High-Entropy Polymer Electrolytes Derived from Multivalent Polymeric Ligands for Solid-State Lithium Metal Batteries with Accelerated Li+ Transport.

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.

Superfast Zincophilic Ion Conductor Enables Rapid Interfacial Desolvation Kinetics for Low-Temperature Zinc Metal Batteries.

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.

Superior Li+ Kinetics by "Low-Activity-Solvent" Engineering for Stable Lithium Metal Batteries.

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).

Electrolyte Design with Dual -C≡N Groups Containing Additives to Enable High-Voltage Na3V2(PO4)2F3-Based Sodium-Ion Batteries.

Na3V2(PO4)2F3 is recognized as a promising cathode for high energy density sodium-ion batteries due to its high average potential of ∼3.95 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.

Atom-Level Tandem Catalysis in Lithium Metal Batteries.

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.

Constructing an Anion-Braking Separator to Regulate Local Li+ Solvation Structure for Stabilizing Lithium Metal Batteries.

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.

Delocalized Isoelectronic Heterostructured FeCoOx Sy Catalysts with Tunable Electron Density for Accelerated Sulfur Redox Kinetics in Li-S batteries.

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 (1413 mAh g-1 at 0.1 A g-1 ). Under the low electrolyte/sulfur ratio, the high loading cell stabilizes the areal capacity of 6.67 mAh cm-2 at 0.2 A g-1 . Impressively, even resting for about 17 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.

Interfacial Modulation of a Self-Sacrificial Synthesized SnO2@Sn Core-Shell Heterostructure Anode toward High-Capacity Reversible Li+ Storage.

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.

Interfacial "Single-Atom-in-Defects" Catalysts Accelerating Li+ Desolvation Kinetics for Long-Lifespan Lithium-Metal Batteries.

The lithium-metal anode is a promising candidate for realizing high-energy-density batteries owing to its high capacity and low potential. However, several rate-limiting kinetic obstacles, such as the desolvation of Li+ solvation structure to liberate Li+ , Li0 nucleation, and atom diffusion, cause heterogeneous spatial Li-ion distribution and fractal plating morphology with dendrite formation, leading to low Coulombic efficiency and depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors to cation vacancy-rich Co1- x S embedded in 3D porous carbon (SAFe/CVRCS@3DPC) is proposed and demonstrated as catalytic kinetic promoters. Numerous free Li ions are electrocatalytically dissociated from the Li+ solvation complex structure for uniform lateral diffusion by reducing desolvation and diffusion barriers via SAFe/CVRCS@3DPC, realizing smooth dendrite-free Li morphologies, as comprehensively understood by combined in situ/ex situ characterizations. Encouraged by SAFe/CVRCS@3DPC catalytic promotor, the modified Li-metal anodes achieve smooth plating with a long lifespan (1600 h) and high Coulombic efficiency without any dendrite formation. Paired with the LiFePO4 cathode, the full cell (10.7 mg cm-2 ) stabilizes a capacity retention of 90.3% after 300 cycles at 0.5 C, signifying the feasibility of using interfacial catalysts for modulating Li behaviors toward practical applications.

Halide Perovskite glues activate two-dimensional covalent organic framework crystallites for selective NO2 sensing.

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.

Ordered Mesoporous Carbon Grafted MXene Catalytic Heterostructure as Li-Ion Kinetic Pump toward High-Efficient Sulfur/Sulfide Conversions for Li-S Battery.

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.

Organic-semiconductor-assisted dielectric screening effect for stable and efficient perovskite solar cells.

Perovskite solar cells (pero-SCs) performance is essentially limited by severe non-radiative losses and ion migration. Although numerous strategies have been proposed, challenges remain in the basic understanding of their origins. Here, we report a dielectric-screening-enhancement effect for perovskite defects by using organic semiconductors with finely tuned molecular structures from the atoms level. Our method produced various perovskite films with high dielectric constant values, reduced charge capture regions, suppressed ion migration, and it provides an efficient charge transport pathway for suppressing non-radiative recombination beyond the passivation effect. The resulting pero-SCs showed a promising power conversion efficiency (PCE) of 23.35% with a high open-circuit voltage (1.22 V); and the 1-cm2 pero-SCs maintained an excellent PCE (21.93%), showing feasibility for scalable fabrication. The robust operational and thermal stabilities revealed that this method paved a new way to understand the degradation mechanism of pero-SCs, promoting the efficiency, stability and scaled fabrication of the pero-SCs.

Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics.

Lithium metal anodes are ideal for realizing high-energy-density batteries owing to their advantages, namely high capacity and low reduction potentials. However, the utilization of lithium anodes is restricted by the detrimental lithium dendrite formation, repeated formation and fracturing of the solid electrolyte interphase (SEI), and large volume expansion, resulting in severe "dead lithium" and subsequent short circuiting. Currently, the researches are principally focused on inhibition of dendrite formation toward extending and maintaining battery lifespans. Herein, we summarize the strategies employed in interfacial engineering and current-collector host designs as well as the emerging electrochemical catalytic methods for evolving-accelerating-ameliorating lithium ion/atom diffusion processes. First, strategies based on the fabrication of robust SEIs are reviewed from the aspects of compositional constituents including inorganic, organic, and hybrid SEI layers derived from electrolyte additives or artificial pretreatments. Second, the summary and discussion are presented for metallic and carbon-based three-dimensional current collectors serving as lithium hosts, including their functionality in decreasing local deposition current density and the effect of introducing lithiophilic sites. Third, we assess the recent advances in exploring alloy compounds and atomic metal catalysts to accelerate the lateral lithium ion/atom diffusion kinetics to average the spatial lithium distribution for smooth plating. Finally, the opportunities and challenges of metallic lithium anodes are presented, providing insights into the modulation of diffusion kinetics toward achieving dendrite-free lithium metal batteries.

Tailoring Electrolyte Solvation for LiF-Rich Solid Electrolyte Interphase toward a Stable Li Anode.

A solid electrolyte interphase (SEI) with robust mechanical property and high ionic conductivity is imperative for high-performance lithium metal batteries since it can efficiently impede the growth of notorious lithium dendrites. However, it is difficult to form such a SEI directly from an electrolyte. In this work, a crowding dilutant modified ionic liquid electrolyte (M-ILE) has been developed for this purpose. Simulations and experiments indicate that the 1,2-difluorobenzene (1,2-dfBen) dilutant not only creates a crowded electrolyte environment to promote the interaction of Li+-FSI-, leading to abundant aggregate ion pairs (AGGs), but also participates in the reduction to construct a robust and high ionic-conductive SEI. With this M-ILE, Li/LiFePO4 cells achieve a capacity retention of 96% over 250 cycles with 9.5 mg cm-2 mass loading, and Li/LiNi0.5Co0.2Mn0.3O2 cells also deliver a discharge capacity of 132 mAh g-1 with a high retention of 88% after 100 cycles. Therefore, the use of a crowding diluent is considered to be an efficient way to construct an advanced SEI for a Li anode.

Lithium Atom Surface Diffusion and Delocalized Deposition Propelled by Atomic Metal Catalyst toward Ultrahigh-Capacity Dendrite-Free Lithium Anode.

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 ∼50 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.

Tuning 4f-Center Electron Structure by Schottky Defects for Catalyzing Li Diffusion to Achieve Long-Term Dendrite-Free Lithium Metal Battery.

Lithium metal is considered as the most prospective electrode for next-generation energy storage systems due to high capacity and the lowest potential. However, uncontrollable spatial growth of lithium dendrites and the crack of solid electrolyte interphase still hinder its application. Herein, Schottky defects are motivated to tune the 4f-center electronic structures of catalysts to provide active sites to accelerate Li transport kinetics. As experimentally and theoretically confirmed, the electronic density is redistributed and affected by the Schottky defects, offering numerous active catalytic centers with stronger ion diffusion capability to guide the horizontal lithium deposition against dendrite growth. Consequently, the Li electrode with artificial electronic-modulation layer remarkably decreases the barriers of desolvation, nucleation, and diffusion, extends the dendrite-free plating lifespan up to 1200 h, and improves reversible Coulombic efficiency. With a simultaneous catalytic effect on the conversions of sulfur species at the cathodic side, the integrated Li-S full battery exhibits superior rate performance of 653 mA h g-1 at 5 C, high long-life capacity retention of 81.4% at 3 C, and a high energy density of 2264 W h kg-1 based on sulfur in a pouch cell, showing the promising potential toward high-safety and long-cycling lithium metal batteries.

Oxygen Vacancy-Mediated Selective C-N Coupling toward Electrocatalytic Urea Synthesis.

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.

Lead-Free Halide Cs2PtI6 Perovskite Favoring Pt-N Bonding for Trace NO Detection.

In recent years, the performance research of perovskite materials is not only concentrated in the field of solar cells or optics, but the field of gas sensing has gradually entered the public view. However, the detection of nitric oxide (NO) by lead-free halide perovskites has not yet been reported. Herein, we use Cs2PtI6 to realize the first example of a halide perovskite applied to NO sensing. Due to favoring Pt-N binding, the material has some excellent properties such as a NO detection limit as low as 100 parts-per-billion (ppb), ultrahigh selectivity to NO, and can work at room temperature for more than 2 months. In situ sum frequency generation (SFG) spectra and crystal orbital Hamilton population (COHP) analysis reveal that the strong bonding interaction between Pt 5s and N 2s ensure the high adsorption energy, and Pt 5d electron back donation to N 2px, N 2pz antibonding causes the conductive change of the sensors. In addition, its flexible wearable technology shows the application potential of the device and promotes the further development of perovskite materials.

Pseudo-zwitterions self-assembled from polycation and anion clusters showing exceptional water-cleanable anti-crude-oil-adhesion property.

It is of great importance and practical value to develop a facile and operable surface treatment method of materials with excellent antipollution and antiadhesion property, but still a huge challenge. In this work, a series of pseudo-zwitterions are prepared from electrostatic assembly of cationic polyethyleneimine and anionic phosphonic clusters. These pseudo-zwitterionic assemblies provide a strong hydration through electrostatic interaction with water and in turn create a barrier against oil foulants, leading to a nearly zero crude oil adhesion force. The pseudo-zwitterions-decorated surfaces exhibit exceptional water-cleanable oil-repellent property, even when they are completely dried and without prehydration before fouled by crude oil. While using these pseudo-zwitterions-modified polymeric membranes for separating surfactant stabilized oil-in-water emulsion, less than 10% decline of permeating flux is observed throughout a 2-h continuous separation experiment, showing excellent emulsion separation ability and antipollution performance for high viscous oil.

Revealing molecular conformation-induced stress at embedded interfaces of organic optoelectronic devices by sum frequency generation spectroscopy.

Interface stresses are pervasive and critical in conventional optoelectronic devices and generally lead to many failures and reliability problems. However, detection of the interface stress embedded in organic optoelectronic devices is a long-standing problem, which causes the unknown relationship between interface stress and organic device stability (one key and unsettled issue for practical applications). In this study, a kind of previously unknown molecular conformation-induced stress is revealed at the organic embedded interface through sum frequency generation (SFG) spectroscopy technique. This stress can be greater than 10 kcal/mol per nm2 and is sufficient to induce molecular disorder in the organic semiconductor layer (with energy below 8 kcal/mol per nm2), finally causing instability of the organic transistor. This study not only reveals interface stress in organic devices but also correlates instability of organic devices with the interface stress for the first time, offering an effective solution for improving device stability.