The lithium–sulfur (Li–S) battery is a promising high‐energy‐density storage system. The strong anchoring of intermediates is widely accepted to retard the shuttle of polysulfides in a working ...battery. However, the understanding of the intrinsic chemistry is still deficient. Inspired by the concept of hydrogen bond, herein we focus on the Li bond chemistry in Li–S batteries through sophisticated quantum chemical calculations, in combination with 7Li nuclear magnetic resonance (NMR) spectroscopy. Identified as Li bond, the strong dipole–dipole interaction between Li polysulfides and Li–S cathode materials originates from the electron‐rich donors (e.g., pyridinic nitrogen (pN)), and is enhanced by the inductive and conjugative effect of scaffold materials with π‐electrons (e.g., graphene). The chemical shift of Li polysulfides in 7Li NMR spectroscopy, being both theoretically predicted and experimentally verified, is suggested to serve as a quantitative descriptor of Li bond strength. These theoretical insights were further proved by actual electrochemical tests. This work highlights the importance of Li bond chemistry in Li–S cell and provides a deep comprehension, which is helpful to the cathode materials rational design and practical applications of Li–S batteries.
Lithium bond chemistry in Li–S batteries is probed by sophisticated quantum chemical calculations in combination with 7Li NMR spectroscopy. The chemical shift in 7Li NMR spectroscopy is suggested to be a quantitative descriptor of Li bond strength, propelling the advances in Li–S chemistry through materials genome design and high throughput screening.
Activation of the phagocytosis of macrophages to tumor cells is an attractive strategy for cancer immunotherapy, but the effectiveness is limited by the fact that many tumor cells express an ...increased level of anti‐phagocytic signals (e.g., CD47 molecules) on their surface. To promote phagocytosis of macrophages, a pro‐phagocytic nanoparticle (SNPACALR&aCD47) that concurrently carries CD47 antibody (aCD47) and a pro‐phagocytic molecule calreticulin (CALR) is constructed to simultaneously modulate the phagocytic signals of macrophages. SNPACALR&aCD47 can achieve targeted delivery to tumor cells by specifically binding to the cell‐surface CD47 and block the CD47‐SIRPα pathway to inhibit the “don't eat me” signal. Tumor cell‐targeted delivery increases the exposure of recombinant CALR on the cell surface and stimulates an “eat me” signal. Simultaneous modulation of the two signals enhances the phagocytosis of 4T1 tumor cells by macrophages, which leads to significantly improved anti‐tumor efficacy in vivo. The findings demonstrate that the concurrent blockade of anti‐phagocytic signals and activation of pro‐phagocytic signals can be effective in macrophage‐mediated cancer immunotherapy.
The phagocytosis of tumor cells by macrophages requires both the coordinated disruption of “don't eat me” signals and simultaneous activation of “eat me” signals. Herein, a nanoparticle‐enabled strategy is proposed to concurrently modulate the cell surface levels of calreticulin (CALR) and CD47 to improve macrophage phagocytosis for improved cancer immunotherapy.
Lithium (Li)‐metal batteries promise energy density beyond 400 Wh kg−1, while their practical operation at an extreme temperature below −30 °C suffers severe capacity deterioration. Such battery ...failure highly relates to the remarkably increased kinetic barrier of interfacial processes, including interfacial desolvation, ion transportation, and charge transfer. In this work, the interfacial kinetics in three prototypical electrolytes are quantitatively probed by three‐electrode electrochemical techniques and molecular dynamics simulations. Desolvation as the limiting step of interfacial processes is validated to dominate the cell impedance and capacity at low temperature. 1,3‐Dioxolane‐based electrolyte with tamed solvent–solute interaction facilitates fast desolvation, enabling the practical Li|LiNi0.5Co0.2Mn0.3O2 cells at −40 °C to retain 66% of room‐temperature capacity and withstand remarkably fast charging rate (0.3 C). The barrier of desolvation dictated by solvent–solute interaction environments is quantitatively uncovered. Regulating the solvent–solute interaction by low‐affinity solvents emerges as a promising solution to low‐temperature batteries.
Desolvation is validated as the predominant contributor to energy loss at low temperatures, largely overwhelming the contributions from other interfacial ion transportation processes. A rational and original design by taming solvent–solute interaction with low‐affinity solvents like 1,3‐dioxolane is proposed to enable high capacity and durable operation of practical lithium‐metal batteries at −40 °C.
Lithium (Li) metal-based battery is among the most promising candidates for next-generation rechargeable high-energy-density batteries. Carbon materials are strongly considered as the host of Li ...metal to relieve the powdery/dendritic Li formation and large volume change during repeated cycles. Herein, we describe the formation of a thin lithiophilic LiC
layer between carbon fibers (CFs) and metallic Li in Li/CF composite anode obtained through a one-step rolling method. An electron deviation from Li to carbon elevates the negativity of carbon atoms after Li intercalation as LiC
, which renders stronger binding between carbon framework and Li ions. The Li/CF | Li/CF batteries can operate for more than 90 h with a small polarization voltage of 120 mV at 50% discharge depth. The Li/CF | sulfur pouch cell exhibits a high discharge capacity of 3.25 mAh cm
and a large capacity retention rate of 98% after 100 cycles at 0.1 C. It is demonstrated that the as-obtained Li/CF composite anode with lithiophilic LiC
layers can effectively alleviate volume expansion and hinder dendritic and powdery morphology of Li deposits. This work sheds fresh light on the role of interfacial layers between host structure and Li metal in composite anode for long-lifespan working batteries.
The lithium–sulfur (Li–S) battery is regarded as a promising high‐energy‐density battery system, in which the dissolution–precipitation redox reactions of the S cathode are critical. However, soluble ...Li polysulfides (LiPSs), as the indispensable intermediates, easily diffuse to the Li anode and react with the Li metal severely, thus depleting the active materials and inducing the rapid failure of the battery, especially under practical conditions. Herein, an organosulfur‐containing solid electrolyte interphase (SEI) is tailored for the stabilizaiton of the Li anode in Li–S batteries by employing 3,5‐bis(trifluoromethyl)thiophenol as an electrolyte additive. The organosulfur‐containing SEI protects the Li anode from the detrimental reactions with LiPSs and decreases its corrosion. Under practical conditions with a high‐loading S cathode (4.5 mgS cm−2), a low electrolyte/S ratio (5.0 µL mgS−1), and an ultrathin Li anode (50 µm), a Li–S battery delivers 82 cycles with an organosulfur‐containing SEI in comparison to 42 cycles with a routine SEI. This work provokes the vital insights into the role of the organic components of SEI in the protection of the Li anode in practical Li–S batteries.
An organosulfur‐containing solid electrolyte interphase (SEI) is tailored for the stabilization of the Li anode in Li–S batteries by employing 3,5‐bis(trifluoromethyl)thiophenol as an electrolyte additive. The organosulfur‐containing SEI protects the Li anode from the detrimental reactions with Li polysulfides (LiPSs). A Li–S battery delivers 82 cycles with an organosulfur‐containing SEI in comparison to 42 cycles with a routine SEI under practical conditions.
Red ginseng polysaccharide (RGP) is an active component of the widely used medicinal plant Panax ginseng C. A. Meyer (Araliaceae), which has displayed promising activities against cancer cells. ...However, the detailed molecular mechanism of RGP in ferroptosis is still unknown.
This study evaluates the effects of RGP in cancer cells.
A549 and MDA-MB-231 cells were used. Cell proliferation was measured by CCK-8 assay after being treated with RGP at concentrations of 0, 50, 100, 200, 400, 800 and 1600 μg/mL at 0, 12, 24 and 48 h. Lipid reactive oxygen species (ROS) levels were assessed by C11-BODIPY assay. The control group was treated with PBS.
RGP inhibited human A549 (IC
50
: 376.2 μg/mL) or MDA-MB-231(IC
50
: 311.3 μg/mL) proliferation and induced lactate dehydrogenase (LDH) release, promoted ferroptosis and suppressed the expression of GPX4. Moreover, the effects of RGP were enhanced by the ferroptosis inducer erastin, while abolished by ferroptosis inhibitor ferrostatin-1.
Our study is the first to demonstrate (1) the anticancer activity of RGP in human lung cancer and breast cancer. (2) RGP presented the anti-ferroptosis effects in lung and breast cancer cells via targeting GPX4.
The innovation on the low dimensional nanomaterials brings the rapid growth of nano community. Developing the controllable production and commercial applications of nanomaterials for sustainable ...society is highly concerned. Herein, carbon nanotubes (CNTs) with sp2 carbon bonding, excellent mechanical, electrical, thermal, as well as transport properties are selected as model nanomaterials to demonstrate the road of nanomaterials towards industry. The engineering principles of the mass production and recent progress in the area of CNT purification and dispersion are described, as well as its bulk application for nanocomposites and energy storage. The environmental, health, and safety considerations of CNTs, and recent progress in CNT commercialization are also included. With the effort from the CNT industry during the past 10 years, the price of multi‐walled CNTs have decreased from 45 000 to 100 $ kg−1 and the productivity increased to several hundred tons per year for commercial applications in Li ion battery and nanocomposites. When the prices of CNTs decrease to 10 $ kg−1, their applications as composites and conductive fillers at a million ton scale can be anticipated, replacing conventional carbon black fillers. Compared with traditional bulk chemicals, the controllable synthesis and applicationsof CNTs on a million ton scale are still far from being achieved due to the challenges in production, purification, dispersion, and commercial application. The basic knowledge of growth mechanisms, efficient and controllable routes for CNT production, the environmental and safety issues, and the commercialization models are still inadequate. The gap between the basic scientific research and industrial development should be bridged by multidisciplinary research for the rapid growth of CNT nano‐industry.
The mass production engineering principles and advances in carbon nanotube (CNT) purification, dispersion, as well as bulk applications for nanocomposite and energy storage are reviewed. The environmental, health, and safety considerations of CNTs, and the recent progress on CNT commercialization are also included. The gap between the basic scientific research and industrial development should be bridged by multidisciplinary research for the rapid growth of CNT nano‐industry.
Heck reaction is one of the most important carbon‐carbon bond forming reactions with wide applications in organic synthesis. Considerable advances of enantioselective Heck reaction have been achieved ...in the past decades. This review focuses on recent development of catalytic asymmetric Heck reaction and reductive Heck reaction, which covers intermolecular and intramolecular versions since 2011. The article is organized in terms of the catalysts and olefin substrates.
Recent progress of catalytic asymmetric Heck reactions and reductive Heck reactions since 2011 is described.
The lifespan of practical lithium (Li)‐metal batteries is severely hindered by the instability of Li‐metal anodes. Fluorinated solid electrolyte interphase (SEI) emerges as a promising strategy to ...improve the stability of Li‐metal anodes. The rational design of fluorinated molecules is pivotal to construct fluorinated SEI. Herein, design principles of fluorinated molecules are proposed. Fluoroalkyl (−CF2CF2−) is selected as an enriched F reservoir and the defluorination of the C−F bond is driven by leaving groups on β‐sites. An activated fluoroalkyl molecule (AFA), 2,2,3,3‐tetrafluorobutane‐1,4‐diol dinitrate is unprecedentedly proposed to render fast and complete defluorination and generate uniform fluorinated SEI on Li‐metal anodes. In Li–sulfur (Li−S) batteries under practical conditions, the fluorinated SEI constructed by AFA undergoes 183 cycles, which is three times the SEI formed by LiNO3. Furthermore, a Li−S pouch cell of 360 Wh kg−1 delivers 25 cycles with AFA. This work demonstrates rational molecular design principles of fluorinated molecules to construct fluorinated SEI for practical Li‐metal batteries.
Design principles of fluorinated molecules were proposed to construct a fluorinated solid electrolyte interphase for practical lithium‐metal batteries.
Smart energy storage has revolutionized portable electronics and electrical vehicles. The current smart energy storage devices have penetrated into flexible electronic markets at an unprecedented ...rate. Flexible batteries are key power sources to enable vast flexible devices, which put forward additional requirements, such as bendable, twistable, stretchable, and ultrathin, to adapt mechanical deformation under the working conditions. This review summarizes the recent advances in construction and configuration of flexible batteries and discusses the general metrics to benchmark various flexible batteries with different materials and chemistries. Moreover, we present advanced prototype flexible batteries developed by some companies to afford general envision of the technological status. Lastly, the critical points are summarized in the development of flexible batteries and remaining challenges are also presented for the future design of flexible batteries in practical perspectives.
Flexible batteries are key power sources to smart energy storage. This review summarizes the recent advances of flexible batteries and affords perspectives on the design of efficient battery components and configurations.
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