Sulfolane-containing aqueous electrolyte solutions for producing efficient ampere-hour-level zinc metal battery pouch cells.

Aqueous zinc metal batteries are appealing candidates for grid energy storage. However, the inadequate electrochemical reversibility of the zinc metal negative electrode inhibits the battery performance at the large-scale cell level. Here, we develop practical ampere-hour-scale aqueous Zn metal battery pouch cells by engineering the electrolyte solution. After identifying the proton reduction as the primary source of H2 evolution during Zn metal electrodeposition, we design an electrolyte solution containing reverse micelle structures where sulfolane molecules constrain water in nanodomains to hinder proton reduction. Furthermore, we develop and validate an electrochemical testing protocol to comprehensively evaluate the cell's coulombic efficiency and zinc metal electrode cycle life. Finally, using the reverse micelle electrolyte, we assemble and test a practical ampere-hour Zn||Zn0.25V2O5•nH2O multi-layer pouch cell capable of delivering an initial energy density of 70 Wh L-1 (based on the volume of the cell components), capacity retention of about 80% after 390 cycles at 56 mA g-1cathode and ~25 °C and prolonged cycling for 5 months at 56 mA g-1cathode and ~25 °C.

Coupling Cobalt Phthalocyanine Molecules on 3D Nitrogen-Doped Vertical Graphene Arrays for Highly Efficient and Robust CO2 Electroreduction.

Metallic phthalocyanines (MePcs) have shown their potential as catalysts for CO2 reduction reactions (CO2 RR). However, their low conductivity, easy agglomeration, and poor stability enslave the further progress of their CO2 RR applications. Herein, an integrated heterogeneous molecular catalyst through anchoring CoPc molecules on 3D nitrogen-doped vertical graphene arrays (NVG) on carbon cloth (CC) is reported. The CoPc-NVG/CC electrodes exhibit superior performance for reducing CO2 to CO with a Faradic efficiency of above 97.5% over a wide potential range (99% at an optimal potential), a very high turnover frequency of 35800 h-1 , and decent stability. It is revealed that NVG interacts with CoPc to form highly efficient channels for electron transfer from NVG to CoPc, facilitating the Co(II)/Co(I) redox of CO2 reduction. The strong coupling effect between NVG and CoPc molecules not only endows CoPc with high intrinsic activity for CO2 RR, but also enhances the stability of electrocatalysts under high potentials. This work paves an efficient approach for developing high-performance heterogeneous catalysts by using rationally designed 3D integrated graphene arrays to host molecular metallic phthalocyanines so as to ameliorate their electronic structures and engineer stable active sites.

Discrete single-cell microRNA analysis for phenotyping the heterogeneity of acute myeloid leukemia.

Acute myeloid leukemia (AML) is a highly heterogenous cancer in hematopoiesis, and its subtype specification is greatly important in the clinical practice for AML diagnosis and prognosis. Increasing evidence has shown the association between microRNA (miRNA) phenotype and AML therapeutic outcomes, emphasizing the need for novel techniques for convenient, sensitive, and efficient miRNA profiling in clinical practices. Here, we describe a nanoneedle-based discrete single-cell microRNA profiling technique for multiplexed phenotyping of AML heterogeneity without the requirement of sequencing or polymerase chain reaction (PCR). In virtue of a biochip-based and non-destructive nature of the assay, the expression of nine miRNAs in large number of living AML cells can be simultaneously analyzed with discrete single-cell level information, thus providing a proof-of-concept demonstration of an AML subtype classifier based on the multidimensional miRNA data. We showed successful analysis of subtype-specific cellular composition with over 90% accuracy and identified drug-responsive leukemia subpopulations among a mixed suspension of cells modeling different AML subtypes. The adoption of machine learning algorithms for processing the large-scale nanoneedle-based miRNA data shows the potential for powerful prediction capability in clinical applications to assist therapeutic decisions. We believe that this platform provides an efficient and cost-effective solution to move forward the translational prognostic usage of miRNAs in AML treatment and can be readily and advantageously applied in analyzing rare patient-derived clinical samples.

"Dual Mediator System" Enables Efficient and Persistent Regulation toward Sulfur Redox Conversion in Lithium-Sulfur Batteries.

Li-S batteries present great potential to realize high-energy-density storage, but their practical implementation is severely hampered by the notorious polysulfide shuttling and the sluggish redox kinetics. While rationally designed redox mediators can optimize polysulfide conversion, the efficiency and stability of such a mediation process still remain formidable challenges. Herein, a strategy of constructing a "dual mediator system" is proposed for achieving efficient and durable modulation of polysulfide conversion kinetics by coupling well-selected solid and electrolyte-soluble mediators. Theoretical prediction and detailed electrochemical analysis reveal the structure-activity relationships of the two mediators in synergistically optimizing the redox conversions of sulfur species, thus achieving a deeper mechanistic understanding of a function-supporting mediator system design toward sulfur electrochemistry promotion. Specifically, such a dual mediator system realizes the bridging of full-range "electrochemical catalysis" and strengthened "chemical reduction" processes of sulfur species as well as greatly suppressed mediator deactivation/loss due to the beneficial interactions between each mediator component. Attributed to these advantageous features, the Li-S batteries enable a slow capacity decay of 0.026% per cycle over 1200 cycles and a desirable capacity of 8.8 mAh cm-2 with 8.2 mg cm-2 sulfur loading and lean electrolyte condition. This work not only proposes an effective mediator system design strategy for promoting Li-S battery performance but also inspires its potential utilization facing other analogous sophisticated electrochemical conversion processes.

Nitrogen-Doped Graphene-Encapsulated Nickel-Copper Alloy Nanoflower for Highly Efficient Electrochemical Hydrogen Evolution Reaction.

Development of high-performance and low-cost nonprecious metal electrocatalysts is critical for eco-friendly hydrogen production through electrolysis. Herein, a novel nanoflower-like electrocatalyst comprising few-layer nitrogen-doped graphene-encapsulated nickel-copper alloy directly on a porous nitrogen-doped graphic carbon framework (denoted as Nix Cuy @ NG-NC) is successfully synthesized using a facile and scalable method through calcinating the carbon, copper, and nickel hydroxy carbonate composite under inert atmosphere. The introduction of Cu can effectively modulate the morphologies and hydrogen evolution reaction (HER) performance. Moreover, the calcination temperature is an important factor to tune the thickness of graphene layers of the Nix Cuy @ NG-NC composites and the associated electrocatalytic performance. Due to the collective effects including unique porous flowered architecture and the synergetic effect between the bimetallic alloy core and graphene shell, the Ni3 Cu1 @ NG-NC electrocatalyst obtained under optimized conditions exhibits highly efficient and ultrastable activity toward HER in harsh environments, i.e., a low overpotential of 122 mV to achieve a current density of 10 mA cm-2 with a low Tafel slope of 84.2 mV dec-1 in alkaline media, and a low overpotential of 95 mV to achieve a current density of 10 mA cm-2 with a low Tafel slope of 77.1 mV dec-1 in acidic electrolyte.