Boosting the Zn2+ storage capacity of MoO3 nanoribbons by modulating the electrons spin states of Mo via Ni doping.

Aqueous zinc-ion batteries (AZIBs) have received considerable potential for their affordability and high reliability. Among potential cathodes, α-MoO3 stands out due to its layered structure aligned with the (010) plane, offering extensive ionic insertion channels for enhanced charge storage. However, its limited electrochemical activity and poor Zn2+ transport kinetics present significant challenges for its deployment in energy storage devices. To overcome these limitations, we introduce a new strategy by doping α-MoO3 with Ni (Ni-MoO3), tuning the electron spin states of Mo. Thus modification can activate the reactivity of Ni-MoO3 towards Zn2+ storage and weaken the interaction between Ni-MoO3 and intercalated Zn2+, thereby accelerating the Zn2+ transport and storage. Consequently, the electrochemical properties of Ni-MoO3 significantly surpass those of pure MoO3, demonstrating a specific capacity of 258 mAh g-1 at 1 A g-1 and outstanding rate performance (120 mAh g-1 at 10 A g-1). After 1000 cycles at 8 A g-1, it retains 76 % of the initial capacity, with an energy density of 154.4 Wh kg-1 and a power density of 11.2 kW kg-1. This work proves that the modulation of electron spin states in cathode materials via metal ion doping can effectively boost their capacity and cycling durability.

Operando monitoring of dendrite formation in lithium metal batteries via ultrasensitive tilted fiber Bragg grating sensors.

Lithium (Li) dendrite growth significantly deteriorates the performance and shortens the operation life of lithium metal batteries. Capturing the intricate dynamics of surface localized and rapid mass transport at the electrolyte-electrode interface of lithium metal is essential for the understanding of the dendrite growth process, and the evaluation of the solutions mitigating the dendrite growth issue. Here we demonstrate an approach based on an ultrasensitive tilted fiber Bragg grating (TFBG) sensor which is inserted close to the electrode surface in a working lithium metal battery, without disturbing its operation. Thanks to the superfine optical resonances of the TFBG, in situ and rapid monitoring of mass transport kinetics and lithium dendrite growth at the nanoscale interface of lithium anodes have been achieved. Reliable correlations between the performance of different natural/artificial solid electrolyte interphases (SEIs) and the time-resolved optical responses have been observed and quantified, enabling us to link the nanoscale ion and SEI behavior with the macroscopic battery performance. This new operando tool will provide additional capabilities for parametrization of the batteries' electrochemistry and help identify the optimal interphases of lithium metal batteries to enhance battery performance and its safety.

A weakly solvating electrolyte towards practical rechargeable aqueous zinc-ion batteries.

Structure deterioration and side reaction, which originated from the solvated H2O, are the main constraints for the practical deployment of both cathode and anode in aqueous Zn-ion batteries. Here we formulate a weakly solvating electrolyte to reduce the solvating power of H2O and strengthen the coordination competitiveness of SO42- to Zn2+ over H2O. Experiment results and theoretical simulations demonstrate that the water-poor solvation structure of Zn2+ is achieved, which can (i) substantially eliminate solvated-H2O-mediated undesirable side reactions on the Zn anode. (ii) boost the desolvation kinetics of Zn2+ and suppress Zn dendrite growth as well as structure aberration of the cathode. Remarkably, the synergy of these two factors enables long-life full cells including Zn/NaV3O8·1.5H2O, Zn/MnO2 and Zn/CoFe(CN)6 cells. More importantly, practical rechargeable AA-type Zn/NVO cells are assembled, which present a capacity of 101.7 mAh and stability of 96.1% capacity retention after 30 cycles at 0.66 C.

Achieving stable Zn metal anode via a hydrophobic and Zn2+-conductive amorphous carbon interface.

High security and low cost enable aqueous zinc ion batteries (AZIBs) with huge application potential in large-scale energy storage. Nevertheless, the loathsome dendrite and side reactions of Zn anode are harmful to the cycling lifespan of AZIBs. Here, a new type of thin amorphous carbon (AC) interface layer (∼100 nm in thickness) is in-situ constructed on the Zn foil (Zn@AC) via a facile low-temperature chemical vapor deposition (LTCVD) method, which owns a hydrophobic peculiarity and a high Zn2+ transference rate. Moreover, this AC coating can homogenize the surface electric field and Zn2+ flux to realize the uniform deposition of Zn. Consequently, dendrite growth and side reactions are concurrently mitigated. Symmetrical cell achieves a dendrite-free Zn plating/stripping over 500 h with a low overpotential of 31 mV at 1 mA cm-2/1 mAh cm-2. Of note, the full cell with a MnO2/CNT cathode harvests a capacity retention of 70.0 % after 550 cycles at 1 A/g. In addition, the assembled flexible quasi-solid-state AZIBs display a stable electrochemical performance under deformation conditions and maintain a capacity of 76.5 mAh/g at 5 A/g after 300 cycles. This innovative amorphous carbon layer is expected to provide a new insight into stabilizing Zn anode.

Unraveling the Mechanism of Cooperative Redox Chemistry in High-Efficient Zn2+ Storage of Vanadium Oxide Cathode.

The inferior capacity and cyclic durability of V2 O5 caused by inadequate active sites and sluggish kinetics are the main problems to encumber the widespread industrial applications of vanadium-zinc batteries (VZBs). Herein, a cooperative redox chemistry (CRC) as "electron carrier" is proposed to facilitate the electron-transfer by capturing/providing electrons for the redox of V2 O5 . The increased oxygen vacancies in V2 O5 provoked in situ by CRC offers numerous Zn2+ storage sites and ion-diffusion paths and reduces the electrostatic interactions between vanadium-based cathode and intercalated Zn2+ , which enhance Zn2+ storage capability and structural stability. The feasibility of this strategy is fully verified by some CRCs. Noticeably, VZB with [Fe(CN)6 ]3- /[Fe(CN)6 ]4- as CRC displays conspicuous specific capacity (433.3 mAh g-1 ), ≈100% coulombic efficiency and superb cyclability (≈3500 cycles without capacity attenuation). Also, the mechanism and selection criteria of CRC are specifically unraveled in this work, which provides insightful perspectives for the development of high-efficiency energy-storage devices.

Promoting OH- Adsorption and Diffusion Enables Ultrahigh Capacity and Rate Capability of Nickel Sulfide Cathode for Aqueous Alkaline Zn-Based Batteries.

Aqueous alkaline Zn-based batteries (AAZBs) possess great promise for large-scale applications thanks to their higher discharging plateau and unique reaction mechanism. However, the capacity and rate capability of Ni-based cathodes are still unsatisfactory due to their insufficient OH- adsorption and diffusion ability. Herein, heterostructured Ni3 S2 /Ni(OH)2 nanosheets with outstanding electrochemical performance are synthesized via a facile chemical etching strategy. The heterostructured Ni3 S2 /Ni(OH)2 nanosheet cathode shows significantly increased capacity and rate capability due to its boosted OH- adsorption and diffusion ability compared to Ni3 S2 . Consequently, the assembled Zn//Ni3 S2 /Ni(OH)2 cell can deliver an ultrahigh capacity of 2.26 mAh cm-2 , an excellent rate performance (0.91 mAh cm-2 at 100 mA cm-2 ) and a satisfying cycling stability (1.01 mAh cm-2 at 20 mA cm-2 after 500 cycles). Moreover, a prominent energy density of 3.86 mWh cm-2 is obtained, which exceeds the majority of recently reported AAZBs. This work is expected to provide a new modification direction for developing high-performance nickel sulfide cathode for AAZBs.

The effects of water, substrate, and intermediate adsorption on the photocatalytic decomposition of air pollutants over nano-TiO2 photocatalysts.

The photocatalytic performance of nano-TiO2 photocatalysts in air pollutant degradation greatly depends on the adsorption of water, substrates, and intermediates. Especially under excessive humidity, substrate concentration, and intermediate concentration, the competitive adsorption of water, substrates, and intermediates can seriously inhibit the photocatalytic performance. In the past few years, extensive studies have been performed to investigate the influence of humidity, substrate concentration, and intermediates on the photocatalytic performance of TiO2, and significant advances have been made in the area. However, to the best of our knowledge, there is no review focusing on the effects of water, substrate, and intermediate adsorption to date. A comprehensive understanding of their mechanisms is key to overcoming the limited application of nano-TiO2 photocatalysts in the photocatalytic decomposition of air pollutants. In this review, the progress in experimental and theoretical fields, including a recent combination of photocatalytic experiments and adsorption and photocatalytic simulations by density functional theory (DFT), to explore the impact of adsorption of various reaction components on nano-TiO2 photocatalysts is comprehensively summarized. Additionally, the mechanism and broad perspective of the impact of their adsorption on the photocatalytic activity of TiO2 in air treatment are also critically discussed. Finally, several solutions are proposed to resolve the current problems related to environmental factors. In general, this review contributes a comprehensive perspective of water, substrate, and intermediate adsorption toward boosting the photocatalytic application of TiO2 nanomaterials.

Weak Solvation Effect Induced Optimal Interfacial Chemistry Enables Highly Durable Zn Anodes for Aqueous Zn-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are emerging as one of the most reliable energy storage technologies for scale-up applications, but still suffer from the instability of Zn anode, which is mainly caused by the undesirable dendrite growth and side reactions. To tackle these issues, we formulate a new aqueous electrolyte with weak solvation effect by introducing low-dielectric-constant acetone to achieve H2 O-poor solvation structure of Zn2+ . Experimental and theoretical calculation studies concurrently reveal that such solvation structure can: i) relieve the solvated H2 O related side reactions, ii) suppress the dendrite growth by boosting the desolvation kinetics of Zn2+ and iii) in situ form solid electrolyte interface (SEI) to synergistically inhibit the side reaction and dendrite growth. The synergy of these three factors prolongs the cycling life of Cu/Zn asymmetric cell from 30 h to more than 800 h at 1 mA cm-2 /1 mAh cm-2 , and can work at more harsh condition of 5 mA cm-2 /5 mAh cm-2 . More encouragingly, Zn/V2 O5 ⋅ nH2 O full cell also shows enhanced cycling stability of 95.9 % capacity retention after 1000 cycles, much better than that with baseline electrolyte (failing at ≈700th  cycle).

Structural and surface engineering promotes Zn-ion energy storage capability of commercial carbon cloth.

Aqueous Zn-ion hybrid supercapacitors (AZHSCs) combining the advantages of high-energy batteries and high-power supercapacitors see a bright future, but they still suffer from the poor capacity of carbonic cathodes. Herein, a functionalized porous carbon cloth (denoted as FPCC) electrode is demonstrated based on commercial carbon cloth (denoted as CC) tuning by structural and surface engineering. The constructed exfoliated porous carbon layer and the negatively charged functionalized interface not only increase the electrical double layer capacitance but also favor the chemical adsorption of Zn2+ to obtain additional pseudocapacitance. Consequently, the FPCC electrode delivers a high capacity of 0.16 mAh cm-2 at 4 mA cm-2, which is 923.8 times higher than CC, and a long cycle life (85.0% capacity retention after 30 000 cycles). More importantly, the Zn//FPCC AZHSC possesses an impressive energy density (3.3 mWh cm-3) and power density (240 mW cm-3), superior to many advanced batteries and supercapacitors. The quasi-solid-state device is also assembled as a demo. This modification strategy may provide new opportunities for high-performance AZHSCs.

Nonplanar π-Conjugated Sulfur Heterocyclic Quinone Polymer Cathode for Air-Rechargeable Zinc/Organic Battery with Simultaneously Boosted Output Voltage, Rate Capability, and Cycling Life.

π-conjugated organic compounds with a good charge transfer ability and rich redox functional groups are promising cathode candidates for air-rechargeable aqueous Zn-based batteries (AAZBs). However, the output voltage of even the state-of-the-art π-conjugated organic cathodes lies well below 0.8 V, resulting in insufficient energy density. Herein, we design a nonplanar π-conjugated sulfur heterocyclic quinone polymer (SHQP) as an advanced cathode material for AAZBs by polymerization 1,4-Benzoquinone (BQ) and S heteroatoms periodically. The extended π-conjugated plane and enhanced aromaticity endow SHQP with a more sensitive charge transfer ability and robust structure. Furthermore, the delocalized π electrons in the whole system are insufficient as the π orbit of the S heteroatom is not in the same plane with the π orbit of BQ due to its folded configuration, resulting in negligible variation of electron density around C═O after the polymerization. Thus, the output voltage of SHQP shows no significant decrease even though the thioether bond (-S-) functions as electron donor. Consequently, the Zn/SHQP AAZBs can deliver a record high midpoint discharging voltage (0.95 V), rate performance (119 mAh g-1 at 10 A g-1), and durability (98.7% capacity retention after 200 cycles) across a wide temperature range.

Oxygen-defective zinc oxide nanoparticles as highly efficient and safe sonosensitizers for cancer therapy.

Herein, an oxygen defect-modulated zinc oxide sonosensitizer is designed, which enhances the absorbance of ultrasound energy and suppresses the recombination of ultrasound-initiated electrons and holes to promote reactive oxygen species yield. It achieves a high tumor inhibition efficiency of 79.9%, which exhibits a potential application for sonodynamic cancer therapy.

A space-confined strategy towards stable α/ß-Bi2O3 heterojunction anode for high-energy aqueous battery.

It is very necessary to design a high-capacity and stable Bi2O3 anode for nickel-bismuth (Ni//Bi) batteries. In this work, a stable α- and ß- phase Bi2O3 heterojunction nanocomposite (α/ß - Bi2O3) was successfully prepared via a simple "space-confined" strategy and it was used as a superior anode for nickel-bismuth (Ni//Bi) battery. The α/ß-Bi2O3 obtained by using MCM-41 as a space-confined template possesses a stable structure and enhanced charge transfer capability. Such superior traits vest the designed α/ß-Bi2O3 electrode with high specific capacity (235 mAh g-1 at 1 A g-1), extraordinary rate performance (137 mAh g-1 at 40 A g-1, and ∼58% capacity retention vs 1 A g-1), and excellent cyclic durability (75% capacity retention after 5000 cycles). Such performances are far superior to that of mono-phase α-Bi2O3 and ß-Bi2O3 electrodes. Furthermore, an excellent Ni//Bi battery with outstanding energy density (∼155 Wh kg-1) and long cycle life was assembled using the obtained α/ß-Bi2O3 electrode and a NiC2O4 electrode as anode and cathode, respectively (NiC2O4//α/ß-Bi2O3). This work opens a new alternative strategy for the rational design of efficient electrodes for reliable aqueous rechargeable batteries.

Molecular dynamics of the spontaneous generation mechanism of natural gas hydrates during methane nanobubble rupture.

Natural gas hydrates have garnered significant attention as a potential new source of alternative energy, and understanding their formation mechanism is of paramount importance for efficient utilization and pipeline transportation. However, there is no consensus among academics on the formation mechanism of natural gas hydrates. In this paper, we propose a method for promoting the rapid formation of natural gas hydrates based on the rupture of methane nanobubbles, which creates local high temperature and pressure to facilitate the mixing of methane and water. The rapid decrease in system temperature and pressure during the process further enhances the formation of gas hydrates. Using molecular dynamics simulations, we theoretically verify the formation of natural gas hydrates. Our results indicate that the instantaneous rupture of methane nanobubbles induced by shock waves leads to a dramatic increase in the local molecular motion velocity around the bubbles. This results in extreme local high temperature and high pressure, leading to complete mixing of methane and water and rapid formation of gas hydrates during the cooling and pressure drop of the mixture. We confirm our findings by analyzing F3-order parameters, F4-order parameters, and water cage statistics.

N, S, O Self-Doped Carbon Derived from Grapefruit Peel for High-Performance Supercapacitors.

The development of high-capacity carbon for supercapacitors is highly desirable but challenging. In this work, we design a N, S, O self-doped carbon electrode (NSOC-800) with high capacitance and good stability via the carbonization of grapefruit peel via a one-step KOH activation method without extra dopants. The existence of heteroatoms enables the NSOC-800 to have a high specific capacitance of 280 F/g and a great cycling performance, with 90.1% capacitance retention after 5000 cycles. Moreover, the symmetric supercapacitor with NSOC-800 electrodes delivers a maximum energy density of 5 Wh/kg with a power density of 473 W/kg. Such a promising method to achieve carbon materials with self-doping heteroatwoms is of great significance for developing highly efficient electrodes for energy storage devices.

Inorganic Sonosensitizers for Sonodynamic Therapy in Cancer Treatment.

The rapid development of nanomedicine and nanobiotechnology has allowed the emergence of various therapeutic modalities with excellent therapeutic efficiency and biosafety, among which, the sonodynamic therapy (SDT), a combination of low-intensity ultrasound and sonosensitizers, is emerging as a promising noninvasive treatment modality for cancer treatment due to its deeper penetration, good patient compliance, and minimal damage to normal tissue. The sonosensitizers are indispensable components in the SDT process because their structure and physicochemical properties are decisive for therapeutic efficacy. Compared to the conventional and mostly studied organic sonosensitizers, inorganic sonosensitizers (noble metal-based, transition metal-based, carbon-based, and silicon-based sonosensitizers) display excellent stability, controllable morphology, and multifunctionality, which greatly expand their application in SDT. In this review, the possible mechanisms of SDT including the cavitation effect and reactive oxygen species generation are briefly discussed. Then, the recent advances in inorganic sonosensitizers are systematically summarized and their formulations and antitumor effects, particularly highlighting the strategies for optimizing the therapeutic efficiency, are outlined. The challenges and future perspectives for developing state-of-the-art sonosensitizers are also discussed. It is expected that this review will shed some light on future screening of decent inorganic sonosensitizers for SDT.

Boosting the capacity and stability of a MoO3 cathode via valence regulation and polypyrrole coating for a rechargeable Zn ion battery.

Molybdenum trioxide (MoO3) is emerging as a hugely competitive cathode material for aqueous zinc ion batteries (ZIBs) for its high theoretical capacity and electrochemical activity. Nevertheless, owing to its undesirable electronic transport capability and poor structural stability, the practical capacity and cycling performance of MoO3 are yet unsatisfactory, which greatly blocks its commercial use. In this work, we report an effective approach to first synthesise nanosized MoO3-x materials to provide more active specific surface areas, while improving the capacity and cycle life of MoO3 by introducing low valence Mo and coated polypyrrole (PPy). MoO3 nanoparticles with low-valence-state Mo and PPy coating (denoted as MoO3-x@PPy) are synthesized via a solvothermal method and subsequent electrodeposition process. The as-prepared MoO3-x@PPy cathode delivers a high reversible capacity of 212.4 mA h g-1 at 1 A g-1 with good cycling life (more than 75% capacity retention after 500 cycles). In contrast, the original commercial MoO3 sample only obtains a capacity of 99.3 mA h g-1 at 1 A g-1, and a cycling stability of 10% capacity retention over 500 cycles. Additionally, the fabricated Zn//MoO3-x@PPy battery obtains a maximum energy density of 233.6 W h kg-1 and a power density of 11.2 kW kg-1. Our results provide an efficient and practical approach to enhance commercial MoO3 materials as high-performance cathodes for AZIBs.

Tendency Regulation of Competing Reactions Toward Highly Reversible Tin Anode for Aqueous Alkaline Batteries.

Investigating dendrite-free stripping/plating anodes is highly significant for advancing the practical application of aqueous alkaline batteries. Sn has been identified as a promising candidate for anode material, but its deposition/dissolution efficiency is hindered by the strong electrostatic repulsion between Sn(OH)3 - and the substrate. Herein, this work constructs a nondense copper layer which serves as stannophile and hydrogen evolution inhibitor to adjust the tendency of competing reactions on Sn foil surface, thus achieving a highly reversible Sn anode. The interactions between the deposited Sn and the substrates are also strengthened to prevent shedding. Notably, the ratio of Sn redox reaction is significantly boosted from ≈20% to ≈100%, which results in outstanding cycling stability over 560 h at 10 mA cm-2 . A Sn//Ni(OH)2 battery device is also demonstrated with capacities from 0.94 to 22.4 mA h cm-2 and maximum stability of 1800 cycles.

Manipulating Molecular Structure to Trigger Ultrafast and Long-Life Potassium Storage of Fe0.4 Ni0.6 S Solid Solution.

Currently, the main obstacle to the widespread utilization of metal chalcogenides (MSx ) as anode for potassium-ion batteries (PIBs) is their poor rate capability and inferior cycling stability as a result of the undesirable electrical conductivity and severe pulverization of the nanostructure during large K-ions intercalation-extraction processes. Herein, an ultrafast and long-life potassium storage of metal chalcogenide is rationally demonstrated by employing Fe0.4 Ni0.6 S solid-solution (FNS/C) through molecular structure engineering. Benefiting from improved electroactivity and intense interactions within the unique solid solution phase, the electrical conductivity and structure durability of Fe0.4 Ni0.6 S are vastly improved. As anticipated, the FNS/C electrode delivers superior rate properties (538.7 and 210.5 mAh g-1 at 0.1 and 10 A g-1 , respectively) and long-term cycle stability (180.8 mAh g-1 at 5 A g-1 after 2000 cycles with a capacity decay of 0.011% per cycle). Moreover, the potassium storage mechanisms of Fe0.4 Ni0.6 S solid solution are comprehensively revealed by several in situ characterizations and theoretical calculations. This innovative molecular structure engineering strategy opens avenues to achieve high-quality metal chalcogenides for future advanced PIBs.

Sodium Ion Pre-Intercalation of δ-MnO2 Nanosheets for High Energy Density Aqueous Zinc-Ion Batteries.

With the merits of low cost, environmental friendliness and rich resources, manganese dioxide is considered to be a promising cathode material for aqueous zinc-ion batteries (AZIBs). However, its low ion diffusion and structural instability greatly limit its practical application. Hence, we developed an ion pre-intercalation strategy based on a simple water bath method to grow in situ δ-MnO2 nanosheets on flexible carbon cloth substrate (MnO2), while pre-intercalated Na+ in the interlayer of δ-MnO2 nanosheets (Na-MnO2), which effectively enlarges the layer spacing and enhances the conductivity of Na-MnO2. The prepared Na-MnO2//Zn battery obtained a fairly high capacity of 251 mAh g-1 at a current density of 2 A g-1, a satisfactory cycle life (62.5% of its initial capacity after 500 cycles) and favorable rate capability (96 mAh g-1 at 8 A g-1). Furthermore, this study revealed that the pre-intercalation engineering of alkaline cations is an effective method to boost the properties of δ-MnO2 zinc storage and provides new insights into the construction of high energy density flexible electrodes.

One-Pot Synthesis of NiSe2 with Layered Structure for Nickel-Zinc Battery.

Transition metal organic framework materials and their selenides are considered to be one of the most promising cathode materials for nickel-zinc (denoted as Ni-Zn) batteries due to their low cost, environmental friendliness, and controllable microstructure. Yet, their low capacity and poor cycling performance severely restricts their further development. Herein, we developed a simple one-pot hydrothermal process to directly synthesize NiSe2 (denotes as NiSe2-X based on the molar amount of SeO2 added) stacked layered sheets. Benefiting from the peculiar architectures, the fabricated NiSe2-1//Zn battery based on NiSe2 and the Zn plate exhibits a high specific capacity of 231.6 mAh g-1 at 1 A g-1, and excellent rate performance (162.8 mAh g-1 at 10 A g-1). In addition, the NiSe2//Zn battery also presents a satisfactory cycle life at the high current density of 8 A g-1 (almost no decay compared to the initial specific capacity after 1000 cycles). Additionally, the battery device also exhibits a satisfactory energy density of 343.2 Wh kg-1 and a peak power density of 11.7 kW kg-1. This work provides a simple attempt to design a high-performance layered cathode material for aqueous Ni-Zn batteries.