Gradient three-dimensional current collector with lithiophilic nanolayer regulation for efficient lithium metal anode construction.

Metallic lithium (Li) is highly desirable for Li battery anodes due to its unique advantages. However, the growth of Li dendrites poses challenges for commercialization. To address this issue, researchers have proposed various three-dimensional (3D) current collectors. In this study, the selective modification of a 3D Cu foam scaffold with lithiophilic elements was explored to induce controlled Li deposition. The Cu foam was selectively modified with Ag and Sn to create uniform Cu foam (U-Cu) and gradient lithiophilic Cu foam (G-Cu) structures. Density Functional Theory (DFT) calculations revealed that Ag exhibited a stronger binding energy with Li compared to Sn, indicating superior Li induction capabilities. Electrochemical testing demonstrated that the half cell with the G-Cu@Ag electrode exhibited excellent cycling stability, maintaining 550 cycles with an average Coulombic efficiency (CE) of 97.35%. This performance surpassed that of both Cu foam and G-Cu@Sn. The gradient modification of the current collectors improved the utilization of the 3D scaffold and prevented Li accumulation at the top of the scaffold. Overall, the selective modification of the 3D Cu foam scaffold with lithiophilic elements, particularly Ag, offers promising prospects for mitigating Li dendrite growth and enhancing the performance of Li batteries.

Architecting the Microenvironment Skeleton of Active Materials in High-Capacity Electrodes by Self-Assembled Nano-Building Blocks.

In analogy to the cell microenvironment in biology, understanding and controlling the active-material microenvironment (ME@AM) microstructures in battery electrodes is essential to the successes of energy storage devices. However, this is extremely difficult for especially high-capacity active materials (AMs) like sulfur, due to the poor controlling on the electrode microstructures. To conquer this challenge, here, a semi-dry strategy based on self-assembled nano-building blocks is reported to construct nest-like robust ME@AM skeleton in a solvent-and-stress-less way. To do that, poly(vinylidene difluoride) nanoparticle binder is coated onto carbon-nanofibers (NB@CNF) via the nanostorm technology developed in the lab, to form self-assembled nano-building blocks in the dry slurry. After compressed into an electrode prototype, the self-assembled dry-slurry is then bonded by in-situ nanobinder solvation. With this strategy, mechanically strong thick sulfur electrodes are successfully fabricated without cracking and exhibit high capacity and good C-rate performance even at a high AM loading (25.0 mg cm-2 by 90 wt% in the whole electrode). This study may not only bring a promising solution to dry manufacturing of batteries, but also uncover the ME@AM structuring mechanism with nano-binder for guiding the design and control on electrode microstructures.

Mass Production of Customizable Core-Shell Active Materials in Seconds by Nano-Vapor Deposition for Advancing Lithium Sulfur Battery.

Rational design and scalable production of core-shell sulfur-rich active materials is vital for not only the practical success of future metal-sulfur batteries but also for a deep insight into the core-shell design for sulfur-based electrochemistry. However, this is a big challenge mainly due to the lack of efficient strategy for realizing precisely controlled core-shell structures. Herein, by harnessing the frictional heating and dispersion capability of the nanostorm technology developed in the authors' laboratory, it is surprisingly found that sulfur-rich active particles can be coated with on-demand shell nanomaterials in seconds. To understand the process, a micro-adhesion guided nano-vapor deposition (MAG-NVD) working mechanism is proposed. Enabled by this technology, customizable nano-shell is realized in a super-efficient and solvent-free way. Further, the different roles of shell characteristics in affecting the sulfur-cathode electrochemical performance are discovered and clarified. Last, large-scale production of calendaring-compatible cathode with the optimized core-shell active materials is demonstrated, and a Li-S pouch-cell with 453 Wh kg-1 @0.65 Ah is also reported. The proposed nano-vapor deposition may provide an attractive alternative to the well-known physical and chemical vapor deposition technologies.

High-Performance Flexible Sulfur Cathodes with Robust Electrode Skeletons Built by a Hierarchical Self-Assembling Slurry.

The electrochemical performance of lithium-sulfur batteries is fundamentally determined by the structural and mechanical stability of their composite sulfur cathodes. However, the development of cost-effective strategies for realizing robust hierarchical composite electrode structures remains highly challenging due to uncontrollable interactions among the components. The present work addresses this issue by proposing a type of self-assembling electrode slurry based on a well-designed two-component (polyacrylonitrile and polyvinylpyrrolidone) polar binder system with carbon nanotubes that forms hierarchical porous structures via optimized water-vapor-induced phase separation. The electrode skeleton is a highly robust and flexible electron-conductive network, and the porous structure provides hierarchical ion-transport channels with strong polysulfide trapping capability. Composite sulfur cathodes prepared with a sulfur loading of 4.53 mg cm-2 realize a very stable specific capacity of 485 mAh g-1 at a current density of 3.74 mA cm-2 after 1000 cycles. Meanwhile, a composite sulfur cathode with a high sulfur loading of 14.5 mg cm-2 in a lithium-sulfur pouch cell provides good flexibility and delivers a high capacity of 600 mAh g-1 at a current density of 0.72 mA cm-2 for 78 cycles.

Regulating Polysulfide Diffusion and Deposition via Rational Design of Core-Shell Active Materials in Li-S Batteries.

Polar host materials with strong adsorption capacity of polysulfides are designed to limit the shuttle effect in sulfur cathodes. However, a critical problem is to control diffusion and deposition of lithium polysulfides during cycling, which significantly impacts cycling stability and sulfur utilization. Here, we report using a sequential adsorption-guided self-assembly to design two types of core-shell sulfur particles with opposite polysulfide adsorption gradients to explore quantitatively the regulation of polysulfide diffusion and deposition. We show that a positive core-shell design of sulfur particles (PCSD@SP), i.e., polysulfide adsorption capability decreasing from the interior to the exterior of the host, is more effective in restricting polysulfide diffusion and regulating polysulfide deposition than the negative core-shell counterpart (NCSD@SP). As a result, the PCSD@SP electrode with a sulfur loading of 7 mg cm-2 exhibits a stable areal capacity of 6 mAh cm-2 over 130 cycles at 0.2C. At intermittent discharge/charge, the PCSD@SP electrode retains excellent stability compared with the NCSD@SP. We conclude that rational design of positive core-shell active materials can be used to regulate polysulfide diffusion and deposition to boost electrochemical reaction dynamics and performance. The reported findings will be of immediate benefit to a range of researchers in the design of high-performance lithium-sulfur batteries.

A Highly Active CoFe Layered Double Hydroxide for Water Splitting.

Highly active, cost-effective, and durable catalysts for oxygen evolution reaction (OER) are required in energy conversion and storage processes. A facile synthesis of CoFe layered double hydroxide (CoFe LDH) is reported as a highly active and stable oxygen evolution catalyst. By varying the concentration of the metal ion precursor, the Co/Fe ratios of LDH products can be tuned from 0.5 to 7.4. The structure and electrocatalytic activity of the obtained catalysts were found to show a strong dependence on the Co/Fe ratios. The Co2 Fe1 LDH sample exhibited the best electrocatalytic performance for OER with an onset potential of 1.52 V (vs. the reversible hydrogen electrode, RHE) and a Tafel slope of 83 mV dec-1 . The Co2 Fe1 LDH was further loaded onto a Ni foam (NF) substrate to form a 3D porous architecture electrode, offering a long-term current density of 100 mA cm-2 at 1.65 V (vs. RHE) towards the OER.

[BjCHI1 from Brassica juncea displays both chitinase and agglutination activity].

The proteins encoded by the Brassica juncea chitinase gene BjCHI1 and its derived genes BjCHI2 and BjCHI3 were expressed by Multi-copy Pichia expression system. The chitinase activity of FPLC purified BjCHI1, BjCHI2 and BjCHI3 were tested and the results showed that all the three proteins degraded both CM-chitin-RBV and colloidal chitin. The Km values of BjCHI1, BjCHI2 and BjCHI3 for CM-chitin-RBV were estimated as 0.799 mg/mL, 0.544 mg/mL and 0.793 mg/mL, respectively. When the colloidal chitin was used as substrate, the Km values were 0.281 mg/mL, 0.388 mg/mL and 1.643 mg/mL, respectively, indicating chitin-binding domain can increase affinity of chitinase to insoluble substrate. In the agglutination activity assay, only BjCHI1 shows activity when the protein concentration was more than 33 micrograms/mL, while BjCHI2 and BjCHI3 without agglutination activity even when the concentration was increased as high as 800 micrograms/mL. This means that the two chitin-binding domains in BjCHI1 are essential for agglutination and BjCHI1 is the first protein which shows both chitinase and agglutination activity identified so far in plants.