Revealing Hydrogen Bond Effect in Rechargeable Aqueous Zinc-Organic Batteries.

The surrounding hydrogen bond (H-bond) interaction around the active sites plays indispensable functions in enabling the organic electrode materials (OEMs) to fulfill their roles as ion reservoirs in aqueous zinc-organic batteries (ZOBs). Despite important, there are still no works could fully shed its real effects light on. Herein, quinone-based small molecules with a H-bond evolution model has been rationally selected to disclose the regulation and equilibration of H-bond interaction between OEMs, and OEM and the electrolyte. It has been found that only a suitable H-bond interaction could make the OEMs fully liberate their potential performance. Accordingly, the 2,5-diaminocyclohexa-2,5-diene-1,4-dione (DABQ) with elaborately designed H-bond structure exhibits a capacity of 193.3 mAh g-1 at a record-high mass loading of 66.2 mg cm-2 and 100 % capacity retention after 1500 cycles at 5 A g-1. In addition, the DABQ//Zn battery also possesses air-rechargeable ability by utilizing the chemistry redox of proton. Our results put forward a specific pathway to precise utilization of H-bond to liberate the performance of OEMs.

Reconfiguring the Hydrogen Networks of Aqueous Electrolyte to Stabilize Iron Hexacyanoferrate for High-Voltage Decoupled Cell.

Prussian blue analogs (PBAs) as insertion-type cathodes have attracted significant attention in various aqueous batteries to accommodate metal or non-metal ions while suffering from serious dissolution and consequent inferior lifespan. Herein, we reveal that the dissolution of PBAs primarily originates from the locally elevated pH of electrolytes that are caused by proton co-insertion during discharge. To address this issue, a water-locking electrolyte (WLE) has been strategically implemented, which interrupts the generation and Grotthuss diffusion of protons by breaking the well-connected hydrogen bonding network in aqueous electrolytes. As a result, the WLE enables the iron hexacyanoferrate to endure over 1000 cycles at a 1C rate and supports a high-voltage decoupled cell with an average voltage of 1.95 V. These findings provide insights for mitigating dissolution problems in electrode materials, thereby enhancing the viability and performance of aqueous batteries.

[Medicinal evolution and modern research progress on Mume Fructus].

Prunus mume is an edible and medicinal material, and Mume Fructus is its processed product, which was first recorded in Shennong's Classic of Materia Medica(Shen Nong Ben Cao Jing). It is an effective drug for stopping diarrhea with astringents and promoting fluid production to quiet ascaris. By consulting the ancient herbal works of the past dynasties, modern codes, and other rela-ted literature, this paper sorted out the medicinal evolution of Mume Fructus, examined the ancient efficacy of Mume Fructus and the main indications, and summarized the inclusion of Mume Fructus in national and provincial standards. It is recorded in the ancient herbal works of the past dynasties that Mume Fructus can be processed by various methods such as roasting, stir-frying or micro-frying, stir-frying with charcoal, single steaming, steaming with wine, and steaming after soaking in wine or vinegar, and prepared into pills, powders, and ointments, which are used in the treatment of fatigue, diabetes, malaria, dysentery, ascariasis, and other diseases. Mume Fructus has been included in nine editions of Chinese Pharmacopoeia and 19 provincial and municipal preparation specifications. The processing method of Mume Fructus is determined, namely, clean P. mume should be softened by moistening in water or steaming and pitted. By reviewing the effects of processing on its chemical composition, pharmacological effects, and its modern clinical application, this paper identified the following issues. The ancient application methods of Mume Fructus are diverse but less commonly used in modern times, there is a lack of standardized research on the processing, and the research on the changes caused by the difference in Mume Fructus before and after processing is not deep. Therefore, it is necessary to further investigate the change pattern of its chemical composition before and after processing and its correlation between its medicinal activity to standardize the processing technology and provide a solid basis for the use of Mume Fructus in parts and its quality control.

In Situ Electrochemical Activation of Hydroxyl Polymer Cathode for High-Performance Aqueous Zinc-Organic Batteries.

The slow reaction kinetics and structural instability of organic electrode materials limit the further performance improvement of aqueous zinc-organic batteries. Herein, we have synthesized a Z-folded hydroxyl polymer polytetrafluorohydroquinone (PTFHQ) with inert hydroxyl groups that could be partially oxidized to the active carbonyl groups through the in situ activation process and then undertake the storage/release of Zn2+ . In the activated PTFHQ, the hydroxyl groups and S atoms enlarge the electronegativity region near the electrochemically active carbonyl groups, enhancing their electrochemical activity. Simultaneously, the residual hydroxyl groups could act as hydrophilic groups to enhance the electrolyte wettability while ensuring the stability of the polymer chain in the electrolyte. Also, the Z-folded structure of PTFHQ plays an important role in reversible binding with Zn2+ and fast ion diffusion. All these benefits make the activated PTFHQ exhibit a high specific capacity of 215 mAh g-1 at 0.1 A g-1 , over 3400 stable cycles with a capacity retention of 92 %, and an outstanding rate capability of 196 mAh g-1 at 20 A g-1 .

A Low-Volatile and Durable Deep Eutectic Electrolyte for High-Performance Lithium-Oxygen Battery.

The lithium-oxygen battery (LOB) with a high theoretical energy density (∼3500 Wh kg-1) has been regarded as a strong competitor for next-generation energy storage systems. However, its performance is still far from satisfactory due to the lack of stable electrolyte that can simultaneously withstand the strong oxidizing environment during battery operation, evaporation by the semiopen feature, and high reactivity of lithium metal anode. Here, we have developed a deep eutectic electrolyte (DEE) that can fulfill all the requirements to enable the long-term operation of LOBs by just simply mixing solid N-methylacetamide (NMA) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) at a certain ratio. The unique interaction of the polar groups in the NMA with the cations and anions in the LiTFSI enables DEE formation, and this NMA-based DEE possesses high ionic conductivity, good thermal, chemical, and electrochemical stability, and good compatibility with the lithium metal anode. As a result, the LOBs with the NMA-based DEE present a high discharge capacity (8647 mAh g-1), excellent rate performance, and superb cycling lifetime (280 cycles). The introduction of DEE into LOBs will inject new vitality into the design of electrolytes and promote the development of high-performance LOBs.

Three Birds with One Stone: An Integrated Cathode-Electrolyte Structure for High-Performance Solid-State Lithium-Oxygen Batteries.

Constructing solid-state lithium-oxygen batteries (SSLOBs) holds a great promise to solve the safety and stability bottlenecks faced by lithium-oxygen batteries (LOBs) with volatile and flammable organic liquid electrolytes. However, the realization of high-performance SSLOBs is full of challenges due to the poor ionic conductivity of solid electrolytes, large interfacial resistance, and limited reaction sites of cathodes. Here, a flexible integrated cathode-electrolyte structure (ICES) is designed to enable the tight connection between the cathode and electrolyte through supporting them on a 3D SiO2 nanofibers (NFs) framework. The intimate cathode-electrolyte structure and the porous SiO2 NFs scaffold combination are favorable for decreasing interfacial resistance and increasing reaction sites. Moreover, the 3D SiO2 NFs framework can also behave as an efficient inorganic filler to enhance the ionic conductivity of the solid polymer electrolyte and its ability to inhibit lithium dendrite growth. As a result, the elaborately designed ICES can simultaneously tackle the issues that limit the performance liberation of SSLOBs, making the batteries deliver a high discharge capacity and a long lifetime of 145 cycles with a cycling capacity of 1000 mAh g-1 at 60 °C, much superior to coventional SSLOBs (50 cycles).

Lithium-Air Batteries: Air-Electrochemistry and Anode Stabilization.

ConspectusIt is a permanent issue for modern society to develop high-energy-density, low-cost, and safe batteries to promote technological innovation and revolutionize the human lifestyle. However, the current popular Li-ion batteries are approaching their ceiling in energy density, and thus other battery systems with more power need to be proposed and studied to guide this revolution. Lithium-air batteries are among the candidates for next-generation batteries because of their high energy density (3500 Wh/kg). The past 20 years have witnessed rapid developments of lithium-air batteries in electrochemistry and material engineering with scientists' collaboration from all over the world. Despite these advances, the investigation on Li-air batteries is still in its infancy, and many bottleneck problems, including fundamental and application difficulties, are waiting to be resolved. For the electrolyte, it is prone to be attacked by intermediates (LiO2, O2-, 1O2, O22-) and decomposed at high voltage, accompanying side reactions that will induce cathode passivation. For the lithium anode, it can be corroded severely by H2O and the side products, thus protection methods are urgently needed. As an integrated system, the realization of high-performance Li-air batteries requires the three components to be optimized simultaneously.In this Account, we are going to summarize our progress for optimizing Li-air batteries in the past decade, including air-electrochemistry and anode optimization. Air-electrochemistry involves the interactions among electrolytes, cathodes, and air, which is a complex issue to understand. The search for stable electrolytes is first introduced because at the early age of its development, the use of incompatible Li-ion battery electrolytes leads to some misunderstandings and troubles in the advances of Li-air batteries. After finding suitable electrolytes for Li-air batteries, the fundamental research in the reaction mechanism starts to boom, and the performance has achieved great improvement. Then, air electrode engineering is introduced to give a general design principle. Examples of carbon-based cathodes and all-metal cathodes are discussed. In addition, to understand the influence of air components on Li-air batteries, the electro-activity of N2 has been tested and the role of CO2 in Li-O2/CO2 has been refreshed. Following this, the strategies for anode optimization, including constructing artificial films, introducing hydrophobic polymer electrolytes, adding electrolyte additives, and designing alloy anodes, have been discussed. Finally, we advocate researchers in this field to conduct cell level optimizations and consider their application scenarios to promote the commercialization of Li-air batteries in the near future.

Progress on the study of nucleosome reorganization during cellular reprogramming.

Cellular reprogramming is the process during which epigenetic markers of nuclear genome are deleted and remodeled during sperm-egg binding or nuclear transplantation, thereby rendering differentiated cells totipotent. The main cellular reprogramming methods are cell fusion, somatic cell nuclear transplantation, and induced pluripotent stem cells. Nucleosomes are the basic structural and functional units of chromatin, and nucleosome localization has an important role in regulating gene expression and the state of the cell. The occupancy and location of nucleosomes also change dramatically during cellular reprogramming, while the occupancy of nucleosomes around the transcriptional start site also decreases to promote the expression of pluripotency genes. In this review, we summarize the role of nucleosome localization in gene activation and repression, chromatin remodeling, and transcription factor recognition, with the aim of providing an important basis for an in-depth analysis of cellular reprogramming mechanisms.

Soluble and Perfluorinated Polyelectrolyte for Safe and High-Performance Li-O2 Batteries.

The severe performance degradation of high-capacity Li-O2 batteries induced by Li dendrite growth and concentration polarization from the low Li+ transfer number of conventional electrolytes hinder their practical applications. Herein, lithiated Nafion (LN) with the sulfonic group immobilized on the perfluorinated backbone has been designed as a soluble lithium salt for preparing a less flammable polyelectrolyte solution, which not only simultaneously achieves a high Li+ transfer number (0.84) and conductivity (2.5 mS cm-1 ), but also the perfluorinated anion of LN produces a LiF-rich SEI for protecting the Li anode from dendrite growth. Thus, the Li-O2 battery with a LN-based electrolyte achieves an all-round performance improvement, like low charge overpotential (0.18 V), large discharge capacity (9508 mAh g-1 ), and excellent cycling performance (225 cycles). Besides, the fabricated pouch-type Li-air cells exhibit promising applications to power electronic equipment with satisfactory safety.

Solvation Effect on the Improved Sodium Storage Performance of N-Heteropentacenequinone for Sodium-Ion Batteries.

The performance of electrode material is correlated with the choice of electrolyte, however, how the solvation has significant impact on electrochemical behavior is underdeveloped. Herein, N-heteropentacenequinone (TAPQ) is investigated to reveal the solvation effect on the performance of sodium-ion batteries in different electrolyte environment. TAPQ cycled in diglyme-based electrolyte exhibits superior electrochemical performance, but experiences a rapid capacity fading in carbonate-based electrolyte. The function of solvation effect is mainly embodied in two aspects: one is the stabilization of anion intermediate via the compatibility of electrode and electrolyte, the other is the interfacial electrochemical characteristics influenced by solvation sheath structure. By revealing the failure mechanism, this work presents an avenue for better understanding electrochemical behavior and enhancing performance from the angle of solvation effect.

Integrated Bismuth Oxide Ultrathin Nanosheets/Carbon Foam Electrode for Highly Selective and Energy-Efficient Electrocatalytic Conversion of CO2 to HCOOH.

Electroreduction of CO2 into formic acid (HCOOH) is of particular interest as a hydrogen carrier and chemical feedstock. However, its conversion is limited by a high overpotential and low stability due to undesirable catalysts and electrode design. Herein, an integrated 3D bismuth oxide ultrathin nanosheets/carbon foam electrode is designed by a sponge effect and N-atom anchor for energy-efficient and selective electrocatalytic conversion of CO2 to HCOOH for the first time. Benefitting from the unique 3D array foam architecture for highly efficient mass transfer, and optimized exposed active sites, as confirmed by density functional theory calculations, the integrated electrode achieves high electrocatalytic performance, including superior partial current density and faradaic efficiency (up to 94.1 %) at a moderate overpotential as well as a high energy conversion efficiency of 60.3 % and long-term durability.

High-Capacity and Stable Li-O2 Batteries Enabled by a Trifunctional Soluble Redox Mediator.

Li-O2 batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by-products. Here, a trifunctional ether-based redox mediator, 2,5-di-tert-butyl-1,4-dimethoxybenzene (DBDMB), is introduced into the electrolyte to capture reactive O2 - and alleviate the rigorous oxidative environment of Li-O2 batteries. Thanks to the strong solvation effect of DBDMB towards Li+ and O2 - , it not only reduces the formation of by-products (a high Li2 O2 yield of 96.6 %), but also promotes the solution growth of large-sized Li2 O2 particles, avoiding the passivation of cathode as well as enabling a large discharge capacity. Moreover, DBDMB makes the oxidization of Li2 O2 and the decomposition of main by-products (Li2 CO3 and LiOH) proceed in a highly effective manner, prolonging the stability of Li-O2 batteries (243 cycles at 1000 mAh g-1 and 1000 mA g-1 ).

An Adjustable-Porosity Plastic Crystal Electrolyte Enables High-Performance All-Solid-State Lithium-Oxygen Batteries.

The limited triple-phase boundaries (TPBs) in solid-state cathodes (SSCs) and high resistance imposed by solid electrolytes (SEs) make the achievement of high-performance all-solid-state lithium-oxygen (ASS Li-O2 ) batteries a challenge. Herein, an adjustable-porosity plastic crystal electrolyte (PCE) has been fabricated by employing a thermally induced phase separation (TIPS) technique to overcome the above tricky issues. The SSC produced through the in-situ introduction of the porous PCE on the surface of the active material, facilitates the simultaneous transfer of Li+ /e- , as well as ensures fast flow of O2 , forming continuous and abundant TPBs. The high Li+ conductivity, softness, and adhesion of the dense PCE significantly reduce the battery resistance to 115 Ω. As a result, the ASS Li-O2 battery based on this adjustable-porosity PCE exhibits superior performances with high specific capacity (5963 mAh g-1 ), good rate capability, and stable cycling life up to 130 cycles at 32 °C. This novel design and exciting results could open a new avenue for ASS Li-O2 batteries.

The Stabilization Effect of CO2 in Lithium-Oxygen/CO2 Batteries.

The lithium (Li)-air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2 ), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O2 - , and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li-air battery. Even worse, the water and/or CO2 in air bring parasitic reactions and safety issues. Therefore, applying such systems in open-air environment is challenging. Herein, contrary to previous assertions, we have found that CO2 can improve the stability of both anode and electrolyte, and a high-performance rechargeable Li-O2 /CO2 battery is developed. The CO2 not only facilitates the in situ formation of a passivated protective Li2 CO3 film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O2 - . Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li2 CO3 . The Li-O2 /CO2 battery achieves a full discharge capacity of 6628 mAh g-1 and a long life of 715 cycles, which is even better than those of pure Li-O2 batteries.

Protecting the Lithium Metal Anode for a Safe Flexible Lithium-Air Battery in Ambient Air.

The flexible Li-air battery (FLAB) with ultrahigh energy density is a hopeful candidate for flexible energy storage devices. However, most current FLAB operate in a pure oxygen atmosphere, which is limited by safety and corrosion issues from the metallic lithium anode and has thus greatly impeded the application of FLAB. Now, inspired by the protection effect of the umbrella, a stable hydrophobic composite polymer electrolyte (SHCPE) film with high flexibility, hydrophobicity, and stability was fabricated to protect the lithium anode. The SHCPE mitigated lithium corrosion and improved the capacity, rate performance, and cycle life (from 24 cycles to 95 cycles) of a battery in the ambient air. Based on the protection of SHCPE and the catalysis of MnOOH, the prepared pouch-type FLAB displayed high flexibility, stable performances, long cycling life (180 cycles), and excellent safety; the battery can bear soaking in water, high temperature, and nail penetration.

An Illumination-Assisted Flexible Self-Powered Energy System Based on a Li-O2 Battery.

The flexible Li-O2 battery is suitable to satisfy the requirements of a self-powered energy system, thanks to environmental friendliness, low cost, and high theoretical energy density. Herein, a flexible porous bifunctional electrode with both electrocatalytic and photocatalytic activity was synthesized and introduced as a cathode to assemble a high-performance Li-O2 battery that achieved an overpotential of 0.19 V by charging with the aid of solar energy. As a proof-of-concept application, a flexible Li-O2 battery was constructed and integrated with a solar cell via a scalable encapsulate method to fabricate a flexible self-powered energy system with excellent flexibility and mechanical stability. Moreover, by exploring the evolution of the electrode morphology and discharge products (Li2 O2 ), the charging process of the Li-O2 battery powered by solar energy and solar cell was demonstrated.

Generating Defect-Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia.

The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect-rich Bi nanoplates as an efficient noble-metal-free N2 reduction electrocatalyst via a low-temperature plasma bombardment approach. When exclusively using 1 H NMR measurements with N2 gas as a quantitative testing method, the defect-rich Bi(110) nanoplates achieved a 15 NH3 production rate of 5.453 µg mgBi -1 h-1 and a Faradaic efficiency of 11.68 % at -0.6 V vs. RHE in aqueous solution at ambient conditions.

Recent Advances toward the Rational Design of Efficient Bifunctional Air Electrodes for Rechargeable Zn-Air Batteries.

Large-scale application of renewable energy and rapid development of electric vehicles have brought unprecedented demand for advanced energy-storage/conversion technologies and equipment. Rechargeable zinc (Zn)-air batteries represent one of the most promising candidates because of their high energy density, safety, environmental friendliness, and low cost. The air electrode plays a key role in managing the many complex physical and chemical processes occurring on it to achieve high performance of Zn-air batteries. Herein, recent advances of air electrodes from bifunctional catalysts to architectures are summarized, and their advantages and disadvantages are discussed to underline the importance of progress in the evolution of bifunctional air electrodes. Finally, some challenges and the direction of future research are provided for the optimized design of bifunctional air electrodes to achieve high performance of rechargeable Zn-air batteries.

In Situ CVD Derived Co-N-C Composite as Highly Efficient Cathode for Flexible Li-O2 Batteries.

To promote the development of high energy Li-O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, activated cobalt-nitrogen-doped carbon nanotube/carbon nanofiber composites (Co-N-CNT/CNF) as the effective cathodes for Li-O2 batteries are prepared by in situ chemical vapor deposition (CVD). The unique architecture of these electrodes facilitates the rapid oxygen diffusion and electrolyte penetration. Meanwhile, the nitrogen-doped carbon nanotube/carbon nanofiber (N-CNT/CNF) and Co/CoNx serve as reaction sites to promote the formation/decomposition of discharge product. Li-O2 batteries with Co-N-CNT/CNF cathodes exhibit superior electrochemical performance in terms of a positive discharge plateau (2.81 V) and a low charge overpotential (0.61 V). Besides, Li-O2 batteries also present a high discharge capacity (11512.4 mAh g-1 at 100 mA g-1 ), and a long cycle life (130 cycles). Meanwhile, the Co-N-CNT/CNF cathode also has an excellent flexibility, thus the assembled flexible battery with Co-N-CNT/CNF can work normally and hold a wonderful capacity rate under various bending conditions.

Organic Carbonyl Compounds for Sodium-Ion Batteries: Recent Progress and Future Perspectives.

Sodium-organic batteries, which use organic materials as the electrodes in sodium-ion batteries, are an attractive alternative to conventional lithium-ion batteries for next-generation sustainable and versatile energy storage devices owing to the abundant sodium resources and environmental friendly features. However, organics used in sodium-ion batteries also encounter some issues such as low redox potential, high solubility in the electrolyte, and low conductivity. In response, altering the aromatic system/attaching electron-withdrawing groups, constructing polymers, and incorporating a conductive matrix are effective strategies. This review summarizes and briefly discusses recent organic carbonyl compounds for sodium-organic batteries from the viewpoint of function-oriented design, including function evolution from small-molecule compounds to polymers, then composites, and finally flexible electrodes. In particular, as a timely overview, carbonyl-based organic flexible electrodes for sodium-organic batteries are also highlighted for the first time.