An Artificial Leaf with Patterned Photocatalysts for Sunlight-Driven Water Splitting.

Plant leaves can turn entirely absorbed light into chemical energy due to their spatially separated photosystems I and II in the thylakoid membrane that enables unidirectional Z-scheme type charge transfer between them. In artificial systems that mimic leaves, a lack of spatial and interfacial control of active units (i.e., hydrogen evolution photocatalyst/HEP and oxygen evolution photocatalyst/OEP) introduces competitive charge transfer channels between them, resulting in deficient Z-scheme type charge transfer. Herein, we demonstrate that a patterned photocatalyst sheet, namely, an artificial leaf, comprising an ordered and separated distribution of the OEP and HEP strips on a conductive substrate, achieves unidirectional Z-scheme type charge transfer as the leaves do. It represents a next-generation photocatalytic system that mimics the leaves to bring breakthrough in photocatalytic over water splitting performance with the combination of highly active HEP and OEP photocatalysts, opening up a promising avenue toward solar energy conversion by artificial photosynthesis.

Surface Catalytic Repair for the Efficient Regeneration of Spent Layered Oxide Cathodes.

Direct recycling is considered to be the next-generation recycling technology for spent lithium-ion batteries due to its potential economic benefits and environmental friendliness. For the spent layered oxide cathode materials, an irreversible phase transition to a rock-salt structure near the particle surface impedes the reintercalation of lithium ions, thereby hindering the lithium compensation process from fully restoring composition defects and repairing failed structures. We introduced a transition-metal hydroxide precursor, utilizing its surface catalytic activity produced during annealing to convert the rock-salt structure into a layered structure that provides fast migration pathways for lithium ions. The material repair and synthesis processes share the same heating program, enabling the spent cathode and added precursor to undergo a topological transformation to form the targeted layered oxide. This regenerated material exhibits a performance superior to that of commercial cathodes and maintains 88.4% of its initial capacity after 1000 cycles in a 1.3 Ah pouch cell. Techno-economic analysis highlights the environmental and economic advantages of surface catalytic repair over pyrometallurgical and hydrometallurgical methods, indicating its potential for practical application.

Highly Thermally Conductive and Flexible Thermal Interface Materials with Aligned Graphene Lamella Frameworks.

Highly thermally conductive and flexible thermal interface materials (TIMs) are desirable for heat dissipation in modern electronic devices. Here, we fabricated a high-crystalline aligned graphene lamella framework (AGLF) with precisely controlled lamella thickness, pore structure, and excellent intergraphene contact by manipulating the thermal expansion behavior of scanning centrifugal casted graphene oxide films. The rational design of the AGLF balances the trade-off between the thermal conductivity and flexibility of TIMs. The AGLF-based TIM (AGLF-TIM) shows a record thermal conductivity of 196.3 W m-1 K-1 with a graphene loading of only 9.4 vol %, which is about 4 times higher than those of reported TIMs at a similar graphene loading. Meanwhile, good flexibility remains comparable to that of commercial TIMs. As a result, an LED device achieves an additional temperature decrease of ∼8 °C with the use of AGLF-TIM compared to high-performance commercial TIMs. This work offers a strategy for the controlled fabrication of graphene macrostructures, showing the potential use of graphene as filler frameworks in thermal management.

A hot-emitter transistor based on stimulated emission of heated carriers.

Hot-carrier transistors are a class of devices that leverage the excess kinetic energy of carriers. Unlike regular transistors, which rely on steady-state carrier transport, hot-carrier transistors modulate carriers to high-energy states, resulting in enhanced device speed and functionality. These characteristics are essential for applications that demand rapid switching and high-frequency operations, such as advanced telecommunications and cutting-edge computing technologies1-5. However, the traditional mechanisms of hot-carrier generation are either carrier injection6-11 or acceleration12,13, which limit device performance in terms of power consumption and negative differential resistance14-17. Mixed-dimensional devices, which combine bulk and low-dimensional materials, can offer different mechanisms for hot-carrier generation by leveraging the diverse potential barriers formed by energy-band combinations18-21. Here we report a hot-emitter transistor based on double mixed-dimensional graphene/germanium Schottky junctions that uses stimulated emission of heated carriers to achieve a subthreshold swing lower than 1 millivolt per decade beyond the Boltzmann limit and a negative differential resistance with a peak-to-valley current ratio greater than 100 at room temperature. Multi-valued logic with a high inverter gain and reconfigurable logic states are further demonstrated. This work reports a multifunctional hot-emitter transistor with significant potential for low-power and negative-differential-resistance applications, marking a promising advancement for the post-Moore era.

An ultraflexible energy harvesting-storage system for wearable applications.

The swift progress in wearable technology has accentuated the need for flexible power systems. Such systems are anticipated to exhibit high efficiency, robust durability, consistent power output, and the potential for effortless integration. Integrating ultraflexible energy harvesters and energy storage devices to form an autonomous, efficient, and mechanically compliant power system remains a significant challenge. In this work, we report a 90 µm-thick energy harvesting and storage system (FEHSS) consisting of high-performance organic photovoltaics and zinc-ion batteries within an ultraflexible configuration. With a power conversion efficiency surpassing 16%, power output exceeding 10 mW cm-2, and an energy density beyond 5.82 mWh cm-2, the FEHSS can be tailored to meet the power demands of wearable sensors and gadgets. Without cumbersome and rigid components, FEHSS shows immense potential as a versatile power source to advance wearable electronics and contribute toward a sustainable future.

Initiating a composite membrane with a localized high iodine concentration layer based on adduct chemistry to enable highly reversible zinc-iodine flow batteries.

The issue of polyiodide crossover at an iodine cathode significantly diminishes the efficiency and practicality of aqueous zinc-iodine flow batteries (ZIFBs). To address this challenge, we have introduced a localized high iodine concentration (LHIC) coating layer onto a porous polyolefin membrane, which featured strong chemical adsorption by exploiting adduct chemistry between the iodine species and a series of low-cost oxides, e.g., MgO, CeO2, ZrO2, TiO2, and Al2O3. Leveraging the LHIC based on the potent iodine adsorption capability, the as-fabricated MgO-LHIC composite membrane effectively mitigates iodine crossover via Donnan repulsion and concentration gradient effects. At a high volumetric capacity of 17.8 Ah L-1, ZIFBs utilizing a MgO-LHIC composite membrane exhibited improved coulombic efficiency (CE) and energy efficiency (EE) of 96.3% and 68.6%, respectively, along with long-term cycling stability of 170 cycles. These results significantly outperform those of ZIFBs based on a blank polyolefin membrane (78.2%/61.9% after 60 cycles) and the widely used commercial Nafion N117 (67.8%/53.0% after 23 cycles). Even under high-temperature conditions (60 °C), the LHIC-based battery still demonstrates superior CE/EE of 95.1%/67.5% compared to those of the blank polyolefin membrane (CE/EE: 61.1%/46.8%). Our pioneering research showcases enormous prospects for developing high-efficiency and low-cost composite membranes based on adduct chemistry for large-scale energy storage applications.

A Dynamically Ion-Sieved Electrolyte towards Ultralong-Lifespan Zn-Ion Batteries.

The practical deployment of Zn-ion batteries faces challenges such as dendrite growth, side reactions and cathode dissolution in traditional electrolytes. Here, we develop a highly conductive and dynamically ion-sieved electrolyte to simultaneously enhance the Zn metal reversibility and suppress the cathode dissolution. The dynamic ion screen at the electrode/electrolyte interface is achieved by numerous pyrane rings with a radius of 3.69 Å, which can selectively facilitate the plating/stripping and insertion/extraction process of [Zn(H2O)6]2+ and Zn2+ on the anode and cathode surfaces. As a proof of concept, Zn//Zn symmetric cells deliver exceptional cyclic stability for over 6,800 h and ultrahigh cumulative plated capacity of 3.9 Ah cm-2. Zn//Na2Mn3O7 cells exhibit satisfactory cycling performance with capacity retention of 82.7% after 4,000 cycles, and the assembled pouch cells achieve excellent stability and durability. This work provides valuable insights into the development of electrolytes aimed at enhancing the interface stability of aqueous batteries.

Electricity generated by upstream proton diffusion in two-dimensional nanochannels.

The movement of ions along the pressure-driven water flow in narrow channels, known as downstream ionic transport, has been observed since 1859 to induce a streaming potential and has enabled the creation of various hydrovoltaic devices. In contrast, here we demonstrate that proton movement opposing the water flow in two-dimensional nanochannels of MXene/poly(vinyl alcohol) films, termed upstream proton diffusion, can also generate electricity. The infiltrated water into the channel causes the dissociation of protons from functional groups on the channel surface, resulting in a high proton concentration inside the channel that drives the upstream proton diffusion. Combined with the particularly sluggish water diffusion in the channels, a small water droplet of 5 µl can generate a voltage of ~400 mV for over 330 min. Benefiting from the ultrathin and flexible nature of the film, a wearable device is built for collecting energy from human skin sweat.

Element Screening of High-Entropy Silicon Anodes for Superior Li-Storage Performance of Li-Ion Batteries.

The high-entropy silicon anodes are attractive for enhancing electronic and Li-ionic conductivity while mitigating volume effects for advanced Li-ion batteries (LIBs), but are plagued by the complicated elements screening process. Inspired by the resemblances in the structure between sphalerite and diamond, we have selected sphalerite-structured SiP with metallic conductivity as the parent phase for exploring the element screening of high-entropy silicon-based anodes. The inclusion of the Zn in the sphalerite structure is crucial for improving the structural stability and Li-storage capacity. Within the same group, Li-storage performance is significantly improved with increasing atomic number in the order of BZnSiP3 < AlZnSiP3 < GaZnSiP3 < InZnSiP3. Thus, InZnSiP3-based electrodes achieved a high capacity of 719 mA h g-1 even after 1,500 cycles at 2,000 mA g-1, and a high-rate capacity of 725 mA h g-1 at 10,000 mA g-1, owing to its superior lithium-ion affinity, faster electronic conduction and lithium-ion diffusion, higher Li-storage capacity and reversibility, and mechanical integrity than others. Additionally, the incorporation of elements with larger atomic sizes leads to greater lattice distortion and more defects, further facilitating mass and charge transport. Following these screening rules, high-entropy disordered-cation silicon-based compounds such as GaCuSnInZnSiP6, GaCu(or Sn)InZnSiP5, and CuSnInZnSiP5, as well as high-entropy compounds with mixed-cation and -anion compositions, such as InZnSiPSeTe and InZnSiP2Se(or Te), are synthesized, demonstrating improved Li-storage performance with metallic conductivity. The phase formation mechanism of these compounds is attributed to the negative formation energies arising from elevated entropy.

Unusually high thermal conductivity in suspended monolayer MoSi2N4.

Two-dimensional semiconductors with high thermal conductivity and charge carrier mobility are of great importance for next-generation electronic and optoelectronic devices. However, constrained by the long-held Slack's criteria, the reported two-dimensional semiconductors such as monolayers of MoS2, WS2, MoSe2, WSe2 and black phosphorus suffer from much lower thermal conductivity than silicon (~142 W·m-1·K-1) because of the complex crystal structure, large average atomic mass and relatively weak chemical bonds. Despite the more complex crystal structure, the recently emerging monolayer MoSi2N4 semiconductor has been predicted to have high thermal conductivity and charge carrier mobility simultaneously. In this work, using a noncontact optothermal Raman technique, we experimentally measure a high thermal conductivity of ~173 W·m-1·K-1 at room temperature for suspended monolayer MoSi2N4 grown by chemical vapor deposition. First-principles calculations reveal that such unusually high thermal conductivity benefits from the high Debye temperature and small Grüneisen parameter of MoSi2N4, both of which are strongly dependent on the high Young's modulus induced by the outmost Si-N bilayers. Our study not only establishes monolayer MoSi2N4 as a benchmark 2D semiconductor for next-generation electronic and optoelectronic devices, but also provides an insight into the design of 2D materials for efficient heat conduction.

Nature-Inspired Incorporation of Precipitants into High-Strength Bulk Aluminum Alloys Enables Life-Long Extraordinary Corrosion Resistance in Diverse Aqueous Environments.

The safe service and wide applications of lightweight high-strength aluminum alloys are seriously challenged by diverse environmental corrosion, since high strength and corrosion resistance are mutually exclusive for metals while surface protection cannot provide life-long corrosion resistance. Here, inspired by fish secreting slime from glands to resist external changes, a strategy of incorporating precipitants as the slime into bulk metals using the inner cavity of opened carbon nanotubes (CNTs) as the glands is developed to enable high-strength aluminum alloys with life-long superior corrosion resistance. The resulting material has ultrahigh tensile strength (≈700 MPa) and extraordinary corrosion resistance in acidic, neutral and alkaline media. Notably, it has the highest resistance to intergranular corrosion, exfoliation corrosion and stress-corrosion cracking, compared with all previously reported aluminum alloys, and its corrosion rate is even much lower than that of corrosion-resistant pure aluminum, which results from the pronounced surface enrichment of precipitants released (secreted) from exposed CNTs forming a protective surface film. Such high corrosion resistance is life-long and self-healing due to the on-demand minimal self-supply of the precipitants dispersed throughout the bulk material. This strategy can be readily expanded to other aluminum alloys, and could pave the way for developing corrosion-resistant high-strength metallic materials.

Extreme Fast Charging of Lithium Metal Batteries Enabled by a Molten-Salt-Derived Nanocrystal Interphase.

The extreme fast charging performance of lithium metal batteries (LMBs) with a long life is an important focus in the development of next-generation battery technologies. The friable solid electrolyte interphase and dendritic lithium growth are major problems. The formation of an inorganic nanocrystal-dominant interphase produced by preimmersing the Li in molten lithium bis(fluorosulfonyl)imide that suppresses the overgrowth of the usual interphase is reported. Its high surface modulus combined with fast Li+ diffusivity enables a reversible dendrite-proof deposition under ultrahigh-rate conditions. It gives a record-breaking cumulative plating/stripping capacity of >240 000 mAh cm-2 at 30 mA cm-2@30 mAh cm-2 for a symmetric cell and an extreme fast charging performance at 6 C for 500 cycles for a Li||LiCoO2 full cell with a high-areal-capacity, thus expanding the use of LMBs to high-loading and power-intensive scenarios. Its usability both in roll-to-roll production and in different electrolytes indicating the scalable and industrial potential of this process for high-performance LMBs.

Sustainable upcycling of mixed spent cathodes to a high-voltage polyanionic cathode material.

Sustainable battery recycling is essential for achieving resource conservation and alleviating environmental issues. Many open/closed-loop strategies for critical metal recycling or direct recovery aim at a single component, and the reuse of mixed cathode materials is a significant challenge. To address this barrier, here we propose an upcycling strategy for spent LiFePO4 and Mn-rich cathodes by structural design and transition metal replacement, for which uses a green deep eutectic solvent to regenerate a high-voltage polyanionic cathode material. This process ensures the complete recycling of all the elements in mixed cathodes and the deep eutectic solvent can be reused. The regenerated LiFe0.5Mn0.5PO4 has an increased mean voltage (3.68 V versus Li/Li+) and energy density (559 Wh kg-1) compared with a commercial LiFePO4 (3.38 V and 524 Wh kg-1). The proposed upcycling strategy can expand at a gram-grade scale and was also applicable for LiFe0.5Mn0.5PO4 recovery, thus achieving a closed-loop recycling between the mixed spent cathodes and the next generation cathode materials. Techno-economic analysis shows that this strategy has potentially high environmental and economic benefits, while providing a sustainable approach for the value-added utilization of waste battery materials.

Designing Temperature-Insensitive Solvated Electrolytes for Low-Temperature Lithium Metal Batteries.

Lithium metal batteries face problems from sluggish charge transfer at interfaces, as well as parasitic reactions between lithium metal anodes and electrolytes, due to the strong electronegativity of oxygen donor solvents. These factors constrain the reversibility and kinetics of lithium metal batteries at low temperatures. Here, a nonsolvating cosolvent is applied to weaken the electronegativity of donor oxygen in ether solvents, enabling the participation of anionic donors in the solvation structure of Li+. This strategy significantly accelerates the desolvation process of Li+ and reduces the side effects of solvents on interfacial transport and stability. The designed anion-aggregated electrolyte has a unique temperature-insensitive solvation structure and enables lithium metal anodes to achieve a high average Coulombic efficiency at room temperature and -20 °C. A high-loading LiFePO4||Li cell exhibited high reversibility with a 100% capacity retention after 150 cycles at room temperature, -20, and -40 °C. The practical 1 Ah-level LiFePO4||Li pouch-cell delivered 81% and 61% of the capacity at room temperature when charged and discharged at -20 and -40 °C, respectively. This strategy of constructing temperature-insensitive solvation by electronegativity regulation offers a novel approach for developing electrolytes of low-temperature batteries.

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.

Metal telluride nanosheets by scalable solid lithiation and exfoliation.

Transition metal tellurides (TMTs) have been ideal materials for exploring exotic properties in condensed-matter physics, chemistry and materials science1-3. Although TMT nanosheets have been produced by top-down exfoliation, their scale is below the gram level and requires a long processing time, restricting their effective application from laboratory to market4-8. We report the fast and scalable synthesis of a wide variety of MTe2 (M = Nb, Mo, W, Ta, Ti) nanosheets by the solid lithiation of bulk MTe2 within 10 min and their subsequent hydrolysis within seconds. Using NbTe2 as a representative, we produced more than a hundred grams (108 g) of NbTe2 nanosheets with 3.2 nm mean thickness, 6.2 µm mean lateral size and a high yield (>80%). Several interesting quantum phenomena, such as quantum oscillations and giant magnetoresistance, were observed that are generally restricted to highly crystalline MTe2 nanosheets. The TMT nanosheets also perform well as electrocatalysts for lithium-oxygen batteries and electrodes for microsupercapacitors (MSCs). Moreover, this synthesis method is efficient for preparing alloyed telluride, selenide and sulfide nanosheets. Our work opens new opportunities for the universal and scalable synthesis of TMT nanosheets for exploring new quantum phenomena, potential applications and commercialization.

Low thermal contact resistance boron nitride nanosheets composites enabled by interfacial arc-like phonon bridge.

Two-dimensional materials with ultrahigh in-plane thermal conductivity are ideal for heat spreader applications but cause significant thermal contact resistance in complex interfaces, limiting their use as thermal interface materials. In this study, we present an interfacial phonon bridge strategy to reduce the thermal contact resistance of boron nitride nanosheets-based composites. By using a low-molecular-weight polymer, we are able to manipulate the alignment of boron nitride nanosheets through sequential stacking and cutting, ultimately achieving flexible thin films with a layer of arc-like structure superimposed on perpendicularly aligned ones. Our results suggest that arc-like structure can act as a phonon bridge to lower the contact resistance by 70% through reducing phonon back-reflection and enhancing phonon coupling efficiency at the boundary. The resulting composites exhibit ultralow thermal contact resistance of 0.059 in2 KW-1, demonstrating effective cooling of fast-charging batteries at a thickness 2-5 times thinner than commercial products.

Near-room-temperature water-mediated densification of bulk van der Waals materials from their nanosheets.

The conventional fabrication of bulk van der Waals (vdW) materials requires a temperature above 1,000 °C to sinter from the corresponding particulates. Here we report the near-room-temperature densification (for example, ∼45 °C for 10 min) of two-dimensional nanosheets to form strong bulk materials with a porosity of <0.1%, which are mechanically stronger than the conventionally made ones. The mechanistic study shows that the water-mediated activation of van der Waals interactions accounts for the strong and dense bulk materials. Initially, water adsorbed on two-dimensional nanosheets lubricates and promotes alignment. The subsequent extrusion closes the gaps between the aligned nanosheets and densifies them into strong bulk materials. Water extrusion also generates stresses that increase with moulding temperature, and too high a temperature causes intersheet misalignment; therefore, a near-room-temperature moulding process is favoured. This technique provides an energy-efficient alternative to design a wide range of dense bulk van der Waals materials with tailored compositions and properties.

Status and Prospect of Two-Dimensional Materials in Electrolytes for All-Solid-State Lithium Batteries.

Replacing liquid electrolytes and separators in conventional lithium-ion batteries with solid-state electrolytes (SSEs) is an important strategy to ensure both high energy density and high safety. Searching for fast ionic conductors with high electrochemical and chemical stability has been the core of SSE research and applications over the past decades. Based on the atomic-level thickness and infinitely expandable planar structure, numerous two-dimensional materials (2DMs) have been exploited and applied to address the most critical issues of low ionic conductivity of SSEs and lithium dendrite growth in all-solid-state lithium batteries. This review introduces the research process of 2DMs in SSEs, then summarizes the mechanisms and strategies of inert and active 2DMs toward Li+ transport to improve the ionic conductivity and enhance the electrode/SSE interfacial compatibility. More importantly, the main challenges and future directions for the application of 2DMs in SSEs are considered, including the importance of exploring the relationship between the anisotropic structure of 2DMs and Li+ diffusion behavior, the exploitation of more 2DMs, and the significance of in situ characterizations in elucidating the mechanisms of Li+ transport and interfacial reactions. This review aims to provide a comprehensive understanding to facilitate the application of 2DMs in SSEs.

High-performance bifacial perovskite solar cells enabled by single-walled carbon nanotubes.

Bifacial perovskite solar cells have shown great promise for increasing power output by capturing light from both sides. However, the suboptimal optical transmittance of back metal electrodes together with the complex fabrication process associated with front transparent conducting oxides have hindered the development of efficient bifacial PSCs. Here, we present a novel approach for bifacial perovskite devices using single-walled carbon nanotubes as both front and back electrodes. single-walled carbon nanotubes offer high transparency, conductivity, and stability, enabling bifacial PSCs with a bifaciality factor of over 98% and a power generation density of over 36%. We also fabricate flexible, all-carbon-electrode-based devices with a high power-per-weight value of 73.75 W g-1 and excellent mechanical durability. Furthermore, we show that our bifacial devices have a much lower material cost than conventional monofacial PSCs. Our work demonstrates the potential of SWCNT electrodes for efficient, stable, and low-cost bifacial perovskite photovoltaics.