Fast-Charging Phosphorus-Based Anodes: Promises, Challenges, and Pathways for Improvement.

Fast-charging batteries are highly sought after. However, the current battery industry has used carbon as the preferred anode, which can suffer from dendrite formation problems at high current density, causing failure after prolonged cycling and posing safety hazards. The phosphorus (P) anode is being considered as a promising successor to graphite due to its safe lithiation potential, low ion diffusion energy barrier, and high theoretical storage capacity. Since 2019, fast-charging P-based anodes have realized the goals of extreme fast charging (XFC), which enables a 10 min recharging time to deliver a capacity retention larger than 80%. Rechargeable battery technologies that use P-based anodes, along with high-capacity conversion-type cathodes or high-voltage insertion-type cathodes, have thus garnered substantial attention from both the academic and industry communities. In spite of this activity, there remains a rather sparse range of high-performance and fast-charging P-based cell configurations. Herein, we first systematically examine four challenges for fast-charging P-based anodes, including the volumetric variation during the cycling process, the electrode interfacial instability, the dissolution of polyphosphides, and the long-lasting P/electrolyte side reactions. Next, we summarize a range of strategies with the potential to circumvent these challenges and rationally control electrochemical reaction processes at the P anode. We also consider both binders and electrode structures. We also propose other remaining issues and corresponding strategies for the improvement and understanding of the fast-charging P anode. Finally, we review and discuss the existing full cell configurations based on P anodes and forecast the potential feasibility of recycling spent P-based full cells according to the trajectory of recent developments in batteries. We hope this review affords a fresh perspective on P science and engineering toward fast-charging energy storage devices.

High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces.

The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.

Rational Molecular Engineering via Electron Reconfiguration toward Robust Dual-Electrode/Electrolyte Interphases for High-Performance Lithium Metal Batteries.

High-energy-density lithium-metal batteries (LMBs) coupling lithium-metal anodes and high-voltage cathodes are hindered by unstable electrode/electrolyte interphases (EEIs), which calls for the rational design of efficient additives. Herein, we analyze the effect of electron structure on the coordination ability and energy levels of the additive, from the aspects of intramolecular electron cloud density and electron delocalization, to reveal its mechanism on solvation structure, redox stability, as-formed EEI chemistry, and electrochemical performances. Furthermore, we propose an electron reconfiguration strategy for molecular engineering of additives, by taking sorbide nitrate (SN) additive as an example. The lone pair electron-rich group enables strong interaction with the Li ion to regulate solvation structure, and intramolecular electron delocalization yields further positive synergistic effects. The strong electron-withdrawing nitrate moiety decreases the electron cloud density of the ether-based backbone, improving the overall oxidation stability and cathode compatibility, anchoring it as a reliable cathode/electrolyte interface (CEI) framework for cathode integrity. In turn, the electron-donating bicyclic-ring-ether backbone breaks the inherent resonance structure of nitrate, facilitating its reducibility to form a N-contained and inorganic Li2O-rich solid electrolyte interface (SEI) for uniform Li deposition. Optimized physicochemical properties and interfacial biaffinity enable significantly improved electrochemical performance. High rate (10 C), low temperature (-25 °C), and long-term stability (2700 h) are achieved, and a 4.5 Ah level Li||NCM811 multilayer pouch cell under harsh conditions is realized with high energy density (462 W h/kg). The proof of concept of this work highlights that the rational ingenious molecular design based on electron structure regulation represents an energetic strategy to modulate the electrolyte and interphase stability, providing a realistic reference for electrolyte innovations and practical LMBs.

CD147 induces asthmatic airway remodeling and activation of circulating fibrocytes in a mouse model of asthma.

BACKGROUND: Airway remodeling is a poorly reversible feature of asthma which lacks effective therapeutic interventions. CD147 can regulate extracellular matrix (ECM) remodeling and tissue fibrosis, and participate in the pathogenesis of asthma. In this study, the role of CD147 in airway remodeling and activation of circulating fibrocytes was investigated in asthmatic mice. METHODS: Asthmatic mouse model was established by sensitizing and challenging mice with ovalbumin (OVA), and treated with anti-CD147 or Isotype antibody. The number of eosinophils in bronchoalveolar lavage fluid (BALF) was examined by microscope, and the levels of interleukin-4 (IL-4), IL-5 and IL-13 in BALF were detected by enzyme-linked immunosorbent assay (ELISA). The number of CD45+ and collagen I (COL-I)+ circulating fibrocytes in BALF was detected by flow cytometry. Lung tissue sections were respectively stained with hematoxylin and eosin (HE), periodic acid-Schiff (PAS) or Masson trichrome staining, or used for immunohistochemistry of CD31 and immunohistofluorescence of α-smooth muscle actin (α-SMA), CD45 and COL-I. The protein expression of α-SMA, vascular endothelial growth factor (VEGF), transforming growth factor-ß1 (TGF-ß1), Fibronectin, and COL-I was determined by western blotting. RESULTS: Anti-CD147 treatment significantly reduced the number of eosinophils and the levels of IL-4, IL-13, and IL-5 in BALF, and repressed airway inflammatory infiltration and airway wall thickening in asthmatic mice. Anti-CD147 treatment also reduced airway goblet cell metaplasia, collagen deposition, and angiogenesis in asthmatic mice, accompanied by inhibition of VEGF and α-SMA expression. The number of CD45+COL-I+ circulating fibrocytes was increased in BALF and lung tissues of OVA-induced asthmatic mice, but was decreased by anti-CD147 treatment. In addition, anti-CD147 treatment also reduced the protein expression of COL-I, fibronectin, and TGF-ß1 in lung tissues of asthmatic mice. CONCLUSION: OVA-triggered airway inflammation and airway remodeling in asthmatic mice can be repressed by anti-CD147 treatment, along with inhibiting the accumulation and activation of circulating fibrocytes.

The Septin Gene StSep4 Contributes to the Pathogenicity of Setosphaeria turcica by Regulating the Morphology, Cell Wall Integrity, and Pathogenic Factor Biosynthesis.

Septins are a conserved group of GTP-binding proteins found in all eukaryotes and are the fourth-most abundant cytoskeletal proteins. Septins of some pathogenic fungi are involved in morphological changes related to infection. Our previous studies have identified four core septins (StSep1-4) in Setosphaeria turcica, the causal agent of northern corn leaf blight, while only StSep4 is significantly upregulated during the invasive process. We therefore used forchlorfenuron (FCF), the specific inhibitor of septin, and ΔStSep4 knockout mutants to further clarify the role of septins in S. turcica pathogenicity. FCF treatment caused a dose-dependent reduction in S. turcica colony growth, delayed the formation of infection structures, and reduced the penetration ability. ΔStSep4 knockout mutants displayed abnormal mycelium morphology, slow mycelial growth, conidiation deficiency, delayed appressorium development, and weakened pathogenicity. StSep4 deletion also broke cell wall integrity, altered chitin distribution, decreased the melanin content, and disrupted normal nuclear localization. A transcriptomic comparison revealed that genes differentially expressed between ΔStSep4 and WT were enriched in terms of ribosomes, protein translation, membrane components, and transmembrane transport activities. Our results demonstrate that StSep4 is required for morphology and pathogenicity in S. turcica, making it a promising target for the development of novel fungicides.

Self-Purifying Primary Solvation Sheath Enables Stable Electrode-Electrolyte Interfaces for Nickel-Rich Cathodes.

Herein, we optimize the primary solvation sheath to investigate the fundamental correlation between battery performance and electrode-electrolyte interfacial properties through electrolyte solvation chemistry. Experimental and theoretical analyses reveal that the primary solvation sheath with a self-purifying feature can "positively" scavenge both the HF and PF5 (hydrolysis of ion-paired LiPF6), stabilize the PF6 anion-derived electrode-electrolyte interfaces, and thus boost the cycling performances. Being attributed with these superiorities, the NCM811//Li Li metal battery (LMB) with the electrolyte containing the optimized solvation sheath delivers 99.9% capacity retention at 2.5 C after 250 cycles. To circumvent the impact of excess Li content of Li metal on the performance of NCM811 cathode, the as-fabricated NCM811//graphite Li ion battery (LIB) also delivers a high-capacity retention of 90.1% from the 5th to the 100th cycle at 1 C. This work sheds light on the strong ability of the primary solvation sheath to regulate cathode interfacial properties.

Retraction Note: Long noncoding RNA LINC00968 inhibits proliferation, migration and invasion of lung adenocarcinoma through targeting miR-22-5p/CDC14A axis.

[This retracts the article DOI: 10.1007/s13205-021-02981-8.].

StRAB4 gene is required for filamentous growth, conidial development, and pathogenicity in Setosphaeria turcica.

Setosphaeria turcica, the fungal pathogen responsible for northern corn leaf blight in maize, forms specialized infectious structures called appressoria that are critical for fungal penetration of maize epidermal cells. The Rab family of proteins play a crucial role in the growth, development, and pathogenesis of many eukaryotic species. Rab4, in particular, is a key regulator of endocytosis and vesicle trafficking, essential for filamentous growth and successful infection by other fungal pathogens. In this study, we silenced StRAB4 in S. turcica to gain a better understanding the function of Rab4 in this plant pathogen. Phenotypically, the mutants exhibited a reduced growth rate, a significant decline in conidia production, and an abnormal conidial morphology. These phenotypes indicate that StRab4 plays an instrumental role in regulating mycelial growth and conidial development in S. turcica. Further investigations revealed that StRab4 is a positive regulator of cell wall integrity and melanin secretion. Functional enrichment analysis of differentially expressed genes highlighted primary enrichments in peroxisome pathways, oxidoreductase and catalytic activities, membrane components, and cell wall organization processes. Collectively, our findings emphasize the significant role of StRab4 in S. turcica infection and pathogenicity in maize and provide valuable insights into fungal behavior and disease mechanisms.

Inhibiting the Dissolution of Lithium Polyphosphides and Enhancing the Reaction Kinetics of a Phosphorus Anode via Screening Functional Additives.

A high-capacity, low-cost phosphorus anode is considered as one of the most promising candidates for next-generation Li-ion batteries. Nevertheless, the dissolution/shuttle effect of lithium polyphosphides and sluggish electrochemical conversion hinder the practical application of a phosphorus anode, similar to the problems of a sulfur cathode. Although the reported functional additives with physical obstruction and chemical adsorption have been successful in improving the performance of a sulfur cathode, they can not be directly applied to phosphorus due to their deterioration and failure in low voltage. To solve the above problems, we made a systematic investigation to rationally select the functional additives (Li2O, Li2S, and LiF) and effectively guide the experiment. These functional additives possess synergetic effects, including the adsorption of soluble lithium polyphosphides and the catalytic conversion of phosphorus species. The design of these functional additives provides a guiding and screening principle for inhibiting the dissolution of polyphosphides and improving the reaction kinetics of a phosphorus anode.

Nonsacrificial Nitrile Additive for Armoring High-Voltage LiNi0.83 Co0.07 Mn0.1 O2 Cathode with Reliable Electrode-Electrolyte Interface toward Durable Battery.

High-capacity Ni-rich layered oxides are considered as promising cathodes for lithium-ion batteries. However, the practical applications of LiNi0.83 Co0.07 Mn0.1 O2  (NCM83) cathode are challenged by continuous transition metal (TM) dissolution, microcracks and mixed arrangement of nickel and lithium sites, which are usually induced by deleterious cathode-electrolyte reactions. Herein, it is reported that those side reactions are limited by a reliable cathode electrolyte interface (CEI) layer formed by implanting a nonsacrificial nitrile additive. In this modified electrolyte, 1,3,6-Hexanetricarbonitrile (HTCN) plays a nonsacrificial role in modifying the composition, thickness, and formation mechanism of the CEI layers toward improved cycling stability. It is revealed that HTCN and 1,2-Bis(2-cyanoethoxy)ethane (DENE) are inclined to coordinate with the TM. HTCN can stably anchor on the NCM83 surface as a reliable CEI framework, in contrast, the prior decomposition of DENE additives will damage the CEI layer. As a result, the NCM83/graphite full cells with the LiPF6-EC/DEC-HTCN (BE-HTCN) electrolyte deliver a high capacity retention of 81.42% at 1 C after 300 cycles at a cutoff voltage of 4.5 V, whereas BE and BE-DENE electrolytes only deliver 64.01% and 60.05%. This nonsacrificial nitrile additive manipulation provides valuable guidance for developing aggressive high-capacity Ni-rich cathodes.

Corrigendum: Metformin Ameliorates Inflammation and Airway Remodeling of Experimental Allergic Asthma in Mice by Restoring AMPKα Activity.

[This corrects the article DOI: 10.3389/fphar.2022.780148.].

Tannic acid-polypyrrole multifunctional coating layer enhancing the interface effect and efficient Li-ion transport of a phosphorus anode.

Phosphorus has been considered a promising anode material for lithium-ion batteries because of its high specific capacity of 2596 mA h g-1 and safe lithiation voltage of 0.7 V. However, the practical application of the phosphorus anode is challenged by its poor cyclability associated with the dissolution of phosphorus intermediates, the enormous volume expansion and the sluggish lithiation reaction kinetics during the cycling process. Herein, a multifunctional coating layer is designed and fabricated on the surface of a phosphorus-carbon nanotube (P-CNT) electrode via the facile in situ polymerization of plant-derived tannic acid (TA) and pyrrole (Py). This coating layer shows strong adsorption of phosphorus and its derivatives, buffers the volumetric expansion of phosphorus and facilitates efficient Li-ion transport, thus enhancing phosphorus utilization during the cycling process. As a result, the P-CNT@TA-PPy hybrid exhibits a stable coulombic efficiency of 99.0% at 520 mA g-1 after 100 cycles and a reduced volumetric expansion of 50% at 260 mA g-1, superior to P-CNT with its unstable coulombic efficiency and large electrode expansion of 329%. This study sheds light on the rational design of advanced phosphorus-based anodes for alkali metal-ion batteries.

Metformin Ameliorates Inflammation and Airway Remodeling of Experimental Allergic Asthma in Mice by Restoring AMPKα Activity.

Metformin has been involved in modulating inflammatory state and inhibiting cell proliferation and angiogenesis. This study aimed to determine whether metformin alleviates airway inflammation and remodeling of experimental allergic asthma and elucidate the underlying mechanism. We sensitized and challenged mice with ovalbumin (OVA) to induce allergic asthma. During the challenge period, metformin was administered by intraperitoneal injection. By histopathological and immunohistochemical analyses, metformin-treated mice showed a significant alleviation in airway inflammation, and in the parameters of airway remodeling including goblet cell hyperplasia, collagen deposition and airway smooth muscle hypertrophy compared to those in the OVA-challenged mice. We also observed elevated levels of multiple cytokines (IL-4, IL-5, IL-13, TNF-α, TGF-ß1 and MMP-9) in the bronchoalveolar lavage fluid, OVA-specific IgE in the serum and angiogenesis-related factors (VEGF, SDF-1 and CXCR4) in the plasma from asthmatic mice, while metformin reduced all these parameters. Additionally, the activity of 5'-adenosine monophosphate-activated protein kinase a (AMPKα) in the lungs from OVA-challenged mice was remarkably lower than control ones, while after metformin treatment, the ratio of p-AMPKα to AMPKα was upregulated and new blood vessels in the sub-epithelial area as evidenced by CD31 staining were effectively suppressed. These results indicate that metformin ameliorates airway inflammation and remodeling in an OVA-induced chronic asthmatic model and its protective role could be associated with the restoration of AMPKα activity and decreased asthma-related angiogenesis.

Manipulating the Zinc Deposition Behavior in Hexagonal Patterns at the Preferential Zn (100) Crystal Plane to Construct Surficial Dendrite-Free Zinc Metal Anode.

Zinc metal has a severe dendrite issue caused by the uneven Zn plating/stripping during continual cycles, which hinders the practical application of ZIBs. The surficial atomic structure of zinc anode plays a decisive role in solving dendrites and improving the electrochemical performance. According to the density functional theory results, Zn (100) plane possesses a much stronger adsorption energy of zinc atom compared with the (002), thus zinc atom preferentially nucleates on the (100) surface. It subsequently continues to grow vertically on (100). Herein, the zinc anode is designed with hexagonal-hole patterns (h-Zn) through a phosphoric acid etching reaction. An abundance of Zn (100) crystal planes are exposed perpendicularly to the anode surface, while the (002) surfaces are at the bottom of these hexagonal holes. Zinc prefers to deposit in hexagonal holes at the (100) surfaces, favoring the restraining of the surficial dendrite growth and accelerating the Zn deposition kinetics. Thus, the symmetric cell using h-Zn exhibits a long cycling lifespan for over 1200 h and extremely low polarization voltage of ≈80 mV at 5 mA cm-2 and 1 mAh cm-2 . This work provides an insight into the surficial structure design and crystal plane regulation to fabricate brilliant zinc metal anodes.

Facile Separator Modification Strategy for Trapping Soluble Polyphosphides and Enhancing the Electrochemical Performance of Phosphorus Anode.

Phosphorus anode is one of the most promising candidates for high-energy-density lithium-ion batteries. Recent studies found the lithiation process of phosphorus is accompanied by the soluble intermediates of lithium polyphosphides. The trans-separator diffusion of polyphosphides is responsible for the capacity decay. Herein, a facile separator modification strategy is proposed for improving the performance of phosphorus anode. The lightweight CNT-modified layer that has a continuous conductive skeleton, a dense structure, and a strong interaction with the soluble lithium polyphosphides can trap, stabilize, and reactivate the active material. Without sophisticated electrode structure design, the cyclability and high-rate performance of the phosphorus anode has been significantly improved, leading to a higher specific capacity of 1505 mAh/g at 250 mA/g (200th cycle) and 1312 mAh/g at 2 A/g. With the advantages of simplicity and low cost, the separator modification strategy provides a new feasible way for further improvement of the phosphorus-based anode.

Long noncoding RNA LINC00968 inhibits proliferation, migration and invasion of lung adenocarcinoma through targeting miR-22-5p/CDC14A axis.

Lung adenocarcinoma (LUAD) is a high aggressive human cancer which usually diagnosed at advanced stages. Accumulating evidences indicate that long noncoding RNAs (lncRNAs) are crucial participants in LUAD progression. In the present study, we found that lncRNA LINC00968 was significantly down-regulated in LUAD tissues and cell lines. LINC00968 level was positively correlated to survival rate, and negatively correlated to tumor node metastasis (TNM) stage, tumor size and lymph node metastasis of LUAD patients. We over-expressed LINC00968 in LUAD cells using lentivirus, inhibited proliferation and cell cycle arrest at G1 phase were detected. LINC00968 over-expression also suppressed migration, invasion and epithelial mesenchymal transition. We further validated that LINC00968 localized in cytoplasm and acted as an upstream regulator of microRNA miR-22-5p, which was up-regulated in LUAD tissues and cell lines. Besides, elevated miR-22-5p expression abolished the effect of LINC00968 over-expression on LUAD progression including in vivo tumor growth. In addition, we first validated that cell division cycle 14A (CDC14A), which was down-regulated in LUAD tissues, was a downstream target of miR-22-5p. We over-expressed CDC14A in LUAD cells and miR-22-5p induced LUAD progression was partially reversed. In conclusion, our study demonstrated that LINC00968 inhibited proliferation, migration and invasion of LUAD by sponging miR-22-5p and further restoring CDC14A. This novel regulatory axis might provide us with promising diagnostic and therapeutic target in LUAD treatment.

The synthesis of greenish phosphorus on carbon substrates.

A phosphorus allotrope called greenish phosphorus was successfully synthesized via a simple chemical vapor deposition method. We revealed that the critical factors in the formation mechanism of greenish phosphorus are the partial pressure of the phosphorus vapor and the structure of the substrate. On the substrates of a glassy carbon wafer and carbon paper, the edge carbon structure can activate P4 molecules, allowing them to polymerize due to strong adsorption (Ead = -1.62 eV). Greenish phosphorus possesses a distinct crystal structure, different from red phosphorus and black phosphorus, thus leading to unique physical and chemical properties, and potential applications in optical, electrical, and magnetic fields.

A Covalent P-C Bond Stabilizes Red Phosphorus in an Engineered Carbon Host for High-Performance Lithium-Ion Battery Anodes.

The red phosphorus (RP) anode has attracted great attention due to its high theoretical specific capacity (2596 mAh/g) and suitable lithiation potential. To solve the inherent poor electrical conductivity and the large volume expansion due to the lithiation process, a vaporization-condensation strategy is considered as a promising method. However, there are two important issues that deserve attention in the vaporization-condensation process. First, the low P mass loading in the carbon-based frameworks (∼30 wt %) limits the energy density. Second, a residual white phosphorus (WP) leads to the safety problems of flammability and high toxicity. Herein, we found that the edge structure of carbon framework can offer the strong adsorption for P4 and form a P-C bond, which accelerate the adsorption and polymerization of P4 leading to high P mass loading and safety. When the porous carbon (PC) with plenty of edge carbons was used as the matrix to load P by vaporization-condensation, the RP loading is close to the highest theoretical mass loading of ∼50 wt % calculated based on the feeding ratio of RP/PC = 1/1. Therefore, the RP-PC anode provides a high specific capacity of 965.2 mAh/g even after 1100 cycles at 1000 mA/g (equivalent to 1 C) and a high-rate capacity of 496.8 mAh/g at 8320 mA/g (equivalent to 16.7 C) after 1000 cycles (the specific capacity and current density are calculated based on the total weight of RP and PC).

Super-Soft DNA/Dopamine-Grafted-Dextran Hydrogel as Dynamic Wire for Electric Circuits Switched by a Microbial Metabolism Process.

Engineering dynamic systems or materials to respond to biological process is one of the major tasks in synthetic biology and will enable wide promising applications, such as robotics and smart medicine. Herein, a super-soft and dynamic DNA/dopamine-grafted-dextran hydrogel, which shows super-fast volume-responsiveness with high sensitivity upon solvents with different polarities and enables creation of electric circuits in response to microbial metabolism is reported. Synergic permanent and dynamic double networks are integrated in this hydrogel. A serials of dynamic hydrogel-based electric circuits are fabricated: 1) triggered by using water as switch, 2) triggered by using water and petroleum ether as switch pair, 3) a self-healing electric circuit; 4) remarkably, a microbial metabolism process which produces ethanol triggering electric circuit is achieved successfully. It is envisioned that the work provides a new strategy for the construction of dynamic materials, particularly DNA-based biomaterials; and the electric circuits will be highly promising in applications, such as soft robotics and intelligent systems.

Design of a LiF-rich solid electrolyte interface layer through salt-additive chemistry for boosting fast-charging phosphorus-based lithium ion battery performance.

A robust and conductive LiF-rich solid electrolyte interface layer was generated at the phosphorus surface through salt-additive chemistry, and it then served as a high-performance fast-charging lithium ion battery anode, delivering a high reversible capacity of 450 mA h g-1 after 450 cycles with a high charging current density of 8 A g-1 (about 3 min).