is also found to be higher in dry oxygen in comparison with dry argon over the whole temperature range of 150-1000 degrees C, characteristic of contribution from p-type charge carriers under oxidising atmospheres. At 550 C the proton conductivity was estimated to be 2.89 x 10(-4) S cm(-1) in wet Ar. Fitting of conductivity data provides a hydration enthalpy change (Delta H-hydr(0)) of -100 +/- 5 kJ/mol and hydration entropy change (Delta S-hydr(0)) of -160 +/- 10 J/mol K. (C) 2013 Elsevier B.V. All rights reserved.

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.

BaTi0.5In0.5O3-delta was prepared by solid state reaction at 1400 degrees C. Rietveld analysis of high resolution X-ray powder diffraction data indicated phase pure as-prepared material that adopts a cubic perovskite structure with a = 4.1536(1) angstrom. Thermogravimetric analysis revealed the presence of significant levels of protons in the as-prepared material and 57% of the theoretically achievable protonation was attained on exposure to a humid environment at 185 degrees C. After hydration the cell parameter increased to 4.1623(1) angstrom. Electrical conductivity was measured both with fixed and variable frequency ac impedance methods as a function of temperature, oxygen-, water vapour- and heavy water vapour partial pressures. In the temperature range 400-800 degrees C a slight increase in the total conductivity with increasing oxygen partial pressure is encountered, characteristic of a contribution from p-type charge carriers. The effect of the water vapour pressure on conductivity below 600 degrees C is much more prominent indicative of dominant proton conduction. At 300 degrees C the total conductivity in wet O-2 was estimated to be 9.30 x 10(-5) S/cm. At T > 800 degrees C the material is a pure oxide ion conductor. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

An impedance spectroscopy cell and humidifier system has been developed to study the ion conducting properties and hydration/dehydration reactions in-situ during neutron powder diffraction experiments. As a model system, acceptor doped barium zirconate, BaZr0.5In0.5O2.75, has been studied during in-situ hydration and dehydration. Rietveld refinement of the collected data shows an increase in lattice parameter, a, upon hydration of BaZr0.5In0.5O2.75. In addition, we show the existence of a two-phase region, containing deuterated and non-deuterated barium zirconate, in the temperature interval ~573K to ~873K. Impedance spectroscopy data collected in-situ on heating and cooling and the corresponding ionic conductivity agree well with the change in deuteron content, as determined from neutron diffraction as a function of temperature. The newly developed in-situ cells make it possible to correlate conducting properties to structural changes under identical conditions and will have applicability to many other proton conducting solids.

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°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°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 system Y-2(Ti1-xZrx)(2)O-7 have been investigated using the neutron powder diffraction technique, including a detailed analysis of the "total scattering" using reverse Monte Carlo modeling to probe the short-range ion-ion correlations over sample range 0.0 <= x <= 1.0. The average crystal structure shows a continuous transformation from the long-range ordered pyrochlore structure (Fd (3) over barm, a = 10.0967(1) angstrom, Z = 8, for x = 0.00, Y2Ti2O7) to a disordered fluorite structure (Fm (3) over barm, a = 5.2042(1) angstrom, Z = 1, for x = 1.00, Zr2Y2O7) in agreement with previous reports. However, on increasing x the disordering of both the cation and the anion sublattices occurs in stages, with the Zr4+ initially only substituting onto the Ti4+ site and adopting a cubic, rather than octahedral, local anion environment. At concentrations in excess of x approximate to 0.4 there is a gradual disordering of the Y3+, Ti4+, and Zr4+ species over all the cation sites, coupled with a redistribution of the O2- which initially only involves those anions on the O1 sites. The relationship between the composition dependences of the structure properties and the ionic conductivity is discussed.

Background and Aim: Genetic susceptibility to the development of chronic obstructive pulmonary disease might depend on variation in the activities of enzymes that detoxify cigarette smoke products. We studied the relationship of GSTP1, GSTM1, and GSTT1 gene polymorphisms with COPD risk in a case- control study of Indian patients and controls. Material and methods: A total of 186 patients with COPD and 160 healthy controls were included in the study. The Frequencies of GSTP1, GSTM1 alleles was determined by using conventional Multiplex PCR and GSTP1 by polymerase chain reaction and restriction fragment length polymorphisms technique. Results: A significant case –control difference was observed for the presence of null GSTM1, (61.8% Vs 55.0 %, P= 0.04). No difference was observed in the frequency of GSTT1 Null genotype and COPD susceptibility. (54.8% vs 50.6% OR: 1.26; CI: 0.87- 1.84; P value = 0.82) For GSTP1 polymorphism we found that Subjects homozygous variants Val/ Val were at increased risk of developing COPD (OR: 2.58; CI: 1.2- 4.8) as compared to heterozygote variants Ile/ Val (OR: 1.28 CI: 0.7-2.14) Also, the mutant allele frequency (Val) was significantly higher in patients as compared to controls and the difference was found to be statistically significant. (OR: 1.8 CI: 1.4- 4.2; P Value =0.001) Conclusion: We propose that subjects with GSTM1 null allele and GST P1 homozygous isoleucine genotypes are at higher risk of COPD and are significant indicators of susceptibility to chronic obstructive pulmonary disease in Indian population. Keywords: Chronic Obstructive Pulmonary Disease, Polymerase chain reaction, Gluthathione S- transferase.

20% Ytterbium (III)-doped perovskite structured barium zirconate, BaZrO3, was prepared by two different synthesis routes: solid state and sol-gel routes. 2 % Zinc (II) was added as an acceptor dopant at the Zr (IV) site according to stoichiometry. It was also added as 2 % excess of the formula. The purpose of this study is to see how zinc (II) acts as a sintering aid in view of synthesis route, densification and conductivity of the material. A dense ceramic (90% of theoretical density) was achieved by the sol-gel method when stoichiometry was adjusted. Phase purity of the samples was checked by X-ray powder diffraction (XRD). Thermogravimetric analysis (TGA) and Impedance spectroscopy (IS) was used to characterize hydration and electrical conductivity respectively.The data shows that the addition of stoichiometric amounts of Zn2+ via sol-gel synthesis route promotes not only densification but also water incorporation and conductivity in comparison with the solid state route, keeping the same final sintering temperature of 1500°C. For example, pre-hydrated BaZr0.78Zn0.02Yb0.2O3-δ, prepared via the sol-gel method shows total conductivity (σtot) value of 3.14*10-5 and 3.8*10-3Scm-1, whereas for the solid state route, σtot values are 1.74*10-5 and 8.87*10-4Scm-1 under dry Ar (heating cycle) at 300° C and 600° C, respectively.

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 structural properties of the binary alkaline-earth halides SrCl2, SrBr2, BaCl2 and BaBr2 have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl2 undergoes a gradual transition to a superionic phase at 900–1100K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3)K, the tetragonal phase of SrBr2 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 SrCl2. BaCl2 and BaBr2 both adopt the cotunnite crystal structure under ambient conditions. BaCl2 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.

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 similar to 2 as x increases from 0.0 to 0.2, while the oxygen anion partial radial distribution function, g(OO)(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 Zr0.8Y0.2O1.9, while in Zr0.8Sc0.2O1.9 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.