Electronic perturbation of Cu nanowire surfaces with functionalized graphdiyne for enhanced CO reduction reaction.

Electronic perturbation of the surfaces of Cu catalysts is crucial for optimizing electrochemical CO reduction activity, yet still poses great challenges. Herein, nanostructured Cu nanowires (NW) with fine-tuned surface electronic structure are achieved via surface encapsulation with electron-withdrawing (-F) and -donating (-Me) group-functionalized graphdiynes (R-GDY, R = -F and -Me) and the resulting catalysts, denoted as R-GDY/Cu NW, display distinct CO reduction performances. electrochemical spectroscopy revealed that the *CO (a key intermediate of the CO reduction reaction) binding affinity and consequent *CO coverage positively correlate with the Cu surface oxidation state, leading to favorable C-C coupling on F-GDY/Cu NW over Me-GDY/Cu NW.

Multistage Linkage Internal Exclusion External Electrolyte Tactic Unlocks Extreme Fast Charge Lithium Metal Batteries.

Lithium metal batteries are booming because of their inherent preponderance, but a negative electric field from concentration dipolarization and slow solid-phase transfer at the electrode interface become blocking modules for extreme fast charging. Achieving an anion-rich solvation shell with a high dielectric constant (ε) is a feasible strategy to bootstrap an interface microenvironment for mass-transport reaction, but it is still an uncultivated field. Herein, the superposition, including the donor number values, the high ε, and the spatial potential resistance, are complementarily considered; we propose a low-cost electrolyte with an internal excluding external tactic to answer the above issue.

Multifunctional Lithium Phytate/Carbon Nanotube Double-Layer-Modified Separators for High-Performance Lithium-Sulfur Batteries.

Li dendrite and the shuttle effect are the two primary hindrances to the commercial application of lithium-sulfur batteries (LSBs). Here, a multifunctional separator has been fabricated via successively coating carbon nanotubes (CNTs) and lithium phytate (LP) onto a commercial polypropylene (PP) separator to improve the performance of LSBs. The LP coating layer with abundant electronegative phosphate group as permselective ion sieve not only reduces the polysulfide shuttle but also facilitates uniform Li flux through the PP separator.

Mitigating Strain Accumulation in LiRuO via Fluorine Doping.

Lithium ruthenium oxide (LiRuO) is an archetypal lithium rich cathode material (LRCM) with both cation and anion redox reactions (ARRs). Commonly, the instability of oxygen redox activities has been regarded as the root cause of its performance degradation in long-term operation. However, we find that not triggering ARRs does not improve and even worsens its cyclability due to the detrimental strain accumulation induced by Ru redox activities.

Tartaric Acid Cross-Linking Polyvinyl Alcohol as Degradable Separators for Rechargeable Lithium Ion Batteries.

The escalating focus on environmental concerns and the swift advancement of eco-friendly biodegradable batteries raises a pressing demand for enhanced material design in the battery field. The traditional polypropylene (PP) that is monopolistically utilized in the commercial LIBs is hard to recycle. In this work, we prepare a novel water degradable separators via the cross-linking of polyvinyl alcohol (PVA) and dibasic acid (tartaric acid, TA).

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite LiOHCl Solid Electrolyte.

Li-rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all-solid-state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling-up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF ) ion doped LiRAP LiOHCl.

Negative enthalpy alloys and local chemical ordering: a concept and route leading to synergy of strength and ductility.

Solid solutions are ubiquitous in metals and alloys. Local chemical ordering (LCO) is a fundamental sub-nano/nanoscale process that occurs in many solid solutions and can be used as a microstructure to optimize strength and ductility. However, the formation of LCO has not been fully elucidated, let alone how to provide efficient routes for designing LCO to achieve synergistic effects on both superb strength and ductility.

Ion Sieve Interface Assisted Zinc Anode with High Zinc Utilization and Ultralong Cycle Life for 61 Wh/kg Mild Aqueous Pouch Battery.

The cycling stability of a thin zinc anode under high zinc utilization has a critical impact on the overall energy density and practical lifetime of zinc ion batteries. In this study, an ion sieve protection layer (ZnSnF@Zn) was constructed on the surface of a zinc anode by chemical replacement. The ion sieve facilitated the transport and desolvation of zinc ions at the anode/electrolyte interface, reduced the zinc deposition overpotential, and inhibited side reactions.

Negative mixing enthalpy solid solutions deliver high strength and ductility.

Body-centred cubic refractory multi-principal element alloys (MPEAs), with several refractory metal elements as constituents and featuring a yield strength greater than one gigapascal, are promising materials to meet the demands of aggressive structural applications. Their low-to-no tensile ductility at room temperature, however, limits their processability and scaled-up application. Here we present a HfNbTiVAl alloy that shows remarkable tensile ductility (roughly 20%) and ultrahigh yield strength (roughly 1,390 megapascals).

Microstructure-dependent CO-responsive microemulsions for deep-cleaning of oil-contaminated soils.

CO-responsive microemulsion (ME) is considered a promising candidate for deep-cleaning and oil recovery from oil-contaminated soils. Understanding the responsive nature of different microstructures (i.e.

Phytic acid cross-linked and Hofmeister effect strengthened polyvinyl alcohol hydrogels for zinc ion storage.

It is a big challenge to retain the water and thus reduce the charge impedance for solid electrolytes used in flexible and wearable zinc ion batteries. Here, we propose novel phytic acid (PA) cross-linked polyvinyl alcohol (PVA) hydrogels as high-performanced solid electrolytes strengthened by the Hofmeister effect. In this approach, freeze-thawing followed by a salting-out procedure anions to induce the Hofmeister effect can greatly improve the tensile strain and flexibility of the hydrogels.

Deciphering Electrolyte Dominated Na Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries.

Although hard carbon (HC) demonstrates superior initial Coulombic efficiency, cycling durability, and rate capability in ether-based electrolytes compared to ester-based electrolytes for sodium-ion batteries (SIBs), the underlying mechanisms responsible for these disparities remain largely unexplored. Herein, ex situ electron paramagnetic resonance (EPR) spectra and in situ Raman spectroscopy are combined to investigate the Na storage mechanism of HC under different electrolytes. Through deconvolving the EPR signals of Na in HC, quasi-metallic-Na is successfully differentiated from adsorbed-Na.

Decoding the Mechanisms of Reversibility Loss in Rechargeable Zinc-Air Batteries.

Attaining high reversibility of the electrodes and electrolyte is essential for the longevity of secondary batteries. Rechargeable zinc-air batteries (RZABs), however, encounter drastic irreversible changes in the zinc anodes and air cathodes during cycling. To uncover the mechanisms of reversibility loss in RZABs, we investigate the evolution of the zinc anode, alkaline electrolyte, and air electrode through experiments and first-principles calculations.

Modulation of Radical Intermediates in Rechargeable Organic Batteries.

Organic materials have been considered as promising electrodes for next-generation rechargeable batteries in view of their sustainability, structural flexibility, and potential recyclability. The radical intermediates generated during the redox process of organic electrodes have profound effect on the reversible capacity, operation voltage, rate performance, and cycling stability. However, the radicals are highly reactive and have very short lifetime during the redox of organic materials.

Ultrafast Strategy to Fabricate Sulfur Cathodes for High-Performance Lithium-Sulfur Batteries.

Based on the different dielectric properties of materials and the selective heating property of microwaves, the ultrafast (30 s) preparation of S-NiS@SP@Bitu as a cathode material for lithium-sulfur batteries was achieved using bitumen, sulfur, Super P, and nickel naphthenate as raw materials for the first time, under microwave treatment. NiS@SP@Bitu forms Li-N, Li-O, Li-S, and Ni-S bonds with polysulfide, which contributes to promoting the adsorption of polysulfide, reducing the precipitation and decomposition energy barrier of LiS, and accelerating the catalytic conversion of polysulfide, as result of inhibiting the "shuttle effect" and improving the electrochemical performance. S-NiS@SP@Bitu as the sulfur cathode material demonstrates outstanding rate performance (518.

Precisely manipulated π-π stacking of catalytic exfoliated iron polyphthalocyanine/reduced graphene oxide hybrid via pyrolysis-free path.

Metal macrocycles with well-defined molecular structures are ideal platforms for the in-depth study of electrochemical oxygen reduction reaction (ORR). Structural integrity of metal macrocycles is vital but remain challenging since the commonly used high-temperature pyrolysis would cause severe structure damage and unidentifiable active sites. Herein, we propose a pyrolysis-free strategy to precisely manipulate the exfoliated 2D iron polyphthalocyanine (FePPc) anchored on reduced graphene oxide (rGO) via π-π stacking using facile high-energy ball milling.

Green synthesis of mesoporous and biodegradable iron silicide nanoparticles for photothermal cancer therapy.

Photothermal nanomaterials have shown great potential for photothermal therapy. In this study, we developed a simple green method of magnesiothermic co-reduction for the synthesis of mesoporous, magnetic and biodegradable iron silicide nanoparticles (FeSi NPs) as applied to photothermal therapy (PTT). Starting from biogenic tabasheer extracted from bamboo and FeO, the resultant FeSi NPs with a much lower band gap exhibited excellent optical absorption with a photothermal conversion efficiency of 76.

Two-Step Redox in Polyimide: Witness by In Situ Electron Paramagnetic Resonance in Lithium-ion Batteries.

Organic materials are promising candidates for future rechargeable batteries, owing to their high natural abundance and rapidly redox reaction. Elaborating the charge/discharge process of organic electrode is critical to unveil the fundamental redox mechanism of lithium-ion batteries (LIBs), but monitoring of this process is still challenging. Here, we report a nondestructive electron paramagnetic resonance (EPR) technique to real-time detect the electron migration step within polyimide cathode.

Realizing High-Performance Cathodes with Cationic and Anionic Redox Reactions in High-Sodium-Content P2-Type Oxides for Sodium-Ion Batteries.

P2-type layered transition-metal oxides with anionic redox reactions are promising cathodes for sodium-ion batteries. In this work, a high-sodium-content P2-type NaLiMgCuMnO (NLMC) cathode material is prepared by substituting Li/Mg/Cu for Mn sites in NaMnO. The Li/Mg ions trigger the anionic redox reaction, while the Cu ions enhance the structure stability during electrochemical cycling.

Manganese Local Environment Modulation via SiO Substitution to Boost Sodium Storage Performance of Na MnCr(PO ).

Manganese-based Na superionic conductors (NASICONs) Na MnCr(PO ) with three-electron reaction are attractive cathode materials for sodium-ion batteries. However, the irreversible distortion of Mn local structure leads to sluggish electrode kinetics, voltage hysteresis, and poor cycling stability. Here, SiO is introduced to substitute PO to modulate the local environment of Mn to activate the redox activity and stabilize the reversibility of Na MnCr(PO ) (SiO ) (NMCP-Si).

Electronic Perturbation of Copper Single-Atom CO Reduction Catalysts in a Molecular Way.

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO reduction catalysts in a molecular way. The elaborately introduced functional groups (-F, -H and -OMe) can regulate the valance state of Cu , which is found to be directly scaled with the selectivity of the electrochemical CO -to-CH conversion.

Single-Atom Yttrium Engineering Janus Electrode for Rechargeable Na-S Batteries.

The development of rechargeable Na-S batteries is very promising, thanks to their considerably high energy density, abundance of elements, and low costs and yet faces the issues of sluggish redox kinetics of S species and the polysulfide shuttle effect as well as Na dendrite growth. Following the theory-guided prediction, the rare-earth metal yttrium (Y)-N unit has been screened as a favorable Janus site for the chemical affinity of polysulfides and their electrocatalytic conversion, as well as reversible uniform Na deposition. To this end, we adopt a metal-organic framework (MOF) to prepare a single-atom hybrid with Y single atoms being incorporated into the nitrogen-doped rhombododecahedron carbon host (Y SAs/NC), which features favorable Janus properties of sodiophilicity and sulfiphilicity and thus presents highly desired electrochemical performance when used as a host of the sodium anode and the sulfur cathode of a Na-S full cell.

N, S-Coordinated Co Single Atomic Catalyst Boosting Adsorption and Conversion of Lithium Polysulfides for Lithium-Sulfur Batteries.

Boosting reversible solid-liquid phase transformation from lithium polysulfides to Li S and suppressing the shuttling of lithium polysulfides from the cathode to the lithium anode are critical challenges in lithium-sulfur batteries. Here, sulfiphilic single atomic cobalt implanted in lithiophilic heteroatoms-dopped carbon (SACo@HC) matrix with a CoN S structure for high-performance lithium-sulfur batteries is reported. Density functional theory calculation and in situ experiments demonstrate that the optimal CoN S structure in SACo@HC can effectively improve the adsorption and redox conversion efficiency of lithium polysulfides.

Unraveling the Role of Aromatic Ring Size in Tuning the Electrochemical Performance of Small-Molecule Imide Cathodes for Lithium-Ion Batteries.

Organic electrode materials have the typical advantages of flexibility, low cost, abundant resources, and recyclability. However, it is challenging to simultaneously optimize the specific capacity, rate capability, and cycling stability. Radicals are inevitable intermediates that critically determine the redox activity and stability during the electrochemical reaction of organic electrodes.