Constructing Bipolar Dual-Active Sites through High-Entropy-Induced Electric Dipole Transition for Decoupling Oxygen Redox.

It remains a significant challenge to construct active sites to break the trade-off between oxidation and reduction processes occurring in battery cathodes with conversion mechanism, especially for the oxygen reduction and evolution reactions (ORR/OER) involved in the zinc-air batteries (ZABs). Here, using a high-entropy-driven electric dipole transition strategy to activate and stabilize the tetrahedral sites is proposed, while enhancing the activity of octahedral sites through orbital hybridization in a FeCoNiMnCrO spinel oxide, thus constructing bipolar dual-active sites with high-low valence states, which can effectively decouple ORR/OER. The FeCoNiMnCrO high-entropy spinel oxide with severe lattice distortion, exhibits a strong 1s→4s electric dipole transition and intense t2g(Co)/eg(Ni)-2p(OL) orbital hybridization that regulates the electronic descriptors, eg and t2g, which leads to the formation of low-valence Co tetrahedral sites (Coth) and high-valence Ni octahedral sites (Nioh), resulting in a higher half-wave potential of 0.87 V on Coth sites and a lower overpotential of 0.26 V at 10 mA cm-2 on Nioh sites as well as a superior performance of ZABs compared to low/mild entropy spinel oxides. Therefore, entropy engineering presents a distinctive approach for designing catalytic sites by inducing novel electromagnetic properties in materials across various electrocatalytic reactions, particularly for decoupling systems.

An extended substrate screening strategy enabling a low lattice mismatch for highly reversible zinc anodes.

Aqueous zinc batteries possess intrinsic safety and cost-effectiveness, but dendrite growth and side reactions of zinc anodes hinder their practical application. Here, we propose the extended substrate screening strategy for stabilizing zinc anodes and verify its availability (dsubstrate: dZn(002) = 1: 1→dsubstrate: dZn(002)=n:1, n = 1, 2). From a series of calculated phyllosilicates satisfying dsubstrate ≈ 2dZn(002), we select vermiculite, which has the lowest lattice mismatch (0.38%) reported so far, as the model to confirm the effectiveness of "2dZn(002)" substrates for zinc anodes protection. Then, we develop a monolayer porous vermiculite through a large-scale and green preparation as a functional coating for zinc electrodes. Unique "planting Zn(002) seeds" mechanism for "2dZn(002)" substrates is revealed to induce the oriented growth of zinc deposits. Additionally, the coating effectively inhibits side reactions and promotes zinc ion transport. Consequently, the modified symmetric cells operate stably for over 300 h at a high current density of 50 mA cm-2. This work extends the substrate screening strategy and advances the understanding of zinc nucleation mechanism, paving the way for realizing high-rate and stable zinc-metal batteries.

Sulfion oxidation assisting self-powered hydrogen production system based on efficient catalysts from spent lithium-ion batteries.

Converting spent lithium-ion batteries (LIBs) and industrial wastewater into high-value-added substances by advanced electrocatalytic technology is important for sustainable energy development and environmental protection. Here, we propose a self-powered system using a home-made sulfide fuel cell (SFC) to power a two-electrode electrocatalytic sulfion oxidation reaction (SOR)-assisted hydrogen (H2) production electrolyzer (ESHPE), in which the sulfion-containing wastewater is used as the liquid fuel to produce clean water, sulfur, and hydrogen. The catalysts for the self-powered system are mainly prepared from spent LIBs to reduce the cost, such as the bifunctional Co9S8 catalyst was prepared from spent LiCoO2 for SOR and hydrogen evolution reaction (HER). The Fe-N-P codoped coral-like carbon nanotube arrays encapsulated Fe2P (C-ZIF/sLFP) catalyst was prepared from spent LiFePO4 for oxygen reduction reaction. The Co9S8 catalyst shows excellent catalytic activities in both SOR and HER, evidenced by the low cell voltage of 0.426 V at 20 mA cm-2 in ESHPE. The SFC with Co9S8 as anode and C-ZIF/sLFP as cathode exhibits an open-circuit voltage of 0.69 V and long discharge stability for 300 h at 20 mA cm-2. By integrating the SFC and ESHPE, the self-powered system delivers an impressive hydrogen production rate of 0.44 mL cm-2 min-1. This work constructs a self-powered system with high-performance catalysts prepared from spent LIBs to transform sulfion-containing wastewater into purified water and prepare hydrogen, which is promising to achieve high economic efficiency, environmental remediation, and sustainable development.

A Polarized Gel Electrolyte for Wide-Temperature Flexible Zinc-Air Batteries.

The development of flexible zinc-air batteries (FZABs) has attracted broad attention in the field of wearable electronic devices. Gel electrolyte is one of the most important components in FZABs, which is urgent to be optimized to match with Zn anode and adapt to severe climates. In this work, a polarized gel electrolyte of polyacrylamide-sodium citric (PAM-SC) is designed for FZABs, in which the SC molecules contain large amount of polarized -COO- functional groups. The polarized -COO- groups can form an electrical field between gel electrolyte and Zn anode to suppress Zn dendrite growth. Besides, the -COO- groups in PAM-SC can fix H2 O molecules, which prevents water from freezing and evaporating. The polarized PAM-SC hydrogel delivers a high ionic conductivity of 324.68 mS cm-1 and water retention of 96.85 % after being exposed for 96 h. FZABs with the PAM-SC gel electrolyte exhibit long cycling life of 700 cycles at -40 °C, showing the application prospect under extreme conditions.

Rational Design of Flexible Zn-Based Batteries for Wearable Electronic Devices.

The advent of 5G and the Internet of Things has spawned a demand for wearable electronic devices. However, the lack of a suitable flexible energy storage system has become the "Achilles' Heel" of wearable electronic devices. Additional problems during the transformation of the battery structure from conventional to flexible also present a severe challenge to the battery design. Flexible Zn-based batteries, including Zn-ion batteries and Zn-air batteries, have long been considered promising candidates due to their high safety, eco-efficiency, substantial reserve, and low cost. In the past decade, researchers have come up with elaborate designs for each portion of flexible Zn-based batteries to improve the ionic conductivities, mechanical properties, environment adaptabilities, and scalable productions. It would be helpful to summarize the reported strategies and compare their pros and cons to facilitate further research toward the commercialization of flexible Zn-based batteries. In this review, the current progress in developing flexible Zn-based batteries is comprehensively reviewed, including their electrolytes, cathodes, and anodes, and discussed in terms of their synthesis, characterization, and performance validation. By clarifying the challenges in flexible Zn-based battery design, we summarize the methodology from previous investigations and propose challenges for future development. In the end, a research paradigm of Zn-based batteries is summarized to fit the burgeoning requirement of wearable electronic devices in an iterative process, which will benefit the future development of Zn-based batteries.

Isolating Contiguous Fe Atoms by Forming a Co-Fe Intermetallic Catalyst from Spent Lithium-Ion Batteries to Regulate Activity for Zinc-Air Batteries.

The recycling of spent lithium-ion batteries (LIBs) has become a necessity for recovering valuable resources and protecting the environment to support sustainable development. We report the design of a highly efficient CoFe/C catalyst by combining the Co and Fe wastes from spent LIBs with sawdust-derived carbon, which were cathode materials in zinc-air batteries (ZABs). As a result of the electrostatic attraction between the Co3+/Fe3+ cations and the hydroxyl groups in sawdust, CoFe nanoparticles are uniformly dispersed in the CoFe/C catalyst after annealing. The Fe atoms in the CoFe nanoparticles are all isolated into single sites by the Co atoms, which redistribute the electrons in the CoFe/C catalyst. The catalyst produced a Pt-like dissociative mechanism, contributing to an excellent oxygen reduction reaction performance. After assembly in ZABs, the CoFe/C catalyst cathode exhibits a long cycling stability of 350 h and an impressive power density of 199.2 mW cm-2. The CoFe/C catalyst cathode has also been used in flexible ZABs to power LEDs or charge a mobile phone. The work combines spent LIBs with sawdust to fabricate high-performance catalysts, which could reduce environmental pollution and realize high economic value.

Recycling spent LiNi1-x-yMnxCoyO2 cathodes to bifunctional NiMnCo catalysts for zinc-air batteries.

SignificanceIn recent years, lithium-ion batteries (LIBs) have been widely applied in electric vehicles as energy storage devices. However, it is a great challenge to deal with the large number of spent LIBs. In this work, we employ a rapid thermal radiation method to convert the spent LIBs into highly efficient bifunctional NiMnCo-activated carbon (NiMnCo-AC) catalysts for zinc-air batteries (ZABs). The obtained NiMnCo-AC catalyst shows excellent electrochemical performance in ZABs due to the unique core-shell structure, with face-centered cubic Ni in the core and spinel NiMnCoO4 in the shell. This work provides an economical and environment-friendly approach to recycling the spent LIBs and converting them into novel energy storage devices.

Designing Electrophilic and Nucleophilic Dual Centers in the ReS2 Plane toward Efficient Bifunctional Catalysts for Li-CO2 Batteries.

Two-dimensional transition metal dichalcogenides (TMDCs) show great potential as efficient catalysts for Li-CO2 batteries. However, the basal plane engineering on TMDCs toward bifunctional catalysts for Li-CO2 batteries is still poorly understood. In this work, density functional theory calculations reveal that nucleophilic N dopants and electrophilic S vacancies in the ReS2 plane tailor the interactions with Li atoms and C/O atoms in intermediates, respectively. The electrophilic and nucleophilic dual centers show suitable adsorption with all intermediates during discharge and charge, resulting in a small energy barrier for the rate-determining step. Thus, an efficient bifunctional catalyst is produced toward Li-CO2 batteries. As a result, the optimal catalyst achieves an ultrasmall voltage gap of 0.66 V and an ultrahigh energy efficiency of 81.1% at 20 µA cm-2, which is superior to those of previous catalysts under similar conditions. The introduction of electrophilic and nucleophilic dual centers provides new avenues for designing excellent bifunctional catalysts for Li-CO2 batteries.

Scalable Wood Hydrogel Membrane with Nanoscale Channels.

Many efforts have been dedicated to exploring nanofluidic systems for various applications including water purification and energy generation. However, creating robust nanofluidic materials with tunable channel orientations and numerous nanochannels or nanopores on a large scale remains challenging. Here, we demonstrate a scalable and cost-effective method to fabricate a robust and highly conductive nanofluidic wood hydrogel membrane in which ions can transport across the membrane. The ionically conductive balsa wood hydrogel membrane is fabricated by infiltrating poly(vinyl alcohol) (PVA)/acrylic acid (AA) hydrogel into the inherent bimodal porous wood structure. The balsa wood hydrogel membrane demonstrates a 3 times higher strength (52.7 MPa) and 2 orders of magnitude higher ionic conductivity compared to those of natural balsa both in the radial direction (coded as R direction) and along the longitudinal direction (coded as L direction). The ionic conductivity of the balsa wood hydrogel membrane is 1.29 mS cm-1 along the L direction and nearly 1 mS cm-1 along the R direction at low salt concentrations (up to 10 mM). In addition, the surface-charge-governed ion transport also renders the balsa wood hydrogel membrane able to harvest electrical energy from salinity gradients. A current density of up to 17.65 µA m-2 and an output power density of 0.56 mW m-2 are obtained under a 1000-fold salt concentration gradient, which can be further improved to 2.7 mW m-2 by increasing the AA content from 25 wt % to 50 wt %. These findings make contributions to develop energy-harvesting systems and other nanofluidic devices from sustainable wood materials.

Aligned Carbon-Based Electrodes for Fast-Charging Batteries: A Review.

Fast-charging batteries have attracted great attention, and are anticipated to charge electrical vehicles and consumer electronics to full-capacity in several minutes. However, commercial electrode materials in batteries generally have a limited rate performance and are difficult to be used in fast-charging batteries. Designing electrodes with an aligned structure is an effective way to shorten the ion transport path and improve the rate performance of a battery. The excellent electronic conductivity of carbon-based electrodes is another key factor for increasing the rate capability of rechargeable batteries. Therefore, aligned carbon-based electrodes (ACBEs) can significantly improve the power density by combining the advantages of an aligned structure and carbon-based materials. In this review, the mechanism, advantages, and challenges of ACBEs for fast-charging batteries are evaluated, and then the design and preparation methods of ACBEs based on their different dimensions are summarized, and their applications in different batteries are illustrated. Finally, the future development of ACBEs for fast-charging batteries is considered.

Lignin-Based Direct Ink Printed Structural Scaffolds.

3D printing of lignocellulosic biomass (cellulose, hemicellulose, and lignin) has attracted increasing attention by using this abundant, sustainable, and ecofriendly material. While cellulose can be easily tailored into a highly viscous ink for 3D printing, after solvent evaporation, the final printed structures become highly porous, fragile, and easily fall apart in water due to its hydrophilic nature. Lignin, another crucial component of natural lignocellulose, has not yet been reported for ink printing due to its unfavorable rheological behavior. Herein, a low-cost direct ink printing strategy is developed to fabricate lignin-based 3D structures with lignin no further refined and a more compact microstructure as well as different functionalities compared with printed cellulose. By using a soft triblock copolymer as the crosslinking agent, the rheology of lignin-based inks can be adjusted from soft to rigid, and even enables vertical printing which requires stiff and self-supporting features. The lignin-based inks contain less water (≈40 wt%) and exhibit a much denser, stiffer structure, resulting in a wet tensile strength of ≈30 MPa, compared to only ≈0.6 MPa for printed cellulose. In addition, the unique macromolecular structure of lignin also demonstrates significantly improved stability in water and under heat, as well as UV-blocking performance.

Surface Hexagonal Pt1Sn1 Intermetallic on Pt Nanoparticles for Selective Propane Dehydrogenation.

A series of 2-3 nm Pt-Sn bimetallic nanoparticles with different Pt-Sn coordination numbers were synthesized by a stepwise approach including electrostatic adsorption and temperature-programmed reduction of metal precursors on the SiO2 support. In situ synchrotron X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) demonstrated a highly ordered hexagonal Pt1Sn1 intermetallic shell on Pt nanoparticles. The turnover rates (TORs), propylene selectivity, and stability of these bimetallic catalysts significantly surpass those of the monometallic Pt catalyst for propane dehydrogenation. At the same time, TORs increase with increasing the Pt-Sn coordination number, whereas propylene selectivity is not significantly influenced by the Pt-Sn coordination number. Combined with experiments and theoretical calculations, the high propylene selectivity of Pt-Sn bimetallic nanoparticles is attributed to the geometric effects of Sn that reduce the Pt ensembles, and the high TORs are due to the electronic effects that weaken Pt-hydrocarbon chemisorption energies.

Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts.

Multi-elemental alloy nanoparticles (MEA-NPs) hold great promise for catalyst discovery in a virtually unlimited compositional space. However, rational and controllable synthesize of these intrinsically complex structures remains a challenge. Here, we report the computationally aided, entropy-driven design and synthesis of highly efficient and durable catalyst MEA-NPs. The computational strategy includes prescreening of millions of compositions, prediction of alloy formation by density functional theory calculations, and examination of structural stability by a hybrid Monte Carlo and molecular dynamics method. Selected compositions can be efficiently and rapidly synthesized at high temperature (e.g., 1500 K, 0.5 s) with excellent thermal stability. We applied these MEA-NPs for catalytic NH3 decomposition and observed outstanding performance due to the synergistic effect of multi-elemental mixing, their small size, and the alloy phase. We anticipate that the computationally aided rational design and rapid synthesis of MEA-NPs are broadly applicable for various catalytic reactions and will accelerate material discovery.

High-throughput, combinatorial synthesis of multimetallic nanoclusters.

Multimetallic nanoclusters (MMNCs) offer unique and tailorable surface chemistries that hold great potential for numerous catalytic applications. The efficient exploration of this vast chemical space necessitates an accelerated discovery pipeline that supersedes traditional "trial-and-error" experimentation while guaranteeing uniform microstructures despite compositional complexity. Herein, we report the high-throughput synthesis of an extensive series of ultrafine and homogeneous alloy MMNCs, achieved by 1) a flexible compositional design by formulation in the precursor solution phase and 2) the ultrafast synthesis of alloy MMNCs using thermal shock heating (i.e., ∼1,650 K, ∼500 ms). This approach is remarkably facile and easily accessible compared to conventional vapor-phase deposition, and the particle size and structural uniformity enable comparative studies across compositionally different MMNCs. Rapid electrochemical screening is demonstrated by using a scanning droplet cell, enabling us to discover two promising electrocatalysts, which we subsequently validated using a rotating disk setup. This demonstrated high-throughput material discovery pipeline presents a paradigm for facile and accelerated exploration of MMNCs for a broad range of applications.

A Strong, Tough, and Scalable Structural Material from Fast-Growing Bamboo.

Lightweight structural materials with high strength are desirable for advanced applications in transportation, construction, automotive, and aerospace. Bamboo is one of the fastest growing plants with a peak growth rate up to 100 cm per day. Here, a simple and effective top-down approach is designed for processing natural bamboo into a lightweight yet strong bulk structural material with a record high tensile strength of ≈1 GPa and toughness of 9.74 MJ m-3 . More specifically, bamboo is densified by the partial removal of its lignin and hemicellulose, followed by hot-pressing. Long, aligned cellulose nanofibrils with dramatically increased hydrogen bonds and largely reduced structural defects in the densified bamboo structure contribute to its high mechanical tensile strength, flexural strength, and toughness. The low density of lignocellulose in the densified bamboo leads to a specific strength of 777 MPa cm3 g-1 , which is significantly greater than other reported bamboo materials and most structural materials (e.g., natural polymers, plastics, steels, and alloys). This work demonstrates a potential large-scale production of lightweight, strong bulk structural materials from abundant, fast-growing, and sustainable bamboo.

General, Vertical, Three-Dimensional Printing of Two-Dimensional Materials with Multiscale Alignment.

Two-dimensional (2D) materials (e.g., boron nitride (BN), graphene, and MoS2) have great potential in emerging energy, environmental, and electronics applications. Assembly of 2D materials into vertically aligned structures is highly desirable (e.g., low tortuosity for rapid ion transport in fast charging-discharging batteries, guiding thermal transport for efficient thermal management), yet extremely challenging due to the energetically unfavorable in processing. Herein, we reported a general three-dimensional (3D) printing method to fabricate vertically aligned 2D materials in multiscale, using BN nanosheet as the proof-of-concept. The 3D-printed macroscale rods are composed of vertically aligned BN nanosheets at the nanoscale. The formation of the hierarchical aligned structure is enabled by the optimized ink that holds a significant shear-thinning behavior and an ultrahigh storage modulus, as identified at a narrow region in the printability diagram. The resulting vertically aligned multiscale structure with 2D nanosheets demonstrated an outstanding through-plane thermal conductivity, up to 5.65 W m-1 K-1, significantly higher than the value of conventional BN based structures where the sheets are horizontally aligned. The vertical 3D printing of 2D BN nanosheets can be expanded to other 2D materials in constructing hierarchically aligned structures for a range of emerging technologies such as batteries, membranes, and structural materials.

High temperature shockwave stabilized single atoms.

The stability of single-atom catalysts is critical for their practical applications. Although a high temperature can promote the bond formation between metal atoms and the substrate with an enhanced stability, it often causes atom agglomeration and is incompatible with many temperature-sensitive substrates. Here, we report using controllable high-temperature shockwaves to synthesize and stabilize single atoms at very high temperatures (1,500-2,000 K), achieved by a periodic on-off heating that features a short on state (55 ms) and a ten-times longer off state. The high temperature provides the activation energy for atom dispersion by forming thermodynamically favourable metal-defect bonds and the off-state critically ensures the overall stability, especially for the substrate. The resultant high-temperature single atoms exhibit a superior thermal stability as durable catalysts. The reported shockwave method is facile, ultrafast and universal (for example, Pt, Ru and Co single atoms, and carbon, C3N4 and TiO2 substrates), which opens a general route for single-atom manufacturing that is conventionally challenging.

Ultrafast, Controllable Synthesis of Sub-Nano Metallic Clusters through Defect Engineering.

Supported metallic nanoclusters (NCs, < 2 nm) are of great interests in various catalytic reactions with enhanced activities and selectivities, yet it is still challenging to efficiently and controllably synthesize ultrasmall NCs with a high-dispersal density. Here we report the in situ synthesis of surfactant-free, ultrasmall, and uniform NCs via a rapid thermal shock on defective substrates. This is achieved by using high-temperature synthesis with extremely fast kinetics while limiting the synthesis time down to milliseconds (e.g., ∼1800 K for 55 ms) to avoid aggregation. Through defect engineering and optimized loading, the particle size can be robustly tuned from >50 nm nanoparticles to <1 nm uniform NCs with a high-dispersal density. We demonstrate that the ultrasmall NCs exhibit drastically improved activities for catalytic CO oxidation as compared to their nanoparticulated counterparts. In addition, the reported method shows generality in synthesizing most metallic NCs (e.g., Pt, Ru, Ir, Ni) in an extremely facile and efficient manner. The ultrafast and controllable synthesis of uniform, high-density, and size-controllable NCs paves the way for the utilization and nanomanufacturing of NCs for a range of catalytic reactions.

Fly-through synthesis of nanoparticles on textile and paper substrates.

The fast and efficient synthesis of nanoparticles on flexible and lightweight substrates is increasingly critical for various medical and wearable applications. However, conventional high temperature (high-T) processes for nanoparticle synthesis are intrinsically incompatible with temperature-sensitive substrates, including textiles and paper (i.e. low-T substrates). In this work, we report a non-contact, 'fly-through' method to synthesize nanoparticles on low-T substrates by rapid radiative heating under short timescales. As a demonstration, textile substrates loaded with platinum (Pt) salt precursor are rapidly heated and quenched as they move across a 2000 K heating source at a continuous production speed of 0.5 cm s-1. The rapid radiative heating method induces the thermal decomposition of various precursor salts and nanoparticle formation, while the short duration ensures negligible change to the respective low-T substrate along with greatly improved production efficiency. The reported method can be generally applied to the synthesis of metal nanoparticles (e.g. gold and ruthenium) on various low-T substrates (e.g. paper). The non-contact and continuous 'fly-through' synthesis offers a robust and efficient way to synthesize supported nanoparticles on flexible and lightweight substrates. It is also promising for ultrafast and roll-to-roll manufacturing to enable viable applications.

Epitaxial Welding of Carbon Nanotube Networks for Aqueous Battery Current Collectors.

Carbon nanomaterials are desirable candidates for lightweight, highly conductive, and corrosion-resistant current collectors. However, a key obstacle is their weak interconnection between adjacent nanostructures, which renders orders of magnitude lower electrical conductivity and mechanical strength in the bulk assemblies. Here we report an "epitaxial welding" strategy to engineer carbon nanotubes (CNTs) into highly crystalline and interconnected structures. Solution-based polyacrylonitrile was conformally coated on CNTs as "nanoglue" to physically join CNTs into a network, followed by a rapid high-temperature annealing (>2800 K, overall ∼30 min) to graphitize the polymer coating into crystalline layers that also bridge the adjacent CNTs to form an interconnected structure. The contact-welded CNTs (W-CNTs) exhibit both a high conductivity (∼1500 S/cm) and a high tensile strength (∼120 MPa), which are 5 and 20 times higher than the unwelded CNTs, respectively. In addition, the W-CNTs display chemical and electrochemical stabilities in strong acidic/alkaline electrolytes (>6 mol/L) when potentiostatically stressing at both cathodic and anodic potentials. With these exceptional properties, the W-CNT films are optimal as high-performance current collectors and were demonstrated in the state-of-the-art aqueous battery using a "water-in-salt" electrolyte.