Organic Cathode with Dual-Type Multielectron Reaction Centers for High-Energy-Density Lithium Primary Batteries.

Organic electrode materials are composed of abundant elements, have diverse and designable molecular structures, and are relatively easily synthesized, promising a bright future for low-cost and large-scale energy storage. However, they are facing low specific capacity and low energy density. Herein, we report a high-energy-density organic electrode material, 1,5-dinitroanthraquinone, which is composed of two kinds of electrochemically active sites of nitro and carbonyl groups. They experience six- and four-electron reduction and are transformed into amine and methylene groups, respectively, in the presence of fluoroethylene carbonate (FEC) in the electrolyte. Drastically increased specific capacity and energy density are demonstrated with an ultrahigh specific capacity of 1321 mAh g-1 and a high voltage of ∼2.62 V, corresponding to a high energy density of 3400 Wh kg-1. This surpasses the electrode materials in commercial lithium batteries. Our findings provide an effective strategy to design high-energy-density and novel lithium primary battery systems.

High-Performance Poly(1-naphthylamine)/Mesoporous Carbon Cathode for Lithium-Ion Batteries with Ultralong Cycle Life of 45000 Cycles at -15 °C.

Organic electrode materials for lithium-ion batteries have attracted significant attention in recent years. Polymer electrode materials, as compared to small-molecule electrode materials, have the advantage of poor solubility, which is beneficial for achieving high cycling stability. However, the severe entanglement of polymer chains often leads to difficulties in preparing nanostructured polymer electrodes, which is vital for achieving fast reaction kinetics and high utilization of active sites. This study demonstrates that these problems can be solved by the in situ electropolymerization of electrochemically active monomers in nanopores of ordered mesoporous carbon (CMK-3), combining the advantages of the nano-dispersion and nano-confinement effects of CMK-3 and the insolubility of the polymer materials. The as-prepared nanostructured poly(1-naphthylamine)/CMK-3 cathode exhibits a high active site utilization of 93.7%, ultrafast rate capability of 60 A g-1 (≈320 C), and an ultralong cycle life of 10000 cycles at room temperature and 45000 cycles at -15 °C. The study herein provides a facile and effective method that can simultaneously solve both the dissolution problem of small-molecule electrode materials and the inhomogeneous dispersion issue of polymer electrode materials.

A nitroaromatic cathode with an ultrahigh energy density based on six-electron reaction per nitro group for lithium batteries.

Organic electrode materials have emerged as promising alternatives to conventional inorganic materials because of their structural diversity and environmental friendliness feature. However, their low energy densities, limited by the single-electron reaction per active group, have plagued the practical applications. Here, we report a nitroaromatic cathode that performs a six-electron reaction per nitro group, drastically improving the specific capacity and energy density compared with the organic electrodes based on single-electron reactions. Based on such a reaction mechanism, the organic cathode of 1,5-dinitronaphthalene demonstrates an ultrahigh specific capacity of 1,338 mAh⋅g-1 and energy density of 3,273 Wh⋅kg-1, which surpass all existing organic cathodes. The reaction path was verified as a conversion from nitro to amino groups. Our findings open up a pathway, in terms of battery chemistry, for ultrahigh-energy-density Li-organic batteries.

Soluble Organic Cathodes Enable Long Cycle Life, High Rate, and Wide-Temperature Lithium-Ion Batteries.

Organic electrode materials free of rare transition metal elements are promising for sustainable, cost-effective, and environmentally benign battery chemistries. However, severe shuttling effect caused by the dissolution of active materials in liquid electrolytes results in fast capacity decay, limiting their practical applications. Here, using a gel polymer electrolyte (GPE) that is in situ formed on Nafion-coated separators, the shuttle reaction of organic electrodes is eliminated while maintaining the electrochemical performance. The synergy of physical confinement by GPE with tunable polymer structure and charge repulsion of the Nafion-coated separator substantially prevents the soluble organic electrode materials with different molecular sizes from shuttling. A soluble small-molecule organic electrode material of 1,3,5-tri(9,10-anthraquinonyl)benzene demonstrates exceptional electrochemical performance with an ultra-long cycle life of 10 000 cycles, excellent rate capability of 203 mAh g-1 at 100 C, and a wide working temperature range from -70 to 100 °C based on the solid-liquid conversion chemistry, which outperforms all previously reported organic cathode materials. The shielding capability of GPE can be designed and tailored toward organic electrodes with different molecular sizes, thus providing a universal resolution to the shuttling effect that all soluble electrode materials suffer.

A poorly soluble organic electrode material for high energy density lithium primary batteries based on a multi-electron reduction.

Here we report an organic cathode material with poor solubility for lithium primary batteries, i.e. indeno[3,2-b]fluorene-6,12-dione. Each carbonyl group experiences a four-electron reduction to a methylene group, resulting in a high energy density of 1392 W h kg-1, which is among the best results for organic electrode materials.

Optimization of Monomer Molecular Structure for Polymer Electrodes Fabricated through in-situ Electro-Polymerization Strategy.

In-situ electro-polymerization of redox-active monomers has been proved to be a novel and facile strategy to prepare polymer electrodes with superior electrochemical performance. The monomer molecular structure would have a profound impact on electro-polymerization behavior and thus electrochemical performance. However, this impact is poorly understood and has barely been investigated yet. Herein, three carbazole-based monomers, 9-phenylcarbazole (CB), 1,4-bis(carbazol-9-yl)benzene (DCB), and 2,6-bis(carbazol-9-yl)naphthalene (DCN), were applied to study the above issue systematically and achieve excellent long cycle performance. The monomers were rationally designed with different polymerizable sites and solubilities. It was found that a monomer with increased polymerizable sites and decreased solubility brought about enhanced electrochemical performance. This is because poor solubility could enhance utilization of the monomer for polymerization and more polymerizable sites could lead to a stable crosslinked polymer network after electro-polymerization. DCN with four polymerizable sites and the poorest solubility displayed the best electrochemical performance, which showed stable cycling up to 5000 cycles with high capacity retention of 76.2 % (among the best cycle in the literature). Our work for the first time reveals the relationship between monomer structure and in-situ electro-polymerization behavior. This work could shed light on the structure design/optimization of monomers for high-performance polymer electrodes prepared through in-situ electro-polymerization.

Metal-Organic Frameworks and Their Derivatives: Designing Principles and Advances toward Advanced Cathode Materials for Alkali Metal Ion Batteries.

Metal-organic frameworks (MOFs) and their derivatives have attracted enormous attention in the field of energy storage, due to their high specific surface area, tunable structure, highly ordered pores, and uniform metal sites. Compared with the wide research of MOFs and their related materials on anode materials for alkali metal ion batteries, few works are on cathode materials. In this review, design principles for promoting the electrochemical performance of MOF-related materials in terms of component/structure design, composite fabrication, and morphology engineering are presented. By summarizing the advancement of MOFs and their derivatives, Prussian blue and its analogs, and MOF surface coating, challenges and opportunities for future outlooks of MOF-related cathode materials are discussed.

Electrolytes and Interphases in Potassium Ion Batteries.

Potassium ion batteries (PIBs) are recognized as one promising candidate for future energy storage devices due to their merits of cost-effectiveness, high-voltage, and high-power operation. Many efforts have been devoted to the development of electrode materials and the progress has been well summarized in recent review papers. However, in addition to electrode materials, electrolytes also play a key role in determining the cell performance. Here, the research progress of electrolytes in PIBs is summarized, including organic liquid electrolytes, ionic liquid electrolytes, solid-state electrolytes and aqueous electrolytes, and the engineering of the electrode/electrolyte interfaces is also thoroughly discussed. This Progress Report provides a comprehensive guidance on the design of electrolyte systems for development of high performance PIBs.

Clusters of 2019 coronavirus disease (COVID-19) cases in Chinese tour groups.

International travel may facilitate the spread of the novel coronavirus disease (COVID-19). The study describes clusters of COVID-19 cases within Chinese tour groups travelling in Europe January 16-28. We compared characteristics of cases and non-cases to determine transmission dynamics. The index case travelled from Wuhan, China, to Europe on 16 January 2020, and to Shanghai, China, on 27 January 2020, within a tour group (group A). Tour groups with the same outbound flight (group B) or the same tourism venue (group D) and all Chinese passengers on the inbound flight (group C) were investigated. The outbreak involved 11 confirmed cases, 10 suspected cases and six tourists who remained healthy. Group A, involving seven confirmed cases and six suspected cases, consisted of familial transmission followed by propagative transmission. There was less pathogenicity with propagative transmission than with familial transmission. Disease was transmitted in shared outbound flights, shopping venues within Europe and inbound flight back to China. The novel coronavirus caused clustered cases of COVID-19 in tour groups. When tourism and travel opens up, governments will need to improve screening at airports and consider increased surveillance of tour groups-particularly those with older tour members.

Performance Enhancement of Polymer Electrode Materials for Lithium-Ion Batteries: From a Rigid Homopolymer to Soft Copolymers.

Synthesizing redox-active units containing polymers is a promising route for improving the cycling stability of organic electrode materials. However, constructing uniform electrode architectures with good polymer dispersion is a big challenge in the case of polymer electrode materials. In this work, we design and synthesize two anthraquinone-containing copolymers and compare their electrochemical performance with that of the corresponding homopolymer. It is uncovered that the copolymers with soft units in the main chain display increased chain flexibility, thus leading to a slightly increased solubility. Because of this, the soft copolymers are less likely to precipitate during solvent volatilization of electrode preparation and thus can form more uniform electrode architectures. The cyclic voltammogram and electrochemical impedance spectroscopy measurements indicate that copolymer electrodes display decreased polarization and improved kinetics compared with the homopolymer electrode. The copolymers exhibit significantly enhanced cycling stability and improved rate performance. After 100 cycles, both copolymers reveal very high capacity retention of above 98%, while the homopolymer retains only 71% of its highest capacity. Moreover, the copolymer can discharge/charge at 1C for over 2000 cycles with almost no capacity fading, indicating excellent long-term cycling performance. This work further demonstrates the importance of molecular structure and electrode architecture in determining the electrochemical performance of polymer electrode materials.

In†Situ Electropolymerization Enables Ultrafast Long Cycle Life and High-Voltage Organic Cathodes for Lithium Batteries.

Organic cathode materials have attracted extensive attention because of their diverse structures, facile synthesis, and environmental friendliness. However, they often suffer from insufficient cycling stability caused by the dissolution problem, poor rate performance, and low voltages. An in situ electropolymerization method was developed to stabilize and enhance organic cathodes for lithium batteries. 4,4',4''-Tris(carbazol-9-yl)-triphenylamine (TCTA) was employed because carbazole groups can be polymerized under an electric field and they may serve as high-voltage redox-active centers. The electropolymerized TCTA electrodes demonstrated excellent electrochemical performance with a high discharge voltage of 3.95 V, ultrafast rate capability of 20 A g-1 , and a long cycle life of 5000 cycles. Our findings provide a new strategy to address the dissolution issue and they explore the molecular design of organic electrode materials for use in rechargeable batteries.

Poorly Soluble 2,6-Dimethoxy-9,10-anthraquinone Cathode for Lithium-Ion Batteries: The Role of Electrolyte Concentration.

In this work, a 9,10-anthraquinone (AQ) derivative functionalized by two methoxy groups, 2,6-dimethoxy-9,10-anthraquinone (DMAQ), was synthesized and its electrochemical performance was comprehensively studied with different electrolyte concentrations. Density functional theory (DFT) calculations demonstrate that there exists a conjugation effect between oxygen atoms of methoxy groups and the AQ skeleton, which could extend the conjugate plane and increase intermolecular interaction. As a result, DMAQ shows considerably reduced solubility in ether solvent/electrolyte and greatly enhanced cycling performance compared with those of AQ. Interestingly, it is found that the electrolyte concentration plays an important role in determining the electrochemical performance. Cycling under a relatively low (2 M) or high (6 M) concentration electrolyte of lithium bis(trifluoromethanesulfonyl)imide in a mixture solvent of 1,3-dioxolane and 1,2-dimethoxyethane (1/1, v/v) displays unsatisfied cell performance. While a moderate electrolyte concentration of 4 M delivers the highest initial capacity and the best cycling stability. The work would shed light on the rational molecular structure design and electrolyte concentration optimization for achieving the high electrochemical performance of organic electrode materials.

Benzoquinone- and Naphthoquinone-Bearing Polymers Synthesized by Ring-Opening Metathesis Polymerization as Cathode Materials for Lithium-Ion Batteries.

Organic electrode materials have attracted great interest for next-generation lithium-ion batteries owing to their merits of low cost, resource sustainability, and environmental friendliness. Dissolution in organic electrolyte is one of critical factors that limit their development, and constructing corresponding polymers is an effective way to prevent it. Herein, the synthesis of benzoquinone- and naphthoquinone-bearing polymers by ring-opening metathesis polymerization of monomers with an exo-type four-membered ring between polymerizable norbornene and redox-active quinone units is reported. They exhibit significantly reduced solubility and clearly enhanced electrochemical performance. In particular, a high capacity (189.7 mAh g-1 at 0.1 C, 1 C=216.1 mA g-1 ), stable cycling (75.6 % capacity retention after 500 cycles at 2 C), and good rate capability (retaining 80.4 % from 0.1 to 2 C) were obtained for the naphthoquinone-bearing polymer, which stand out among naphthoquinone-bearing polymer electrode materials. This work offers rational molecular design and a new polymerization strategy to construct high-performance polymer electrode materials.

An Insoluble Anthraquinone Dimer with Near-Plane Structure as a Cathode Material for Lithium-Ion Batteries.

Conjugated carbonyl-based organic electrode materials for lithium-ion batteries have gained increasing interests owing to their many advantages such as resource abundance and sustainable development. However, serious dissolution in organic liquid electrolytes is often encountered, resulting in inferior electrochemical performance such as poor cycling stability. Herein, a new molecular design strategy was developed to address the dissolution issue of 9,10-anthraquinone (AQ). An AQ dimer with near-plane molecular structure, 1,4-bis(9,10-anthraquinonyl)benzene (BAQB), was facilely synthesized. The near-plane structure was proved by DFT calculations. It was found that the obtained BAQB was insoluble in ether electrolyte. Compared to AQ, BAQB displayed remarkably enhanced cycling stability. After 100 cycles at 0.2 C, a high capacity retention of 91.6 % was achieved (195 mAh g-1 ). BAQB also exhibited excellent rate performance (138 mAh g-1 at 10 C). The results demonstrate the effectiveness of the near-plane molecular design concept. This work provides a new idea for rational molecular design to inhibit the dissolution of conjugated carbonyl-based organic electrode materials.

A Lithium-Organic Primary Battery.

Lithium primary batteries are still widely used in military, aerospace, medical, and civilian applications despite the omnipresence of rechargeable Li-ion batteries. However, these current primary chemistries are exclusively based on inorganic materials with high cost, low energy density or severe safety concerns. Here, a novel lithium-organic primary battery chemistry that operates through a synergetic reduction of 9,10-anthraquinone (AQ) and fluoroethylene carbonate (FEC) is reported. In FEC-presence, the equilibrium between the carbonyl and enol structures is disabled, and replaced by an irreversible process that corresponds to a large capacity along with methylene and inorganic salts (such as LiF, Li2 CO3 ) generated as products. This irreversible chemistry of AQ yields a high energy density of 1300 Wh/(kg of AQ) at a stable discharge voltage platform of 2.4 V as well as high rate capability (up to 313 mAh g-1 at a current density of 1000 mA g-1 ), wide temperature range of operation (-40 to 40 °C) and low self-discharge rate. Combined with the advantages of low toxicity, facile and diverse synthesis methods, and easy accessibility of AQ, Li-organic primary battery chemistry promises a new battery candidate for applications that requires low cost, high environmental friendliness, and high energy density.

Optimization of Molecular Structure and Electrode Architecture of Anthraquinone-Containing Polymer Cathode for High-Performance Lithium-Ion Batteries.

Molecular structure and electrode architecture play very important roles in electrochemical performance of polymer electrode materials for lithium-ion batteries. Here, a series of anthraquinone-containing polymers with linear (with different molecular weights (MWs)) or cross-linked polymer structures were synthesized by (living) ring-opening metatheses (co)polymerization method. The influences of the molecular structures and electrode preparation process on the architectures and electrochemical performance of polymer electrodes were systematically investigated. It was found that the low MW linear polymers suffer from severe dissolution and thus result in low initial capacity and poor cycling stability. Under optimized electrode preparation process, high MW linear polymers can be uniformly composited with conductive additives and binders and deliver stable cycling performance. Cross-linked polymer shows significantly reduced solubility but a severe aggregation problem, leading to very poor electrochemical performance. Our findings shed light on the molecular structure design and electrode preparation process of polymer electrode materials for high-performance rechargeable batteries.

Spontaneously Healable Thermoplastic Elastomers Achieved through One-Pot Living Ring-Opening Metathesis Copolymerization of Well-Designed Bulky Monomers.

We report here a series of novel spontaneously healable thermoplastic elastomers (TPEs) with a combination of improved mechanical and good autonomic self-healing performances. Hard-soft diblock and hard-soft-hard triblock copolymers with poly[exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-l,4-methanoanthracene] (PHBM) as the hard block and secondary amide group containing norbornene derivative polymer as the soft block were synthesized via living ring-opening metathesis copolymerization by use of Grubbs third-generation catalyst through sequential monomer addition. The microstructure, mechanical, self-healing, and surface morphologies of the block copolymers were thoroughly studied. Both excellent mechanical performance and self-healing capability were achieved for the block copolymers because of the interplayed physical cross-link of hard block and dynamic interaction formed by soft block in the self-assembled network. Under an optimized hard block (PHBM) weight ratio of 5%, a significant recovery of tensile strength (up to 100%) and strain at break (ca. 85%) was achieved at ambient temperature without any treatment even after complete rupture. Moreover, the simple reaction operations and well-designed monomers offer versatility in tuning the architectures and properties of the resulting block copolymers.

[The Molluscicidal Effect of Chlorosalicylicamide Sustained-release Granules on Oncomelania hupensis].

Objective: To evaluate the molluscicidal effect of the chlorosalicylicamide sustained-release granules (LDS-SRG) on Oncomelania hupensis. Methods: Seven effective concentrations or dosages of LDS-SRG, 0.1, 0.2, 0.4, 0.8, 1.6, 3.2 and 6.4 mg/L （for immersion test） or g/m2（for spraying test）, were prepared from the original 5% and 10% concentrations or dosages in the laboratory. In the immersion test, each concentration of LDS-SRG was incubated with 3 packs of snails（30 snails in each pack）, and each pack was taken for snail counting at 24, 48 and 72 h respectively. In the spraying test, each dosage of LDS-SRG was applied to 200 snails, and the snail mortality was calculated in 50 randmoly collected snails on days 3 and 7, and in the whole on day 14 after administration. In the field immersion test, LDS-SRG at concentrations of 0.4, 0.8 and 1.6 g/m3 was incubated with 6 packs of snails （30 snails in each pack）, and each 2 packs were taken at 24, 48, and 72 h to calculate the snail mortality. In the field spraying test, 0.8, 1.6 and 3.2 g/m2 LDS-SRG was sprayed in 3 snail-positive ditches （～100 m2）, and 10 boxes of snails were selected in each ditch on days 3, 7 and 14 to calculate the snail mortality. The 50% wettable powder of niclosamide ethanolamine salt （WPN） with effective concentrations or dosages of 1.0 mg/L （or g/m2 and g/m3） was used as the positive control. Fresh water served as the blank control. Results: In the labratory immersion test using the original concentration of 5%, both 0.1-6.4 mg/L LDS-SRG for 72 h and 1.6-6.4 mg/L LDS-SRG for 48 h caused 100% mortality; and the concentration lethal to 50% （LC50） at 24, 48 and 72 h was 0.70, 0.01 and 0.01 mg/L respectively. When using the original concentration of 10%, both 0.1-6.4 mg/L LDS-SRG for 72 h and 0.2-6.4 mg/L LDS-SRG for 48 h caused 100% mortality; and the LC50 at 24, 48 and 72 h was 0.15, 0.01 and 0.01 mg/L respectively. The labratory spraying test showed that 7-day administration of 1.6 and 6.4 g/m2 LDS-SRG as well as 14-day administration of 3.2 and 6.4 g/m2 LDS-SRG prepared from 5% dosage, resulted in a snail mortality>95%, with the LD50 on days 3, 7 and 14 being 0.06, 0.16, and 0.18 g/m2; 14-day administration of 1.6 g/m2 LDS-SRG as well as 7-day administration of 6.4 g/m2 LDS-SRG prepared from 10% dosage, resulted in a snail mortality>95%, with the LD50 on days 3, 7 and 14 being 3.29, 0.75, and 0.16 g/m2. The mortality by various dosages of LDS-SRG prepared from 5% dosage was significantly higher than that of the control group (P<0.05). In the field immersion test, the snail mortality by 1.6 g/m3 LDS-SRG prepared from 5% and 10% concentrations for 72 h was 96.43% and 98.21% respectively (P>0.05 versus the control group). In the field spraying test, the snail mortality by 3.2 g/m2 LDS-SRG prepared from 5% dosage for 3, 7 and 14 days was 93.99%, 91.18% and 86.48% respectively, and that from 10% dosage was 94.95%, 93.50% and 85.43%, all significantly higher than that of the control group （82.83%, 72.38% and 48.38%）（P<0.05）; the snail mortality by 0.8 g/m2 LDS-SRG prepared from 5% dosage for 14 days（66.51%） and that by 1.6 g/m2 LDS-SRG prepared from 5% dosage for 3 days（84.61%） were both significantly higher than that by 10% LDS-SRG（20.13% and 43.06%） （P<0.05）. Conclusion: The 5% and 10% LDS-SRG used separately in the immersion test and the spraying test both meet the requirements of the national standard of Efficacy Test Methods and Evaluation of Molluscicide for Pesticide Registration.

Double closed-loop cascade control for lower limb exoskeleton with elastic actuation.

Unlike traditional rigid actuators, the significant features of Series Elastic Actuator (SEA) are stable torque control, lower output impedance, impact resistance and energy storage. Recently, SEA has been applied in many exoskeletons. In such applications, a key issue is how to realize the human-exoskeleton movement coordination. In this paper, double closed-loop cascade control for lower limb exoskeleton with SEA is proposed. This control method consists of inner SEA torque loop and outer contact force loop. Utilizing the SEA torque control with a motor velocity loop, actuation performances of SEA are analyzed. An integrated exoskeleton control system is designed, in which joint angles are calculated by internal encoders and resolvers and contact forces are gathered by external pressure sensors. The double closed-loop cascade control model is established based on the feedback signals of internal and external sensor. Movement experiments are accomplished in our prototype of lower limb exoskeleton. Preliminary results indicate the exoskeleton movements with pilot can be realized stably by utilizing this double closed-loop cascade control method. Feasibility of the SEA in our exoskeleton robot and effectiveness of the control method are verified.

Antigenic and genetic variation in the hemagglutinins of H1N1 and H3N2 human influenza a viruses in the Shanghai area from 2005 to 2008.

Continued rapid evolution of the influenza A virus is responsible for annual epidemics and occasional pandemics in the Shanghai area. In the present study, the representative strains of A/H1N1 and A/H3N2 influenza viruses isolated in the Shanghai area from 2005 to 2008 were antigenically and genetically characterized. The antigenic cartography method was carried out to visualize the hemagglutination-inhibition data. Antigenic differences were detected between circulating A/H1N1 strains isolated from 2005 to 2006 and the epidemic A/H1N1 strains isolated in 2008, which were found to be associated with the amino acid substitution K140E in HA1. The present vaccine strain A/Brisbane/59/2007 is considered to be capable of providing sufficient immunity against most of the circulating A/H1N1 viruses isolated in 2008 from the Shanghai population. The study showed that there were significant antigenic differences between the epidemic A/H3N2 strains isolated in 2007 and 2008, suggesting that antigenic drift had occurred in the A/H3N2 strains isolated in 2008. The P194L mutation was thought to be responsible for the antigenic evolution of influenza A/H3N2 viruses isolated from Shanghai in 2008. Evidence of antigenic drift suggests that the influenza A/H3N2 vaccine component needs to be updated.