Phase segregation and nanoconfined fluid O2 in a lithium-rich oxide cathode.

Lithium-rich oxide cathodes lose energy density during cycling due to atomic disordering and nanoscale structural rearrangements, which are both challenging to characterize. Here we resolve the kinetics and thermodynamics of these processes in an exemplar layered Li-rich (Li1.2-xMn0.8O2) cathode using a combined approach of ab initio molecular dynamics and cluster expansion-based Monte Carlo simulations. We identify a kinetically accessible and thermodynamically favourable mechanism to form O2 molecules in the bulk, involving Mn migration and driven by interlayer oxygen dimerization. At the top of charge, the bulk structure locally phase segregates into MnO2-rich regions and Mn-deficient nanovoids, which contain O2 molecules as a nanoconfined fluid. These nanovoids are connected in a percolating network, potentially allowing long-range oxygen transport and linking bulk O2 formation to surface O2 loss. These insights highlight the importance of developing strategies to kinetically stabilize the bulk structure of Li-rich O-redox cathodes to maintain their high energy densities.

Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics.

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development.

The persistence of memory in ionic conduction probed by nonlinear optics.

Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries1-3. For ionic conduction, the collective mechanisms4,5, variation of conductivity with timescales6-8 and confinement9,10, and ambiguity in the phononic origin of translation11,12, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.

Seasonal variation, contamination and ecological risk assessment of heavy metals in sediments of coastal wetlands along the Bay of Bengal.

Functioning of coastal wetland habitats is essential for the ecosystem integrity and sustainability of coastal development that enables human progress along transitional waterways. However, these habitats are continuously being affected by a variety of pollutants including metallic elements. In this study, seasonal variation, pollution status and ecological risks of heavy metals (Cr, Mn, Co, Ni, As, Cu, Zn and Pb) in surface sediment of the several types of coastal wetlands (estuaries, mudflats, sandy beaches, mangroves, and saltmarshes) were detected by using X-ray fluorescence (EDXRF) spectrometry. The results showed that the mean concentration level of metals in the surficial sediment samples followed the order of Cu (84.06 ± 8.60 µg/g) > Zn (51.00 ± 8.97 µg/g) > Mn (38.25 ± 11.34 µg/g) > Cr (3.52 ± 0.91 µg/g) > Pb (0.27 ± 0.13 µg/g) > Co (0.24 ± 0.13 µg/g) > As (0.21 ± 0.12 µg/g) > Ni (0.16 ± 0.08 µg/g). In comparison to the pre-monsoon period, the post-monsoon season had higher concentrations of heavy metals while the overall accumulation level of metals in the wetlands exhibited a pattern of estuarine wetland (28.47 ± 31.35 µg/g) > mangrove (22.23 ± 30.79 µg/g) > mudflat (21.79 ± 29.71 µg/g) > sandy beach (21.47 ± 28.15 µg/g) > saltmarsh (21.28 ± 30.02 µg/g). Although, the pollution assessment indices e.g., contamination factor (CF), degree of contamination (CD), geoaccumulation index (Igeo) and pollution load index (PLI) showed minimal levels of contamination in the studied sites, enrichment factor (EF) suggested greater enrichment of the metals in the pre-monsoon season but with the lowest ecological risk (RI < 40) in both seasons. Cluster analysis, principal component analysis (PCA), and Pearson's correlation were performed to determine the sources of heavy metals in collected samples which specified that Pb, As, Co and Ni predominantly came from natural sources whereas Cu, Mn, Zn and Cr emerged from anthropogenic sources such as industrial effluents, domestic wastewater, fertilizer or pesticide consumption on farmland along the riverbank, vessel emissions, and the confluence of tributary rivers.

Food safety policy enforcement and associated actions reduce lead chromate adulteration in turmeric across Bangladesh.

Turmeric adulterated with lead chromate pigment has been previously identified as a primary source of lead exposure in Bangladesh. This study assesses the impact of a multi-faceted intervention between 2017 and 2021 to reduce lead-tainted turmeric in Bangladesh. The intervention involved: i) disseminating findings from scientific studies via news media that identified turmeric as a source of lead poisoning, ii) educating consumers and businesspeople about the risks of lead chromate in turmeric via public notices and face-to-face meetings, and iii) collaborating with the Bangladesh Food Safety Authority to utilize a rapid lead detection technology to enforce policy disallowing turmeric adulteration. Before and after the intervention, evidence of lead chromate turmeric adulteration was assessed at the nation's largest turmeric wholesale market and at turmeric polishing mills across the country. Blood lead levels of workers at two mills were also assessed. Forty-seven interviews were conducted with consumers, businesspeople, and government officials to assess changes in supply, demand, and regulatory capacity. The proportion of market turmeric samples containing detectable lead decreased from 47% pre-intervention in 2019 to 0% in 2021 (n = 631, p < 0.0001). The proportion of mills with direct evidence of lead chromate adulteration (pigment on-site) decreased from 30% pre-intervention in 2017 to 0% in 2021 (n = 33, p < 0.0001). Blood lead levels dropped a median of 30% (IQR: 21-43%), while the 90th percentile dropped 49% from 18.2 µg/dL to 9.2 µg/dL 16 months after the intervention (n = 15, p = 0.033). Media attention, credible information, rapid lead detection tools and swift government action to enforce penalties all contributed to the intervention's success. Subsequent efforts should evaluate if this is an example of an effective intervention that can be replicated to reduce lead chromate adulteration of spices globally.

Draft Genome Sequence of the Multidrug-Resistant Citrobacter freundii 132-2 Strain Isolated from a Domestic Duck in Bangladesh.

We sequenced a multidrug-resistant strain of Citrobacter freundii, 132-2, isolated from a cloacal swab sample of a domestic duck. The whole genome of the C. freundii 132-2 strain had a length of 5,097,592 bp, 62 contigs, two plasmids, and an average G+C content of 51.85%, with a 105.0× genome coverage.

Anion-polarisation-directed short-range-order in antiperovskite Li2FeSO.

Short-range ordering in cation-disordered cathodes can have a significant effect on their electrochemical properties. Here, we characterise the cation short-range order in the antiperovskite cathode material Li2FeSO, using density functional theory, Monte Carlo simulations, and synchrotron X-ray pair-distribution-function data. We predict partial short-range cation-ordering, characterised by favourable OLi4Fe2 oxygen coordination with a preference for polar cis-OLi4Fe2 over non-polar trans-OLi4Fe2 configurations. This preference for polar cation configurations produces long-range disorder, in agreement with experimental data. The predicted short-range-order preference contrasts with that for a simple point-charge model, which instead predicts preferential trans-OLi4Fe2 oxygen coordination and corresponding long-range crystallographic order. The absence of long-range order in Li2FeSO can therefore be attributed to the relative stability of cis-OLi4Fe2 and other non-OLi4Fe2 oxygen-coordination motifs. We show that this effect is associated with the polarisation of oxide and sulfide anions in polar coordination environments, which stabilises these polar short-range cation orderings. We propose that similar anion-polarisation-directed short-range-ordering may be present in other heterocationic materials that contain cations with different formal charges. Our analysis illustrates the limitations of using simple point-charge models to predict the structure of cation-disordered materials, where other factors, such as anion polarisation, may play a critical role in directing both short- and long-range structural correlations.

Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes.

Lithium-rich disordered rocksalt cathodes display high capacities arising from redox chemistry on both transition-metal ions (TM-redox) and oxygen ions (O-redox), making them promising candidates for next-generation lithium-ion batteries. However, the atomic-scale mechanisms governing O-redox behaviour in disordered structures are not fully understood. Here we show that, at high states of charge in the disordered rocksalt Li2MnO2F, transition metal migration is necessary for the formation of molecular O2 trapped in the bulk. Density functional theory calculations reveal that O2 is thermodynamically favoured over other oxidised O species, which is confirmed by resonant inelastic X-ray scattering data showing only O2 forms. When O-redox involves irreversible Mn migration, this mechanism results in a path-dependent voltage hysteresis between charge and discharge, commensurate with the hysteresis observed electrochemically. The implications are that irreversible transition metal migration should be suppressed to reduce the voltage hysteresis that afflicts O-redox disordered rocksalt cathodes.

Examining the discourse regarding the delivery of occupational infection prevention and control training to healthcare workers: a scoping review of pandemic plans of 23 countries.

BACKGROUND: Over the years, countries reformed their pandemic plans but still healthcare systems were unprepared to handle the COVID-19 pandemic. Throughout the COVID-19 pandemic, healthcare workers (HCWs) raised issues around shortage of personal protective equipment (PPE), inadequate occupational infection prevention and control (IPC) training, lack of guidance regarding reuse/extended use of PPE and absence of HCWs. OBJECTIVE: The objective of this scoping review was to compare national and transnational pandemic plans and COVID-19 guidelines for the inclusion of recommendations regarding pandemic-specific occupational IPC training for HCWs, as well as strategies for managing the surge in PPE needs and staffing. INCLUSION CRITERIA: From each of the six WHO defined world regions, four countries with the highest burden of COVID-19 cases (as of mid-2020) were selected and attempted to locate the relevant pandemic plans and COVID-19 guidelines. METHODS: Searches were undertaken of 1: National Guidelines Clearinghouse, 2: websites of international public healthcare agencies such as WHO, the European Centre for Disease Prevention and Control (ECDC) and, 3: in-country health departments/Ministry of Health/Department of Public Health, between June 2020 and July 2021. The data were summarised under six themes drawn from publicly available pandemic plans and COVID-19 (IPC) guidelines of WHO, ECDC and 23 countries. RESULTS: The WHO, ECDC and 14 countries reported pandemic-specific IPC training; however, only four discussed training HCWs on correct PPE use; six countries listed strategies to manage the surge in demand of HCWs, while only five discussed managing the shortage of PPE. None of the COVID-19 guidelines recommended training HCWs for correct reuse or extended use of PPE and only one country's guideline outlined mandatory HCWs attendance and delivery of training in a regional language. CONCLUSION: Pandemic plans should be revised to include guiding principles regarding the delivery of pandemic specific IPC training. There is also a need to provide guidance on when countries should consider reuse and extended use of PPE. This discourse should also be reflected in disease-specific pandemic guidelines, like COVID-19 (IPC) guidelines. The aim of this review is to assist international health agencies in generating evidence-based guideline updates.

Defect-driven anomalous transport in fast-ion conducting solid electrolytes.

Solid-state ionic conduction is a key enabler of electrochemical energy storage and conversion. The mechanistic connections between material processing, defect chemistry, transport dynamics and practical performance are of considerable importance but remain incomplete. Here, inspired by studies of fluids and biophysical systems, we re-examine anomalous diffusion in the iconic two-dimensional fast-ion conductors, the ß- and ß″-aluminas. Using large-scale simulations, we reproduce the frequency dependence of alternating-current ionic conductivity data. We show how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder and leads to persistent subdiffusive ion transport at macroscopic timescales. We deconvolute the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects, and geometric crowding on ionic conductivity. Finally, our characterization of memory effects in transport connects atomistic defect chemistry to macroscopic performance with minimal assumptions and enables mechanism-driven 'atoms-to-device' optimization of fast-ion conductors.

A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li10GeP2S12 Solid Electrolyte.

The discovery of the lithium superionic conductor Li10GeP2S12 (LGPS) has led to significant research activity on solid electrolytes for high-performance solid-state batteries. Despite LGPS exhibiting a remarkably high room-temperature Li-ion conductivity, comparable to that of the liquid electrolytes used in current Li-ion batteries, nanoscale effects in this material have not been fully explored. Here, we predict that nanosizing of LGPS can be used to further enhance its Li-ion conductivity. By utilizing state-of-the-art nanoscale modeling techniques, our results reveal significant nanosizing effects with the Li-ion conductivity of LGPS increasing with decreasing particle volume. These features are due to a fundamental change from a primarily one-dimensional Li-ion conduction mechanism to a three-dimensional mechanism and major changes in the local structure. For the smallest nanometric particle size, the Li-ion conductivity at room temperature is three times higher than that of the bulk system. These findings reveal that nanosizing LGPS and related solid electrolytes could be an effective design approach to enhance their Li-ion conductivity.

Entropy Stabilization Effects and Ion Migration in 3D "Hollow" Halide Perovskites.

A recently discovered new family of 3D halide perovskites with the general formula (A)1-x(en)x(Pb)1-0.7x(X)3-0.4x (A = MA, FA; X = Br, I; MA = methylammonium, FA = formamidinium, en = ethylenediammonium) is referred to as "hollow" perovskites owing to extensive Pb and X vacancies created on incorporation of en cations in the 3D network. The "hollow" motif allows fine tuning of optical, electronic, and transport properties and bestowing good environmental stability proportional to en loading. To shed light on the origin of the apparent stability of these materials, we performed detailed thermochemical studies, using room temperature solution calorimetry combined with density functional theory simulations on three different families of "hollow" perovskites namely en/FAPbI3, en/MAPbI3, and en/FAPbBr3. We found that the bromide perovskites are more energetically stable compared to iodide perovskites in the FA-based hollow compounds, as shown by the measured enthalpies of formation and the calculated formation energies. The least stable FAPbI3 gains stability on incorporation of the en cation, whereas FAPbBr3 becomes less stable with en loading. This behavior is attributed to the difference in the 3D cage size in the bromide and iodide perovskites. Configurational entropy, which arises from randomly distributed cation and anion vacancies, plays a significant role in stabilizing these "hollow" perovskite structures despite small differences in their formation enthalpies. With the increased vacancy defect population, we have also examined halide ion migration in the FA-based "hollow" perovskites and found that the migration energy barriers become smaller with the increasing en content.

Patient-derived gene and protein expression signatures of NGLY1 deficiency.

N-Glycanase 1 (NGLY1) deficiency is a rare and complex genetic disorder. Although recent studies have shed light on the molecular underpinnings of NGLY1 deficiency, a systematic characterization of gene and protein expression changes in patient-derived cells has been lacking. Here, we performed RNA-sequencing and mass spectrometry to determine the transcriptomes and proteomes of 66 cell lines representing four different cell types derived from 14 NGLY1 deficient patients and 17 controls. Although NGLY1 protein levels were up to 9.5-fold downregulated in patients compared with parents, residual and likely non-functional NGLY1 protein was detectable in all patient-derived lymphoblastoid cell lines. Consistent with the role of NGLY1 as a regulator of the transcription factor Nrf1, we observed a cell type-independent downregulation of proteasomal genes in NGLY1 deficient cells. In contrast, genes involved in ribosome biogenesis and mRNA processing were upregulated in multiple cell types. In addition, we observed cell type-specific effects. For example, genes and proteins involved in glutathione synthesis, such as the glutamate-cysteine ligase subunits GCLC and GCLM, were downregulated specifically in lymphoblastoid cells. We provide a web application that enables access to all results generated in this study at https://apps.embl.de/ngly1browser. This resource will guide future studies of NGLY1 deficiency in directions that are most relevant to patients.

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy.

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (ß, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

Coupled effect of particle size of the source materials and calcination temperature on the direct synthesis of hydroxyapatite.

We report the effect of controlled particle size (obtained by using 80, 100, 120, 140 and 200 mesh) of the source materials on the synthesis of a well-known biomaterial, hydroxyapatite (Hap). In addition to this, we have also mapped the consequence of applied temperature (700°C, 800°C and 900°C) on the crystallographic properties and phase composition of the obtained Hap. Nevertheless, although with Hap, in each case, ß-tricalcium phosphate (ß-TCP) was registered as the secondary phase the ANOVA test revealed that the results of the crystallographic parameters are significantly different for the applied sintering temperature 700°C and 800°C (p < 0.05), while the data obtained for calcination temperature 800°C are not significantly different from that acquired at 900°C (p > 0.05). Fourier transform infrared spectrophotometer data ensured that, irrespective of mesh size and calcination temperature, the synthesized Hap samples were of carbonated apatite with B-type substitution. Interestingly, for all cases, the % of carbonate content was below the maximum limit (8%) of the CO 3 2 - ion present in bone tissue hydroxyapatite.

Degradation mechanism of hybrid tin-based perovskite solar cells and the critical role of tin (IV) iodide.

Tin perovskites have emerged as promising alternatives to toxic lead perovskites in next-generation photovoltaics, but their poor environmental stability remains an obstacle towards more competitive performances. Therefore, a full understanding of their decomposition processes is needed to address these stability issues. Herein, we elucidate the degradation mechanism of 2D/3D tin perovskite films based on (PEA)0.2(FA)0.8SnI3 (where PEA is phenylethylammonium and FA is formamidinium). We show that SnI4, a product of the oxygen-induced degradation of tin perovskite, quickly evolves into iodine via the combined action of moisture and oxygen. We identify iodine as a highly aggressive species that can further oxidise the perovskite to more SnI4, establishing a cyclic degradation mechanism. Perovskite stability is then observed to strongly depend on the hole transport layer chosen as the substrate, which is exploited to tackle film degradation. These key insights will enable the future design and optimisation of stable tin-based perovskite optoelectronics.

Context matters: Examining the factors impacting the implementation of tuberculosis infection prevention and control guidelines in health settings in seven high tuberculosis burden countries.

BACKGROUND: Healthcare workers (HCWs) in high tuberculosis (TB) burden countries are at increased risk of TB infection due to increased exposures to TB patients and inadequate implementation of TB infection prevention and control (TB IPC) measures in health settings. While various guidelines on TB IPC exist, there is little understanding of the content of these guidelines, whether they are relevant to the context and are being appropriately implemented in low-and middle-income high TB burden countries. This study aimed to critically examine the implementation of TB IPC guidelines, along with factors impacting TB IPC implementation in health settings in seven high TB burden countries. METHODS: The WHO 2009 and national level TB IPC guidelines and the published literature from seven TB high burden countries were reviewed and relevant information extracted. Eleven key-stakeholders from the case study countries were interviewed to elucidate further facilitators and barriers impacting TB IPC guidelines implementation. RESULTS: Our study identified that all the study countries adopted the WHO 2009 guidelines with no or minimal modifications for the local context. Therefore, the subsequent translation of the TB IPC recommendations into practice has been limited and impaired in some settings. Poor infrastructure, inadequate space for isolation, lack of TB IPC training, limited supply of personal protective equipment, the discomfort of using N95 respirators, and a high number of TB patients were some of the factors impacting the implementation of TB IPC guidelines. CONCLUSION: The implementation of TB IPC guidelines in all seven countries was limited. It was affected by the diverse context where each of the countries and each of the facilities had a different health infrastructure and TB disease burdens. The findings warrant re-assessment of the current context prevailing in these high TB burden countries and subsequent revisions of national guidelines based to account for local context and evidence.

Child lead exposure near abandoned lead acid battery recycling sites in a residential community in Bangladesh: Risk factors and the impact of soil remediation on blood lead levels.

Lead is a potent neurotoxin that is particularly detrimental to children's cognitive development. Batteries account for at least 80% of global lead use and unsafe battery recycling is a major contributor to childhood lead poisoning. Our objectives were to assess the intensity and nature of child lead exposure at abandoned, informal used lead acid battery (ULAB) recycling sites in Kathgora, Savar, Bangladesh, as well as to assess the feasibility and effectiveness of a soil remediation effort to reduce exposure. ULAB recycling operations were abandoned in 2016 due to complaints from residents, but the lead contamination remained in the soil after operations ceased. We measured soil and blood lead levels (BLLs) among 69 children living within 200 m of the ULAB recycling site once before, and twice after (7 and 14 months after), a multi-part remediation intervention involving soil capping, household cleaning, and awareness-raising activities. Due to attrition, the sample size of children decreased from 69 to 47 children at the 7-month post-intervention assessment and further to 25 children at 14 months. We conducted non-parametric tests to assess changes in soil lead levels and BLLs. We conducted baseline surveys, as well as semi-structured interviews and observations with residents throughout the study period to characterize exposure behaviors and the community perceptions. We conducted bivariate and multivariate regression analyses of exposure characteristics to determine the strongest predictors of baseline child BLLs. Prior to remediation, median soil lead concentrations were 1400 mg/kg, with a maximum of 119,000 mg/kg and dropped to a median of 55 mg/kg after remediation (p < 0.0001). Among the 47 children with both baseline and post-intervention time 1 measurements, BLLs dropped from a median of 21.3 µg/dL to 17.0 µg/dL at 7 months (p < 0.0001). Among the 25 children with all three measurements, BLLs dropped from a median of 22.6 µg/dL to 14.8 µg/dL after 14 months (p < 0.0001). At baseline, distance from a child's residence to the nearest abandoned ULAB site was the strongest predictor of BLLs and baseline BLLs were 31% higher for children living within 50 m from the sites compared to those living further away (n = 69, p = 0.028). Women and children spent time in the contaminated site daily and relied on it for their livelihoods and for recreation. Overall, this study highlights the intensity of lead exposure associated with the ULAB recycling industry. Additionally, we document the feasibility and effectiveness of a multi-part remediation intervention at a contaminated site embedded within a residential community; substantially reducing child BLLs and soil lead concentrations.

Redox Chemistry and the Role of Trapped Molecular O2 in Li-Rich Disordered Rocksalt Oxyfluoride Cathodes.

In the search for high energy density cathodes for next-generation lithium-ion batteries, the disordered rocksalt oxyfluorides are receiving significant attention due to their high capacity and lower voltage hysteresis compared with ordered Li-rich layered compounds. However, a deep understanding of these phenomena and their redox chemistry remains incomplete. Using the archetypal oxyfluoride, Li2MnO2F, we show that the oxygen redox process in such materials involves the formation of molecular O2 trapped in the bulk structure of the charged cathode, which is reduced on discharge. The molecular O2 is trapped rigidly within vacancy clusters and exhibits minimal mobility unlike free gaseous O2, making it more characteristic of a solid-like environment. The Mn redox process occurs between octahedral Mn3+ and Mn4+ with no evidence of tetrahedral Mn5+ or Mn7+. We furthermore derive the relationship between local coordination environment and redox potential; this gives rise to the observed overlap in Mn and O redox couples and reveals that the onset potential of oxide ion oxidation is determined by the degree of ionicity around oxygen, which extends models based on linear Li-O-Li configurations. This study advances our fundamental understanding of redox mechanisms in disordered rocksalt oxyfluorides, highlighting their promise as high capacity cathodes.