A capillary-aided microfiber Bragg grating pH sensor for hydrovoltaic technology.

Hydrovoltaic is an emerging technology that aims to harvest energy from water flow and evaporation, in which the plasmonic hydrogen ions are generated by the interaction between water and hydrovoltaic device. However, the volume of the water sample for the interaction is usually ultra-small due to the compact size of hydrovoltaic device, making the quantification and characterization of the hydrogen ions in such water sample an elusive goal. To address this issue, a miniature fiber-optic pH probe is proposed using a unilaterally tapered-microfiber Bragg grating. The microfiber Bragg grating has an intrinsic Bragg reflection signal with a narrow linewidth. The fiber probe is functionalized by coating the sodium alginate, which can respond to the variation of pH mediated by the alteration of the hydrophilicity. The rigidity and robustness of microfiber Bragg grating facilitates the encapsulation of the sensor into a sampling capillary, allowing for the detection of trace aqueous sample less than 2 µL. The pH sensitivity of the tapered-µFBG-based sensor is 62.8 p.m./pH (R2 = 0.995) with a limit resolution of 0.096 pH. The sensor performed a practical application in the monitoring and characterization of the hydrovoltaic microdevice, which can generate microcurrent as soaked in the water. This work demonstrates a promising technology in the fields of materials, energy, biology and medicine, in which the detection of the microsamples is inevitable.

Facile Fabrication of Flexible and High-Performing Thermoelectrics by Direct Laser Printing on Plastic Foil.

The emerging fields of wearables and the Internet of Things introduce the need for electronics and power sources with unconventional form factors: large area, customizable shape, and flexibility. Thermoelectric (TE) generators can power those systems by converting abundant waste heat into electricity, whereas the versatility of additive manufacturing suits heterogeneous form factors. Here, additive manufacturing of high-performing flexible TEs is proposed. Maskless and large-area patterning of Bi2Te3-based films is performed by laser powder bed fusion directly on plastic foil. Mechanical interlocking allows simultaneous patterning, sintering, and attachment of the films to the substrate without using organic binders that jeopardize the final performance. Material waste could be minimized by recycling the unexposed powder. The particular microstructure of the laser-printed material renders the-otherwise brittle-Bi2Te3 films highly flexible despite their high thickness. The films survive 500 extreme-bending cycles to a 0.76 mm radius. Power factors above 1500 µW m-1K-2 and a record-low sheet resistance for flexible TEs of 0.4 Ω sq-1 are achieved, leading to unprecedented potential for power generation. This versatile fabrication route enables innovative implementations, such as cuttable arrays adapting to specific applications in self-powered sensing, and energy harvesting from unusual scenarios like human skin and curved hot surfaces.

Activation of trace LiNO3 additives by BF3 in high-concentration electrolytes towards stable lithium metal batteries.

The activation of trace LiNO3 additives in high-concentration electrolytes is achieved by BF3 due to its Lewis acidity. This advanced electrolyte can promote the decomposition of LiNO3 into Li3N, attaining enhanced cycle reversibility of lithium anodes, which broadens the application of LiNO3 additives.

3D Printed Template-Assisted Assembly of Additive-Free Ti3C2Tx MXene Microlattices with Customized Structures toward High Areal Capacitance.

Ti3C2Tx MXene is a promising material for electrodes in microsupercapacitors. Recent efforts have been made to fabricate MXene electrodes with designed structures using 3D printing to promote electrolyte permeation and ion diffusion. However, challenges remain in structural design diversity due to the strict ink rheology requirement and limited structure choices caused by existing extrusion-based 3D printing. Herein, additive-free 3D architected MXene aerogels are fabricated via a 3D printed template-assisted method that combines 3D printed hollow template and cation-induced gelation process. This method allows the use of MXene ink with a wide range of concentrations (5 to 150 mg mL-1) to produce MXene aerogels with high structural freedom, fine feature size (>50 µm), and controllable density (3 to 140 mg cm-3). Through structure optimization, the 3D MXene aerogel shows high areal capacitance of 7.5 F cm-2 at 0.5 mA cm-2 with a high mass loading of 54.1 mg cm-2. It also exhibits an ultrahigh areal energy density of 0.38 mWh cm-2 at a power density of 0.66 mW cm-2.

Anionic Redox Regulated via Metal-Ligand Combinations in Layered Sulfides.

The increasing demand for energy storage is calling for improvements in cathode performance. In traditional layered cathodes, the higher energy of the metal 3d over the O 2p orbital results in one-band cationic redox; capacity solely from cations cannot meet the needs for higher energy density. Emerging anionic redox chemistry is promising to access higher capacity. In recent studies, the low-lying O nonbonding 2p orbital was designed to activate one-band oxygen redox, but they are still accompanied by reversibility problems like oxygen loss, irreversible cation migration, and voltage decay. Herein, by regulating the metal-ligand energy level, both extra capacities provided by anionic redox and highly reversible anionic redox process are realized in NaCr1- y Vy S2 system. The simultaneous cationic and anionic redox of Cr/V and S is observed by in situ X-ray absorption near edge structure (XANES). Under high d-p hybridization, the strong covalent interaction stabilizes the holes on the anions, prevents irreversible dimerization and cation migration, and restrains voltage hysteresis and voltage decay. The work provides a fundamental understanding of highly reversible anionic redox in layered compounds, and demonstrates the feasibility of anionic redox chemistry based on hybridized bands with d-p covalence.

Stable Interface Chemistry and Multiple Ion Transport of Composite Electrolyte Contribute to Ultra-long Cycling Solid-State LiNi0.8 Co0.1 Mn0.1 O2 /Lithium Metal Batteries.

Severe interfacial side reactions of polymer electrolyte with LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) cathode and Li metal anode restrict the cycling performance of solid-state NCM811/Li batteries. Herein, we propose a chemically stable ceramic-polymer-anchored solvent composite electrolyte with high ionic conductivity of 6.0×10-4  S cm-1 , which enables the solid-state NCM811/Li batteries to cycle 1500 times. The Li1.4 Al0.4 Ti1.6 (PO4 )3 nanowires (LNs) can tightly anchor the essential N, N-dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), greatly enhancing its electrochemical stability and suppressing the side reactions. We identify the ceramic-polymer-liquid multiple ion transport mechanism of the LNs-PVDF-DMF composite electrolyte by tracking the 6 Li and 7 Li substitution behavior via solid-state NMR. The stable interface chemistry and efficient ion transport of LNs-PVDF-DMF contribute to superior performances of the solid-state batteries at wide temperature range of -20-60 °C.

Graphite prelithiation by solid electrochemical corrosion of lithium metal with a superficial mosaic structure.

A transformative concept of solid electrochemical corrosion has been put forward, in which solid-state electrolyte LiPON has been applied to replace the liquid one to prelithiate graphite with Li-metal. Thus, high prelithiation efficiency and low polarization of the treated anode can be obtained, with a unique mosaic structure left at the surface.

In†Situ Construction of an Ultra-Stable Conductive Composite Interface for High-Voltage All-Solid-State Lithium Metal Batteries.

The garnet electrolyte presents poor wettability with Li metal, resulting in an extremely large interfacial impedance and drastic growth of Li dendrites. Herein, a novel ultra-stable conductive composite interface (CCI) consisting of Liy Sn alloy and Li3 N is constructed in situ between Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) pellet and Li metal by a conversion reaction of SnNx with Li metal at 300 °C. The Liy Sn alloy as a continuous and robust bridge between LLZTO and Li metal can effectively reduce the LLZTO/Li interfacial resistance from 4468.0â€…Ω to 164.8 Ω. Meanwhile, the Li3 N as a fast Li-ion channel can efficiently transfer Li ions and give their uniform distribution at the LLZTO/Li interface. Therefore, the Li/LLZTO@CCI/Li symmetric battery stably cycles for 1200 h without short circuit, and the all-solid-state high-voltage Li/LLZTO@CCI/LiNi0.5 Co0.2 Mn0.3 O2 battery achieves a specific capacity of 161.4 mAh g-1 at 0.25 C with a capacity retention rate of 92.6 % and coulombic efficiency of 100.0 % after 200 cycles at 25 °C.

Capacity Loss Mechanism of the Li4Ti5O12 Microsphere Anode of Lithium-Ion Batteries at High Temperature and Rate Cycling Conditions.

Li4Ti5O12 (LTO) as the anode of lithium (Li) ion batteries has high interfacial side reactivity with the electrolyte, which leads to severe gassing behavior and poor cycling stability. Herein, the capacity loss mechanism of the high-tap density LTO microsphere anode under different temperatures (25, 45, and 60 °C) and charge/discharge rates (1 and 5 C) is systematically investigated. The capacity retentions of the LTO/Li cell after 500 cycles at 1 C are 95.6, 90.0, and 87.1% under three temperatures, which drop to 91.9, 58.3, and 20.9% when cycling at 5 C, respectively. Results show that the high temperature and rate almost do not damage the structure of LTO, but greatly affect the thickness and components of the solid electrolyte interface (SEI), and consequently reduce the performance of the LTO/Li cells. An SEI mainly consisting of inorganic species forms on LTO after 500 cycles at 1 C, while organic compounds are observed after 500 cycles at 5 C. The capacity of cycled LTO cannot recover again because of the thick SEI although using new Li metal anodes, separators, and electrolytes. This work demonstrates that it is of great significance for LTO to construct a stable SEI for achieving excellent cycling performance at a high rate and temperature.