Deciphering the Formation and Accumulation of Solid-Electrolyte Interphases in Na and K Carbonate-Based Batteries.

The continuous solid-electrolyte interphase (SEI) accumulation has been blamed for the rapid capacity loss of carbon anodes in Na and K ethylene carbonate (EC)/diethyl carbonate (DEC) electrolytes, but the understanding of the SEI composition and its formation chemistry remains incomplete. Here, we explain this SEI accumulation as the continuous production of organic species in solution-phase reactions. By comparing the NMR spectra of SEIs and model compounds we synthesized, alkali metal ethyl carbonate (MEC, M = Na or K), long-chain alkali metal ethylene carbonate (LCMEC, M = Na or K), and poly(ethylene oxide) (PEO) oligomers with ethyl carbonate ending groups are identified in Na and K SEIs. These components can be continuously generated in a series of solution-phase nucleophilic reactions triggered by ethoxides. Compared with the Li SEI formation chemistry, the enhancement of the nucleophilicity of an intermediate should be the cause of continuous nucleophilic reactions in the Na and K cases.

Mechanistic Insight into Ultrafast Kinetics of Sodium Cointercalation in Few-Layer Graphitic Carbon.

Fast-charging sodium ion batteries remain deeply challenged by the lack of suitable carbonaceous anodes that exhibit intercalation plateau with fast kinetics. Here we develop a few-layer graphitic carbon with nanoscale architecture, which enables shortened Na+ ion diffusion path and fast formation of fully intercalated phase at the same time. Combined in situ Raman and electrochemical test reveal that this graphitic carbon with highly crystalline few layers follows surface-controlled intercalation rather than typical diffusion-controlled kinetics observed in natural graphite. As a result, a few-layer graphitic carbon anode maintains the reversible capacity of 106 mAh g-1 at 10 A g-1 and achieves 87% capacity retention even after 10 000 cycles at 1 A g-1. This work provides new insight on the Na storage mechanism in fast-charging graphitic carbon as well as the design of carbon anodes for high-rate sodium ion batteries.

Key Factor Determining the Cyclic Stability of the Graphite Anode in Potassium-Ion Batteries.

Graphite is the most commonly used anode material for not only commercialized lithium-ion batteries (LIBs) but also the emerging potassium-ion batteries (PIBs). However, the graphite anode in PIBs using traditional dilute ester-based electrolyte systems shows obvious capacity fading, which is in contrast with the extraordinary cyclic stability in LIBs. More interestingly, the graphite in concentrated electrolytes for PIBs exhibits outstanding cyclic stability. Unfortunately, this significant difference in cycling performance has not raised concern up to now. In this work, by comparing the cyclic stability and graphitization degree of the graphite anode upon cycling, we reveal that the underlying mechanism of the capacity fading of the graphite anode in PIBs is not the larger volume expansion of graphite caused by the intercalation of potassium ions but the continual accumulation of the solid electrolyte interphase (SEI) on the surface of graphite. By X-ray photoelectron and nuclear magnetic resonance spectroscopies combined with chemical synthesis, it is concluded that the accumulation of the SEI may mainly come from the continual deposition of a kind of oligomer component, which blocks intercalation and deintercalation of potassium ions in graphite anodes. The designed SEI-cleaning experiment further verifies the above conclusion. This finding clarifies the crucial factor determining the cyclic stability of graphite and provides scientific guidance for application of the graphite anode for PIBs.

Plant-derived smoke enhances plant growth through ornithine-synthesis pathway and ubiquitin-proteasome pathway in soybean.

To investigate the mechanism of promotive effect of plant-derived smoke on the soybean growth, a gel-free/label-free proteomics was performed. Smoke solutions were irrigated on soybean or supplied simultaneously with flooding stress. Morphological and physiological analyses were performed for the confirmation of proteomic result. Metabolomic change was investigated to correlate proteomic change with metabolism regulation. Under normal condition, the length of root including hypocotyl increased in soybean treated with 2000 ppm plant-derived smoke within 4 days, as well as nitric oxide content. Proteins related to protein synthesis especially arginine metabolism were altered; metabolites related to amino acid, carboxylic acids, and sugars were mostly altered. Integrated analysis of omics data indicated that plant-derived smoke regulated nitrogen­carbon transformation through ornithine synthesis pathway and promoted soybean normal growth. Under flooding, the number of lateral roots increased with root tip degradation in soybean treated with smoke solutions. Proteins related to ubiquitin-proteasome pathway were altered and led to sacrifice-for-survival-mechanism-driven degradation of root tip in soybean, which enabled accumulation of metabolites and guaranteed lateral root development during soybean recovery after flooding. These findings suggest that plant-derived smoke improves early stage of growth in soybean with regulation of ornithine-synthesis pathway and ubiquitin-proteasome pathway. BIOLOGICAL SIGNIFICANCE: Plant-derived smoke plays a key role in crop growth, however, the understanding of soybean in response to smoke treatment remains premature. Therefore, gel-free/label-free proteomic analysis was used for comprehensive study on the dual effect of smoke to soybean under normal and flooding conditions. Under normal condition, plant-derived smoke regulated nitrogen­carbon transformation through ornithine synthesis pathway and resulted in the increase of the length of root including hypocotyl in soybean within 4 days. Under flooding condition, plant-derived smoke induced inhibition of ubiquitin-proteasome pathway and led to sacrifice-for-survival-mechanism-driven degradation of root tip in soybean, which enabled accumulation of metabolites and promoted lateral root development during soybean recovery after flooding.

An improved model for analyzing the performance of photocatalytic oxidation reactors in removing volatile organic compounds and its application.

An improved photocatalytic oxidation (PCO) reactor model was developed to analyze the removal of volatile organic compounds (VOCs) in indoor air. One new parameter, the average total removing factor Kt, together with the other two parameters, the number of mass transfer units NTUm and the fractional conversion epsilon, are found to be the main parameters influencing the photooxidation performance of PCO reactors. Three new parameters, the ideal reaction number of mass transfer units, NTUm,ir; the ideal reaction fractional conversion, epsilonir; and the reaction effectiveness, eta, also are defined. These concepts are helpful to the structural design and optimization for PCO reactors. The application of the model in designing a plate-type PCO reactor is demonstrated. This study shows that the present model is an effective tool for designing PCO reactors and for evaluating VOC removal performance of available PCO reactors.