Rational Composition Optimization of the Lithium-Rich Li₃OCl_1–<i>x</i>Br_<i>x</i> Anti-Perovskite Superionic Conductors

The newly discovered lithium-rich antiperovskite (LRAP) superionic conductors are an extremely interesting class of materials with potential applications as solid electrolytes in Li-ion batteries. In this work, we present a rational composition optimization strategy for maximizing the Li⁺ conductivity in the LRAP guided by a combination of first-principles calculations and percolation theory. Using nudged elastic band (NEB) calculations, we show that a Cl-rich channel with Br-rich end points configuration leads to low vacancy migration barriers in the LRAP structure. By incorporating the halide-environment-dependent NEB barriers in a bond percolation model, we predict that there are potentially higher conductivity Li₃OCl_1–<i>x</i>Br_<i>x</i> structures near 0.235 ≤ <i>x</i> ≤ 0.395. This prediction is confirmed by AIMD simulation that finds Li₃OCl_0.75Br_0.25 to have a higher Li⁺ conductivity than Li₃OCl_0.5Br_0.5, the highest conductivity LRAP identified experimentally thus far. These results highlight that there is scope for further enhancing the conductivity in the LRAP chemistry. The general approach developed can potentially be extended to other ion-conducting systems, such as the structurally similar perovskite oxygen-ion conductors of interest in solid-oxide fuel cells as well as other superionic conductors

Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors

We present a detailed exposition of how first-principles methods can be used to guide alkali superionic conductor (ASIC) study and design. Using the argyrodite Li₆PS₅Cl as a case study, we demonstrate how modern information technology (IT) infrastructure and software tools can facilitate the assessment of alkali superionic conductors in terms of various critical properties of interest such as phase and electrochemical stability and ionic conductivity. The emphasis is on well-documented, reproducible analysis code that can be readily generalized to other material systems and design problems. For our chosen Li₆PS₅Cl case study material, we show that Li excess is crucial to enhancing its conductivity by increasing the occupancy of interstitial sites that promote long-range Li⁺ diffusion between cage-like frameworks. The predicted room-temperature conductivities and activation barriers are in reasonably good agreement with experimental values

Role of Na⁺ Interstitials and Dopants in Enhancing the Na⁺ Conductivity of the Cubic Na₃PS₄ Superionic Conductor

In this work, we performed a first-principles investigation of the phase stability, dopant formation energy and Na⁺ conductivity of pristine and doped cubic Na₃PS₄ (c-Na₃PS₄). We show that pristine c-Na₃PS₄ is an extremely poor Na ionic conductor, and the introduction of Na⁺ excess is the key to achieving reasonable Na⁺ conductivities. We studied the effect of aliovalent doping of M⁴⁺ for P⁵⁺ in c-Na₃PS₄, yielding Na_3+<i>x</i>M_<i>x</i>P_1–<i>x</i>S₄ (M = Si, Ge, and Sn with <i>x</i> = 0.0625; M = Si with <i>x</i> = 0.125). The formation energies in all the doped structures with dopant concentration of <i>x</i> = 0.0625 are found to be relatively low. Using <i>ab initio</i> molecular dynamics simulations, we predict that 6.25% Si-doped c-Na₃PS₄ has a Na⁺ conductivity of 1.66 mS/cm, in excellent agreement with previous experimental results. Remarkably, we find that Sn⁴⁺ doping at the same concentration yields a much higher predicted Na⁺ conductivity of 10.7 mS/cm, though with a higher dopant formation energy. A higher Si⁴⁺ doping concentration of <i>x</i> = 0.125 also yields a significant increase in Na⁺ conductivity with an even higher dopant formation energy. Finally, topological and van Hove correlation function analyses suggest that the channel volume and correlation in Na⁺ motions may play important roles in enhancing Na⁺ conductivity in this structure

Comparison of nanoparticle generation by two plasma techniques: Dielectric barrier discharge and spark discharge

<p>Dielectric barrier discharge (DBD) and spark discharge, two versatile atmospheric pressure plasma-based techniques, have been employed to generate nanoparticles. This study compares the characteristics of metal nanoparticles generated by a DBD reactor and a spark discharge generator with argon as the working gas. The gas temperature in the discharge region of the DBD reactor remained near room temperature, while that of the spark reactor varied from 470 to 1120 K and generally increased with increasing applied voltage amplitude in the range of 2–10 kV and driving frequency in the range of 1–10 kHz. Comparing to spark-generated nanoparticles under the same voltage, frequency, and flow rate, DBD-generated nanoparticles have smaller sizes, better monodispersity, and lower number concentrations. The number concentration of DBD-generated particles decreases significantly under high working voltage and frequency, while the number concentration of spark-generated particles increases with increasing working voltage. Under continuous operations over several hours, the DBD reactor has better temporal stability in generating nanoparticles than the spark generator.</p> <p>© 2017 American Association for Aerosol Research</p

Table_1_TRAF3IP3 Is Cleaved by EV71 3C Protease and Exhibits Antiviral Activity.DOCX

Enterovirus 71 (EV71) is one of the major pathogens of hand, foot, and mouth disease, which poses a major risk to public health and infant safety. 3C protease (3Cpro), a non-structural protein of EV71, promotes viral protein maturation by cleaving polyprotein precursors and facilitates viral immune escape by cleaving host proteins. In this study, we screened for human proteins that could interact with EV71 3Cpro using a yeast two-hybrid assay. Immune-associated protein TRAF3 Interacting Protein 3 (TRAF3IP3) was selected for further study. The results of co-immunoprecipitation and immunofluorescence demonstrated the interaction between TRAF3IP3 and EV71 3Cpro. A cleavage band was detected, indicating that both transfected 3Cpro and EV71 infection could cleave TRAF3IP3. 87Q-88G was identified as the only 3Cpro cleavage site in TRAF3IP3. In Jurkat and rhabdomyosarcoma (RD) cells, TRAF3IP3 inhibited EV71 replication, and 3Cpro cleavage partially resisted TRAF3IP3-induced inhibition. Additionally, the nuclear localization signal (NLS) and nuclear export signal (NES) of TRAF3IP3 were identified. The NES contributed to TRAF3IP3 alteration of 3Cpro localization and inhibition of EV71 replication. Together, these results indicate that TRAF3IP3 inhibits EV71 replication and 3Cpro resists such inhibition via proteolytic cleavage, providing a new example of virus-host interaction.</p

Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries

In this work, we performed a comprehensive study of Prussian blue and its analogues (PBAs), one of the most promising cathode materials for aqueous sodium-ion batteries for large-scale energy-storage systems, using first-principles calculations. It is confirmed that dry PBAs generally undergo a phase transition from a rhombohedral Na2PR­(CN)6 (where P and R are transition metals) to a tetragonal/cubic PR­(CN)6 during Na extraction, in agreement with experimental observations. Using a grand potential phase diagram construction, we show that water and Na co-intercalation result in fundamentally different phase transition behavior and, hence, electrochemical voltage profiles in wet versus dry electrolytes. Lattice water increases the average voltage and reduces the volume change during electrochemical cycling, resulting in both higher energy density and better cycling stability. Finally, we identified four new PBA compositions, Na2CoMn­(CN)6, Na2NiMn­(CN)6, Na2CuMn­(CN)6, and Na2ZnMn­(CN)6, that show great promise as cathodes for aqueous rechargeable Na-ion batteries

DataSheet1_Temperature-dependent compatibility study on halide solid-state electrolytes in solid-state batteries.docx

All-solid-state lithium batteries (ASSLBs) have attracted much attention owing to their high safety and energy density compared to conventional organic electrolytes. However, the interfaces between solid-state electrolytes and electrodes retain some knotty problems regarding compatibility. Among the various SSEs investigated in recent years, halide SSEs exhibit relatively good interfacial compatibility. The temperature-dependent interfacial compatibility of halide SSEs in solid-state batteries is investigated by thermal analysis using simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC) and X-ray diffraction (XRD). Halide SSEs, including rock-salt-type Li3InCl6 and anti-perovskite-type Li2OHCl, show good thermal stability with oxides LiCoO2, LiMn2O4, and Li4Ti5O12 up to 320 °C. Moreover, anti-perovskite-type Li2OHCl shows a chemical reactivity with other battery materials (eg., LiFePO4, LiNi0.8Co0.1Mn0.1O2, Si-C, and Li1.3Al0.3Ti1.7(PO4)3) at 320°C, which reaches the melting point of Li2OHCl. It indicated that Li2OHCl has relatively high chemical reactivity after melting. In contrast, rock-salt-type Li3InCl6 shows higher stability and interfacial compatibility. This work delivers insights into the selection of suitable battery materials with good compatibility for ASSLBs.</p

Image_1_Genome-Wide Identification and Analysis of Small Nucleolar RNAs and Their Roles in Regulating Latex Regeneration in the Rubber Tree (Hevea brasiliensis).TIF

Small nucleolar RNAs (snoRNAs) are a class of conserved nuclear RNAs that play important roles in the modification of ribosomal RNAs (rRNAs) in plants. In rubber trees, rRNAs are run off with latex flow during tapping and need to be regenerated for maintaining the functions of the laticifer cells. SnoRNAs are expected to play essential roles in the regeneration of rRNAs. However, snoRNAs in the rubber tree have not been sufficiently characterized thus far. In this study, we performed nuclear RNA sequencing (RNA-seq) to identify snoRNAs globally and investigate their roles in latex regeneration. We identified a total of 3,626 snoRNAs by computational prediction with nuclear RNA-seq data. Among these snoRNAs, 50 were highly expressed in latex; furthermore, the results of reverse transcription polymerase chain reaction (RT-PCR) showed the abundant expression of 31 of these snoRNAs in latex. The correlation between snoRNA expression and adjusted total solid content (TSC/C) identified 13 positively yield-correlated snoRNAs. To improve the understanding of latex regeneration in rubber trees, we developed a novel insulated tapping system (ITS), which only measures the latex regenerated in specific laticifers. Using this system, a laticifer-abundant snoRNA, HbsnoR28, was found to be highly correlated with latex regeneration. To the best of our knowledge, this is the first report to globally identify snoRNAs that might be involved in latex regeneration regulation and provide new clues for unraveling the mechanisms underlying the regulation of latex regeneration.</p

Oxygen-Loss-Induced Structural Degradation in ε‑LiVOPO₄

The ε-LiVOPO4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO4. We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO4 → α-Li3V2(PO4)3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core–shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li3V2(PO4)3 is reoxidized to ε-LiVOPO4. By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints

Oxygen-Loss-Induced Structural Degradation in ε‑LiVOPO₄

The ε-LiVOPO4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO4. We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO4 → α-Li3V2(PO4)3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core–shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li3V2(PO4)3 is reoxidized to ε-LiVOPO4. By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints