Weakly Polarized Organic Cation-Modified Hydrated Vanadium Oxides for High-Energy Efficiency Aqueous Zinc-Ion Batteries

Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.

Isotype Heterojunction‑Boosted CO_(2) Photoreduction to CO

Photocatalytic conversion of CO_(2) to high-value products plays a crucial role in the global pursuit of carbon–neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to navigate the photocatalytic CO_(2) reduction reaction(CRR).Herein,we elucidate the behaviors of isotype heterojunctions toward photocatalytic CRR over a representative photocatalyst,g-C_(3)N_(4).Impressively,the isotype heterojunctions possess a significantly higher efficiency for the spatial separation and transfer of photogenerated carriers than the single components.Along with the intrinsically outstanding stability,the isotype heterojunctions exhibit an exceptional and stable activity toward the CO_(2) photoreduction to CO.More importantly,by combining quantitative in situ technique with the first-principles modeling,we elucidate that the enhanced photoinduced charge dynamics promotes the production of key intermediates and thus the whole reaction kinetics.

Enhanced Reversible Zinc Ion Intercalation in Deficient Ammonium Vanadate for High-Performance Aqueous Zinc-Ion Battery

Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.

Au-Ag alloy nanoparticles with tunable cavity for plasmon-enhanced photocatalytic H2 evolution

Au-Ag alloy nanoparticles with different cavity sizes have great potential for improving photocatalytic performance due to their tunable plasmon effect.In this study,galvanic replacement was combined with co-reduction with the reaction kinetics processes regulated to rapidly synthesize Au-Ag hollow alloy nanoparticles with tunable cavity sizes.The position of the localized surface plasmon resonance(LSPR)peak could be effectively adjusted between 490 nm and 713 nm by decreasing the cavity size of the Au-Ag hollow nanoparticles from 35 nm to 20 nm.The plasmon-enhanced photocatalytic H2 evolution of alloy nanoparticles with different cavity sizes was investigated.Compared with pure P25(TiO2),intact and thin-shelled Au-Ag hollow nanoparticles(HNPs)-supported photocatalyst exhibited an increase in the photocatalytic H2 evolution rate from 0.48μmol h^−1 to 4μmol h^−1 under full-spectrum irradiation.This improved photocatalytic performance was likely due to the plasmon-induced electromagnetic field effect,which caused strong photogenerated charge separation,rather than the generation of hot electrons.

Building Ultra-Stable and Low-Polarization Composite Zn Anode Interface via Hydrated Polyzwitterionic Electrolyte Construction

Aqueous zinc metal batteries are noted for their costeffectiveness,safety and environmental friendliness.However,the water-induced notorious issues such as continuous electrolyte decomposition and uneven Zn electrochemical deposition remarkably restrict the development of the long-life zinc metal batteries.In this study,zwitterionic sulfobetaine is introduced to copolymerize with acrylamide in zinc perchlorate(Zn(ClO;);)solution.The designed gel framework with hydrophilic and charged groups can firmly anchor water molecules and construct ion migration channels to accelerate ion transport.The in situ generated hybrid interface,which is composed of the organic functionalized outer layer and inorganic Clcontaining inner layer,can synergically lower the mass transfer overpotential,reduce water-related side reactions and lead to uniform Zn deposition.Such a novel electrolyte configuration enables Zn//Zn cells with an ultra-long cycling life of over 3000 h and a low polarization potential(~0.03 V)and Zn//Cu cells with high Coulombic efficiency of 99.18%for 1000 cycles.Full cells matched with MnO;cathodes delivered laudable cycling stability and impressive shelving ability.Besides,the flexible quasi-solid-state batteries which are equipped with the anti-vandalism ability(such as cutting,hammering and soaking)can successfully power the LED simultaneously.Such a safe,processable and durable hydrogel promises significant application potential for long-life flexible electronic devices.

Wire-in-Wire TiO_(2)/C Nanofibers Free-Standing Anodes for Li-Ion and K-Ion Batteries with Long Cycling Stability and High Capacity

Wearable and portable mobile phones play a critical role in the market, and one of the key technologies is the flexible electrode with high specific capacity and excellent mechanical flexibility. Herein, a wire-in-wire TiO_(2)/C nanofibers (TiO_(2) ww/CN) film is synthesized via electrospinning with selenium as a structural inducer. The interconnected carbon network and unique wire- in-wire nanostructure cannot only improve electronic conductivity and induce effective charge transports, but also bring a superior mechanic flexibility. Ulti-mately, TiO_(2) ww/CN film shows outstanding electrochemical performance as free-standing electrodes in Li/K ion batteries. It shows a discharge capacity as high as 303 mAh g^(−1) at 5 A g^(−1) after 6000 cycles in Li half-cells, and the unique structure is well-reserved after long-term cycling. Moreover, even TiO_(2) has a large diffusion barrier of K^(+), TiO_(2) ww/CN film demonstrates excellent perfor-mance (259 mAh g^(−1) at 0.05 A g^(−1) after 1000 cycles) in K half-cells owing to extraordinary pseudocapacitive contribution. The Li/K full cells consisted of TiO_(2) ww/CN film anode and LiFePO_(4)/Perylene-3,4,9,10-tetracarboxylic dianhydride cathode possess outstanding cycling stability and demonstrate practical application from lighting at least 19 LEDs. It is, therefore, expected that this material will find broad applications in portable and wearable Li/K-ion batteries.

Three-Dimensional Self-assembled Hairball-Like VS4 as High-Capacity Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)are considered to be attractive candidates for large-scale energy storage systems because of their rich earth abundance and consistent performance.However,there are still challenges in developing desirable anode materials that can accommodate rapid and stable insertion/extraction of Na+and can exhibit excellent electrochemical performance.Herein,the self-assembled hairball-like VS4 as anodes of SIBs exhibits high discharge capacity(660 and 589 mAh g−1 at 1 and 3 A g−1,respectively)and excellent rate property(about 100%retention at 10 and 20 A g−1 after 1000 cycles)at room temperature.Moreover,the VS4 can also exhibit 591 mAh g−1 at 1 A g−1 after 600 cycles at 0°C.An unlike traditional mechanism of VS4 for Na+storage was proposed according to the dates of ex situ characterization,cyclic voltammetry,and electrochemical kinetic analysis.The capacities of the final stabilization stage are provided by the reactions of reversible transformation between Na2S and S,which were considered the reaction mechanisms of Na–S batteries.This work can provide a basis for the synthesis and application of sulfur-rich compounds in fields of batteries,semiconductor devices,and catalysts.

Oxygen-deficient TiO_(2) Yolk-shell Spheres for Enhanced Lithium Storage Properties

Anatase TiO_(2) is a promising anode material for lithium-ion batteries(LIBs)owing to its low cost and stability.However,the intrinsically kinetic limits seriously hindered its lithium-ion storage capability.Here we present that anatase TiO_(2) with rich oxygen vacancies can enhance its lithium-ion storage performance.We synthesize anatase TiO_(2) with well-retained hierarchical structure by annealing the H_(2)Ti_(5)O_(11)·3H_(2)O yolk-shell spheres precursor in nitrogen atmosphere.EPR and XPS data evidence that the oxygen-deficient environment could generate abundant oxygen vacancies in the as-derived anatase TiO_(2),which leads to improved electron conductivity and reduced charge-transfer resistance.The rich oxygen vacancies and high structural integrity of the hierarchical yolk-shell spheres enable the as-derived anatase TiO_(2) yolk-shell spheres with a high specific capacity of 280 mAh g^(-1) at 100 mA g^(-1) and 71%of capacity retention after 5000 cycles at 2 A g^(-1).

Electrophoretic Deposition of Titanium Oxide Nanoparticle Films for Dye-Sensitized Solar Cell Applications

Films of titanium oxide nanocrystalline particles (P25) were deposited using an electrophoretic deposition. The film’s characteristics were tuned for applications in dye-sensitized solar cells. Electrophoretic deposition allows control of film characteristics such as porosity and thickness by changing deposition parameters, such as the electric field and deposition time. To increase the efficiency of the dye-sensitized solar cells with films created using electrophoretic deposition, the problem of an electrolyte contamination in the film, which occurred during deposition, was addressed. With the proper chemical post treatment, efficiency of 2.93% with fill factor of 0.55 was obtained when the films were annealed at 450℃. A low annealing temperature of 150℃ resulted in efficiencys of 1.99% with fill factor of 0.68. When the P25 was replaced by hydrothermally fabricated titanium oxide nanocrystalline particles, efficiency of 4.91% with fill factor of 0.55 was obtained.

The Role of Oxide Thin Layer in Inverted Structure Polymer Solar Cells

The role of wide band gap oxide thin layer in inverted structure polymer solar cells was investigated by employing oxide films of TiO2 and Nb2O5approximately 10 nm in thickness deposited onto FTO substrates. The experimental results demonstrated that the thin oxide layer serving to separate the electron collecting electrode and the photoactive film of a blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) was necessary to promote the formation of continuous uniform PCBM film to block holes in P3HT from being recombined with electrons in collecting electrode. A use of TiO2 buffer layer leads to power conversion efficiency as high as 2.8%. As for Nb2O5, in spite the fact that its conduction band is higher than the LUMO level of PCBM polymer acting as electron transport material, a power conversion of 2.7%, which was only slightly different from the 2.8% achieved for the cell employing TiO2. These experimental results suggest a tunneling mechanism for the electrons to transport from the PCBM to collecting electrode over the oxide film, instead of a diffusion through the oxide film arising from either energy or concentration difference of the photogenerated electrons.

Visualization of oxygen vacancies in nanomaterials

Oxygen vacancies are one of the most common defects.Defects are imperfections in the regular geometrical arrangement of the atoms in crystalline solid.There are point defects,linear defects,plane defects and volume defects in crystals.In an elemental crystal,point defects are formed when atoms are removed from the position that should be filled in the crystal,creating vacancies,or when atoms occupy interstitial sites where no atom would ordinarily appear,causing interstitialcy[1].

Superior efficiency and stability of YbO_(x)-enhanced perovskite solar cells

Perovskite solar cells represent a revolutionary class of photovoltaic devices that have gained substantial attention for their exceptional performance and potential to provide an affordable and efficient solution for harnessing solar energy. These cells utilize perovskite-structured materials, typically hybrid organicinorganic lead halide compounds, as the light-absorbing layer.

高倍率水系碲化铋–锌电池的电荷存储机理研究

近十年来,因特有的安全性、低成本和环境友好等特点,水系锌基电池受到了广泛关注.然而,正极材料的反应动力学较差,极大地阻碍了锌电池的发展.近期,铋系的硫属化物在锌电池中展现了优异的电化学性能和巨大的使用潜能.相关研究有待继续开展,以期探明该材料的电化学储能机理,并进一步提升材料的电池性能.在本工作中,采用溶剂热法制备了正六边形的Bi_(2)Te_(3)薄片,并将其用于锌电池的正极材料.通过非原位表征测试和相关电化学分析,我们发现在水系碲化铋–锌电池中存在三个电化学过程:(1)质子嵌入与脱出;(2) Zn_(4)SO_(4)-(OH)_(6)·0.5H_(2)O放电产物的生成与分解;(3)锌离子嵌入与脱出.其中,质子嵌入与脱出占支配地位.因此,相应的碲化铋–锌电池具有较好的倍率性能、循环稳定性和一定的低温电池性能.本工作将有力地推动高性能水系锌电池的发展.

构建具有应变缓冲结构的超细FeS/C复合材料用于持久储锂/钠

FeS因具有较高的比容量和优异的环境友好性,被认为是一种极具竞争力的锂/钠离子电池负极材料.然而,循环过程中缓慢的电荷转移动力学和较大的体积变化阻碍了它的实际应用.本文通过在超薄FeS/C复合材料中构建应变缓冲(气泡膜状)结构,从根本上解决了FeS动力学缓慢和体积变化大的问题.有限元模拟和非原位透射电镜结果验证了气泡膜状碳基质可作为保护壳层缓解FeS的巨大体积变化,还能提高其电子导电性.得益于这种独特的结构设计,该电极材料表现出显著增强的性能.其在5 A g^(-1)下的储锂容量为469 mA h g^(-1),在1 A g^(-1)下循环1500次后的储钠容量为354 mA h g^(-1).此外,由该电极与LiFePO_(4)正极组装的全电池即使在100次循环后也能提供558 mA h g^(-1)的比容量,展现出优异的循环稳定性.这一策略也可应用于其它导电性差、体积变化大的负极材料,以促进高倍率和长寿命电池的发展.

Ultrahigh Li ion diffusivity in anodic SEI suppresses dendrite growth in lithium metal batteries

New chemistry and new materials for high-energy-density batteries are in great demands as advanced portable electronics and long-range electric vehicles require ever increasing energy and power;current lithium(Li)-ion batteries based on graphite anode(a theoretical specific capacity of 372 mA h g^(-1))reach the limited theoretical energy density of 350 W h kg^(-1)[1].

Hole transport layer-free inverted perovskite solar cells with power conversion efficiency exceeding 25%and much improved stability

Organic-inorganic hybrid perovskites possess a unique combination of excellent electronic and photoelectrochemical properties that can be readily tailored by partial or complete substitution of their constituent elements owing to their nonclose packing anion lattice[1,2].Perovskite solar cells(PSCs)employing hybrid perovskites as an active layer have seen rapid improvements and have achieved high power conversion efficiencies(PCEs)now exceeding 25%[2].

Localized Electrons Accelerated Ionic and Charge Transfer for Superior Lithium Storage

The electrochemical energy storage performance is greatly determined by the charge transfer and ion transportation occurring in the electrode materials.Therefore,the enhancement of electric conductivity and ionic mobility is vital for high-performing and stable metal ion batteries.Here,we report the properties of oxygen vacancies(VO)and carbon co-doped TiO_(2) hollow spheres(HS-TiO_(2))and compared them with fully oxidized white TiO_(2) hollow spheres(W-TiO_(2)).Theoretical calculations and experimental results revealed that the introduction of carbon dopant and VO in anatase TiO_(2) reduced the bandgap and the existence of localized electrons,leading to a lower migration barrier of Li ions that promoted faster ion diffusion kinetics,enabling the HS-TiO_(2) with higher reversibility during the insertion and extraction of Li ions than the W-TiO_(2).This HS-TiO_(2) delivered superior lithium storage properties with a specific discharge capacity of 214.6 mAh g^(-1) for the 100th cycle at 200 mA g^(-1) and 116.3 mAh g^(-1) over 2000 cycles at a high rate of 2 A g^(-1).

Necklace-like Si@C nano?bers as robust anode materials for high performance lithium ion batteries

Silicon is believed to be a promising anode material for lithium ion batteries because of its highest theoretical capacity and low discharge potential. However, severe pulverization and capacity fading caused by huge volume change during cycling limits its practical application. In this work, necklace-like N-doped carbon wrapped mesoporous Si nanofibers(NL-Si@C) network has been synthesized via electrospinning method followed by magnesiothermic reduction reaction process to suppress these issues. The mesoporous Si nanospheres are wrapped with N-doped carbon shells network to form yolk-shell structure.Interestingly, the distance of adjacent Si@C nanospheres can be controllably adjusted by different addition amounts of SiO_2 nanospheres. When used as an anode material for lithium ion batteries, the NL-Si@C-0.5 exhibits best cycling stability and rate capability. The excellent electrochemical performances can be ascribed to the necklace-like network structure and N-doped carbon layers, which can ensure fast ions and electrons transportation, facilitate the electrolyte penetration and provide finite voids to allow large volume expansion of inner Si nanoparticles. Moreover, the protective carbon layers are also beneficial to the formation of stable solid electrolyte interface film.

Integration of micro-supercapacitors with triboelectric nanogenerators for a flexible self-charging power unit

The rapid development of portable and wearable electronic devices has increased demand for flexible and efficient energy harvesting and storage units. Conventionally, these are built and used separately as discrete components. Herein, we propose a simple and cost-effective laser engraving technique for fabricating a flexible self-charging micro-supercapacitor power unit （SCMPU）, by integrating a triboelectric nanogenerator （TENG） and a micro-supercapacitor （MSC） array into a single device. The SCMPU can be charged directly by ambient mechanical motion. We demonstrate the ability of the SCMPU to continuously power light-emitting diodes and a commercial hygrothermograph. This inves- tigation may promote the development of sustainable self-powered systems and provide a promising new research application for supercapacitors.

Metal-organic framework-derived porous shuttle-like vanadium oxides for sodium-ion battery application

Vanadium oxides with a layered structure are promising candidates for both lithium-ion batteries and sodium-ion batteries （SIBs）. The self-template approach, which involves a transformation from metal-organic frameworks （MOFs） into porous metal oxides, is a novel and effective way to achieve desirable electrochemical performance. In this stud~ porous shuttle-like vanadium oxides （i.e., V205, V203/C） were successfully prepared by using MIL-88B （V） as precursors with a specific calcination process. As a proof-of-concept application, the as- prepared porous shuttle-like VaOdC was used as an anode material for SIBs. The porous shuttle-like V203/C, which had an inherent layered structure with metallic behavior, exhibited excellent electrochemical properties. Remarkable rate capacities of 417, 247, 202, 176, 164, and 149 mAh.g-1 were achieved at current densities of 50, 100, 200, 500, 1,000, and 2,000 mA.g-1, respectively. Under cycling at 2 A.g-1, the specific discharge capacity reached 181 mAh.g-1, with a low capacity fading rate of 0.032% per cycle after 1,000 cycles. Density functional theory calculation results indicated that Na ions preferred to occupy the interlamination rather than the inside of each layer in the V203. Interestingly, the special layered structure with a skeleton of dumbbell-like V-V bonds and metallic behavior was maintained after the insertion of Na ions, which was beneficial for the cycle performance. We consider that the MOF precursor of MIL-88B （V） can be used to synthesize other porous V-based materials for various applications.