Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu-doped NiCo Alloy Supported on Nickel Foam.

Electrooxidation of biomass-derived glycerol which is regarded as a main byproduct of industrial biodiesel production, is an innovative strategy to produce value-added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high-efficiency electrooxidation of glycerol into formate via a Cu doped NiCo alloy catalyst supported on nickel foam (Cu-NiCo/NF) in a coupled system paired with nitrate reduction. The designed Cu-NiCo/NF delivers only 1.23 V vs. RHE at 10 mA cm-2, and a record Faraday efficiency of formate of 93.8%. The superior performance is ascribed to the rapid generation of NiIII-OOH and CoIII-OOH and favorable coupling of surface *O with reactive intermediates. Using Cu-NiCo/NF as a bifunctional catalyst, the coupled system synchronously produces NH3 and formate, showing 290 mV lower than the coupling of hydrogen evolution reaction, together with excellent long-term stability for up to 144 h. This work lays out new guidelines and reliable strategies from catalyst design to system coupling for biomass-derived electrochemical refinery.

Solid Lithiation and Exfoliation for Scalable Synthesis of Two-Dimensional Nanosheets toward Industrialization.

Two-dimensional (2D) materials show intriguing and diverse properties in different fields, stimulating chemists to develop synthetic and functional methodologies for producing solution-processable nanosheets on a large scale. However, it is still challenging to prepare 2D materials for industrial applications without sacrificing their lab-scale properties. Solid lithiation and exfoliation can achieve the hundred-gram-scale production of transition metal telluride nanosheets, making it one of the most effective strategies for mass production of 2D nanomaterials. In this Perspective, we highlight the advantages, propose the challenges, and discuss the opportunities of solid lithiation and exfoliation as a promising and commercially viable production method for 2D nanomaterials.

Intrinsically Flexible Phase Change Fibers for Intelligent Thermal Regulation.

Owing to the significant latent heat generated at constant temperatures, phase change fibers (PCFs) have recently received much attention in the field of wearable thermal management. However, the phase change materials involved in the existing PCFs still experience a solid-liquid transition process, severely restricting their practicality as wearable thermal management materials. Herein, we, for the first time, developed intrinsically flexible PCFs (polyethylene glycol/4,4'-methylenebis(cyclohexyl isocyanate) fibers, PMFs) through polycondensation and wet-spinning process, exhibiting an inherent solid-solid phase transition property, adjustable phase transition behaviors, and outstanding knittability. The PMFs also present superior mechanical strength (28 MPa), washability (>100 cycles), thermal cycling stability (>2000 cycles), facile dyeability, and heat-induced recoverability, all of which are highly significant for practical wearable applications. Additionally, the PMFs can be easily recycled by directly dissolving them in solvents for reprocessing, revealing promising applications as sustainable materials for thermal management. Most importantly, the applicability of the PMFs was demonstrated by knitting them into permeable fabrics, which exhibit considerably improved thermal management performance compared with the cotton fabric. The PMFs offer great potential for intelligent thermal regulation in smart textiles and wearable electronics.

2.4 V ultrahigh-voltage aqueous MXene-based asymmetric micro-supercapacitors with high volumetric energy density toward a self-sufficient integrated microsystem.

Two-dimensional MXenes are key high-capacitance electrode materials for micro-supercapacitors (MSCs) catering to integrated microsystems. However, the narrow electrochemical voltage windows of conventional aqueous electrolytes (≤ 1.23 V) and symmetric MXene MSCs (typically ≤ 0.6 V) substantially limit their output voltage and energy density. Highly concentrated aqueous electrolytes exhibit lower water molecule activity, which inhibits water splitting and consequently widens the operating voltage window. Herein, we report ultrahigh-voltage aqueous planar asymmetric MSCs (AMSCs) based on a highly concentrated LiCl-gel quasi-solid-state electrolyte with MXene (Ti3C2T x ) as the negative electrode and MnO2 nanosheets as the positive electrode (MXene//MnO2-AMSCs). The MXene//MnO2-AMSCs exhibit a high voltage of up to 2.4 V, attaining an ultrahigh volumetric energy density of 53 mWh cm-3. Furthermore, the in-plane geometry and the quasi-solid-state electrolyte enabled excellent mechanical flexibility and performance uniformity in the serially/parallel connected packs of our AMSCs. Notably, the MXene//MnO2-AMSC-based integrated microsystem, in conjunction with solar cells and consumer electronics, could efficiently realize simultaneous energy harvesting, storage, and conversion. The findings of this study provide insights for constructing high-voltage aqueous MXene-based AMSCs as safe and self-sufficient micropower sources in smart integrated microsystems.

Redox Promoted Rapid and Deep Reconstruction of Defect-Rich Nickel Precatalysts for Efficient Water Oxidation.

Understanding the reconstruction mechanism to rationally design cost-effective electrocatalysts for oxygen evolution reaction (OER) is still challenging. Herein, a defect-rich NiMoO4 precatalyst is used to explore its OER activity and reconstruction mechanism. In situ generated oxygen vacancies, distorted lattices, and edge dislocations expedite the deep reconstruction of NiMoO4 to form polycrystalline Ni (oxy)hydroxides for alkaline oxygen evolution. It only needs ≈230 and ≈285 mV to reach 10 and 100 mA cm-2, respectively. The reconstruction boosted by the redox of Ni is confirmed experimentally by sectionalized cyclic voltammetry activations at different specified potential ranges combined with ex situ characterization techniques. Subsequently, the reconstruction route is presented based on the acid-base electronic theory. Accordingly, the dominant contribution of the adsorbate evolution mechanism to reconstruction during oxygen evolution is revealed. This work develops a novel route to synthesize defect-rich materials and provides new tactics to investigate the reconstruction.

Hybrid ion/electron interfacial regulation stabilizes the cobalt/oxygen redox of ultrahigh-voltage lithium cobalt oxide for fast-charging cyclability.

High-voltage and fast-charging LiCoO2 (LCO) is key to high-energy/power-density Li-ion batteries. However, unstable surface structure and unfavorable electronic/ionic conductivity severely hinder its high-voltage fast-charging cyclability. Here, we construct a Li/Na-B-Mg-Si-O-F-rich mixed ion/electron interface network on the 4.65 V LCO electrode to enhance its rate capability and long-term cycling stability. Specifically, the resulting artificial hybrid conductive network enhances the reversible conversion of Co3+/4+/O2-/n- redox by the interfacial ion-electron cooperation and suppresses interface side reactions, inducing an ultrathin yet compact cathode electrolyte interphase. Simultaneously, the derived near-surface Na+/Mg2+/Si4+-pillared local intercalation structure greatly promotes the Li+ diffusion around the 4.55 V phase transition and stabilizes the cathode interface. Finally, excellent 3 C (1 C = 274 mA g-1) fast charging performance is demonstrated with 73.8% capacity retention over 1000 cycles. Our findings shed new insights to the fundamental mechanism of interfacial ion/electron synergy in stabilizing and enhancing fast-charging cathode materials.

The status and challenging perspectives of 3D-printed micro-batteries.

In the era of the Internet of Things and wearable electronics, 3D-printed micro-batteries with miniaturization, aesthetic diversity and high aspect ratio, have emerged as a recent innovation that solves the problems of limited design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-casting method. Thus, a comprehensive understanding of the rational design of 3D-printed materials, inks, methods, configurations and systems is critical to optimize the electrochemical performance of customizable 3D-printed micro-batteries. In this review, we offer a key overview and systematic discussion on 3D-printed micro-batteries, emphasizing the close relationship between printable materials and printing technology, as well as the reasonable design of inks. Initially, we compare the distinct characteristics of various printing technologies, and subsequently emphatically expound the printable components of micro-batteries and general approaches to prepare printable inks. After that, we focus on the outstanding role played by 3D printing design in the device architecture, battery configuration, performance improvement, and system integration. Finally, the future challenges and perspectives concerning high-performance 3D-printed micro-batteries are adequately highlighted and discussed. This comprehensive discussion aims at providing a blueprint for the design and construction of next-generation 3D-printed micro-batteries.

Monolithically integrated micro-supercapacitors with high areal number density produced by surface adhesive-directed electrolyte assembly.

Accurately placing very small amounts of electrolyte on tiny micro-supercapacitors (MSCs) arrays in close proximity is a major challenge. This difficulty hinders the development of densely-compact monolithically integrated MSCs (MIMSCs). To overcome this grand challenge, we demonstrate a controllable electrolyte directed assembly strategy for precise isolation of densely-packed MSCs at micron scale, achieving scalable production of MIMSCs with ultrahigh areal number density and output voltage. We fabricate a patterned adhesive surface across MIMSCs, that induce electrolyte directed assembly on 10,000 highly adhesive MSC regions, achieving a 100 µm-scale spatial separation between each electrolyte droplet within seconds. The resultant MIMSCs achieve an areal number density of 210 cells cm-2 and a high areal voltage of 555 V cm-2. Further, cycling the MIMSCs at 190 V over 9000 times manifests no performance degradation. A seamlessly integrated system of ultracompact wirelessly-chargeable MIMSCs is also demonstrated to show its practicality and versatile applicability.

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.

Electrochemically Exfoliated Graphene Additive-Free Inks for 3D Printing Customizable Monolithic Integrated Micro-Supercapacitors on a Large Scale.

Three-dimensional (3D) printing technology with enhanced fidelity can achieve multiple functionalities and boost electrochemical performance of customizable planar micro-supercapacitors (MSCs), however, precise structural control of additive-free graphene-based macro-assembly electrode for monolithic integrated MSCs (MIMSCs) remains challenging. Here, the large-scale 3D printing fabrication of customizable planar MIMSCs is reported utilizing additive-free, high-quality electrochemically exfoliated graphene inks, which is not required the conventional cryogenic assistance during the printing process and any post-processing reduction. The resulting MSCs reveal an extremely small engineering footprint of 0.025 cm2, exceptionally high areal capacitance of 4900 mF cm-2, volumetric capacitance of 195.6 F cm-3, areal energy density of 2.1 mWh cm-2, and unprecedented volumetric energy density of 23 mWh cm-3 for a single cell, surpassing most previously reported 3D printed MSCs. The 3D printed MIMSC pack is further demonstrated, with the maximum areal cell count density of 16 cell cm-2, the highest output voltage of 192.5 V and the largest output voltage per unit area of 56 V cm-2 up to date are achieved. This work presents an innovative solution for processing high-performance additive-free graphene ink and realizing the large-scale production of 3D printed MIMSCs for planar energy storage.

Recent advancement and key opportunities of MXenes for electrocatalysis.

MXenes are promising materials for electrocatalysis due to their excellent metallic conductivity, hydrophilicity, high specific surface area, and excellent electrochemical properties. Herein, we summarize the recent advancement of MXene-based materials for electrocatalysis and highlight their key challenges and opportunities. In particular, this review emphasizes on the major design principles of MXene-based electrocatalysts, including (1) coupling MXene with active materials or heteroatomic doping to create highly active synergistic catalyst sites; (2) construction of 3D MXene structure or introducing interlayer spacers to increase active areas and form fast mass-charge transfer channel; and (3) protecting edge of MXene or in situ transforming the surface of MXene to stable active substance that inhibits the oxidation of MXene and then enhances the stability. Consequently, MXene-based materials exhibit outstanding performance for a variety of electrocatalytic reactions. Finally, the key challenges and promising prospects of the practical applications of MXene-based electrocatalysts are briefly proposed.

Breaking the Ru-O-Ru Symmetry of a RuO2 Catalyst for Sustainable Acidic Water Oxidation.

Proton exchange membrane water electrolysis is a highly promising hydrogen production technique for sustainable energy supply, however, achieving a highly active and durable catalyst for acidic water oxidation still remains a formidable challenge. Herein, we propose a local microenvironment regulation strategy for precisely tuning In-RuO2 /graphene (In-RuO2 /G) catalyst with intrinsic electrochemical activity and stability to boost acidic water oxidation. The In-RuO2 /G displays robust acid oxygen evolution reaction performance with a mass activity of 671 A gcat -1 at 1.5 V, an overpotential of 187 mV at 10 mA cm-2 , and long-lasting stability of 350 h at 100 mA cm-2 , which arises from the asymmetric Ru-O-In local structure interactions. Further, it is unraveled theoretically that the asymmetric Ru-O-In structure breaks the thermodynamic activity limit of the traditional adsorption evolution mechanism which significantly weakens the formation energy barrier of OOH*, thus inducing a new rate-determining step of OH* absorption. Therefore, this strategy showcases the immense potential for constructing high-performance acidic catalysts for water electrolyzers.

Recent Advances in Flexible Wearable Supercapacitors: Properties, Fabrication, and Applications.

A supercapacitor is a potential electrochemical energy storage device with high-power density (PD) for driving flexible, smart, electronic devices. In particular, flexible supercapacitors (FSCs) have reliable mechanical and electrochemical properties and have become an important part of wearable, smart, electronic devices. It is noteworthy that the flexible electrode, electrolyte, separator and current collector all play key roles in overall FSCs. In this review, the unique mechanical properties, structural designs and fabrication methods of each flexible component are systematically classified, summarized and discussed based on the recent progress of FSCs. Further, the practical applications of FSCs are delineated, and the opportunities and challenges of FSCs in wearable technologies are proposed. The development of high-performance FSCs will greatly promote electricity storage toward more practical and widely varying fields. However, with the development of portable equipment, simple FSCs cannot satisfy the needs of integrated and intelligent flexible wearable devices for long durations. It is anticipated that the combining an FSC and a flexible power source such as flexible solar cells is an effective strategy to solve this problem. This review also includes some discussions of flexible self-powered devices.

Protocol for fabrication of Pt/RuO2/graphene bifunctional oxygen catalyst in Li-O2 batteries.

The commercial mass production of bifunctional oxygen catalysts with high activity and stability is critical for constructing high-performance lithium-oxygen (Li-O2) batteries, but remains challenging. Herein, we describe a protocol for the scalable fabrication of a 2D bifunctional electrocatalyst of Pt/RuO2/graphene by spatial confinement strategy and elaborately evaluate its oxygen reduction/evolution reactions for advanced Li-O2 batteries. We then detail the synthesis steps for preparing materials followed by assembly and evaluation of the three-electrode systems and coin-type Li-O2 batteries. For complete details on the use and execution of this protocol, please refer to Li et al. (2023).1.

A Biodegradable High-Performance Microsupercapacitor for Environmentally Friendly and Biocompatible Energy Storage.

Biodegradable and biocompatible microscale energy storage devices are very crucial for environmentally friendly microelectronics and implantable medical applications. Herein, a biodegradable and biocompatible microsupercapacitor (BB-MSC) with satisfying overall performance is realized via the combination of three-dimensional (3D) printing technique and biodegradable materials. Due to the 3D-interconnected structure of electrodes and elaborated design of electrolyte, the as-prepared BB-MSC exhibits superior overall performance than most of biodegradable devices, including a wide operation voltage of 1.8 V, high areal specific capacitance of 251 mF/cm2, good cycle stability, and favorable low-temperature resistance (-20 °C), demonstrative of reliability and practicality of our devices even in frosty environments. Importantly, the smooth degradation has been realized for the BB-MSC after being buried in natural soil for ∼90 days, and its implantation does not affect the healthy status of SD rats. Therefore, this work explores avenues for the design and construction of environmentally friendly and biocompatible microscale energy storage devices.

Natural-Wood-Inspired Ultrastrong Anisotropic Hybrid Hydrogels Targeting Artificial Tendons or Ligaments.

Hydrogels are able to mimic the flexibility of biological tissues or skin, but they still cannot achieve satisfactory strength and toughness, greatly limiting their scope of application. Natural wood can offer inspiration for designing high-strength hydrogels attributed to its anisotropic structure. Herein, we propose an integrated strategy for efficient preparation of ultrastrong hydrogels using a salting-assisted prestretching treatment. The as-prepared poly(vinyl alcohol)/cellulose nanofiber hybrid hydrogels show distinct wood-like anisotropy, including oriented molecular fiber bundles and extended grain size, which endows materials with extraordinarily comprehensive mechanical properties of ultimate breaking strength exceeding 40 MPa, strain approaching 250%, and toughness exceeding 60 MJ·m-3, and outstanding tear resistance. Impressively, the breaking strength and toughness of the reswollen preoriented hydrogels approach 10 MPa and 25 MJ·m-3, respectively. In vitro and in vivo tests demonstrate that the reswollen hydrogels do not affect the growth and viability of the cells, nor do they cause the inflammation or rejection of the mouse tissue, implying extremely low biotoxicity and perfect histocompatibility, showcasing bright prospects for application in artificial ligaments or tendons. The strategy provided in this study can be generalized to a variety of biocompatible polymers for the fabrication of high-performance hydrogels with anisotropic structures.