Ammonium Sulfate to Modulate Crystallization for High-Performance Rigid and Flexible Perovskite Solar Cells.

Perovskite solar cells (PSCs) are attracting widespread research and attention as highly promising candidates in the field of electronic photovoltaics owing to their exceptional power conversion efficiency (PCE). However, rigid or flexible PSCs still face challenges in preparing full-coverage and low-defect perovskite films, as well as achieving highly reproducible and highly stable devices. Herein, a multifunctional additive 2-aminoethyl hydrogen sulfate (AES) is designed to regulate the film crystallization and thereby form flat and pinhole-free perovskite films. It is found that the introduction of AES can effectively passivate defects, restrain charge carrier recombination, and then achieve a higher fill factor. As seen with grazing incidence wide-angle X-ray scattering (GIWAXS), this approach does not affect the crystal orientation distribution. It is observed that AES addition shows a universality across different perovskite components since the PCE is improved up to 20.7% for FA0.97MA0.03Pb(I0.97Br0.03)3-AES, 22.85% for Cs0.05FA0.95PbI3-AES, 22.23% for FAPbI2.7Br0.3-AES, and 23.32% for FAPI-AES rigid devices. Remarkably, the non-encapsulated flexible Cs0.05 (FA0.85MA0.15)0.95Pb(I0.85Br0.15)3 device with AES additive delivers a PCE of 20.1% and maintains over 97% of its initial efficiency under ambient conditions (25 ± 5% relative humidity) over 2280 h of aging.

Synergy of Weakly Solvated Electrolyte and LiF-Reinforced Interphase Enables Long-Term Operation of Li-Metal Batteries at Low Temperatures.

Hindered by the high diffusion energy barrier of Li+ in graphite anode layers, the low-temperature application of traditional Li-ion batteries is limited. Lithium metal without intercalation and with excellent specific capacity is expected to support battery operation at low temperatures. However, due to the low conductivity, high freezing point, and strong solvation energy of traditional carbonate electrolytes, the application of lithium-metal batteries at low temperatures remains challenged. In this paper, an all-ester-based ternary solvent electrolyte based on fluorinated carbonate and methyl acetate is developed to improve the cyclic efficiency of the Li-metal anode at subzero temperatures. Methyl acetate, with low viscosity and low freezing point, endows Li+ with efficient transfer in the bulk phase at low temperatures. Fluorinated cosolvent regulates the solvation structure, thereby facilitating Li+ desolvation while forming a LiF-rich solid electrolyte interphase. The electrolyte exhibits good compatibility with the Li-metal anode, as confirmed by the significantly reduced kinetic barrier of Li+ diffusion at the interface. The theoretical calculations suggest that anions occupy the dominant positions within the inner solvation sheath. The in situ/ex situ characterizations provide straightforward evidence of a dendrite-free Li-metal electrode during cycling. As a result, the symmetric Li||Li cell is able to cycle stably for thousands of hours at current densities of 0.5 mA cm-2 and 1 mAh cm-2. When paired with a LiFePO4 cathode, the battery at 0.2 C (1 C = 170 mA g-1) has a capacity retention of 95.4% after 200 cycles at -15 °C and 92.6% after 100 cycles at -20 °C, respectively.

Hybridizing carbonate and ether at molecular scales for high-energy and high-safety lithium metal batteries.

Commonly-used ether and carbonate electrolytes show distinct advantages in active lithium-metal anode and high-voltage cathode, respectively. While these complementary characteristics hold promise for energy-dense lithium metal batteries, such synergy cannot be realized solely through physical blending. Herein, a linear functionalized solvent, bis(2-methoxyethyl) carbonate (BMC), is conceived by intramolecularly hybridizing ethers and carbonates. The integration of the electron-donating ether group with the electron-withdrawing carbonate group can rationalizes the charge distribution, imparting BMC with notable oxidative/reductive stability and relatively weak solvation ability. Furthermore, BMC also offers advantages including the ability to slightly dissolve LiNO3, excellent thermostability and nonflammability. Consequently, the optimized BMC-based electrolyte, even with typical concentrations in the single solvent, demonstrates high-voltage tolerance (4.4 V) and impressive Li plating/stripping Coulombic efficiency (99.4%). Moreover, it fulfills practical lithium metal batteries with satisfactory cycling performance and exceptional tolerance towards thermal/mechanical abuse, showcasing its suitability for safe high-energy lithium metal batteries.

USP46 promotes the interferon antiviral signaling in black carp by deubiquitinating TBK1.

Ubiquitin-specific peptidase 46 (USP46) functions as a deubiquitinating enzyme, facilitating the removal of ubiquitin molecules attached to substrate proteins and playing a critical role in cancer and neurodegenerative diseases. However, its function in innate antiviral immunity is unknown. In this study we cloned and identified bcUSP46, a homolog of USP46 from black carp. We discovered that overexpression of bcUSP46 enhanced the transcription of interferon (IFN) promoters and increased the expression of IFN, PKR, and Mx1. In addition, bcUSP46 knockdown significantly inhibited the expression of ISG genes, as well as the antiviral activity of the host cells. Interestingly, when bcUSP46 was co-expressed with the RLR factors, it significantly enhanced the activity of the IFN promoter mediated by these factors, especially TANK-binding kinase 1 (TBK1). The subsequent co-immunoprecipitation (co-IP) and immunofluorescence (IF) assay confirmed the association between bcUSP46 and bcTBK1. Noteworthily, co-expression of bcUSP46 with bcTBK1 led to an elevation of bcTBK1 protein level. Further analysis revealed that bcUSP46 stabilized bcTBK1 by eliminating the K48-linked ubiquitination of bcTBK1. Overall, our findings highlight the unique role of USP46 in modulating TBK1/IFN signaling and enrich our knowledge of the function of deubiquitination in regulating innate immunity in vertebrates.

Multifunctional Umbrella: In Situ Interface Film Forming on the High-Voltage LiCoO2 Cathode by a Tiny Amount of Nanoporous Polymer Additives for High-Energy-Density Li-Ion Batteries.

The LiCoO2 (LCO) cathode is foreseen for extensive commercial applications owing to its high specific capacity and stability. Therefore, there is considerable interest in further enhancing its specific capacity by increasing the charging voltage. However, single-crystal LCO suffers from a significant capacity degradation when charged to 4.5 V due to the irreversible phase transition and unstable structure. Herein, an ultra-small amount (0.5% wt. in the electrode) of multi-functional PIM-1 (a polymer with intrinsic microporosity) additive is utilized to prepare a kind of binder-free electrode. PIM-1 modulates the solvation structure of LiPF6 due to its unique structure, which helps to form a stable, robust, and inorganic-rich cathod-eelectrolyte interphase (CEI) film on the surface of LCO at a high voltage of 4.5 V. This reduces the irreversible phase transition of LCO, thereby enhancing the cyclic stability and improving the rate performance, providing new perspectives for the electrodes fabrication and improving LCO-based high-energy-density cathodes.

Boosting Cathode Activity and Anode Stability of Lithium-Sulfur Batteries with Vigorous Iodic Species Triggered by Nitrate.

Lithium-sulfur (Li-S) battery with a sulfurized polyacrylonitrile cathode is a promising alternative to Li-ion systems. However, the sluggish charge transfer of cathode and accumulation of inactive Li on anode remain persistent challenges. An advanced electrolyte additive with function towards both cathode and anode holds great promise to address these issues. Herein, we present a new strategy to boost sulfur activity and rejuvenate dead Li simultaneously. In the polar electrolyte containing I2-LiNO3 additives, I3 -/IO3 - are triggered significantly by the reaction between NO3 - and I- ions. The I3 -/IO3 - are reactive to insulated Li2S product of cathode and inactive Li on anode, thus accelerating the conversion reaction of sulfur and recovering Li sources back to battery cycling. The in situ/ex situ spectroscopic and morphologic monitoring reveal the crucial role of iodine in promoting Li2S dissociation and inhibiting dendritic Li growth. With the modified electrolyte, the symmetric Li||Li cells deliver a lifespan of 4000 h with an overpotential less than 12 mV at 0.5 mA cm-2. For Li-S cells, 100 % capacity retention up to thousands of cycles and enhanced rate capability are available. This work demonstrates a feasible strategy on electrolyte engineering for practical applications of Li-S batteries.

Dendritic Copper Current Collectors as a Capacity Boosting Material for Polymer-Templated Si/Ge/C Anodes in Li-Ion Batteries.

Dendritic copper offers a highly effective method for synthesizing porous copper anodes due to its intricate branching structure. This morphology results in an elevated surface area-to-volume ratio, facilitating shortened electron pathways during aqueous and electrolyte permeation. Here, we demonstrate a procedure for a time- and cost-efficient synthesis routine of fern-like copper microstructures as a host for polymer-templated Si/Ge/C thin films. Dissolvable Zintl clusters and sol-gel chemistry are used to synthesize nanoporous coating as the anode. Cyclic voltammetry (CV) with KOH as the electrolyte is used to estimate the surface area increase in the dendritic copper current collectors (CCs). Half cells are assembled and tested with battery-related techniques such as CV, galvanostatic cycling, and electrochemical impedance spectroscopy, showing a capacity increase in the dendritic copper cells. Energy-dispersive X-ray spectroscopy is used to estimate the removal of K in the bulk after oxidizing the Zintl phase K12Si8Ge9 in the polymer/precursor blend with SiCl4. Furthermore, scanning electron microscopy images are provided to depict the thin films after synthesis and track the degradation of the half cells after cycling, revealing that the morphological degradation through alloying/dealloying is reduced for the dendritic Cu CC anodes as compared with the bare reference. Finally, we highlight this time- and cost-efficient routine for synthesizing this capacity-boosting material for low-mobility and high-capacity anode coatings.

Negative-carbon recycling of copper from waste as secondary resources using deep eutectic solvents.

Copper plays a crucial role in the low-carbon transformation of global communities with prevalent use of electric vehicles. This study proposed an environmentally friendly approach that utilizes a deep eutectic solvent (DES), choline chloride-ethylene glycol (ChCl-EG), as green solvent for the selective extraction of copper from scrap materials. With hydrogen peroxide as an oxidizing agent, the copper species from the printed circuit boards (PCBs) scraps were efficiently leached by the DES through oxidation-complexation reactions (conditions: 25 min, 20 °C, and 5 wt% H2O2). Molecular dynamics and density functional theory were performed to simulate the intricate cascade of interactions between copper species and hydrogen bond donors/acceptors of DES, providing insights into the mechanistic processes involved. Copper was selectively recovered from the DES leachate containing impurities (e.g., Pb2+, Sn2+, and Al3+) through electrodeposition via a diffusion-controlled reaction under a constant potential mode. A comprehensive life cycle assessment of the process demonstrated that the utilisation of DES in the extraction of copper from waste PCBs could result in significant reduction in carbon dioxide emissions (-93.6 kg CO2 eq of 1000 kg waste PCBs), thus mitigating the carbon footprint of global copper use through the proposed solvometallurgical recycling process of secondary resources.

TRIM25 negatively regulates IKKε-mediated interferon signaling in black carp.

IKKε plays an important role in the activation of IRF3/IRF7 and the production of interferon (IFN), however, its regulation remains obscure in human. E3 ligase TRIM25 has been reported to manipulate the K63-linked ubiquitination of RIG-I, leading to the activation of RIG-I/IFN signaling. To elucidate the role of TRIM25 in teleost, a TRIM25 homolog (bcTRIM25) was cloned and characterized from black carp (Mylopharyngodon piceus). bcTRIM25 contains 653 amino acids, possessing conservative RING, B-box and SPRY domain, which is highly expressed in muscle, spleen and skin. bcTRIM25 knock-down enhanced the antiviral ability of host cells. bcTRIM25 over-expression alone in EPC cells attenuated bcIFNa promoter transcription in the reporter assays and impeded PKR and MX1 expression in qRT-PCR. Interestingly, co-IP assays indicated that bcTRIM25 interacted with bcIKKε and the induced bcIFNa promoter transcription by bcIKKε was notably hindered by bcTRIM25. Furthermore, bcIKKε-induced expression of interferon stimulated genes (ISGs) and antiviral activity were dampened by bcTRIM25. Further exploration showed that bcTRIM25 visibly enhanced the ubiquitination of bcIKKε but significantly attenuated the phosphorylation of bcIKKε. Thus, our data demonstrate for the first time in vertebrate that TRIM25 negatively regulates IKKε through enhancing its ubiquitination, which sheds a light on the regulation of IKKε/IFN signaling.

hnRNPM suppressed IRF7-mediated IFN signaling in the antiviral innate immunity in triploid hybrid fish.

Mammalian heterogeneous nuclear ribonucleoproteins M (hnRNPM) is a critical splicing regulatory protein that has been reported to negatively regulate the RLR signaling pathway by impairing the binding of RIG-I and MDA5 to viral RNA. To explore the role of hnRNPM in the antiviral innate immune response in teleost fish, the hnRNPM homologue of triploid fish (3nhnRNPM) has been cloned and identified in this paper. The CDS of 3nhnRNPM gene is composed of 2016 nucleotides and encodes 671 amino acids. 3nhnRNPM migrated around 71 kDa in immunoblotting assay and was mainly detected in the nucleus in nucleo-cytoplasmic separation assay and immunofluorescent staining test. When 3nhnRNPM and 3nIRF7 were co-expressed in EPC cells, 3nhnRNPM significantly reduced the 3nIRF7-induced interferon (IFN) promoter transcription. Correspondingly, the mRNA levels of the SVCV-M, -N, -P, and -G genes were noteworthily enhanced, but the transcription levels of epcIFNφ1, epcMx1, epcPKR, and epcISG15 were dramatically decreased. Additionally, the knockdown of 3nhnRNPM resulted in restricted SVCV replication and enhanced host cell antiviral activity. Furthermore, the association between 3nhnRNPM and 3nIRF7 has been identified by the co-immunoprecipitation assay. In addition, we found that 3nIRF7 was detained in the nucleus when co-expressed with 3nhnRNPM. To sum up, our data supported the conclusion that 3nhnRNPM suppressed 3nIRF7-mediated IFN signaling in the antiviral innate immunity.

A Test Method for Finding Early Dynamic Fracture of Rock: Using DIC and YOLOv5.

Intelligent monitoring and early warning of rock mass failure is vital. To realize the early intelligent identification of dynamic fractures in the failure process of complex fractured rocks, 3D printing of the fracture network model was used to produce rock-like specimens containing 20 random joints. An algorithm for the early intelligent identification of dynamic fractures was proposed based on the YOLOv5 deep learning network model and DIC cloud. The results demonstrate an important relationship between the overall strength of the specimen with complex fractures and dynamic fracture propagation, and the overall specimen strength can be judged semi-quantitatively by counting dynamic fracture propagation. Before the initiation of each primary fracture, a strain concentration area appears, which indicates new fracture initiation. The dynamic evolution of primary fractures can be divided into four types: primary fractures, stress concentration areas, new fractures, and cross fractures. The cross fractures have the greatest impact on the overall strength of the specimen. The overall identification accuracy of the four types of fractures identified by the algorithm reached 88%, which shows that the method is fast, accurate, and effective for fracture identification and location, and classification of complex fractured rock masses.

Stable Electrode/Electrolyte Interface for High-Voltage NCM 523 Cathode Constructed by Synergistic Positive and Passive Approaches.

Increasing the working voltage of lithium-ion batteries (LIBs) is an efficient way to increase energy density. However, high voltage triggers excessive electrolyte decomposition at the electrode-electrolyte interfaces, where the electrochemical performance such as cyclic stability and rate capability is seriously deteriorated. A new synergistic positive and passive approach is proposed in this work to construct a stable electrode-electrolyte interface at high voltage. As a positive approach, inorganic lithium sulfide salt (Li2S) is used as an electrolyte additive to build a stable cathode electrolyte interface (CEI) at the LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode surface. In a passive way, acetonitrile (AN) is applied as a solvent additive to suppress oxidative decomposition of a carbonate electrolyte via preferential solvation with a lithium ion. Because of the synergistic interaction between the positive and passive approaches, the cyclic stabilities of NCM523/Li cells improved with a tiny amount of Li2S (0.01 mg mL-1) and AN (0.5 vol %). The capacity retention increased to 80.74% after 200 cycles compared to the cells with the blank electrolyte (67.98%) and AN-containing electrolyte (75.8%). What is more, the capacity retention of the NCM523/graphite full cell is increased from 65 to 81% with the addition of the same amount of Li2S and AN after 180 cycles. The mechanism is revealed on the basis of the theoretical calculations and various characterizations. The products derived from the preferential adsorption and oxidation of Li2S on the surface of NCM523 effectively increase the content of inorganic ingredients. However, the presence of AN prevents oxidation of the solvent. This study provides new principle guiding studies on a high-voltage lithium-ion battery with excellent electrochemical performance.

Sulfur is a New High-Performance Additive toward High-Voltage LiNi0.5Co0.2Mn0.3O2 Cathode: Tiny Amount, Huge Impact.

Increasing working voltage of cathode has been identified as one of the most promising strategies to increase energy density of the lithium-ion batteries. It is of crucial importance to suppress side reactions and control the formation of a cathode electrolyte interface (CEI) on the cathode surface in a high voltage range. In this work, sulfur is utilized to increase the working voltage of LiNi0.5Co0.2Mn0.3O2(NCM 523) to 4.5 V as demonstrated by both the NCM523/Li half-cell and NCM 523/graphite full cell. When a tiny amount of sulfur (0.1 mg mL-1) is added to the blank electrolyte of ethylene carbonate (EC) and dimethyl carbonate (DMC) (3:7 by volume), the cycling stability and rate performance are greatly improved in the NCM523/Li half-cell. The capacity retention over 200 cycles at 170 mA g-1 (1.0 C) is increased from 61.2 to 82.0%. The capacity at a high current density of 850 mA g-1 (5.0 C) is increased from 92 mAh g-1 to 120 mAh g-1. Because the addition of sulfur also enhances the performance of the Li/graphite half-cell, improved performance is demonstrated by the NCM 523/graphite full cell as well. The mechanism is interpreted based on various characterizations. It is revealed that the preferential oxidation of sulfur at the cathode surface suppress decomposition of electrolyte solvent. Because only a tiny amount of sulfur is added into the electrolyte solution, excessive decomposition of sulfur is avoided, leading to improved electrochemical performance.