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Solid-state polymer-based electrolytes (SSPEs) exhibit great possibilities in realizing high-energy-density solid-state lithium metal batteries (SSLMBs). However, current SSPEs suffer from low ionic conductivity and unsatisfactory interfacial compatibility with metallic Li because of the high crystallinity of polymers and sluggish Li+ movement in SSPEs. Herein, differing from common strategies of copolymerization, a new strategy of constructing a high-entropy SSPE from multivariant polymeric ligands is proposed. As a protocol, poly(vinylidene fluoride-co-hexafluoropropylene) (PH) chains are grafted to the demoed polyethylene imine (PEI) with abundant -NH2 groups via a click-like reaction (HE-PEIgPHE). Compared to a PH-based SSPE, our HE-PEIgPHE shows a higher modulus (6.75 vs 5.18 MPa), a higher ionic conductivity (2.14 × 10-4 vs 1.03 × 10-4 S cm-1), and a higher Li+ transference number (0.55 vs 0.42). A Li|HE-PEIgPHE|Li cell exhibits a long lifetime (1500 h), and a Li|HE-PEIgPHE|LiFePO4 cell delivers an initial capacity of 160 mAh g-1 and a capacity retention of 98.7%, demonstrating the potential of our HE-PEIgPHE for the SSLMBs.
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The structure of solvated Li+ has a significant influence on the electrolyte/electrode interphase (EEI) components and desolvation energy barrier, which are two key factors in determining the Li+ diffusion kinetics in lithium metal batteries. Herein, the "solvent activity" concept is proposed to quantitatively describe the correlation between the electrolyte elements and the structure of solvated Li+. Through fitting the correlation of the electrode potential and solvent concentration, we suggest a "low-activity-solvent" electrolyte (LASE) system for deriving a stable inorganic-rich EEI. Nano LiF particles, as a model, were used to capture free solvent molecules for the formation of a LASE system. This advanced LASE not only exhibits outstanding antidendrite growth behavior but also delivers an impressive performance in Li/LiNi0.8Co0.1Mn0.1O2 cells (a capacity of 169 mAh g-1 after 250 cycles at 0.5 C).
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Na3V2(PO4)2F3 is recognized as a promising cathode for high energy density sodium-ion batteries due to its high average potential of â¼3.95 V (vs Na/Na+). A high-voltage-resistant electrolyte is of high importance due to the long duration of 4.2 V (vs Na/Na+) when improving cyclability. Herein, a targeted electrolyte containing additives with two -C≡N groups like succinonitrile has been designed. In this design, one -C≡N group is accessible to the solvation sheath and enables the other -C≡N in dinitrile being exposed and subsequently squeezed into the electric double layer. Then, the squeezed -C≡N group is prone to a preferential adsorption on the electrode surface prior to the exposed -CH2/-CH3 in Na+-solvent and oxidized to construct a stable and electrically insulating interface enriched CN-/NCO-/Na3N. The Na3V2(PO4)2F3-based sodium-ion batteries within a high-voltage of 2-4.3 V (vs Na/Na+) can accordingly achieve an excellent cycling stability (e.g., 95.07% reversible capacity at 1 C for 1,5-dicyanopentane and 98.4% at 2 C and 93.0% reversible capacity at 5 C for succinonitrile after 1000 cycles). This work proposes a new way to design high-voltage electrolytes for high energy density sodium-ion batteries.
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Traditional ethylene carbonate (EC)-based electrolytes constrain the applications of silicon carbon (Si-C) anodes under fast-charging and low-temperature conditions due to sluggish Li+ migration kinetics and unstable solid electrolyte interphase (SEI). Herein, inspired by the efficient water purification and soil stabilization of aquatic plants, a stable SEI with a 3D desolvation interface is designed with gel polymer electrolyte (GPE), accelerating Li+ desolvation and migration at the interface and within stable SEI. As demonstrated by theoretical simulations and experiment results, the resulting poly(1,3-dioxolane) (PDOL), prepared by in situ ring-opening polymerization of 1,3-dioxolane (DOL), creates a 3D desolvation area, improving the Li+ desolvation at the interface and yielding an amorphous GPE with a high Li+ ionic conductivity (5.73 mS cm-1). Furthermore, more anions participate in the solvated structure, forming an anion-derived stable SEI and improving Li+ transport through SEI. Consequently, the Si-C anode achieves excellent rate performance with GPE at room temperature (RT) and low temperature (-40 °C). The pouch full cell coupled with LiFePO4 cathode obtains 97.42 mAh g-1 after 500 cycles at 5 C/5 C. This innovatively designed 3D desolvation interface and SEI represent significant breakthroughs for developing fast-charging and low-temperature batteries.
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Sn-based anodes are promising high-capacity anode materials for low-cost lithium ion batteries. Unfortunately, their development is generally restricted by rapid capacity fading resulting from large volume expansion and the corresponding structural failure of the solid electrolyte interphase (SEI) during the lithiation/delithiation process. Herein, heterostructural core-shell SnO2-layer-wrapped Sn nanoparticles embedded in a porous conductive nitrogen-doped carbon (SOWSH@PCNC) are proposed. In this design, the self-sacrificial Zn template from the precursors is used as the pore former, and the LiF-Li3N-rich SEI modulation layer is motivated to average uniform Li+ flux against local excessive lithiation. Meanwhile, both the chemically active nitrogen sites and the heterojunction interfaces within SnO2@Sn are implanted as electronic/ionic promoters to facilitate fast reaction kinetics. Consequently, the as-converted SOWSH@PCNC electrodes demonstrate a significantly boosted Li+ capacity of 961 mA h g-1 at 200 mA g-1 and excellent cycling stability with a low capacity decaying rate of 0.071% after 400 cycles at 500 mA g-1, suggesting their great promise as an anode material in high-performance lithium ion batteries.
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Lithium metal anode possesses overwhelming capacity and low potential but suffers from dendrite growth and pulverization, causing short lifespan and low utilization. Here, a fundamental novel insight of using single-atomic catalyst (SAC) activators to boost lithium atom diffusion is proposed to realize delocalized deposition. By combining electronic microscopies, time-of-flight secondary ion mass spectrometry, theoretical simulations, and electrochemical analyses, we have unambiguously depicted that the SACs serve as kinetic activators in propelling the surface spreading and lateral redistribution of the lithium atoms for achieving dendrite-free plating morphology. Under the impressive capacity of 20 mA h cm-2, the Li modified with SAC-activator exhibits a low overpotential of â¼50 mV at 5 mA cm-2, a long lifespan of 900 h, and high Coulombic efficiencies during 150 cycles, much better than most literature reports. The so-coupled lithium-sulfur full battery delivers high cycling and rate performances, showing great promise toward the next-generation lithium metal batteries.
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High interconversion energy barriers, depressive reaction kinetics of sulfur species, and sluggish Li+ transport inhibit the wide development of high-energy-density lithium sulfur (Li-S) batteries. Herein, differing from random mixture of selected catalysts, the composite catalyst with outer delocalized isoelectronic heterostructure (DIHC) is proposed and optimized, enhancing the catalytic efficiency for decreasing related energy barriers. As a proof-of-content, the FeCoOx Sy composites with different degrees of sulfurization are fabricated by regulating atoms ratio between O and S. The relationship of catalytic efficiency and principal mechanism in DIHCs are deeply understood from electrochemical experiments to in situ/operando spectral spectroscopies i.e., Raman, XRD and UV/Vis. Consequently, the polysulfide conversion and Li2 S precipitation/dissolution experiments strongly demonstrate the volcano-like catalytic efficiency of various DIHCs. Furthermore, the FeCoOx Sy -decorated cell delivers the high performance (1413â mAh g-1 at 0.1â A g-1 ). Under the low electrolyte/sulfur ratio, the high loading cell stabilizes the areal capacity of 6.67â mAh cm-2 at 0.2â A g-1 . Impressively, even resting for about 17â days for possible polysulfide shuttling, the high-mass-loading FeCoOx Sy -decorated cell stabilizes the same capacity, showing the practical application of the DIHCs in improving catalytic efficiency and reaching high electrochemical performance.
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The electrocatalytic C-N coupling for one-step urea synthesis under ambient conditions serves as the promising alternative to the traditional urea synthetic protocol. However, the hydrogenation of intermediate species hinders the efficient urea synthesis. Herein, the oxygen vacancy-enriched CeO2 was demonstrated as the efficient electrocatalyst with the stabilization of the crucial intermediate of *NO via inserting into vacant sites, which is conducive to the subsequent C-N coupling process rather than protonation, whereas the poor selectivity of C-N coupling with protonation was observed on the vacancy-deficient catalyst. The oxygen vacancy-mediated selective C-N coupling was distinguished and validated by the in situ sum frequency generation spectroscopy. The introduction of oxygen vacancies tailors the common catalyst carrier into an efficient electrocatalyst with a high urea yield rate of 943.6 mg h-1 g-1, superior than that of partial noble-metal-based electrocatalysts. This work provides novel insights into the catalyst design and developments of coupling systems.
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Oxigênio , Catálise , HidrogenaçãoRESUMO
Lithium metal electrodes have shown great promise for high capacity and the lowest potential. However, wide application is restricted by uncontrollable plating/stripping lithium behaviors, an uneven solid electrolyte interphase, and a lithium dendrite. Herein, the highly active single metal atom anchored in vacant catalyst is synthesized on the hierarchical porous nanocarbon (SACo/ADFS@HPSC). Acting as an artificial protective modulation layer on the lithium surface, the numerous atomic sites show the superiority in modulating lithium ion behaviors and smoothing the lithium surface without dendrite growth. As a consequence, the SACo/ADFS@HPSC-modified Li electrode lowers nucleation barrier (15 mV), extends the smooth plating lifespan (1600 h), and improves Coulombic efficiency, significantly accelerating the horizonal deposition of plated lithium. Coupled with a sulfur cathode, the fabricated pouch cell with 5.4 mg cm-2 delivers a high capacity of 3.78 mA h cm-2 corresponding to 1505 Wh kg-1, showing the promising practical application.
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Three-dimensional (3D) perovskites have been demonstrated as an effective strategy to achieve efficient light-emitting diodes (LEDs) at high brightness. However, most 3D perovskite LEDs still suffer from serious efficiency roll-off. Here, using FAPbI3 as a model system, we find that the main reason for efficiency droop and degradation in 3D perovskite LEDs is defects and the ion migration under electrical stress. By introducing bifunctional-molecule 3-chlorobenzylamine additive into the perovskite precursor solution, the detrimental effects can be significantly suppressed through the growth of high crystalline perovskites and defect passivation. This approach leads to bright near-infrared perovskite LEDs with a peak external quantum efficiency of 16.6%, which sustains 80% of its peak value at a high current density of 460 mA cm-2, corresponding to a high brightness of 300 W sr-1 m-2. Moreover, the device exhibits a record half-lifetime of 49 h under a constant current density of 100 mA cm-2.
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Organic electrical gas sensors have been developed for many decades because of their high sensitivity and selectivity. However, their industrialization is severely hindered by their intrinsic humidity susceptibility and poor recovery. Conventional organic sensory materials can only operate at room temperature owing to their weak intermolecular interactions. Herein, we demonstrate using a croconate polymer (poly-4,4'-biphenylcroconate) that the "ion-in-conjugation" concept enables organic gas sensors to operate at 100 °C and 70 % relative humidity with almost complete recovery. The fabricated sensor had a parts-per-billion (ppb) detection limit for NO2 and showed the highest sensitivity (2526â ppm-1 at 40â ppb) of all reported NO2 chemiresistive sensors. Furthermore, charge transfer increased with temperature. Theoretical calculations and in situ FTIR spectra confirmed the ion-in-conjugation-inspired hydrogen bond as key for excellent sensitivity. A NO2 alarm system was assembled to demonstrate the feasibility of this sensor.
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2,5-Furandicarboxylic acid was obtained from the electrooxidation of 5-hydroxymethylfurfural (HMF) with non-noble metal-based catalysts. Moreover, combining the biomass oxidation with the hydrogen evolution reaction (HER) increased the energy conversion efficiency of an electrolyzer and also generated value-added products at both electrodes. Here, the reaction pathway on the surface of a carbon-coupled nickel nitride nanosheet (Ni3 N@C) electrode was evaluated by surface-selective vibrational spectroscopy using sum frequency generation (SFG) during the electrochemical oxidation. The Ni3 N@C electrode shows catalytic activities for HMF oxidation and the HER. As the first in situ SFG study on transition-metal nitride for the electrooxidation upgrade of HMF, this work not only demonstrates that the reaction pathway of electrochemical oxidation but also provides an opportunity for nonprecious metal nitrides to simultaneously upgrade biomass and produce H2 under ambient conditions.
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Lanthanide (Ln(3+) )-doped upconversion nanoparticles (UCNPs) as a new generation of multimodal bioprobes have attracted great interest for theranostic purpose. Herein, red emitting nonstoichiometric Na0.52 YbF3.52 :Er UCNPs of high luminescence intensity and color purity are synthesized via a facile solvothermal method. The red UC emission from the present nanophosphors is three times more intense than the well-known green emission from the ≈30 nm sized hexagonal-phase NaYF4 :Yb,Er UCNPs. By utilizing Na0.52 YbF3.52 :Er@SrF2 UCNPs as multifunctional nanoplatforms, highly efficient in vitro and in vivo 915 nm light-triggered photodynamic therapies are realized for the first time, with dramatically diminished overheating yet similar therapeutic effects in comparison to those triggered by 980 nm light. Moreover, by virtue of the high transverse relaxivity (r 2 ) and the strong X-ray attenuation ability of Yb(3+) ions, these UCNPs also demonstrate good performances as contrast agents for high contrast magnetic resonance and X-ray computed tomography dual-modal imaging. Our research shows the great potential of the red emitting Na0.52 YbF3.52 :Er UCNPs for multimodal imaging-guided photodynamic therapy of tumors.
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Nanopartículas/química , Fotoquimioterapia/métodos , Tomografia Computadorizada por Raios X/métodos , Meios de Contraste/química , Fluoretos/química , Luminescência , Itérbio/químicaRESUMO
Most simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)6 ][AlCl4 ]2 was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5â V vs. Mg), and high ionic conductivity (8.5â mS cm(-1) ). Magnesium/sulfur cells employing the as-prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3-2.6â V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.
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Lithium metal batteries (LMBs) offer significant advantages in energy density and output voltage, but they are severely limited by uncontrollable Li dendrite formation resulting from uneven Li+ behaviors and high reactivity with potential co-solvent plating. Herein, to uniformly enhance the Li behaviors in desolvation and diffusion, the local Li+ solvation shell structure is optimized by constructing an anion-braking separator, hence dynamically reducing the self-amplifying behavior of dendrites. As a prototypal, two-dimensional lithiated-montmorillonite (LiMMT) is blade-coated on the commercial separator, where abundant -OH groups as Lewis acidic sites and electron acceptors could selectively adsorb corresponding FSI- anions, regulating the solvation shell structure and restricting their migration. Meanwhile, the weakened anion mobility delays the time of breaking electrical neutrality, and the Li nucleation density is quantified through the respective experimental, theoretical and spectroscopical results, providing a comprehensive understanding of modifying anion and cation behaviors on dendritic growth suppression. As anticipated, a long Li plating/stripping lifespan up to 1800 h and a significantly increased average Coulombic efficiency of 98.8% are achieved under 3.0 mAh cm-2. The fabricated high-loading Li-LFP or Li-NCM523 full-cells display the cycle durability with enhanced capacity retention of nearly 100%, providing the instructive guide towards realizing dendrite-free LMBs.
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Low-temperature rechargeable aqueous zinc metal batteries (AZMBs) as highly promising candidates for energy storage are largely hindered by huge desolvation energy barriers and depressive Zn2+ migration kinetics. In this work, a superfast zincophilic ion conductor of layered zinc silicate nanosheet (LZS) is constructed on a metallic Zn surface, as an artificial layer and ion diffusion accelerator. The experimental and simulation results reveal the zincophilic ability and layer structure of LZS not only promote the desolvation kinetics of [Zn(H2O)6]2+ but also accelerate the Zn2+ transport kinetics across the anode/electrolyte interface, guiding uniform Zn deposition. Benefiting from these features, the LZS-modified Zn anodes showcase long-time stability (over 3300 h) and high Coulombic efficiency with ≈99.8% at 2 mA cm-2, respectively. Even reducing the environment temperature down to 0 °C, ultralong cycling stability up to 3600 h and a distinguished rate performance are realized. Consequently, the assembled Zn@LZS//V2O5-x full cells deliver superior cyclic stability (344.5 mAh g-1 after 200 cycles at 1 A g-1) and rate capability (285.3 mAh g-1 at 10 A g-1) together with a low self-discharge rate, highlighting the bright future of low-temperature AZMBs.
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High-energy-density lithium metal batteries (LMBs) are limited by reaction or diffusion barriers with dissatisfactory electrochemical kinetics. Typical conversion-type lithium sulfur battery systems exemplify the kinetic challenges. Namely, before diffusing or reacting in the electrode surface/interior, the Li(solvent)x + dissociation at the interface to produce isolated Li+, is usually a prerequisite fundamental step either for successive Li+ "reduction" or for Li+ to participate in the sulfur conversions, contributing to the related electrochemical barriers. Thanks to the ideal atomic efficiency (100 at%), single atom catalysts (SACs) have gained attention for use in LMBs toward resolving the issues caused by the five types of barrier-restricted processes, including polysulfide/Li2S conversions, Li(solvent)x + desolvation, and Li0 nucleation/diffusion. In this perspective, the tandem reactions including desolvation and reaction or plating and corresponding catalysis behaviors are introduced and analyzed from interface to electrode interior. Meanwhile, the principal mechanisms of highly efficient SACs in overcoming specific energy barriers to reinforce the catalytic electrochemistry are discussed. Lastly, the future development of high-efficiency atomic-level catalysts in batteries is presented.
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AlGaN/GaN high-electron-mobility transistors (HEMTs) are widely used in high-frequency and high-power applications owing to the high two-dimensional electron gas (2DEG) concentration. However, the microscopic origin of the 2DEG remains unclear. This hinders the development of device fabrication technologies, such as threshold voltage modulation, current collapse suppression, and 2DEG concentration enhancement technologies, as well as AlGaN/GaN sensors with very high sensitivity to polar liquids. To clarify the 2DEG microscopic origin, we studied the effects of gas molecules on AlGaN/GaN surfaces through various experiments and first-principles calculations. The results indicated that the adsorption of gas molecules on the AlGaN/GaN surface is an important phenomenon, clarifying the microscopic origin of the 2DEG. This study elucidates the properties of AlGaN/GaN heterojunctions and promotes the development of new fabrication technologies for AlGaN/GaN devices.
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Lithium-sulfur (Li-S) batteries exhibit unparalleled theoretical capacity and energy density than conventional lithium ion batteries, but they are hindered by the dissatisfactory "shuttle effect" and the sluggish conversion kinetics owing to the low lithium ion transport kinetics, resulting in rapid capacity fading. Herein, a catalytic two-dimensional heterostructure composite is prepared by evenly grafting mesoporous carbon on the MXene nanosheet (denoted as OMC-g-MXene), serving as interfacial kinetic accelerators in Li-S batteries. In this design, the grafted mesoporous carbon in the heterostructure can not only prevent the stack of MXene nanosheets with the enhanced mechanical property but also offer a facilitated pump for accelerating ion diffusion. Meanwhile, the exposed defect-rich OMC-g-MXene heterostructure inhibits the polysulfide shuttling with chemical interactions between OMC-g-MXene and polysulfides and thus simultaneously enhances the electrochemical conversion kinetics and efficiency, as fully investigated by in situ/ex situ characterizations. Consequently, the cells with OMC-g-MXene ion pumps achieve a high cycling capacity (966 mAh g-1 at 0.2 C after 200 cycles), a superior rate performance (537 mAh g-1 at 5 C), and an ultralow decaying rate of 0.047% per cycle after 800 cycles at 1 C. Even employed with a high sulfur loading of 7.08 mg cm-2 under lean electrolyte, an ultrahigh areal capacity of 4.5 mAh cm-2 is acquired, demonstrating a future practical application.
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Two-dimensional covalent organic frameworks (2D COFs) are promising for gas sensing owing to the large surface area, abundant active sites, and their semiconducting nature. However, 2D COFs are usually produced in the form of insoluble micro-crystallites. Their poor contacts between grain boundaries severely suppress the conductivity, which are too low for chemresistive gas sensing. Here, we demonstrate that halide perovskites can be employed as electric glues to bond 2D COF crystallites to improve their conductivity by two orders of magnitude, activating them to detect NO2 with high selectivity and sensitivity. Resonant microcantilever, grand canonical Monte Carlo, density functional theory and sum-frequency generation analyses prove that 2D COFs can enrich and transfer electrons to NO2 molecules, leading to increased device conductivity. This work provides a facile approach for improving the conductivity of polycrystalline 2D COF films and may expand their applications in semiconductor devices, such as sensors, resistors, memristors and field-emission transistors.