Lithium-rich layered oxides with the capability to realize extraordinary capacity through anodic redox as well as classical cationic redox have spurred extensive attention. However, the oxygen-involving process inevitably leads to instability of the oxygen framework and ultimately lattice oxygen release from the surface, which incurs capacity decline, voltage fading, and poor kinetics. Herein, it is identified that this predicament can be diminished by constructing a spinel Li Mn O coating, which is inherently stable in the lattice framework to prevent oxygen release of the lithium-rich layered oxides at the deep delithiated state. The controlled KMnO oxidation strategy ensures uniform and integrated encapsulation of Li Mn O with structural compatibility to the layered core. With this layer suppressing oxygen release, the related phase transformation and catalytic side reaction that preferentially start from the surface are consequently hindered, as evidenced by detailed structural evolution during Li extraction/insertion. The heterostructure cathode exhibits highly competitive energy-storage properties including capacity retention of 83.1% after 300 cycles at 0.2 C, good voltage stability, and favorable kinetics. These results highlight the essentiality of oxygen framework stability and effectiveness of this spinel Li Mn O coating strategy in stabilizing the surface of lithium-rich layered oxides against lattice oxygen escaping for designing high-performance cathode materials for high-energy-density lithium-ion batteries.

[1] Bubbles play an important role in the exchange of gases between the atmosphere and ocean, altering both the rate of exchange and the equilibrium gas saturation state. We develop a parameterization of bubble-mediated gas fluxes for use in Earth system models. The parameterization is derived from a mechanistic model of the oceanic boundary layer that simulates turbulent flows and the size spectrum of bubbles across a range of wind speeds and is compared against other published formulations. Bubble-induced surface supersaturation increases rapidly with wind speed and is inversely related to temperature at a given wind speed, making the effect of bubbles greatest in regions that ventilate the deep ocean. The bubble-induced supersaturation in high-latitude surface waters compensates a substantial fraction of the undersaturation caused by surface cooling. Using a global ocean transport model, we show that this parameterization reproduces observed saturation rate profiles of the noble gas Argon in the deep Atlantic and Pacific Oceans. The abyssal argon supersaturation caused by bubbles varies according to gas solubility, ranging from 0.7% for soluble gases like CO 2 to 1.7% for less soluble gases such as N 2 . Bubble-induced supersaturation may be significant for biologically active gases such as oxygen.Citation: Liang, J.-H., C. Deutsch, J. C. McWilliams, B. Baschek, P. P. Sullivan, and D. Chiba (2013), Parameterizing bubble-mediated air-sea gas exchange and its effect on ocean ventilation, Global Biogeochem. Cycles, 27,[894][895][896][897][898][899][900][901][902][903][904][905]

The fast-ionic-conducting ceramic electrolyte is promising for next-generation high-energy-density Li-metal batteries, yet its application suffers from the high interfacial resistance and poor interfacial stability. In this study, the compatible solid-state electrolyte was designed by coating Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) with polyacrylonitrile (PAN) and polyethylene oxide (PEO) oppositely to satisfy deliberately the disparate interface demands. Wherein, the upper PAN constructs soft-contact with LiNi 0.6 Mn 0.2 Co 0.2 O 2 , and the lower PEO protects LATP from being reduced, guaranteeing high-voltage tolerance and improved stability toward Li-metal anode performed in one ceramic. Moreover, the core function of LATP is amplified to guide homogeneous ions distribution and hence suppresses the formation of a space-charge layer across interfaces, uncovered by the COMSOL Multiphysics concentration field simulation. Thus, such a bifunctional modified ceramic electrolyte integrates the respective superiority to render Li-metal batteries with excellent cycling stability (89% after 120 cycles), high Coulombic efficiency (exceeding 99.5% per cycle), and a dendrite-free Li anode at 60 °C, which represents an overall design of ceramic interface engineering for future practical solid battery systems.

The “transfer efficiency” of organic particles from the surface to depth is a critical determinant of ocean carbon sequestration. Recently, direct observations and geochemical analyses have revealed a systematic geographical pattern of transfer efficiency, which is highest in high latitude regions and lowest in the subtropical gyres. We evaluate the possible causes of this pattern using a mechanistic model of sinking particle dynamics. The model represents the size distribution of particles, the effects of mineral ballast, seawater temperature (which influences both particle settling velocity and microbial metabolic rates), and O2. Parameters are optimized within reasonable ranges to best match the observational constraints. Our model shows that no single factor can explain the observed pattern of transfer efficiency, but the biological effect of temperature on remineralization rate and particle size effects together can reproduce most of the regional variability with both factors contributing to low transfer efficiency in the subtropical gyres and high transfer efficiency in high latitudes. Particle density from mineral ballast has a similar directional effect to temperature and size but plays a substantially smaller role in our optimum solution, due to the opposing patterns of silicate and calcium carbonate ballasting. Oxygen effects modestly improved model fit by depressing remineralization rates and thus increasing transfer efficiency in the Eastern Tropical Pacific. Our model implies that climate‐driven changes to upper ocean temperature and associated changes in surface plankton size distribution would reduce the carbon sequestration efficiency in a warmer ocean.

The rapid capacity decay caused by the poor contact and large polarization at the interface between the cathode and solid electrolytes is still a big challenge to overcome for high-power-density solid batteries. In this study, a superior Li conductive transition layer LiAlTi(PO) is introduced to coat LiNiCoMnO, as a model cathode, to mitigate polarization and enhance dynamic characteristics. The critical attribute for such superior dynamics is investigated by the atomic force microscopy with boundary potential analysis, revealing that the formed interfacial transition layer provides a gradual potential slope and sustain-released polarization, and endows the battery with improved cycling stability (90% after 100 cycles) and excellent rate capability (116 mA h g at 2 C) at room temperature, which enlightens the comprehension of interface engineering in the future solid batteries systems.

Large-eddy simulations are made for the canonical Ekman layer problem of a steady wind above a uniformly rotating, constant-density ocean. The focus is on the influence of surface gravity waves: namely, the wave-averaged Stokes-Coriolis and Stokes-vortex forces and parameterized wave breaking for momentum and energy injection. The wave effects are substantial: the boundary layer is deeper, the turbulence is stronger, and eddy momentum flux is dominated by breakers and Langmuir circulations with a vertical structure inconsistent with both the conventional logarithmic layer and eddy viscosity relations. The surface particle mean drift is dominated by Stokes velocity with Langmuir circulations playing a minor role. Implications are assessed for parameterization of the mean velocity profile in the Ekman layer with wave effects by exploring several parameterization ideas. The authors find that the K-profile parameterization (KPP) eddy viscosity is skillful for the interior of the Ekman layer with wave-enhanced magnitude and depth scales. Furthermore, this parameterization form is also apt in the breaker and Stokes layers near the surface when it is expressed as a Lagrangian eddy viscosity (i.e., turbulent Reynolds stress proportional to vertical shear of the Lagrangian mean flow, inclusive of Stokes drift) with a derived eddy-viscosity shape and with a diagnosed vertical profile of a misalignment angle between Reynolds stress and Lagrangian mean shear.

The key issue holding back the application of solid polymeric electrolytes in high‐energy density lithium metal batteries is the contradictory requirements of high ion conductivity and mechanical stability. In this work, self‐healable solid polymeric electrolytes (SHSPEs) with rigid‐flexible backbones and high ion conductivity are synthesized by a facile condensation polymerization approach. The all‐solid Li metal full batteries based on the SHSPEs possess freely bending flexibility and stable cycling performance as a result of the more disciplined metal Li plating/stripping, which have great implications as long‐lifespan energy sources compatible with other wearable devices.

The problem is posed and solved for the oceanic surface boundary layer in the presence of wind stress, stable density stratification, equilibrium wind-waves, and remotely generated swell-waves. The addition of swell causes an amplification of the Lagrangian-mean current and rotation toward the swell-wave direction, a fattening of the Ekman velocity spiral and associated vertical Reynolds stress profile, an amplification of the inertial current response, an enhancement of turbulent variance and buoyancy entrainment rate from the pycnocline, and-for very large swell-an upscaling of the coherent Langmuir circulation patterns. Implications are discussed for the parameterization of Langmuir turbulence influences on the mean current profile and the material entrainment rate in oceanic circulation models. In particular, even though the turbulent kinetic energy monotonically increases with wave amplitude inversely expressed by the turbulent Langmuir number La, the Lagrangian shear eddy viscosity profile k L (z) is a nonmonotonic function of La, first increasing with increasing wave amplitude up to approximately the wind-wave equilibrium level, then decreasing with additional swell-wave amplitude. In contrast, the pycnocline entrainment rate is a monotonic function ;La 22 .