Accessing Mg-Ion Storage in V2PS10 via Combined Cationic-Anionic Redox with Selective Bond Cleavage.

Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg2+ and the host structure. V2PS10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g-1 is achieved with fast Mg2+ diffusion of 7.2 × ${\times }$ 10-11-4 × ${\times }$ 10-14 cm2 s-1. The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S2)2- site; enabled by reversible cleavage of S-S bonds, identified by X-ray photoelectron and X-ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.

Superionic lithium transport via multiple coordination environments defined by two-anion packing.

Fast cation transport in solids underpins energy storage. Materials design has focused on structures that can define transport pathways with minimal cation coordination change, restricting attention to a small part of chemical space. Motivated by the greater structural diversity of binary intermetallics than that of the metallic elements, we used two anions to build a pathway for three-dimensional superionic lithium ion conductivity that exploits multiple cation coordination environments. Li7Si2S7I is a pure lithium ion conductor created by an ordering of sulphide and iodide that combines elements of hexagonal and cubic close-packing analogously to the structure of NiZr. The resulting diverse network of lithium positions with distinct geometries and anion coordination chemistries affords low barriers to transport, opening a large structural space for high cation conductivity.

Effect of angiotensin II on irradiation exacerbated decompression sickness.

In some complicated situations, decompression sickness (DCS) combined with other injuries, such as irradiation, will seriously endanger life safety. However, it is still unclear whether irradiation will increase the incidence of DCS. This study was designed to investigate the damage effects of irradiation on decompression injury and the underlying mechanism. Sprague-Dawley rats were exposed to irradiation followed by hyperbaric decompressing and the mortality and decompression symptoms were observed. Lung tissue and bronchoalveolar lavage fluid were collected to detect the lung lesion, inflammation response, activity of the angiotensin system, oxidative stress, and relative signal pathway by multiple methods, including Q-PCR, western blot, and ELISA. As a result, pre-exposure to radiation significantly exacerbated disease outcomes and lung lesions of DCS. Mechanically, the up-regulation of angiotensin-converting enzyme expression and angiotensin II levels was responsible for the exacerbated DCS and lung lesions caused by predisposing irradiation exposure. Oxidative stress and PI3K/AKT signal pathway activation in pulmonary tissue were enhanced after irradiation plus decompression treatment. In conclusion, our results suggested that irradiation could exacerbate lung injury and the outcomes of DCS by activating the angiotensin system, which included eliciting oxidative stress and activation of the PI3K/AKT signal pathway.

Elastomeric Electrolyte for High Capacity and Long-Cycle-Life Solid-State Lithium Metal Battery.

High room-temperature ionic conductivity and good compatibility with lithium metal and cathode materials are prerequisites for solid-state electrolytes used in lithium metal batteries. Here, the solid-state polymer electrolytes (SSPE) are prepared by combining the traditional two-roll milling technology with interface wetting. The as-prepared electrolytes consisting of elastomer matrix and high-mole-loading of LiTFSI salt show a high room temperature ionic conductivity of 4.6×10-4 S cm-1 , a good electrochemical oxidation stability up to 5.08 V, and improved interface stability. These phenomena are rationalized with the formation of continuous ion conductive paths based on sophisticated structure characterization including synchrotron radiation Fourier-transform infrared microscopy, wide- and small-angle X-ray scattering. Moreover, at room temperature, the Li||SSPE||LFP coin cell shows a high capacity (161.5 mAh g-1 at 0.1 C), long-cycle-life (retaining 50% capacity and 99.8% Coulombic efficiency after 2000 cycles), and good C-rate compatibility up to 5 C. This study, therefore, provides a promising solid-state electrolyte that meets both the electrochemical and mechanical requirements of practical lithium metal batteries.

Grafting and Solubilization of Redox-Active Organic Materials for Aqueous Redox Flow Batteries.

This study concerns the development of sustainable design strategies of aqueous electrolytes for redox flow batteries using redox-active organic materials. A green spontaneous grafting reaction occurs between a redox-active organic radical and an electrochemically activated structural modifier at room temperature through a simple mixing step. Then, a physical mixing method is used to formulate a structured aqueous electrolyte and enables aqueous solubilization of the organic solute from below 0.5 to 1.5 m beyond the conventional dissolution limit. The as-obtained concentrated mixture can be readily used as catholyte for a redox flow battery. A record high discharge cell voltage (1.6 V onset output voltage) in aqueous non-hybrid flow cell is attained by using the studied electrolytes.

Redox Flow Batteries: Electrolyte Chemistries Unlock the Thermodynamic Limits.

Redox flow batteries (RFBs) represent a promising approach to enabling the widespread integration of intermittent renewable energy. Rapid developments in RFB materials and electrolyte chemistries are needed to meet the cost and performance targets. In this review, special emphasis is given to the recent advances how electrolyte design could circumvent the main thermodynamic restrictions of aqueous electrolytes. The recent success of aqueous electrolyte chemistries has been demonstrated by extending the electrochemical stability window of water beyond the thermodynamic limit, the operating temperature window beyond the thermodynamic freezing temperature of water and crystallization of redox-active materials, and the aqueous solubility beyond the thermodynamic solubility limit. They would open new avenues towards enhanced energy storage and all-climate adaptability. Depending on the constituent, concentration and condition of electrolytes, the performance gain has been correlated to the specific solvation environment, interactions among species and ion association at a molecular level.

Control of Ionic Conductivity by Lithium Distribution in Cubic Oxide Argyrodites Li6+xP1-xSixO5Cl.

Argyrodite is a key structure type for ion-transporting materials. Oxide argyrodites are largely unexplored despite sulfide argyrodites being a leading family of solid-state lithium-ion conductors, in which the control of lithium distribution over a wide range of available sites strongly influences the conductivity. We present a new cubic Li-rich (>6 Li+ per formula unit) oxide argyrodite Li7SiO5Cl that crystallizes with an ordered cubic (P213) structure at room temperature, undergoing a transition at 473 K to a Li+ site disordered F4̅3m structure, consistent with the symmetry adopted by superionic sulfide argyrodites. Four different Li+ sites are occupied in Li7SiO5Cl (T5, T5a, T3, and T4), the combination of which is previously unreported for Li-containing argyrodites. The disordered F4̅3m structure is stabilized to room temperature via substitution of Si4+ with P5+ in Li6+xP1-xSixO5Cl (0.3 < x < 0.85) solid solution. The resulting delocalization of Li+ sites leads to a maximum ionic conductivity of 1.82(1) × 10-6 S cm-1 at x = 0.75, which is 3 orders of magnitude higher than the conductivities reported previously for oxide argyrodites. The variation of ionic conductivity with composition in Li6+xP1-xSixO5Cl is directly connected to structural changes occurring within the Li+ sublattice. These materials present superior atmospheric stability over analogous sulfide argyrodites and are stable against Li metal. The ability to control the ionic conductivity through structure and composition emphasizes the advances that can be made with further research in the open field of oxide argyrodites.

Cation Disorder and Large Tetragonal Supercell Ordering in the Li-Rich Argyrodite Li7Zn0.5SiS6.

A tetragonal argyrodite with >7 mobile cations, Li7Zn0.5SiS6, is experimentally realized for the first time through solid state synthesis and exploration of the Li-Zn-Si-S phase diagram. The crystal structure of Li7Zn0.5SiS6 was solved ab initio from high-resolution X-ray and neutron powder diffraction data and supported by solid-state NMR. Li7Zn0.5SiS6 adopts a tetragonal I4 structure at room temperature with ordered Li and Zn positions and undergoes a transition above 411.1 K to a higher symmetry disordered F43m structure more typical of Li-containing argyrodites. Simultaneous occupation of four types of Li site (T5, T5a, T2, T4) at high temperature and five types of Li site (T5, T2, T4, T1, and a new trigonal planar T2a position) at room temperature is observed. This combination of sites forms interconnected Li pathways driven by the incorporation of Zn2+ into the Li sublattice and enables a range of possible jump processes. Zn2+ occupies the 48h T5 site in the high-temperature F43m structure, and a unique ordering pattern emerges in which only a subset of these T5 sites are occupied at room temperature in I4 Li7Zn0.5SiS6. The ionic conductivity, examined via AC impedance spectroscopy and VT-NMR, is 1.0(2) × 10-7 S cm-1 at room temperature and 4.3(4) × 10-4 S cm-1 at 503 K. The transition between the ordered I4 and disordered F43m structures is associated with a dramatic decrease in activation energy to 0.34(1) eV above 411 K. The incorporation of a small amount of Zn2+ exercises dramatic control of Li order in Li7Zn0.5SiS6 yielding a previously unseen distribution of Li sites, expanding our understanding of structure-property relationships in argyrodite materials.

Varied effects exerted on sudden sensorineural hearing loss through HBO2 therapeutic pressure.

This study aimed to compare the efficacy of two commonly used therapeutic pressures, 2.0 atmospheres absolute (ATA) versus 2.2 ATA, applied in hyperbaric oxygen (HBO2) therapy for sudden sensorineural hearing loss (SSNHL). We retrospectively reviewed the clinical records of 160 SSNHL patients treated by typical therapy or additional HBO2 therapy with pressure 2.0 or 2.2 ATA at Yijishan Hospital, the First Affiliated Hospital of Wannan Medical College, from February 2018 to May 2020. The pure-tone threshold audiometry results pre- and post-treatment were compared across three groups. In the range of frequencies 250-500 Hz, P2.0 (20.92±26.11 dB, p=0.047) and P2.2 group (20.47±±21.54 dB, p=0.012) both acquired higher hearing gain compared to the control group (11.94±23.32 dB). While in the range of frequencies 1,000-2,000 Hz, only the P2.2 group showed significant improvement of the hearing gain compared to the control group (19.70±21.13 dB vs.10.56±25.24 dB, p=0.015). In the range of frequencies 4,000-8,000, both the P2.0 and P2.2 groups failed to reach the desired effect. Our results suggest that the therapeutic effect is associated with HBO2 therapeutic pressure when applying HBO2 treatment combined with standard medical therapy. Within the range of appropriate pressure, the higher pressure, which means higher partial pressure of oxygen, has better therapeutic efficacy for SSNHL.

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability.

Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li3P5O14 and Li4P6O17 based on extended layers and chains of phosphate, respectively. Li3P5O14 presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li6O1626- chains. Li4P6O17 features a new type of loop-branched chain defined by six PO43- tetrahedra. The ionic conductivities and electrochemical properties of Li3P5O14 were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li3P5O14 enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10-7 S cm-1 at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li-P-O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li3P5O14, which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries.

Element selection for crystalline inorganic solid discovery guided by unsupervised machine learning of experimentally explored chemistry.

The selection of the elements to combine delimits the possible outcomes of synthetic chemistry because it determines the range of compositions and structures, and thus properties, that can arise. For example, in the solid state, the elemental components of a phase field will determine the likelihood of finding a new crystalline material. Researchers make these choices based on their understanding of chemical structure and bonding. Extensive data are available on those element combinations that produce synthetically isolable materials, but it is difficult to assimilate the scale of this information to guide selection from the diversity of potential new chemistries. Here, we show that unsupervised machine learning captures the complex patterns of similarity between element combinations that afford reported crystalline inorganic materials. This model guides prioritisation of quaternary phase fields containing two anions for synthetic exploration to identify lithium solid electrolytes in a collaborative workflow that leads to the discovery of Li3.3SnS3.3Cl0.7. The interstitial site occupancy combination in this defect stuffed wurtzite enables a low-barrier ion transport pathway in hexagonal close-packing.

Polymorph of LiAlP2O7: Combined Computational, Synthetic, Crystallographic, and Ionic Conductivity Study.

We report a new polymorph of lithium aluminum pyrophosphate, LiAlP2O7, discovered through a computationally guided synthetic exploration of the Li-Mg-Al-P-O phase field. The new polymorph formed at 973 K, and the crystal structure, solved by single-crystal X-ray diffraction, adopts the orthorhombic space group Cmcm with a = 5.1140(9) Å, b = 8.2042(13) Å, c = 11.565(3) Å, and V = 485.22(17) Å3. It has a three-dimensional framework structure that is different from that found in other LiMIIIP2O7 materials. It transforms to the known monoclinic form (space group P21) above ∼1023 K. Density functional theory (DFT) calculations show that the new polymorph is the most stable low-temperature structure for this composition among the seven known structure types in the AIMIIIP2O7 (A = alkali metal) families. Although the bulk Li-ion conductivity is low, as determined from alternating-current impedance spectroscopy and variable-temperature static 7Li NMR spectra, a detailed analysis of the topologies of all seven structure types through bond-valence-sum mapping suggests a potential avenue for enhancing the conductivity. The new polymorph exhibits long (>4 Å) Li-Li distances, no Li vacancies, and an absence of Li pathways in the c direction, features that could contribute to the observed low Li-ion conductivity. In contrast, we found favorable Li-site topologies that could support long-range Li migration for two structure types with modest DFT total energies relative to the new polymorph. These promising structure types could possibly be accessed from innovative doping of the new polymorph.

A Comparative Review of Electrolytes for Organic-Material-Based Energy-Storage Devices Employing Solid Electrodes and Redox Fluids.

Electrolyte chemistry is critical for any energy-storage device. Low-cost and sustainable rechargeable batteries based on organic redox-active materials are of great interest to tackle resource and performance limitations of current batteries with metal-based active materials. Organic active materials can be used not only as solid electrodes in the classic lithium-ion battery (LIB) setup, but also as redox fluids in redox-flow batteries (RFBs). Accordingly, they have suitability for mobile and stationary applications, respectively. Herein, different types of electrolytes, recent advances for designing better performing electrolytes, and remaining scientific challenges are discussed and summarized. Due to different configurations and requirements between LIBs and RFBs, the similarities and differences for choosing suitable electrolytes are discussed. Both general and specific strategies for promoting the utilization of organic active materials are covered.

First-principles calculations and experimental investigation on SnO2@ZnO heterojunction photocatalyst with enhanced photocatalytic performance.

In this study, branch-like SnO2@ZnO heterojunction photocatalyst was successfully fabricated via a simple two-step hydrothermal process. The optical and electronic properties were characterized in detail and the results indicated that SnO2@ZnO nanocomposites (TZNCs) exhibited superior photocatalytic performance under visible light irradiation as compared to pure SnO2 and ZnO. The excellent photocatalytic performance of TZNCs can be ascribed to the heterojunction structure between ZnO and SnO2 which depresses the recombination of photogenerated electron-hole pairs. In addition, the branch-like morphology can provide large specific surface. Moreover, the density functional theory (DFT) computation on the Fermi level results confirmed that heterojunction structure between ZnO and SnO2 is more favor of the transfer of photogenerated eletrons from ZnO to SnO2, effectively improving separation of photogenerated electron-hole pairs. Noteworthy, this work would pave the route for the two semiconductor materials with a big work function difference which would lead to the high contact potential difference, surely contributing to improving the performance of photocatalysts.

High-Voltage and Low-Temperature Aqueous Supercapacitor Enabled by "Water-in-Imidazolium Chloride" Electrolytes.

Symmetric aqueous high voltage supercapacitors up to 3 V have been demonstrated using concentrated aqueous 1-butyl-3-methylimidazolium chloride ([BMIm]Cl), namely, "water-in-imidazolium chloride", as working electrolytes, and graphene nanoplatelets-coated carbon paper as electrodes. Performance enhancement was further achieved either through adding redox species such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4hT) into the electrolytes (110 Wh kg-1 for a 20 m [BMIm]Cl/H2 O with 0.1 m 4hT) or by pre-inserting ClO4 - anions into the graphene platelets. Moreover, the newly studied aqueous electrolytes allow low-temperature operation at -20 °C and even at -32 °C, retaining competitive energy storage capability (maximum energy densities of 36 and 21 Wh kg-1 , respectively).

One-Step Cationic Grafting of 4-Hydroxy-TEMPO and its Application in a Hybrid Redox Flow Battery with a Crosslinked PBI Membrane.

By using a one-step epoxide ring-opening reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO) and glycidyltrimethylammonium cation (GTMA+ ), we synthesized a cation-grafted TEMPO (g+ -TEMPO) and studied its electrochemical performance against a Zn2+ /Zn anode in a hybrid redox flow battery. To conduct Cl- counter anions, a crosslinked methylated polybenzimidazole (PBI) membrane was prepared and placed between the catholyte and anolyte. Compared to 4-hydroxy-TEMPO, the positively charged g+ - TEMPO exhibits enhanced reaction kinetics. Moreover, flow battery tests with g+ -TEMPO show improved Coulombic, voltage, and energy efficiencies and cycling stability over 140 cycles. Crossover of active species through the membrane was not detected.

Identifying the redox activity of cation-disordered Li-Fe-V-Ti oxide cathodes for Li-ion batteries.

Cation-disordered oxides have recently shown promising properties on the way to explore high-performance intercalation cathode materials for rechargeable Li-ion batteries. Here, stoichiometric cation-disordered Li2FeVyTi1-yO4 (y = 0, 0.2, 0.5) nanoparticles are studied. The substitution of V for Ti in Li2FeVyTi1-yO4 increases the content of active transition metals (Fe and V) and accordingly the amount of Li(+) (about (1 + y)Li(+) capacity per formula unit) that can be reversibly intercalated. It is found that Fe(3+)/Fe(2+) and V(4+)/V(3+) redox couples contribute to the overall capacity performance, whereas Ti(4+) remains mainly inert. There is no evidence for the presence of Fe(4+) species after charging to 4.8 V, as confirmed from the ex situ(57)Fe Mössbauer spectroscopy and the Fe K-edge absorption spectra. The redox couple reactions for iron and vanadium are examined by performing in situ synchrotron X-ray absorption spectroscopy. During charging/discharging, the spectral evolution of the K-edges for Fe and V confirms the reversible Fe(3+)/Fe(2+) and V(4+)/V(3+) redox reactions during cycling between 1.5 and 4.8 V.

Mental abilities and performance efficacy under a simulated 480-m helium-oxygen saturation diving.

Stress in extreme environment severely disrupts human physiology and mental abilities. The present study investigated the cognition and performance efficacy of four divers during a simulated 480 meters helium-oxygen saturation diving. We analyzed the spatial memory, 2D/3D mental rotation functioning, grip strength, and hand-eye coordination ability in four divers during the 0-480 m compression and decompression processes of the simulated diving. The results showed that except for its mild decrease on grip strength, the high atmosphere pressure condition significantly impaired the hand-eye coordination (especially above 300 m), the reaction time and correct rate of mental rotation, as well as the spatial memory (especially as 410 m), showing high individual variability. We conclude that the human cognition and performance efficacy are significantly affected during deep water saturation diving.

Li(+) intercalation in isostructural Li2VO3 and Li2VO2F with O(2-) and mixed O(2-)/F(-) anions.

Mixed-anion materials for Li-ion batteries have been attracting attention in view of their tunable electrochemical properties. Herein, we compare two isostructural (Fm3̅m) model intercalation materials Li2VO3 and Li2VO2F with O(2-) and mixed O(2-)/F(-) anions, respectively. Synchrotron X-ray diffraction and pair distribution function data confirm large structural similarity over long-range and at the atomic scale for these materials. However, they show distinct electrochemical properties and kinetic behaviour arising from the different anion environments and the consequent difference in cationic electrostatic repulsion. In comparison with Li2VO3 with an active V(4+/5+) redox reaction, the material Li2VO2F with oxofluoro anions and the partial activity of V(3+/5+) redox reaction favor higher theoretical capacity (460 mA h g(-1)vs. 230 mA h g(-1)), higher voltage (2.5 V vs. 2.2 V), lower polarization (0.1 V vs. 0.3 V) and faster Li(+) chemical diffusion (∼10(-9) cm(2) s(-1)vs. ∼10(-11) cm(2) s(-1)). This work not only provides insights into the understanding of anion chemistry, but also suggests the rational design of new mixed-anion battery materials.

[Effects of simulated nitrogen-oxygen saturation exposure at a water depth of 50m on expression of inflammatory mediators in external auditory canal of rabbits].

OBJECTIVE: To investigate the effects of simulated nitrogen-oxygen saturation exposure at a water depth of 50 m on the expression of inflammatory mediators including interleukin-6 (IL-6), interleukin-10 (IL-10), and tumor necrosis factor-alpha (TNF-α) in the external auditory canal (EAC) of rabbits. METHODS: Two batches of New Zealand rabbits were exposed to nitrogen-oxygen saturated at a water depth of 50 m. After exposure, the epithelial tissue in the EAC was analyzed using hematoxylin-eosin (HE) staining, and the changes in expression of inflammatory mediators including IL-6, IL-10, and TNF-α in the EAC of rabbits were determined by real-time polymerase chain reaction (PCR). RESULTS: According to the result of HE staining, more inflammatory cell infiltration, small vascular congestion, and mucosal edema in the EAC of rabbits were observed in the exposure group than in the control group. Additionally, compared with the control group, the exposure group had increased expression of IL-6 and TNF-α and reduced expression of IL-10 in the EAC of rabbits according to the result of real-time PCR. CONCLUSION: The nitrogen-oxygen saturation exposure at a water depth of 50 m can cause inflammatory injuries in the EAC of rabbits. The mechanism may be associated with increased expression of IL-6 and TNF-α and reduced expression of IL-10.