Anchoring Active Li Metal in Oriented Channel by In Situ Formed Nucleation Sites Enabling Durable Lithium-Metal Batteries.

Lithium metal is the ultimate anode material for pursuing the increased energy density of rechargeable batteries. However, fatal dendrites growth and huge volume change seriously hinder the practical application of lithium metal batteries (LMBs). In this work, a lithium host that preinstalled CoSe nanoparticles on vertical carbon vascular tissues (VCVT/CoSe) is designed and fabricated to resolve these issues, which provides sufficient Li plating space with a robust framework, enabling dendrite-free Li deposition. Their inherent N sites coupled with the in situ formed lithiophilic Co sites loaded at the interface of VCVT not only anchor the initial Li nucleation seeds but also accelerate the Li+ transport kinetics. Meanwhile, the Li2 Se originated from the CoSe conversion contributes to constructing a stable solid-electrolyte interphase with high ionic conductivity. This optimized Li/VCVT/CoSe composite anode exhibits a prominent long-term cycling stability over 3000 h with a high areal capacity of 10 mAh cm-2 . When paired with a commercial nickel-rich LiNi0.83 Co0.12 Mn0.05 O2 cathode, the full-cell presents substantially enhanced cycling performance with 81.7% capacity retention after 300 cycles at 0.2 C. Thus, this work reveals the critical role of guiding Li deposition behavior to maintain homogeneous Li morphology and pave the way to stable LMBs.

Multifunctional Interlayer Engineering for Silkworm Excrement-Derived Porous Carbon Enabling High-Energy Lithium Sulfur Batteries.

Lithium-sulfur (Li-S) batteries show advantage of high theoretical capacity. However, the shuttle effect of polysulfides and sluggish sulfur redox kinetics seriously reduce their service life. Inspired by the porous structural features of biomass materials, herein, a functional interlayer is fabricated by silkworm excrement-derived three-dimensional porous carbon accommodating nano sized CoS2 particles (SC@CoS2 ). The porous carbon delivers a high specific surface area, which provides adequate adsorption sites, being responsible for suppressing the shuttle effect of polysulfides. Meanwhile, the porous carbon is favorable for hindering the aggregation of CoS2 and maintaining its high activity during extended cycles, which effectively accelerates the polysulfides conversion kinetics. Moreover, the SC@CoS2 functional interlayer effectively limits the formation of Li dendrites and promotes the uniform deposition of Li on the Li electrode surface. As a result, the CMK-3/S cathode achieves a high initial capacity of 1599.1 mAh g-1 at 0.2 C rate assisted by the polypropylene separator coated with the functional interlayer and 1208.3 mAh g-1 is maintained after the long cycling test. This work provides an insight into the designing of long-lasting catalysts for stable functional interlayer, which encourages the application of biomass-derived porous carbon in high-energy Li-S batteries.

Work-Function-Induced Interfacial Electron/Ion Transport in Carbon Hosts toward Dendrite-Free Lithium Metal Anodes.

Coupled electron/ion transport is a decisive feature of Li plating/stripping, wherein the compatibility of electron/ion transport rates determines the morphology of deposited Li. Local Li+ hotspots form due to inhomogeneous interfacial charge transfer and lead to uncontrolled Li deposition, which decreases the Li utilization rate and safety of Li metal anodes. Herein, we report a method to obtain dendrite-free Li metal anodes by driving electron pumping and accumulating and boosting Li ion diffusion by tuning the work function of a carbon host using cobalt-containing catalysts. The results reveal that increasing the work function provides an electron deviation from C to Co, and electron-rich Co shows favorable binding to Li+ . The Co catalysts boost Li+ diffusion on the carbon fiber scaffolds without local aggregation by reducing the Li+ migration barrier. The as-obtained dendrite-free Li metal anode exhibits a Coulombic efficiency of 99.0 %, a cycle life of over 2000 h, a Li utilization rate of 50 %, and a capacity retention of 83.4 % after 130 cycles in pouch cells at a negative/positive capacity ratio of 2.5. These findings provide a novel strategy to stabilize Li metal by regulating the work function of materials using electrocatalysts.

Ni/TiO2 heterostructures derived from phase separation for enhanced electrocatalysis of hydrogen evolution and biomass oxidative upgrading in anion exchange membrane electrolyzers.

The construction of heterostructures is an effective strategy to enhance electrocatalysis for hydrogen evolution reactions (HERs) and biomass oxidative upgrading. In this work, a Ni/TiO2 heterostructure prepared by a phase-separation strategy was adopted as a bifunctional electrocatalyst for HERs and biomass oxidation in alkaline media. Due to the optimized hydrogen adsorption energetics as well as the interfacial water structure and hydrogen bond connectivity in the electrical double layer, Ni/TiO2 exhibited high activity for HERs with an overpotential of 28 mV at 10 mA cm-2 and good durability at 1000 mA cm-2 for over 100 h in an anion exchange membrane (AEM) electrolyzer. In addition, Ni/TiO2 showed high catalytic performance for the oxidation of biomass-based platform compound 5-hydroxymethylfurfural (HMF) to high-value added compound 2,5-furandicarboxylic acid (FDCA). Continuous production of FDCA with a yield >95% was achieved in the AEM electrolyzer for over 50 h. The superior HMF oxidation performance on the Ni/TiO2 heterostructure compared to Ni resulted from stronger HMF adsorption, lower Ni3+-O formation potential, longer Ni3+-O bond and smaller Ni crystal size.

Building a Self-Adaptive Protective Layer on Ni-Rich Layered Cathodes to Enhance the Cycle Stability of Lithium-Ion Batteries.

Layered Ni-rich lithium transition metal oxides are promising battery cathodes due to their high specific capacity, but their poor cycling stability due to intergranular cracks in secondary particles restricts their practical applications. Surface engineering is an effective strategy for improving a cathode's cycling stability, but most reported surface coatings cannot adapt to the dynamic volume changes of cathodes. Herein, a self-adaptive polymer (polyrotaxane-co-poly(acrylic acid)) interfacial layer is built on LiNi0.6 Co0.2 Mn0.2 O2 . The polymer layer with a slide-ring structure exhibits high toughness and can withstand the stress caused by particle volume changes, which can prevent the cracking of particles. In addition, the slide-ring polymer acts as a physicochemical barrier that suppresses surface side reactions and alleviates the dissolution of transition metallic ions, which ensures stable cycling performance. Thus, the as-prepared cathode shows significantly improved long-term cycling stability in situations in which cracks may easily occur, especially under high-rate, high-voltage, and high-temperature conditions.

Fatigue-Resistant Interfacial Layer for Safe Lithium Metal Batteries.

The plating/stripping of Li dendrites can fracture the static solid electrolyte interphase (SEI) and cause significant dynamic volume variations in the Li anode, which give rise to poor cyclability and severe safety hazards. Herein, a tough polymer with a slide-ring structure was designed as a self-adaptive interfacial layer for Li anodes. The slide-ring polymer with a dynamically crosslinked network moves freely while maintaining its toughness and fracture resistance, which allows it can to dissipate the tension induced by Li dendrites on the interphase layer. Moreover, the slide-ring polymer is highly stretchable, elastic, and displays an ultrafast self-healing ability, which allows even pulverized Li to remain coalesced without disintegrating upon consecutive cycling. The Li anodes demonstrate greatly improved suppression of Li dendrite formation, as evidenced by the high critical current density (6 mA cm-2 ) and stable cycling for the full cells with high-areal capacity LiFePO4 , high-voltage NCM, and S cathodes.

Bioselective Synthesis of a Porous Carbon Collector for High-Performance Sodium-Metal Anodes.

Biomass-derived carbon materials prepared via pyrolysis from natural wood structures show potential for a storage application. Natural wood is composed of multiple carbon sources, including lignin, hemicellulose, and cellulose, which influence the formation and microstructure of pyrolysis carbon. However, the mechanism is not fully understood. In this work, vast lignin is selectively consumed via biodegradation with fungi from basswood. The results demonstrate that the as-prepared carbon material has a short-range ordered graphitic structure after thermal treatment. The improved graphitization degree of carbon suggests that cellulose is beneficial to graphite formation during pyrolysis. The elevated graphitization degree helps to improve the charge transfer and the thermodynamic stability of the electrode reaction. As a proof of concept, the obtained carbon current collector as a sodium-metal anode can undergo cycling at an areal capacity of 10 mAh cm-2 for over 4500 h and yield an excellent Coulombic efficiency of >99.5%.

Ni17 W3 -W Interconnected Hybrid Prepared by Atmosphere- and Thermal-Induced Phase Separation for Efficient Electrocatalysis of Alkaline Hydrogen Evolution.

The development of efficient and stable noble-metal-free electrocatalysts for hydrogen evolution reaction (HER) in alkaline media is still a challenge. Herein, a hybrid material formed by the interconnection of Ni17 W3 intermetallic compound with metallic W is demonstrated for HER. The Ni17 W3 -W hybrid is prepared by the atmosphere- and thermal-induced phase-separation strategy from a single-phase precursor (NiWO4 ), which gives Ni17 W3 -W hybrid abundant and tight interfaces. The theoretical calculation manifests that Ni17 W3 shows more optimized energetics for adsorbed H atom, while W has lower energy barrier for water dissociation, and the synergistic effect between them is believed to facilitate the HER kinetics. Moreover, Ni17 W3 presents a proper adsorption strength for both adsorbed OH and H, and thus Ni17 W3 may also act as a high HER catalyst by itself. As a result, the Ni17 W3 -W hybrid demonstrates high activity and durability for HER in liquid alkaline electrolyte; the electrolyzer assembled by Ni17 W3 -W hybrid and Ni-Fe-layered double hydroxide (LDH) as, respectively, the cathode and anode electrocatalysts presents superior performance to Pt/C-IrO2 benchmark. In addition, the Ni17 W3 -W hybrid also works well in the water electrolyzer based on solid hydroxide exchange membrane. The present work provides a promising pathway to the design of high-performance electrocatalysts.

An Outlook on Low-Volume-Change Lithium Metal Anodes for Long-Life Batteries.

Rechargeable Li metal batteries are one of the most attractive energy storage systems due to their high energy density. However, the hostless nature of Li, the excessive dendritic growth, and the accumulation of nonactive Li induce severe volume variation of Li anodes. The volume variation can give rise to a fracture of solid electrolyte interphase, continuous consumption of Li and electrolytes, low Coulombic efficiency, fast performance degradation, and finally short cycle life. This Outlook provides a comprehensive understanding of the origin and consequences of Li volume variation. Recent strategies to address this challenge are reviewed from liquid to gel to solid-state electrolyte systems. In the end, guidelines for structural design and fabrication suggestions for future long-life Li composite anodes are presented.

Amorphous Ni-Fe-Mo Suboxides Coupled with Ni Network as Porous Nanoplate Array on Nickel Foam: A Highly Efficient and Durable Bifunctional Electrode for Overall Water Splitting.

It is a great challenge to fabricate electrode with simultaneous high activity for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Herein, a high-performance bifunctional electrode formed by vertically depositing a porous nanoplate array on the surface of nickel foam is provided, where the nanoplate is made up by the interconnection of trinary Ni-Fe-Mo suboxides and Ni nanoparticles. The amorphous Ni-Fe-Mo suboxide and its in situ transformed amorphous Ni-Fe-Mo (oxy)hydroxide acts as the main active species for HER and OER, respectively. The conductive network built by Ni nanoparticles provides rapid electron transfer to active sites. Moreover, the hydrophilic and aerophobic electrode surface together with the hierarchical pore structure facilitate mass transfer. The corresponding water electrolyzer demonstrates low cell voltage (1.50 V @ 10 mA cm-2 and 1.63 V @ 100 mA cm-2) with high durability at 500 mA cm-2 for at least 100 h in 1 m KOH.

Confined Red Phosphorus in Edible Fungus Slag-Derived Porous Carbon as an Improved Anode Material in Sodium-Ion Batteries.

Red phosphorus (RP) as the anode material for the sodium-ion battery (SIB) possesses a high energy density, but the poor electronic conductivity and huge volume change during Na+ insertion/extraction restrict its application. In this work, the edible fungus slag-derived porous carbon (PC) is adopted as a carbon matrix to combine with RP to form PC@RP composites through a facile vaporization-condensation approach. The conductive porous carbon architecture improves the transfer of electron and Na+ in the composite. The robust carbon framework together with the chemical bonding between PC and RP effectively buffer the huge volumetric change of RP. As a result, the PC@RP composite material delivers a specific capacity of 655.1 mA h g-1 at 0.1 A g-1 with a capacity retention of 87% after 100 charging/discharging cycles. In particular, the full SIB assembled with P2-Na2/3Ni1/3Mn1/3Ti1/3O2 as the cathode material and PC@RP as the anode material exhibits a specific capacity of 77.3 mA h g-1 (based on the mass of cathode material) at 0.5 C, and 85% capacity is retained after 100 charging/discharging cycles.

Edible fungus slag derived nitrogen-doped hierarchical porous carbon as a high-performance adsorbent for rapid removal of organic pollutants from water.

In this work, agricultural waste edible fungus slag derived nitrogen-doped hierarchical porous carbon (EFS-NPC) was prepared by a simple carbonization and activation process. Owing to the biodegradation and infiltrability of hyphae, this EFS-NPC possessed an ultra-high specific surface area (3342 m2/g), large pore volume (1.84 cm3/g) and abundant micropores and mesopores. The obtained EFS-NPC could effectively adsorb bisphenol A (BPA) with the maximal adsorption capacity of 1249 mg/g and the removal process reached 89.9% of the equilibrium uptake in the first 0.5 h. Besides, the EFS-NPC showed much better removal performance towards 2,4-dichlorophenol (2,4-DCP) and methylene blue (MB) than commercial activated carbons (Norit RO 0.8 and DARCO granular activated carbon). Furthermore, adsorption isotherms, thermodynamics and kinetics researches indicated that the adsorption process of BPA was monolayer, exothermic and spontaneous. This research has given evidence that the low-cost EFS-NPC can serve as a high-efficient adsorbent for removing organic contaminants from water.

Guiding Uniform Li Plating/Stripping through Lithium-Aluminum Alloying Medium for Long-Life Li Metal Batteries.

The uncontrolled growth of Li dendrites upon cycling might result in low coulombic efficiency and severe safety hazards. Herein, a lithiophilic binary lithium-aluminum alloy layer, which was generated through an in situ electrochemical process, was utilized to guide the uniform metallic Li nucleation and growth, free from the formation of dendrites. Moreover, the formed LiAl alloy layer can function as a Li reservoir to compensate the irreversible Li loss, enabling long-term stability. The protected Li electrode shows superior cycling over 1700 h in a Li|Li symmetric cell.

Fungi-Enabled Synthesis of Ultrahigh-Surface-Area Porous Carbon.

The growth of white-rot fungi is related to the superior infiltrability and biodegradability of hyphae on a lignocellulosic substrate. The superior biodegradability of fungi toward plant substrates affords tailored microstructures, which benefits subsequently high efficient carbonization and chemical activation. Here, the mechanism underlying the direct growth of mushrooms toward the lignocellulosic substrate is elucidated and a fungi-enabled method for the preparation of porous carbons with ultrahigh specific surface area (3439 m2 g-1 ) is developed. Such porous carbons could have potential applications in energy storage, environment treatment, and electrocatalysis. The present study reveals a novel pore formation mechanism in root-colonizing fungi and anticipates a valuable function for fungi in developing the useful porous carbons with a high specific surface area.

Co Nanoparticles/Co, N, S Tri-doped Graphene Templated from In-Situ-Formed Co, S Co-doped g-C3N4 as an Active Bifunctional Electrocatalyst for Overall Water Splitting.

The development of high-performance electrocatalyst with earth-abundant elements for water-splitting is a key factor to improve its cost efficiency. Herein, a noble metal-free bifunctional electrocatalyst was synthesized by a facile pyrolysis method using sucrose, urea, Co(NO3)2 and sulfur powder as raw materials. During the fabrication process, Co, S co-doped graphitic carbon nitride (g-C3N4) was first produced, and then this in-situ-formed template further induced the generation of a Co, N, S tri-doped graphene coupled with Co nanoparticles (NPs) in the following pyrolysis process. The effect of pyrolysis temperature (700, 800, and 900 °C) on the physical properties and electrochemical performances of the final product was studied. Thanks to the increased number of graphene layer encapsulated Co NPs, higher graphitization degree of carbon matrix and the existence of hierarchical macro/meso pores, the composite electrocatalyst prepared under 900 °C presented the best activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) with outstanding long-term durability. This work presented a facile method for the fabrication of non-noble-metal-based carbon composite from in-situ-formed template and also demonstrated a potential bifunctional electrocatalyst for the future investigation and application.

Photocatalytic CO2 Reduction by Carbon-Coated Indium-Oxide Nanobelts.

Indium-oxide (In2O3) nanobelts coated by a 5-nm-thick carbon layer provide an enhanced photocatalytic reduction of CO2 to CO and CH4, yielding CO and CH4 evolution rates of 126.6 and 27.9 µmol h-1, respectively, with water as reductant and Pt as co-catalyst. The carbon coat promotes the absorption of visible light, improves the separation of photoinduced electron-hole pairs, increases the chemisorption of CO2, makes more protons from water splitting participate in CO2 reduction, and thereby facilitates the photocatalytic reduction of CO2 to CO and CH4.

Facile Synthesis of Carbon-Coated Spinel Li4Ti5O12/Rutile-TiO2 Composites as an Improved Anode Material in Full Lithium-Ion Batteries with LiFePO4@N-Doped Carbon Cathode.

The spinel Li4Ti5O12/rutile-TiO2@carbon (LTO-RTO@C) composites were fabricated via a hydrothermal method combined with calcination treatment employing glucose as carbon source. The carbon coating layer and the in situ formed rutile-TiO2 can effectively enhance the electric conductivity and provide quick Li+ diffusion pathways for Li4Ti5O12. When used as an anode material for lithium-ion batteries, the rate capability and cycling stability of LTO-RTO@C composites were improved in comparison with those of pure Li4Ti5O12 or Li4Ti5O12/rutile-TiO2. Moreover, the potential of approximately 1.8 V rechargeable full lithium-ion batteries has been achieved by utilizing an LTO-RTO@C anode and a LiFePO4@N-doped carbon cathode.

Suppression of Immunotherapy on Group 2 Innate Lymphoid Cells in Allergic Rhinitis.

BACKGROUND: Group 2 innate lymphoid cells (ILC2s) are regarded as a novel population of lineage-negative cells that induce innate Type 2 responses by producing the critical Th2-type cytokines interleukin (IL)-5 and IL-13. ILC2s as key players in the development of allergic rhinitis (AR) have been proved, however, the effect of subcutaneous immunotherapy (SCIT) with dermatophagoides pteronyssinus extract (Der p-SCIT) on ILC2s in AR patients is not clear. This study aimed to investigate the response of ILC2s of peripheral blood in house dust mites (HDM)-sensitized Chinese patients with AR who received SCIT with Der P extract. METHODS: Seven healthy controls without symptoms of AR who had negative reactions to any of the allergens from skin-prick testing, nine patients diagnosed with persistent AR according to the Allergic Rhinitis and its Impact on Asthma (ARIA) guidelines, and 24 AR patients who received Der p-SCIT for 1.0-3.5 years were recruited for the study. ILC2s in the peripheral blood were evaluated using flow cytometry. The severity of their symptoms of all participants was rated based on the Total 5 symptom score. RESULTS: Among 40 participants, 9 AR patients were assigned to the untreated group, 24 AR patients receiving Der p-SCIT were assigned to the immunotherapy group, and 7 healthy controls without symptoms of AR were assigned to healthy control group. The mean Total 5 symptom score of immunotherapy group was significantly lower than that of untreated group (4.3 ± 1.4 vs. 10.1 ± 2.5, P< 0.001). Similarly, the levels of ILC2s in the peripheral blood of immunotherapy group were significantly reduced compared with that in untreated group (P < 0.001), but were not significantly different from healthy controls (P = 0.775). Further subgroup analysis based on the duration of SCIT therapy (1.0-2.0 years [SCIT1-2], 2.0-3.0 years [SCIT2-3], and 3.0-3.5 years [SCIT3-3.5]) showed that the percentage of ILC2s was not significantly different between SCIT1-2, SCIT2-3, and SCIT3-3.5groups (SCIT1-2 vs. SCIT2-3: P = 0.268; SCIT1-2vs. SCIT3-3.5: P = 0.635; and SCIT2-3 vs. SCIT3-3.5: P = 0.787). CONCLUSIONS: The present study highlighted the suppression of Der p-SCIT on ILC2s in HDM-AR patients. ILC2s identified in peripheral blood can be used as an effective biomarker for Der p-SCIT.

Investigating ego modules involved in TGFß3-induced chondrogenesis in mesenchymal stem cells based on ego network.

OBJECTIVE: This paper aimed to investigate ego modules for TGFß3-induced chondrogenesis in mesenchymal stem cells (MSCs) using ego network algorithm. METHODS: The ego network algorithm comprised three parts, extracting differential expression network (DEN) based on gene expression data and protein-protein interaction (PPI) data; exploring ego genes by reweighting DEN; and searching ego modules by ego gene expansions. Subsequently, permutation test was carried out to evaluate the statistical significance of the ego modules. Finally, pathway enrichment analysis was conducted to investigate ego pathways enriched by the ego modules. RESULTS: A total of 15 ego genes were obtained from the DEN, such as PSMA4, HNRNPM and WDR77. Starting with each ego genes, 15 candidate modules were gained. When setting the thresholds of the area under the receiver operating characteristics curve (AUC) ≥0.9 and gene size ≥4, three ego modules (Module 3, Module 8 and Module 14) were identified, and all of them had statistical significances between normal and TGFß3-induced chondrogenesis in MSCs. By mapping module genes to confirmed pathway database, their ego pathways were detected, Cdc20:Phospho-APC/C mediated degradation of Cyclin A for Module 3, Mitotic G1-G1/S phases for Module 8, and mRNA Splicing for Module 14. CONCLUSIONS: We have successfully identified three ego modules, evaluated their statistical significances and investigated their functional enriched ego pathways. The findings might provide potential biomarkers and give great insights to reveal molecular mechanism underlying this process.

Conductive Carbon Network inside a Sulfur-Impregnated Carbon Sponge: A Bioinspired High-Performance Cathode for Li-S Battery.

A highly conductive sulfur cathode is crucial for improving the kinetic performance of a Li-S battery. The encapsulation of sulfur in porous nanocarbons is expected to benefit the Li(+) migration, yet the e(-) conduction is still to be improved due to a low graphitization degree of a conventional carbon substrate, especially that pyrolyzed from carbohydrates or polymers. Aiming at facilitating the e(-) conduction in the cathode, here we propose to use ketjen black, a highly graphitized nanocarbon building block to form a conductive network for electrons in a biomass-derived, hierarchically porous carbon sponge by a easily scaled-up approach at a low cost. The specifically designed carbon host ensures a high loading and good retention of active sulfur, while also provides a faster electron transmission to benefit the lithiation/delithiation kinetics of sulfur. The sulfur cathode prepared from the carbon network shows excellent cycling and rate performance in a Li-S battery, rendering its practicality for emerging energy storage opportunities such as grids or automobiles.