Sufficient Utilization of Mn2+/Mn3+/Mn4+ Redox in NASICON Phosphate Cathodes towards High-Energy Na-Ions Batteries

Na superionic conductor of Na₃MnTi(PO₄)₃ only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn²⁺ ions resided in Na⁺ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. These findings indicate that the sodium excess Na_3.5MnTi_0.5Ti_0.5(PO₄)₃ cathode with Ti⁴⁺ reduction has a lowest Mn²⁺ occupation on the Na⁺ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na_3.6Mn_1.15Ti_0.85(PO₄)₃ cathode achieved a high energy density over 380 Wh kg⁻¹ (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries.     

Toward Flexible Embodied Energy: Scale-Inspired Overlapping Lithium-Ion Batteries with High-Energy-Density and Variable Stiffness

High performance flexible batteries are essential ingredients for flexible devices. However, general isolated flexible batteries face critical challenges in developing multifunctional embodied energy systems, owing to the lack of integrative design. Herein, inspired by scales in creatures, overlapping flexible lithium-ion batteries (FLIBs) consisting of energy storage scales and connections using LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) and graphite electrodes are presented. The scale-dermis structure ensures a high energy density of 374.4 Wh L⁻¹ as well as a high capacity retention of 93.2% after 200 charge/discharge cycles and 40 000 bending times. A variable stiffness property is revealed that can be controlled by battery configurations and deformation modes. Furthermore, the overlapping FLIBs can be housed directly into the architecture of several flexible devices, such as robots and grippers, allowing to create multifunctionalities that go far beyond energy storage and include load-bearing and variable flexibility. This study broadens the versatility of FLIBs toward energy storage structure engineering of flexible devices.     

Amorphization Boost Multi-Ions Storage for High-Performance Aqueous Batteries

Regarding the complex properties of various cations, the design of aqueous batteries that can simultaneously store multi-ions with high capacity and satisfactory rate performance is a great challenge. Here an amorphization strategy to boost cation-ion storage capacities of anode materials is reported. In monovalent (H⁺, Li⁺, K⁺), divalent (Mg²⁺, Ca²⁺, Zn²⁺) and even trivalent (Al³⁺) aqueous electrolytes, the capacity of the resulting amorphous MoO_x is more than quadruple than that of crystalline MoO_x and exceeds those of other reported multiple-ion storage materials. Both experimental and theoretical calculations reveal the generation of ample active sites and isotropic ions in the amorphous phase, which accelerates cation migration within the electrode bulk. Amorphous MoO_x can be coupled with multi-ion storage cathodes to realize electrochemical energy storage devices with different carriers, promising high energy and power densities. The power density exceeded 15000 W kg⁻¹, demonstrating the great potential of amorphous MoO_x in advanced aqueous batteries.     

Probing into Reverse Bias Dark Current in Perovskite Photodiodes: Critical Role of Surface Defects

Minimizing reverse bias dark current density (J_dark) while retaining high external quantum efficiency is crucial for promising applications of perovskite photodiodes, and it remains challenging to elucidate the ultimate origin of J_dark. It is demonstrated in this study that the surface defects induced by iodine vacancies are the main cause of J_dark in perovskite photodiodes. In a targeted way, the surface defects are thoroughly passivated through a simple treatment with butylamine hydroiodide to form ultrathin 2D perovskite on its 3D bulk. In the passivated perovskite photodiodes, J_dark as low as 3.78 × 10^-10 A cm^-2 at -0.1 V is achieved, and the photoresponse is also enhanced, especially at low light intensities. A combination of the two improvements realizes high specific detectivity up to 1.46 × 10¹² Jones in the devices. It is clarified that the trap states induced by the surface defects can not only raise the generation-recombination current density associated with the Shockley–Read–Hall mechanisms in the dark (increasing J_dark), but also provide additional carrier recombination paths under light illumination (decreasing photocurrent). The critical role of surface defects on J_dark of perovskite photodiodes suggests that making trap-free perovskite thin films, for example, by fine preparation and/or surface engineering, is a top priority for high-performance perovskite photodiodes.     

Optoelectronic Synapses and Photodetectors Based on Organic Semiconductor/Halide Perovskite Heterojunctions: Materials,Devices, and Applications

Both photodetectors (PDs) and optoelectronic synaptic devices (OSDs) are optoelectronic devices converting light signals into electrical responses. Optoelectronic devices based on organic semiconductors and halide perovskites have aroused tremendous research interest owing to their exceptional optical/electrical characteristics and low-cost processability. The heterojunction formed between organic semiconductors and halide perovskites can modify the exciton dissociation/recombination efficiency and modulate the charge-trapping effect. Consequently, organic semiconductor/halide perovskite heterojunctions can endow PDs and OSDs with high photo responsivity and the ability to simulate synaptic functions respectively, making them appropriate for the development of energy-efficient artificial visual systems with sensory and recognition functions. This article summarizes the recent advances in this research field. The physical/chemical properties and preparation methods of organic semiconductor/halide perovskite heterojunctions are briefly introduced. Then the development of PDs and OSDs based on organic semiconductor/halide perovskite heterojunctions, as well as their innovative applications, are systematically presented. Finally, some prospective challenges and probable strategies for the future development of optoelectronic devices based on organic semiconductor/halide perovskite heterojunctions are discussed.     

Boosted Photocurrent via Heating BiFeo3 Thin Film for UV Photodetector at Wide Temperature Range

The current research on ferroelectric photovoltaic materials is concentrated on enhancing the output photocurrent. As solar cells operate at high temperatures, it is crucial to take into account the effect of increasing temperatures on ferroelectric photovoltaics. In this study, an LNO (lanthanum nickelate, LaNiO₃)/BFO (bismuth ferrate, BiFeO₃)/ITO (indium tin oxide) device is constructed on a mica substrate by sol–gel method. The device achieves output photocurrent enhancement at a wide temperature range (33–183 °C), with the largest photocurrent enhancement at 130 °C, which is 178% relative to room temperature, and the output power is also increased by 9.88 times. At the same time, compared with BFO bulk, it is found that the performance of BFO film is always higher than that of bulk in the test temperature range, and the output photocurrent of BFO film at room temperature is 104 times higher than that of bulk. This article investigates the effect of high temperatures on ferroelectric photovoltaics and also provides a strategy for enhancing the photovoltaic performance of ferroelectric films, providing guidance for future applications of ferroelectric films in flexible solar cells and other applications.     

An Artificial Autonomic Nervous System That Implements Heart and Pupil as Controlled by Artificial Sympathetic and Parasympathetic Nerves

The autonomic nervous system maintains homeostasis in organisms through complex neural pathways and responds adaptively to changes in the external and internal environment. The fabrication of an artificial autonomic nervous system is reported that replicates combined effects of sympathetic and parasympathetic nerves on cardiac activity and pupillary control, to mimic the regulation of autonomic nervous system to external changes. The artificial autonomic nerve-controlled pupil contraction and relaxation, modulating the rate of heartbeats for normal cardiac rhythm and arrhythmia as reflected by blink rates of a signal indicator. These functions are switched by using a parallel-channeled synaptic transistor with a special n-i-p heterostructure that has a 2D h-BN insulator in the middle to provide barrier against ion injection into the 2D MoS₂ bottom n-channel and enable short-term plasticity as induced by acetylcholine, and the electrochemical doping reaction occurred at the P3HT nanowire p-channels on top to enable relatively long-term plasticity as induced by noradrenaline. Low-energy consumption down to femtojoule and an ultrahigh paired-pulse facilitation index up to ≈455% are demonstrated. An artificial neural network based on device characteristics achieves a high recognition accuracy for electrocardiogram patterns. This study extends insights into artificial nerves-inspired biological signal processing and recognition.     

Gradient “Single-Crystal” Li-Rich Cathode Materials for High-Stable Lithium-Ion Batteries

As one of the high-energy cathode materials of lithium-ion batteries (LIBs), lithium-rich-layered oxide with “single-crystal” characteristic (SC-LLO) can effectively restrain side reactions and cracks due to the reduced inner boundaries and enhanced mechanical stabilities. However, there are still high challenges for SC-LLO with diverse performance requirements, especially on their cycle stability improvement. Herein, a novel concentration gradient “single-crystal” LLO (GSC-LLO), with gradually decreasing Mn and increasing Ni contents from center to surface, is designed and prepared by combining co-precipitation and molten-salt sintering methods, yielding a capacity retention of 97.6% and an energy density retention of 95.8% within 100 cycles at 0.1 C. The enhanced performance is mostly attributed to the gradient-induced stabilized structure, free of cracks and less spinel-like structure formation after long-term cycling. Furthermore, the gradient design is also beneficial to the safety of LLOs as suggested by the improved thermal stability and reduced gas release. This study provides an effective strategy to prepare high-energy, high-stability, and high-safety LLOs for advanced LIBs.     

Ultra-Wideband Electrostrictive Mechanical Antenna

Mechanical antennas based on piezoelectric materials can effectively reduce the size of long wave antennas down to 1/1000 of the wavelength (from km scale to mm level). However, the narrow bandwidth and weak field intensity seriously restrict its practical applications in transmission distance and channel capacity. Here, a mechanical antenna-based electrostrictive effect of relaxor ferroelectric ceramic (PMN-PT) is proposed to improve radiation capacity and achieve ultra-wideband characteristics (10 kHz–1 MHz). Due to the ultra-high dielectric constant at working temperature and the relationship between the strain and applied field intensity, the proposed antenna gets rid of the dependence on the poled materials and exhibits excellent communication properties beyond traditional mechanical antennas, which are experimentally demonstrated by a practical wireless communication system. Only using a single proposed mechanical antenna with 8 mm diameter and 3 mm thickness, the effective communication with a transmission distance of 200 m can be realized. This design offers a promising way of constructing mechanical antennas for long-wave communication.     

In Situ Deformation Topology of COFs with Shortened Channels and High Redox Properties for Li–S Batteries

Covalent organic frameworks (COFs) with various topologies are typically synthesized by selecting and designing connecting units with rich shapes. However, this process is time-consuming and labour-intensive. Besides, the tight stacking of COFs layers greatly restrict their structural advantages. It is crucial to effectively exploit the high porosity and active sites of COFs by topological design. Herein, for the first time, inducing in situ topological changes in sub-chemometric COFs by adding graphene oxide (GO) without replacing the monomer, is proposed. Surprisingly, GO can slow down the intermolecular stacking and induce rearrangement of COFs nanosheets. The channels of D- [4+3] COFs are significantly altered while the stacking of periodically expanded framework is weakened. This not only maximizes the exposure of pore area and polar groups, but also shortens the channels and increases the redox activity, which enables high loading while enhancing host-guest interactions. This topological transformation to exhibit the structural features of COFs for efficient application is an innovative molecular design strategy.