Direct ink writing 3D printing of low-dimensional nanomaterials for micro-supercapacitors.

Micro-supercapacitors (MSCs) have attracted significant attention for potential applications in miniaturized electronics due to their high power density, rapid charge/discharge rates, and extended lifespan. Despite the unique properties of low-dimensional nanomaterials, which hold tremendous potential for revolutionary applications, effectively integrating these attributes into MSCs presents several challenges. 3D printing is rapidly emerging as a key player in the fabrication of advanced energy storage devices. Its ability to design, prototype, and produce functional devices incorporating low-dimensional nanomaterials positions it as an influential technology. In this review, we delve into recent advancements and innovations in micro-supercapacitor manufacturing, with a specific focus on the incorporation of low-dimensional nanomaterials using direct ink writing (DIW) 3D printing techniques. We highlight the distinct advantages offered by low-dimensional nanomaterials, from quantum effects in 0D nanoparticles that result in high capacitance values to rapid electron and ion transport in 1D nanowires, as well as the extensive surface area and mechanical flexibility of 2D nanosheets. Additionally, we address the challenges encountered during the fabrication process, such as material viscosity, printing resolution, and seamless integration of active materials with current collectors. This review highlights the remarkable progress in the energy storage sector, demonstrating how the synergistic use of low-dimensional nanomaterials and 3D printing technologies not only overcomes existing limitations but also opens new avenues for the development and production of advanced micro-supercapacitors. The convergence of low-dimensional nanomaterials and DIW 3D printing heralds the advent of the next generation of energy storage devices, making a significant contribution to the field and laying the groundwork for future innovations.

3D Printed MXene-Based Wire Strain Sensors with Enhanced Sensitivity and Anisotropy.

Stretchable strain sensors play a crucial role in intelligent wearable systems, serving as the interface between humans and environment by translating mechanical strains into electrical signals. Traditional fiber strain sensors with intrinsic uniform axial strain distribution face challenges in achieving high sensitivity and anisotropy. Moreover, existing micro/nano-structure designs often compromise stretchability and durability. To address these challenges, a novel approach of using 3D printing to fabricate MXene-based flexible sensors with tunable micro and macrostructures.  Poly(tetrafluoroethylene) (PTFE) as a pore-inducing agent is added into 3D printable inks to achieve controllable microstructural modifications. In addition to microstructure tuning, 3D printing is employed for macrostructural design modifications, guided by finite element modeling (FEM) simulations. As a result, the 3D printed sensors exhibit heightened sensitivity and anisotropy, making them suitable for tracking static and dynamic displacement changes. The proposed approach presents an efficient and economically viable solution for standardized large-scale production of advanced wire strain sensors.

A deep learning-based quantitative prediction model for the processing potentials of soybeans as soymilk raw materials.

Current technologies as correlation analysis, regression analysis and classification model, exhibited various limitations in the evaluation of soybean possessing potentials, including single, vague evaluation and failure of quantitative prediction, and thereby hindering more efficient and profitable soymilk industry. To solve this problem, 54 soybean cultivars and their corresponding soymilks were subjected to chemical, textural, and sensory analyses to obtain the soybean physicochemical nature (PN) and the soymilk profit and quality attribute (PQA) datasets. A deep-learning based model was established to quantitatively predict PQA data using PN data. Through 45 rounds of training with the stochastic gradient descent optimization, 9 remaining pairs of PN and PQA data were used for model validation. Results suggested that the overall prediction performance of the model showed significant improvements through iterative training, and the trained model eventually reached satisfying predictions (|relative error| ≤ 20%, standard deviation of relative error ≤ 40%) on 78% key soymilk PQAs. Future model training using big data may facilitate better prediction on soymilk odor qualities.

Recent progress in the study of integrated solar cell-energy storage systems.

As fossil fuels continue to deplete, the development of sustainable and green energy sources has become crucial for human societal advancement. Among the various renewable energies, solar energy stands out as a promising substitute for conventional fossil fuels, offering widespread availability and a pollution-free solution. Solar cells, as devices that convert solar energy, are garnering significant focus. However, the intermittent nature of solar energy results in a high dependence on weather conditions of solar cells. Integrated solar cell-energy storage systems that integrate solar cells and energy storage devices may solve this problem by storing the generated electricity and managing the energy output. This review delves into the latest developments in integrated solar cell-energy storage systems, marrying various solar cells with either supercapacitors or batteries. It highlights their construction, material composition, and performance. Additionally, it discusses prevailing challenges and future possibilities, aiming to spark continued advancement and innovation in the sector.

Three-Dimensional Printing of Hydrogels for Flexible Sensors: A Review.

The remarkable flexibility and heightened sensitivity of flexible sensors have drawn significant attention, setting them apart from traditional sensor technology. Within this domain, hydrogels-3D crosslinked networks of hydrophilic polymers-emerge as a leading material for the new generation of flexible sensors, thanks to their unique material properties. These include structural versatility, which imparts traits like adhesiveness and self-healing capabilities. Traditional templating-based methods fall short of tailor-made applications in crafting flexible sensors. In contrast, 3D printing technology stands out with its superior fabrication precision, cost-effectiveness, and satisfactory production efficiency, making it a more suitable approach than templating-based strategies. This review spotlights the latest hydrogel-based flexible sensors developed through 3D printing. It begins by categorizing hydrogels and outlining various 3D-printing techniques. It then focuses on a range of flexible sensors-including those for strain, pressure, pH, temperature, and biosensors-detailing their fabrication methods and applications. Furthermore, it explores the sensing mechanisms and concludes with an analysis of existing challenges and prospects for future research breakthroughs in this field.

MXene-mediated Interfacial Growth of 2D-2D Heterostructured Nanomaterials as Cathodes for Zn-based Aqueous Batteries.

In this study, we introduce a novel approach for synthesizing two-dimensional (2D) MXene heterostructures featuring a sandwiched and cross-linked network structure. This method addresses the common issue of activity degradation in 2D nanomaterials caused by inevitable aggregation. By utilizing the distinct surface characteristics of MXene, we successfully induced the growth of various 2D nanomaterials on MXene substrates. This strategy effectively mitigates self-stacking defects and augments the exposure of surface areas. In particular, the obtained 2D-2D MXene@NiCo-layered double hydroxide (MH-NiCo) heterostructures exhibit enhanced structural stability, improved chemical reversibility, and heightened charge transfer efficiency, outperforming pure NiCo LDH. The aqueous MH-Ni4Co1//Zn@carbon cloth (MH-Ni4Co1//Zn@CC) battery demonstrates exceptional performance with a remarkable specific capacity of 0.61 mAh cm-2, maintaining 96.6 % capacitance after 2300 cycles. Additionally, it achieves an energy density of 1.047 mWh cm-2 and a power density of 32.899 mW cm-2. This research not only paves the way for new design paradigms in energy-related nanomaterials but also offers invaluable insights for the application and optimization of 2D-2D heterostructures in advanced electrochemical devices.

Potassium ion pre-intercalated MnO2 for aqueous multivalent ion batteries.

Manganese dioxide (MnO2), as a cathode material for multivalent ion (such as Mg2+ and Al3+) storage, is investigated due to its high initial capacity. However, during multivalent ion insertion/extraction, the crystal structure of MnO2 partially collapses, leading to fast capacity decay in few charge/discharge cycles. Here, through pre-intercalating potassium-ion (K+) into δ-MnO2, we synthesize a potassium ion pre-intercalated MnO2, K0.21MnO2·0.31H2O (KMO), as a reliable cathode material for multivalent ion batteries. The as-prepared KMO exhibits a high reversible capacity of 185 mAh/g at 1 A/g, with considerable rate performance and improved cycling stability in 1 mol/L MgSO4 electrolyte. In addition, we observe that aluminum-ion (Al3+) can also insert into a KMO cathode. This work provides a valid method for modification of manganese-based oxides for aqueous multivalent ion batteries.

Long-Lasting Zinc-Iodine Batteries with Ultrahigh Areal Capacity and Boosted Rate Capability Enabled by Nickel Single-Atom Electrocatalysts.

Zinc-iodine (Zn-I2) batteries have garnered significant attention for their high energy density, low cost, and inherent safety. However, several challenges, including polyiodide dissolution and shuttling, sluggish iodine redox kinetics, and low electrical conductivity, limit their practical applications. Herein, we designed a highly efficient electrocatalyst for Zn-I2 batteries by uniformly dispersing Ni single atoms (NiSAs) on hierarchical porous carbon skeletons (NiSAs-HPC). In situ Raman analysis revealed that the conversion of soluble polyiodides (I3- and I5-) was significantly accelerated using NiSAs-HPC because of the remarkable electrocatalytic activity of NiSAs. The resulting Zn-I2 batteries with NiSAs-HPC/I2 cathodes delivered exceptional rate capability (121 mAh g-1 at 50 C), and ultralong cyclic stability (over 40 000 cycles at 50 C). Even under 11.6 mg cm-2 iodine, Zn-I2 batteries still exhibited an impressive cyclic stability with a capacity retention of 93.4% and 141 mAh g-1 after 10 000 cycles at 10 C.

MXene-Based Functional Platforms for Tumor Therapy.

Recently, 2D transition metal carbide, nitride, and carbonitrides (MXenes) materials stand out in the field of tumor therapy, particularly in the construction of functional platforms for optimal antitumor therapy due to their high specific surface area, tunable performance, strong absorption of near-infrared light as well as preferable surface plasmon resonance effect. In this review, the progress of MXene-mediated antitumor therapy is summarized after appropriate modifications or integration procedures. The enhanced antitumor treatments directly performed by MXenes, the significant improving effect of MXenes on different antitumor therapies, as well as the MXene-mediated imaging-guided antitumor strategies are discussed in detail. Moreover, the existing challenges and future development directions of MXenes in tumor therapy are presented.

Ethanol-Induced Ni2+ -Intercalated Cobalt Organic Frameworks on Vanadium Pentoxide for Synergistically Enhancing the Performance of 3D-Printed Micro-Supercapacitors.

The synthesis of metal-organic framework (MOF) nanocomposites with high energy density and excellent mechanical strength is limited by the degree of lattice matching and crystal surface structure. In this study, dodecahedral ZIF-67 is synthesized uniformly on vanadium pentoxide nanowires. The influence of the coordination mode on the surface of ZIF-67 in ethanol is also investigated. Benefitting from the different coordination abilities of Ni2+ , Co2+ , and N atoms, spatially separated surface-active sites are created through metal-ion exchange. Furthermore, the incompatibility between the d8 electronic configuration of Ni2+ and the three-dimensional (3D) structure of ZIF-67 afforded the synthesis of hollow structures by controlling the amount of Ni doping. The formation of NiCo-MOF@CoOOH@V2 O5 nanocomposites is confirmed using X-ray absorption fine structure analysis. The high performance of the obtained composite is illustrated by fabricating a 3D-printed micro-supercapacitor, exhibiting a high area specific capacitance of 585 mF cm-2 and energy density of 159.23 µWh cm-2 (at power density = 0.34 mW cm-2 ). The solvent/coordination tuning strategy demonstrated in this study provides a new direction for the synthesis of high-performance nanomaterials for electrochemical energy storage applications.

Co-Intercalation of Dual Charge Carriers in Metal-Ion-Confining Layered Vanadium Oxide Nanobelts for Aqueous Zinc-Ion Batteries.

Vanadium-based oxides with high theoretical specific capacities and open crystal structures are promising cathodes for aqueous zinc-ion batteries (AZIBs). In this work, the confined synthesis can insert metal ions into the interlayer spacing of layered vanadium oxide nanobelts without changing the original morphology. Furthermore, we obtain a series of nanomaterials based on metal-confined nanobelts, and describe the effect of interlayer spacing on the electrochemical performance. The electrochemical properties of the obtained Al2.65 V6 O13 ⋅ 2.07H2 O as cathodes for AZIBs are remarkably improved with a high initial capacity of 571.7 mAh ⋅ g-1 at 1.0 A g-1 . Even at a high current density of 5.0 A g-1 , the initial capacity can still reach 205.7 mAh g-1 , with a high capacity retention of 89.2 % after 2000 cycles. This study demonstrates that nanobelts confined with metal ions can significantly improve energy storage applications, revealing new avenues for enhancing the electrochemical performance of AZIBs.

Hydrogen Stabilization and Activation of Dry-Quenched Coke for High-Rate-Performance Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) have rapidly come to dominate the market owing to their high power and energy densities. However, several factors have considerably limited their widespread commercial application, including high cost, poor high-rate performance, and complex synthetic conditions. Herein, we use earth-abundant and low-cost dry-quenched coke (DQC) to prepare low-crystalline carbon as anode material for LIBs and tailor the carbon skeleton via a facile green and sustainable hydrogen treatment. In particular, DQC is initially pyrolyzed at 1000 °C, followed by hydrogen treatment at 600 °C to obtain C-1000 H2-600. The resultant C-1000 H2-600 possesses abundant active defect sites and oxygen functional groups, endowing it with high-rate capabilities (C-1000 H2-600 vs. commercial graphite: 223.98 vs. 198.5 mAh g-1 at 1 A g-1 with a capacity retention of about 72.79% vs. 58.05%, 196.97 vs. 109.1 mAh g-1 at 2 A g-1 for 64.01% vs. 31.91%), and a stable cycling life (205.5 mAh g-1 for 1000 cycles at 2 A g-1) for LIBs. This proves that as a simple moderator, hydrogen effectively tailors the microstructure and surface-active sites of carbon materials and transforms low-cost DQC into high-value advanced carbon anodes by a green and sustainable route to improve the lithium storage performance.

Unlocking the High Capacity Ammonium-Ion Storage in Defective Vanadium Dioxide.

Aqueous ammonium-ion storage has been considered a promising energy storage competitor to meet the requirements of safety, affordability, and sustainability. However, ammonium-ion storage is still in its infancy in the absence of reliable electrode materials. Here, defective VO2 (d-VO) is employed as an anode material for ammonium-ion batteries with a moderate transport pathway and high reversible capacity of ≈200 mAh g-1 . Notably, an anisotropic or anisotropic behavior of structural change of d-VO between c-axis and ab planes depends on the state of charge (SOC). Compared with potassium-ion storage, ammonium-ion storage delivers a higher diffusion coefficient and better electrochemical performance. A full cell is further fabricated by d-VO anode and MnO2 cathode, which delivers a high energy density of 96 Wh kg-1 (based on the mass of VO2 ), and a peak energy density of 3254 W kg-1 . In addition, capacity retention of 70% can be obtained after 10 000 cycles at a current density of 1 A g-1 . What's more, the resultant quasi-solid-state MnO2 //d-VO full cell based on hydrogel electrolyte also delivers high safety and decent electrochemical performance. This work will broaden the potential applications of the ammonium-ion battery for sustainable energy storage.

Phase-transition tailored nanoporous zinc metal electrodes for rechargeable alkaline zinc-nickel oxide hydroxide and zinc-air batteries.

Secondary alkaline Zn batteries are cost-effective, safe, and energy-dense devices, but they are limited in rechargeability. Their short cycle life is caused by the transition between metallic Zn and ZnO, whose differences in electronic conductivity, chemical reactivity, and morphology undermine uniform electrochemical reactions and electrode structural stability. To circumvent these issues, here we propose an electrode design with bi-continuous metallic zinc nanoporous structures capable of stabilizing the electrochemical transition between metallic Zn and ZnO. In particular, via in situ optical microscopy and electrochemical impedance measurements, we demonstrate the kinetics-controlled structural evolution of Zn and ZnO. We also tested the electrochemical energy storage performance of the nanoporous zinc electrodes in alkaline zinc-nickel oxide hydroxide (NiOOH) and zinc-air (using Pt/C/IrO2-based air-electrodes) coin cell configurations. The Zn | |NiOOH cell delivers an areal capacity of 30 mAh/cm2 at 60% depth of discharging for 160 cycles, and the Zn | |Pt/C/IrO2 air cell demonstrates 80-hour stable operation in lean electrolyte condition.

Ionically Conductive Tunnels in h-WO3 Enable High-Rate NH4 + Storage.

Compared to the commonly applied metallic ion charge carriers (e.g., Li+ and Na+ ), batteries using nonmetallic charge carriers (e.g., H+ and NH4 + ) generally have much faster kinetics and high-rate capability thanks to the small hydrated ionic sizes and nondiffusion control topochemistry. However, the hosts for nonmetallic charge carriers are still limited. In this work, it is suggested that mixed ionic-electronic conductors can serve as a promising host for NH4 + storage. Using hexagonal tungsten oxide (h-WO3 ) as an example, it is shown that the existence of ionic conductive tunnels greatly promotes the high-rate NH4 + storage. Specifically, a much higher capacity of 82 mAh g-1 at 1 A g-1 is achieved on h-WO3 , in sharp contrast to 14 mAh g-1 of monoclinic tungsten oxide (m-WO3 ). In addition, unlike layered materials, the insertion and desertion of NH4 + ions are confined within the tunnels of the h-WO3 , which minimizes the damage to the crystal structure. This leads to outstanding stability of up to 200 000 cycles with 68% capacity retention at a high current of 20 A g-1 .

Monolithic Nanoporous Zn Anode for Rechargeable Alkaline Batteries.

The fabrication of monolithic nanoporous zinc bears its significance in safe and inexpensive energy storage; it can provide the much needed electrical conductivity and specific area in a practical alkaline battery to extend the short cycle life of a zinc anode. Although this type of structure has been routinely fabricated by dealloying, that is, the selective dissolution of an alloy, it has not led to a rechargeable zinc anode largely because the need for more reactive metal as the dissolving component in dealloying limits the choices of alloy precursors. Here, we apply the mechanism of dealloying, percolation dissolution, to design a process of reduction-induced decomposition of a zinc compound (ZnCl2) for nanoporous zinc. Using naphthalenide solution, we confine the selective dissolution of chloride to the compound/electrolyte interface, triggering the spontaneous formation of a network of 70 nm wide percolating zinc ligaments that retain the shape of a 200 µm thick monolith. We further reveal that this structure, when electrochemically oxidized and reduced in an alkaline electrolyte, undergoes surface-diffusion-controlled coarsening toward a quasi-steady-state with a length scale of ∼500 nm. The coarsening dynamics preserves the continuous zinc phase, enabling its uniform reaction and 200 cycles of stable performance at 40% depth of discharge (328 mAh/g) in a Ni-Zn battery.

All-polymer particulate slurry batteries.

Redox flow batteries are promising for large-scale energy storage, but some long-standing problems such as safety issues, system cost and cycling stability must be resolved. Here we demonstrate a type of redox flow battery that is based on all-polymer particulate slurry electrolytes. Micro-sized and uniformly dispersed all-polymer particulate suspensions are utilized as redox-active materials in redox flow batteries, breaking through the solubility limit and facilitating the application of insoluble redox-active materials. Expensive ion-exchange membranes are replaced by commercial dialysis membranes, which can simultaneously realize the rapid shuttling of H+ ions and cut off the migration of redox-active particulates across the separator via size exclusion. In result, the all-polymer particulate slurry redox flow batteries exhibit a highly reversible multi-electron redox process, rapid electrochemical kinetics and ultra-stable long-term cycling capability.

Efficient photocatalytic nitrogen fixation under ambient conditions enabled by the heterojunctions of n-type Bi2MoO6 and oxygen-vacancy-rich p-type BiOBr.

N2 fixation is one of the most important chemical reactions in the ecosystem of our planet. However, the industrial Haber-Bosch ammonia synthesis process is restricted by harsh reaction conditions (350-550 °C, 150-350 atm) and undesirable environmental effects (a large amount of CO2 emission). Photocatalytic N2 fixation is promising for achieving sustainable ammonia synthesis under ambient conditions with lower energy input and less environmental issues. However, the known photocatalysts for N2 reduction under mild conditions still face the great challenge of very low energy conversion efficiency. Herein, we report a facile solution-phase method to prepare the heterojunctions based on n-type Bi2MoO6 nanorods and oxygen-vacancy-rich p-type BiOBr nanosheets (Bi2MoO6/OV-BiOBr). Originating from the formation of p-n junctions and suitable bandgap configuration, the Bi2MoO6/OV-BiOBr heterojunctions exhibit effective light utilization and photogenerated electron-hole separation properties. Moreover, it is confirmed that the oxygen vacancies on BiOBr nanosheets are propitious to the adsorption and activation of N2 molecules. Benefiting from these merits, the Bi2MoO6/OV-BiOBr heterojunctions exhibit improved photocatalytic performance for N2 conversion to ammonia without any noble metal co-catalysts and sacrificial reagents under ambient conditions.

The dealloying-lithiation/delithiation-realloying mechanism of a breithauptite (NiSb) nanocrystal embedded nanofabric anode for flexible Li-ion batteries.

Antimony (Sb) based anodes with high conductivity and capability have shown great promise for applications in lithium ion batteries (LIBs). However, they often suffer from poor cycling stability because of the drastic volume variation and structural degradation on undergoing lithiation-delithiation processes. Here we demonstrate a novel Sb-based anode with a free-standing structure realized by uniformly implanting intermetallic compound breithauptite (nickel antimonide, NiSb) nanocrystals into nitrogen-doped carbon nanofibers (NiSb@NCNFs). The discharge/charge behavior of NiSb@NCNFs was systematically investigated by ex situ characterization, which revealed a special "dealloying-lithiation/delithiation-realloying" cycling mechanism. The NiSb nanocrystals possess high lithium storage capacity, and the interconnected network of NCNFs can accommodate the volume variation of encapsulated NiSb nanoparticles, while also providing smooth pathways for charge transport. Compared to other Sb-based anodes, the NiSb@NCNF anode presents exceptional reversible capacity (720 mA h g-1 at a current density of 100 mA g-1) and greatly enhanced cycling life at high rates (510 mA h g-1 after 2000 cycles at 2000 mA g-1). Furthermore, the free-standing NiSb@NCNF anode is free of binders, conductive additives and metal current collectors, exhibiting high flexibility and remarkable performances for the construction of flexible and bendable soft-packed full Li-ion pouch cells.

eg occupancy as an effective descriptor for the catalytic activity of perovskite oxide-based peroxidase mimics.

A peroxidase catalyzes the oxidation of a substrate with a peroxide. The search for peroxidase-like and other enzyme-like nanomaterials (called nanozymes) mainly relies on trial-and-error strategies, due to the lack of predictive descriptors. To fill this gap, here we investigate the occupancy of eg orbitals as a possible descriptor for the peroxidase-like activity of transition metal oxide (including perovskite oxide) nanozymes. Both experimental measurements and density functional theory calculations reveal a volcano relationship between the eg occupancy and nanozymes' activity, with the highest peroxidase-like activities corresponding to eg occupancies of ~1.2. LaNiO3-δ, optimized based on the eg occupancy, exhibits an activity one to two orders of magnitude higher than that of other representative peroxidase-like nanozymes. This study shows that the eg occupancy is a predictive descriptor to guide the design of peroxidase-like nanozymes; in addition, it provides detailed insight into the catalytic mechanism of peroxidase-like nanozymes.