Recent Advances in Mn-Rich Layered Materials for Sodium-Ion Batteries

Branded with low cost and a high degree of safety, with an ambitious aim of substituting lithium-ion batteries in many fields, sodium-ion batteries have received fervid attention in recent years after being dormant for decades. Layered materials are a major focus of study owing to the extensive experience already gained in lithium-ion batteries, and the pursuit of a Mn-rich composition is critical to reduce the cost while retaining the performance. This review provides a timely update of the recent progress of Mn-rich layered materials for sodium-ion batteries based on the understandings of the phase forming principles, structure transformation upon cycling and charge compensation mechanisms and discusses potential ambiguities in the pursuit of high-performance materials.     

Ultra-Damping Composites Enhanced by Yolk–Shell Piezoelectric Damping Mechanism

High-performance damping materials are significant toward reducing vibration and maintaining stability for industrial applications. Herein, a yolk–shell piezoelectric damping mechanism is reported, which can enhance mechanical energy dissipation and improve damping capability. With the addition of yolk–shell particles and carbon nanotube (CNT) conductive network, damping properties of various resin matrices are enhanced with the energy dissipation path of mechanical to electrical to heat energy. Particularly, the peak loss factor of epoxy composites reaches 1.91 and tan δ area increases by 25.72% at 20 °C. The results prove the general applicability of yolk–shell piezoelectric damping mechanism. Besides, the novel damping materials also exhibit excellent flexibility, stretchability, and resilience, offering a promising application toward damping coating, indicating broad scope of application in transportation and sophisticated electronics, etc.     

Direct Growth of Uniform Bimetallic Core-Shell or Intermetallic Nanoparticles on Carbon via a Surface-Confinement Strategy for Electrochemical Hydrogen Evolution Reaction

Due to the surface inhomogeneity of the solid supports, direct growth of uniform bimetallic nanoparticles (NPs) with controllable structure and size thereon is particularly challenging. Herein, a surface-confinement strategy is reported to directly prepare ultrafine bimetallic Pt M NPs (MFe, Cu, and Co) with structure of core-shell or intermetallic compounds on an N functionalized carbon support (NC). It is found that the N species of NC support can atomically disperse metal cations of precursors, which largely renders uniform nucleation and growth of bimetallic NPs and fine structure modulation of them. In another regard, metal transfer is confined to a narrow region on NC via N-mediation, hence greatly favoring localized particle growth and formation of ultrafine bimetallic NPs. Remarkably, the ultrafine 3.1 ± 0.7 nm intermetallic Pt₃Fe NPs on NC displayed excellent catalytic activity and durability toward electrochemical hydrogen evolution reaction.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Proximity-Induced Fully Ferromagnetic Order with Eightfold Magnetic Anisotropy in Heavy Transition Metal Oxide CaRuO3

Ferromagnetic materials with a strong spin-orbit coupling (SOC) have attracted much attention in recent years because of their exotic properties and potential applications in energy-efficient spintronics. However, such materials are scarce in nature. Here, a proximity-induced paramagnetic to ferromagnetic transition for the heavy transition metal oxide CaRuO₃ in (001)-(LaMnO₃/CaRuO₃) superlattices is reported. Anomalous Hall effect is observed in the temperature range up to 180 K. Maximal anomalous Hall conductivity and anomalous Hall angle are as large as ∼15 Ω⁻¹ cm⁻¹ and ∼0.93%, respectively, by one to two orders of magnitude larger than those of the typical 3d ferromagnetic oxides such as La_0.67Sr_0.33MnO₃. Density functional theory calculations indicate the existence of avoid band crossings in the electronic band structure of the ferromagnetic CRO layer, which enhances Berry curvature thus strong anomalous Hall effects. Further evidences from polarized neutron reflectometry show that the CaRuO₃ layers are in a fully ferromagnetic state (∼0.8 μ_B/Ru), in sharp contrast to the proximity-induced canted antiferromagnetic state in 5d oxides SrIrO₃ and CaIrO₃ (∼0.1 μ_B/Ir). More than that, the magnetic anisotropy of the (001)-(LaMnO₃/CaRuO₃) superlattices is eightfold symmetric, showing potential applications in the technology of multistate data storage.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

A Hybrid Strategy-Based Ultra-Narrow Stretchable Microelectrodes with Cell-Level Resolution

Stretchable ultra-narrow (e.g., 10 µm in width) microelectrodes are crucial for the electrophysiological monitoring of single cells providing the fundamental understanding to the working mechanism of neuro network or other electrically functional cells. Current fabrication strategies either focus on the preparation of normal stretchable electrodes with hundreds of micrometers or millimeters in width by using inorganic conductive materials or develop conductive organic polymer gel for ultra-narrow electrodes which suffer from low stretchability and instability for long-term implantation, therefore, it is still highly desirable to explore bio-interfacial ultra-narrow stretchable inorganic electrodes. Herein, a hybrid strategy is reported to prepare ultra-narrow multi-channel stretchable microelectrodes without using photolithography or laser-assisting etching. A 10 µm × 10 µm monitoring window is fabricated with enhanced interfacial impedance by the special rough surface. The stretchability achieves to 120% for this 10 µm-width stretchable electrode. Supported by these superior properties, it is demonstrated that the stretchable microelectrodes can detect electrophysiological signals of single cells in vitro and collect electrophysiological signals more precisely in vivo. The reported strategy will open up the accessible preparation of the fine-size stretchable microelectrode. It will significantly improve the resolution of monitoring and stimulation of inorganic stretchable electrodes.     

Durable Integrated K-Metal Anode with Enhanced Mass Transport through Potassiphilic Porous Interconnected Mediator

K-metal batteries have become one of the promising candidates for the large-scale energy storage owing to the virtually inexhaustible and widely potassium resources. The uneven K⁺ deposition and dendrite growth on the anode causes the batteries prematurely failure to limit the further application. An integrated K-metal anode is constructed by cold-rolling K metal with a potassiphilic porous interconnected mediator. Based on the experimental results and theoretical calculations, it demonstrates that the potassiphilic porous interconnected mediator boosts the mass transportation of K-metal anode by the K affinity enhancement, which decreases the concentration polarization and makes a dendrite-free K-metal anode interface. The interconnected porous structure mitigates the internal stress generated during repetitive deposition/stripping, enabling minimized the generation of electrode collapse. As a result, a durable K-metal anode with excellent cycling ability of exceed 1, 000 h at 1 mA cm⁻²/1 mAh cm⁻² and lower polarization voltage in carbonate electrolyte is obtained. This proposed integrated anode with fast K⁺ kinetics fabricated by a repeated cold rolling and folding process provides a new avenue for constructing a high-performance dendrites-free anode for K-metal batteries.     

Fixed-time distributed optimization for multi-agent systems with external disturbances over directed networks

This article considers the fixed-time distributed optimization problem of multi-agent systems with external disturbances, in which the global optimization objective is a convex combination of local objective functions. To solve this issue, a directed communication network is carefully designed, and an integral sliding mode control protocol is proposed based on the gradient of global objective function first. Moreover, two distributed optimal protocols are designed by using the gradient and the Hessian matrix of local objective function, respectively. By employing Lyapunov stability theory, graph theory, convex analysis, and inequality techniques, we prove that all proposed protocols can make agents achieve consensus and converge accurately to the optimal solution of the considered problem in some fixed-time intervals. Finally, some numerical simulations are given to verify the feasibility of the theoretical results.     

Development,integration, and field evaluation of an autonomous citrus-harvesting robot

Citrus harvesting is a labor-intensive and time-intensive task. As the global population continues to age, labor costs are increasing dramatically. Therefore, the citrus-harvesting robot has attracted considerable attention from the business and academic communities. However, robotic harvesting in unstructured and natural citrus orchards remains a challenge. This study aims to address some challenges faced in commercializing citrus-harvesting robots. We present a fully integrated, autonomous, and innovative solution for citrus-harvesting robots to overcome the harvesting difficulties derived from the natural growth characteristics of citrus. This solution uses a fused simultaneous localization and mapping algorithm based on multiple sensors to perform high-precision localization and navigation for the robot in the field orchard. Besides, a novel visual method for estimating fruit poses is proposed to cope with the randomization of citrus growth orientations. Further, a new end-effector is designed to improve the success and conformity rate of citrus stem cutting. Finally, a fully autonomous harvesting robot system has been developed and integrated. Field evaluations showed that the robot could harvest citrus continuously with an overall success rate of 87.2% and an average picking time of 10.9 s/fruit. These efforts provide a solid foundation for the future commercialization of citrus-harvesting robots.