RESUMEN

The advanced oxygen reduction reaction (ORR) catalysts, integrating with well-dispersed single atom (SA) and atomic cluster (AC) sites, showcase potential in bolstering catalytic activity. However, the precise structural modulation and in-depth investigation of their catalytic mechanisms pose ongoing challenges. Herein, a proactive cluster lockdown strategy is introduced, relying on the confinement of trinuclear clusters with metal atom exchange in the covalent organic polymers, enabling the targeted synthesis of a series of multicomponent ensembles featuring FeCo (Fe or Co) dual-single-atom (DSA) and atomic cluster (AC) configurations (FeCo-DSA/AC) via thermal pyrolysis. The designed FeCo-DSA/AC surpasses Fe- and Co-derived counterparts by 18 mV and 49 mV in ORR half-wave potential, whilst exhibiting exemplary performance in Zn-air batteries. Comprehensive analysis and theoretical simulation elucidate the enhanced activity stems from adeptly orchestrating dz2-dxz and O 2p orbital hybridization proximate to the Fermi level, fine-tuning the antibonding states to expedite OH* desorption and OOH* formation, thereby augmenting catalytic activity. This work elucidates the synergistic potentiation of active sites in hybrid electrocatalysts, pioneering innovative targeted design strategies for single-atom-cluster electrocatalysts.

RESUMEN

Zinc ion batteries (ZIBs) encounter interface issues stemming from the water-rich electrical double layer (EDL) and unstable solid-electrolyte interphase (SEI). Herein, we propose the dynamic EDL and self-repairing hybrid SEI for practical ZIBs via incorporating the horizontally-oriented dual-site additive. The rearrangement of distribution and molecular configuration of additive constructs the robust dynamic EDL under different interface charges. And, a self-repairing organic-inorganic hybrid SEI is constructed via the electrochemical decomposition of additive. The dynamic EDL and self-repairing SEI accelerate interfacial kinetics, regulate deposition and suppress side reactions in the both stripping and plating during long-term cycles, which affords high reversibility for 500 h at 42.7% depth of discharge or 50 mA·cm-1. Remarkably, Zn//NVO full cells deliver the impressive cycling stability for 10000 cycles with 100% capacity retention at 3 A·g-1 and for over 3000 cycles even at lean electrolyte (7.5 µL·mAh-1) and high loading (15.26 mg·cm-2). Moreover, effectiveness of this strategy is further demonstrated in the low-temperature full cell (-30 oC).

RESUMEN

In situ construction of solid electrolyte interfaces (SEI) is an effective strategy to enhance the reversibility of zinc (Zn) anodes. However, in situ SEI to afford high reversibility under high current density conditions (≥20 mA cm-2) is highly desired yet extremely challenging. Herein, we propose a dual reaction strategy of spontaneous electrostatic reaction and electrochemical decomposition for the in situ construction of SEI, which is composed of organic-rich upper layer and inorganic-rich inner layer. Particularly, in situ SEI performs as "growth binder" at small current density and "orientation regulator" at high current density, which significantly suppresses side reactions and dendrite growth. The in situ SEI affords the record-breaking reversibility of Zn anode under practical conditions, Zn//Zn symmetric cells can stably cycle for over 1300 h and 400 h at current densities of 50 mA cm-2 and 100 mA cm-2, respectively, showcasing an exceptional cumulative capacity of 67.5 Ah cm-2. Furthermore, the practicality of this in situ SEI is verified in Zn//PANI pouch cells with high mass loading of 25.48 mg cm-2. This work provides a universal strategy to design advanced SEI for practical Zn-ion batteries.

RESUMEN

Flexible zinc-air batteries are leading power sources for next-generation smart wearable electronics. However, flexible zinc-air batteries suffer from the highly-corrosive safety risk and limited lifespan due to the absence of reliable solid-state electrolytes (SSEs). Herein, a single-anion conductive SSE with high-safety is constructed by incorporating a highly amorphous dual-cation ionomer into a robust hybrid matrix of functional carbon nanotubes and polyacrylamide polymer. The as-fabricated SSE obtains dual-penetrating ionomer-polymer networks and hierarchical ionic highways, which contribute to mechanical robustness with 1200 % stretchability, decent water uptake and retention, and superhigh ion conductivity of 245 mS ⋅ cm-1 and good Zn anode reversibility. Remarkably, the flexible solid-state zinc-air batteries delivers a high specific capacity of 764 mAh ⋅ g-1 and peak power density of 152 mW ⋅ cm-2 as well as sustains excellent cycling stability for 1050 cycles (350 hours). This work offers a new paradigm of OH- conductors and broadens the definition and scope of OH- conductors.

RESUMEN

Flexible zinc-air batteries are the leading candidates as the next-generation power source for flexible/wearable electronics. However, constructing safe and high-performance solid-state electrolytes (SSEs) with intrinsic hydroxide ion (OH-) conduction remains a fundamental challenge. Herein, by adopting the natural and robust cellulose nanofibers (CNFs) as building blocks, the biomass SSEs with penetrating ion and water channels are constructed by knitting the OH--conductive CNFs and water-retentive CNFs together via an energy-efficient tape casting. Benefiting from the abundant ion and water channels with interconnected hydrated OH- wires for fast OH- conduction under a nanoconfined environment, the biomass SSEs reveal the high water-uptake, impressive OH- conductivity of 175 mS cm-1 and mechanical robustness simultaneously, which overcomes the commonly existed dilemma between ion conductivity and mechanical property. Remarkably, the flexible zinc-air batteries assemble with biomass SSEs deliver an exceptional cycle lifespan of 310 h and power density of 126 mW cm-2. The design methodology for water and ion channels opens a new avenue to design high-performance SSEs for batteries.

RESUMEN

Despite many additives have been reported for aqueous zinc ion batteries, steric-hindrance effect of additives and its correlation with Zn2+ solvation structure have been rarely reported. Herein, large-sized sucrose biomolecule is selected as a paradigm additive, and steric-hindrance electrolytes (STEs) are developed to investigate the steric-hindrance effect for solvation structure regulation. Sucrose molecules do not participate in Zn2+ solvation shell, but significantly homogenize the distribution of solvated Zn2+ and enlarge Zn2+ solvation shell with weakened Zn2+-H2O interaction due to the steric-hindrance effect. More importantly, STEs afford the water-shielding electric double layer and in situ construct the organic and inorganic hybrid solid electrolyte interface, which effectively boost Zn anode reversibility. Remarkably, Zn//NVO battery presents high capacity of 3.9 mAh ⋅ cm-2 with long cycling stability for over 650 cycles at lean electrolyte of 4.5 µL ⋅ mg-1 and low N/P ratio of 1.5, and the stable operation at wide temperature (-20 °C~+40 °C).

RESUMEN

Catalyst supports play an essential role in catalytic reactions, hinting at pronounced metal-support effects. Zeolites are a propitious support in heterogeneous catalysts, while their use in the electrocatalytic CO2 reduction reaction has been limited as yet because of their electrically insulating nature and serious competing hydrogen evolution reaction (HER). Enlightened by theoretical prediction, herein, we implant zinc ions into the structural skeleton of a zeolite Y to strategically tailor a favorable electrocatalytic platform with remarkably enhanced electronic conduction and strong HER inhibition capability, which incorporates ultrafine cadmium oxide nanoclusters as guest species into the supercages of the tailored 12-ring window framework. The metal d-bandwidth tuning of cadmium by skeletal zinc steers the extent of substrate-molecule orbital mixing, enhancing the stabilization of the key intermediate *COOH while weakening the CO poisoning effect. Furthermore, the strong cadmium-zinc interplay causes a considerable thermodynamic barrier for water dissociation in the conversion of H+ to *H, potently suppressing the competing HER. Therefore, we achieve an industrial-level partial current density of 335 mA cm-2 and remarkable Faradaic efficiency of 97.1% for CO production and stably maintain Faradaic efficiency above 90% at the industrially relevant current density for over 120 h. This work provides a proof of concept of tailored conductive zeolite as a favorable electrocatalytic support for industrial-level CO2 electrolysis and will significantly enhance the adaptability of conductive zeolite-based electrocatalysts in a variety of electrocatalysis and energy conversion applications.

RESUMEN

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta3N5-x) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x. The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1, long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2. This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

RESUMEN

Aqueous Zn-ion batteries are well regarded among a next-generation energy-storage technology due to their low cost and high safety. However, the unstable stripping/plating process leading to severe dendrite growth under high current density and low temperature impede their practical application. Herein, it is demonstrated that the addition of 2-propanol can regulate the outer solvation shell structure of Zn2+ by replacing water molecules to establish a "eutectic solvation shell", which provides strong affinity with the Zn (101) crystalline plane and fast desolvation kinetics during the plating process, rendering homogeneous Zn deposition without dendrite formation. As a result, the Zn anode exhibits promising cycle stability over 500 h under an elevated current density of 15 mA cm-2 and high depth of discharge of 51.2%. Furthermore, remarkable electrochemical performance is achieved in a 150 mAh Zn|V2 O5 pouch cell over 1000 cycles at low temperature of -20 °C. This work not only offers a new strategy to achieve excellent performance of aqueous Zn-ion batteries under harsh conditions, but also reveals electrolyte structure designs that can be applied in related energy storage and conversion fields.

RESUMEN

Electrochemical CO2 reduction to CO is a potential sustainable strategy for alleviating CO2 emission and producing valuable fuels. In the quest to resolve its current problems of low-energy efficiency and insufficient durability, a dual-scale design strategy is proposed by implanting a non-noble active Sn-ZnO heterointerface inside the nanopores of high-surface-area carbon nanospheres (Sn-ZnO@HC). The metal d-bandwidth tuning of Sn and ZnO alters the extent of substrate-molecule orbital mixing, facilitating the breaking of the *COOH intermediate and the yield of CO. Furthermore, the confinement effect of tailored nanopores results in a beneficial pH distribution in the local environment around the Sn-ZnO nanoparticles and protects them against leaching and aggregating. Through integrating electronic and nanopore-scale control, Sn-ZnO@HC achieves a quite low potential of -0.53 V vs reversible hydrogen electrode (RHE) with 91% Faradaic efficiency for CO and an ultralong stability of 240 h. This work provides proof of concept for the multiscale design of electrocatalysts.

RESUMEN

The construction of robust (quasi)-solid-state electrolyte (SSE) for flexible lithium-metal batteries is desirable but extremely challenging. Herein, a novel, flexible, and robust quasi-solid-state electrolyte (QSSE) with a "tree-trunk" design is reported for ultralong-life lithium-metal batteries (LMBs). An in-situ-grown metal-organic framework (MOF) layer covers the cellulose-based framework to form hierarchical ion-channels, enabling rapid ionic transfer kinetics and excellent durability. A conductivity of 1.36 × 10-3  S cm-1 , a transference number of 0.72, an electrochemical window of 5.26 V, and a good rate performance are achieved. The flexible LMBs fabricated with as-designed QSSEs deliver areal capacity of up to 3.1 mAh cm-2 at the initial cycle with high mass loading of 14.8 mg cm-2 in Li-NCM811 cells and can retain ≈80% capacity retention after 300 cycles. An ultralong-life of 3000 cycles (6000 h) is also achieved in Li-LiFePO4 cells. This work presents a promising route in constructing a flexible QSSE toward ultralong-life LMBs, and also provides a design rationale for material and structure development in the area of energy storage and conversion.

RESUMEN

Porous organic polymers (POPs), a versatile class of materials that possess many tunable properties such as high chemical absorptivity and ionic conductivity, are emerging candidate electrode materials, permselective membranes, ionic conductors, interfacial stabilizers and functional precursors to synthesize advanced porous carbon. Based on their crystal structure features, the emerging POPs can be classified into two subclasses: amorphous POPs (hyper cross-linked polymers, polymers with intrinsic microporosity, conjugated microporous polymers, porous aromatic frameworks, etc.) and crystalline POPs (covalent organic frameworks, etc.). This tutorial review provides a brief introduction of different types of POPs in terms of their classification and functions for tackling the remaining challenges in various types of Li-chemistry-based batteries. In situ and ex situ characterization studies are also discussed to highlight their importance and applicability for the structural investigation of POPs to reveal the underlying mechanism of POPs over the course of the electrochemical process. Although some revolutionary advances have been achieved, the development of POPs in Li-chemistry-based batteries is still in its infancy. Perspectives regarding future application and mechanistic insights of POPs in battery studies are outlined at the end.

RESUMEN

With the rising level of atmospheric CO2 worsening climate change, a promising global movement toward carbon neutrality is forming. Sustainable CO2 management based on carbon capture and utilization (CCU) has garnered considerable interest due to its critical role in resolving emission-control and energy-supply challenges. Here, a comprehensive review is presented that summarizes the state-of-the-art progress in developing promising materials for sustainable CO2 management in terms of not only capture, catalytic conversion (thermochemistry, electrochemistry, photochemistry, and possible combinations), and direct utilization, but also emerging integrated capture and in situ conversion as well as artificial-intelligence-driven smart material study. In particular, insights that span multiple scopes of material research are offered, ranging from mechanistic comprehension of reactions, rational design and precise manipulation of key materials (e.g., carbon nanomaterials, metal-organic frameworks, covalent organic frameworks, zeolites, ionic liquids), to industrial implementation. This review concludes with a summary and new perspectives, especially from multiple aspects of society, which summarizes major difficulties and future potential for implementing advanced materials and technologies in sustainable CO2 management. This work may serve as a guideline and road map for developing CCU material systems, benefiting both scientists and engineers working in this growing and potentially game-changing area.

RESUMEN

Manufacturing advanced solid-state electrolytes (SSEs) for flexible rechargeable batteries becomes increasingly important but remains grand challenge. The sophisticated structure of robust animal dermis and good water-retention of plant cell in nature grant germane inspirations for designing high-performance SSEs. Herein, tough bioinspired SSEs with intrinsic hydroxide ion (OH- ) conduction are constructed by in situ formation of OH- conductive ionomer network within a hollow-polymeric-microcapsule-decorated hydrogel polymer network. By virtue of the bioinspired design and dynamic dual-penetrating network structure, the bioinspired SSEs simultaneously obtain mechanical robustness with 1800% stretchability, good water uptake of 107 g g-1 and water retention, and superhigh ion conductivity of 215 mS cm-1 . The nanostructure of bioinspired SSE and related ion-conduction mechanism are revealed and visualized by molecular dynamics simulation, where plenty of compact and superfast ion-transport channels are constructed, contributing to superhigh ion conductivity. As a result, the flexible solid-state zinc-air batteries assembled with bioinspired SSEs witness high power density of 148 mW cm-2 , specific capacity of 758 mAh g-1 and ultralong cycling stability of 320 h as well as outstanding flexibility. The bioinspired methodology and deep insight of ion-conduction mechanism will shed light on the design of advanced SSEs for flexible energy conversion and storage systems.

Asunto(s)

RESUMEN

The construction of safe and environmentally-benign solid-state electrolytes (SSEs) with intrinsic hydroxide ion-conduction for flexible zinc-air batteries is highly desirable yet extremely challenging. Herein, hierarchically nanostructured CCNF-PDIL SSEs with reinforced concrete architecture are constructed by nanoconfined polymerization of dual-cation ionic liquid (PDIL, concrete) within a robust three-dimensional porous cationic cellulose nanofiber matrix (CCNF, reinforcing steel), where plenty of penetrating ion-conductive channels are formed and undergo dynamic self-rearrangement under different hydrated levels. The CCNF-PDIL SSEs synchronously exhibit good flexibility, mechanical robustness, superhigh ion conductivity of 286.5 mS cm-1 , and decent water uptake. The resultant flexible solid-state zinc-air batteries deliver a high-power density of 135 mW cm-2 , a specific capacity of 775 mAh g-1 and an ultralong cycling stability with continuous operation of 240 hours for 720 cycles, far outperforming those of the state-of-the-art solid-state batteries. The marriage of biomaterials with the diversity of ionic liquids creates enormous opportunities to construct advanced SSEs for solid-state batteries.

RESUMEN

Transition-metal carbides (MXenes), multifunctional 2D materials, have caught the interest of researchers in the fabrication of high-performance nanocomposite membranes. However, several issues regarding MXenes still remain unresolved, including low ambient stability; facile restacking and agglomeration; and poor compatibility and processability. To address the aforementioned challenges, we proposed a facile, green, and cost-efficient approach for coating a stable layer of plant-derived polyphenol tannic acid (TA) on the surface of MXene (Ti3C2Tx) nanosheets. Then, high-performance reverse osmosis polyamide thin film nanocomposite (RO-PA-TFN) membranes were fabricated by the incorporation of modified MXene (Ti3C2Tx-TA) nanosheets in the polyamide selective layer through interfacial polymerization. The strong negative charge and hydrophilic multifunctional properties of TA not only boosted the chemical compatibility between Ti3C2Tx MXene nanosheets and the polyamide matrix to overcome the formation of nonselective voids but also generated a tight network with selective interfacial pathways for efficient monovalent salt rejection and water permeation. In comparison to the neat thin film composite membrane, the optimum TFN (Ti3C2Tx-TA) membrane with a loading of 0.008 wt % nanofiller revealed a 1.4-fold enhancement in water permeability, a well-maintained high NaCl rejection rate of 96% in a dead-end process, and enhanced anti-fouling tendency. This research offers a facile way for the development of modified MXene nanosheets to be successfully integrated into the polyamide-selective layer to improve the performance and fouling resistance of TFN membranes.

RESUMEN

Although one of the most mature battery technologies, lithium-ion batteries still have many aspects that have not reached the desired requirements, such as energy density, current density, safety, environmental compatibility, and price. To solve these problems, all-solid-state lithium batteries (ASSLB) based on lithium metal anodes with high energy density and safety have been proposed and become a research hotpot in recent years. Due to the advanced electrochemical properties of 2D materials (2DM), they have been applied to mitigate some of the current problems of ASSLBs, such as high interface impedance and low electrolyte ionic conductivity. In this work, the background and fabrication method of 2DMs are reviewed initially. The improvement strategies of 2DMs are categorized based on their application in the three main components of ASSLBs: The anode, cathode, and electrolyte. Finally, to elucidate the mechanisms of 2DMs in ASSLBs, the role of in situ characterization, synchrotron X-ray techniques, and other advanced characterization are discussed.

RESUMEN

Mn and N codoped carbon materials are proposed as one of the most promising catalysts for the oxygen reduction reaction (ORR) but still confront a lot of challenges to replace Pt. Herein, a novel gas-phase migration strategy is developed for the scale synthesis of atomically dispersed Mn and N codoped carbon materials (g-SA-Mn) as highly effective ORR catalysts. Porous zeolitic imidazolate frameworks serve as the appropriate support for the trapping and anchoring of Mn-containing gaseous species and the synchronous high-temperature pyrolysis process results in the generation of atomically dispersed Mn-Nx active sites. Compared to the traditional liquid phase synthesis method, this unique strategy significantly increases the Mn loading and enables homogeneous dispersion of Mn atoms to promote the exposure of Mn-Nx active sites. The developed g-SA-Mn-900 catalyst exhibits excellent ORR performance in the alkaline media, including a high half-wave potential (0.90 V vs reversible hydrogen electrode), satisfactory durability, and good catalytic selectivity. In the practical application, the Zn-air battery assembled with g-SA-Mn-900 catalysts shows high power density and prominent durability during the discharge process, outperforming the commercial Pt/C benchmark. Such a gas-phase synthetic methodology offers an appealing and instructive guide for the logical synthesis of atomically dispersed catalysts.

RESUMEN

Lithium anode-based batteries (LBs) are highly demanded in society owing to the high theoretical capacity and low reduction potential of metallic lithium. They are expected to see increasing deployment in performance critical areas including electric vehicles, grid storage, space, and sea vehicle operations. Unfortunately, competitive performance cannot be achieved when LBs operating under extreme temperature conditions where the lithium-ion chemistry fail to perform optimally. In this review, a brief overview of the challenges in developing LBs for low temperature (<0 °C) and high temperature (>60 °C) operation are provided followed by electrolyte design strategies involving Li salt modification, solvation structure optimization, additive introduction, and solid-state electrolyte utilization for LBs are introduced. Specifically, the prospects of using lithium metal batteries (LMBs), lithium sulfur (Li-S) batteries, and lithium oxygen (Li-O2 ) batteries for performance under low and high temperature applications are evaluated. These three chemistries are presented as prototypical examples of how the conventional low temperature charge transfer resistances and high temperature side reactions can be overcome. This review also points out the research direction of extreme temperature electrolyte design toward practical applications.

RESUMEN

Electrochemical CO2 reduction (CO2RR) using renewable energy sources represents a sustainable means of producing carbon-neutral fuels. Unfortunately, low energy efficiency, poor product selectivity, and rapid deactivation are among the most intractable challenges of CO2RR electrocatalysts. Here, we strategically propose a "two ships in a bottle" design for ternary Zn-Ag-O catalysts, where ZnO and Ag phases are twinned to constitute an individual ultrafine nanoparticle impregnated inside nanopores of an ultrahigh-surface-area carbon matrix. Bimetallic electron configurations are modulated by constructing a Zn-Ag-O interface, where the electron density reconfiguration arising from electron delocalization enhances the stabilization of the *COOH intermediate favorable for CO production, while promoting CO selectivity and suppressing HCOOH generation by altering the rate-limiting step toward a high thermodynamic barrier for forming HCOO*. Moreover, the pore-constriction mechanism restricts the bimetallic particles to nanosized dimensions with abundant Zn-Ag-O heterointerfaces and exposed active sites, meanwhile prohibiting detachment and agglomeration of nanoparticles during CO2RR for enhanced stability. The designed catalysts realize 60.9% energy efficiency and 94.1 ± 4.0% Faradaic efficiency toward CO, together with a remarkable stability over 6 days. Beyond providing a high-performance CO2RR electrocatalyst, this work presents a promising catalyst-design strategy for efficient energy conversion.