Lithium Metal-Compatible Antifluorite Electrolytes for Solid-State Batteries.

Lithium (Li) metal solid-state batteries feature high energy density and improved safety and thus are recognized as promising alternatives to traditional Li-ion batteries. In practice, using Li metal anodes remains challenging because of the lack of a superionic solid electrolyte that has good stability against reduction decomposition at the anode side. Here, we propose a new electrolyte design with an antistructure (compared to conventional inorganic structures) to achieve intrinsic thermodynamic stability with a Li metal anode. Li-rich antifluorite solid electrolytes are designed and synthesized, which give a high ionic conductivity of 2.1 × 10-4 S cm-1 at room temperature with three-dimensional fast Li-ion transport pathways and demonstrate high stability in Li-Li symmetric batteries. Reversible full cells with a Li metal anode and LiCoO2 cathode are also presented, showing the potential of Li-rich antifluorites as Li metal-compatible solid electrolytes for high-energy-density solid-state batteries.

The Multifunctionality of Lanthanum-Strontium Cobaltite Nanopowder: High-Pressure Magnetic Studies and Excellent Electrocatalytic Properties for OER.

Simultaneous study of magnetic and electrocatalytic properties of cobaltites under extreme conditions expands the understanding of physical and chemical processes proceeding in them with the possibility of their further practical application. Therefore, La0.6Sr0.4CoO3 (LSCO) nanopowders were synthesized at different annealing temperatures tann = 850-900 °C, and their multifunctional properties were studied comprehensively. As tann increases, the rhombohedral perovskite structure of the LSCO becomes more single-phase, whereas the average particle size and dispersion grow. Co3+ and Co4+ are the major components. It has been found that LSCO-900 shows two main Curie temperatures, TC1 and TC2, associated with a particle size distribution. As pressure P increases, average ⟨TC1⟩ and ⟨TC2⟩ increase from 253 and 175 K under ambient pressure to 268 and 180 K under P = 0.8 GPa, respectively. The increment of ⟨dTC/dP⟩ for the smaller and bigger particles is sufficiently high and equals 10 and 13 K/GPa, respectively. The magnetocaloric effect in the LSCO-900 nanopowder demonstrates an extremely wide peak δTfwhm > 50 K that can be used as one of the composite components, expanding its working temperature window. Moreover, all LSCO samples showed excellent electrocatalytic performance for the oxygen evolution reaction (OER) process (overpotentials of only 265-285 mV at a current density of 10 mA cm-2) with minimal η10 for LSCO-900. Based on the experimental data, it was concluded that the formation of a dense amorphous layer on the surface of the particles ensures high stability as a catalyst (at least 24 h) during electrolysis in 1 M KOH electrolyte.

Novel NASICON-Type Na-V-Mn-Ni-Containing Cathodes for High-Rate and Long-Life SIBs.

Partial substitution of V by other transition metals in Na3 V2 (PO4 )3 (NVP) can improve the electrochemical performance of NVP as a cathode for sodium-ion batteries (SIBs). Herein, phosphate Na-V-Mn-Ni-containing composites based on NASICON (Natrium Super Ionic Conductor)-type structure have been fabricated by sol-gel method. The synchrotron-based X-ray study, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) studies show that manganese/nickel combinations successfully substitute the vanadium in its site within certain limits. Among the received samples, composite based on Na3.83 V1.17 Mn0.58 Ni0.25 (PO4 )3 (VMN-0.5, 108.1 mAh g-1 at 0.2 C) shows the highest electrochemical ability. The cyclic voltammetry, galvanostatic intermittent titration technique, in situ XRD, ex situ XPS, and bond valence site energy calculations exhibit the kinetic properties and the sodium storage mechanism of VMN-0.5. Moreover, VMN-0.5 electrode also exhibits excellent electrochemical performance in quasi-solid-state sodium metal batteries with PVDF-HFP quasi-solid electrolyte membranes. The presented work analyzes the advantages of VMN-0.5 and the nature of the substituted metal in relation to the electrochemical properties of the NASICON-type structure, which will facilitate further commercialization of SIBs.

Visible-light driven rapid bacterial inactivation on red phosphorus/titanium oxide nanofiber heterostructures.

Photocatalytic water disinfection has emerged as a promising approach for water purification. However, exploring efficient and rapid visible light driven materials for photocatalytic bacterial inactivation is still a challenging problem. Herein, red phosphorus/titanium oxide (TiO2@RP) nanofibers were developed for effective water disinfection by a vacuum ampoule strategy. The complete E. coli and S. aureus (7-log CFU mL-1) could be rapidly killed within 25 min and 30 min over the optimized TiO2@RP heterostructure under the white LED irradiation. The efficient photocatalytic antibacterial activity should be mainly ascribed to the synergetic enhancement in light absorption by RP decoration and charge migration and separation by the interface between TiO2 and RP. And then more unpaired photo-carriers would be transferred to the surface to facilitate the generation of photo-holes, •O2- radicals, and H2O2 species, which could destroy the bacterial cells efficiently.

Rietveld refinement of the langbeinite-type phosphate K2Ni0.5Hf1.5(PO4)3.

Polycrystalline potassium nickel(II) hafnium(IV) tris-(orthophosphate), a langbeinite-type phosphate, was synthesized by a solid-state method. The three-dimensional framework of the title compound is built up from two types of [MO6] octa-hedra [the M sites are occupied by Hf:Ni in ratios of 0.754 (8):0.246 (8) and 0.746 (8):0.254 (8), respectively] and [PO4] tetra-hedra are connected via O vertices. The K+ cations are located in two positions within large cavities of the framework, having coordination numbers of 9 and 12. The Hf, Ni and K sites lie on threefold rotation axes, while the P and O atoms are situated in general positions.

Bi(nanoparticles)/CNx(nanosheets) nanocomposites as high capacity and stable electrode materials for supercapacitors: the role of urea.

The evolution of high-performance and stable electrode materials for supercapacitors plays a vital role in the next generation of energy storage devices. In this work we present a simple method for preparing Bi(nanoparticles)/CNx(nanosheets) nanocomposites as electrode materials for supercapacitors, which were synthesized by thermally treating bismuth citrate and urea at 550-700 °C under an Ar atmosphere. According to physicochemical studies (XRD, SEM, TG-DTA, XPS, FTIR, and BET), a "smeared" bismuth formation or the formation of nanoparticles on the CNx surface of interwoven 2D-nanosheets at different calcination temperatures was observed. Electrochemical measurements show that the specific capacity of the composites can reach 1251 F g-1 (more than 90% of the theoretical value) at a current density of 500 mA g-1 in a 6 M KOH electrolyte, and most two-dimensional CNx-based nanostructures remain intact after multiple galvanostatic charge-discharge processes, which is promising for the development of highly efficient supercapacitors. A supercapacitor composed of Bi/CNx nanocomposites for the negative electrode and Ni-layered hydroxide for the positive electrode demonstrates a high energy density of 58 W h kg-1 with a power density of 800 W kg-1 accompanied by a good cycle life (the parameters decreased down to only 78% after 1000 charge-discharge cycles). Our current results indicate that the addition of urea not only determines the morphology of the composites, but also lays the foundation for the development of new types of nanocomposites for the power industry.

Na4Ni3P4O15-Ni(OH)2 core-shell nanoparticles as hybrid electrocatalysts for the oxygen evolution reaction in alkaline electrolytes.

There is wide interest in developing efficient, robust and low-cost electrode materials for the electrolysis of water to produce clean hydrogen fuel. It is especially important to improve the performance and durability of electrocatalysts for the OER. Here we have shown that the transformation of nanoparticle (n-NNP) and crystalline (c-NNP) forms of mixed phosphate Na4Ni3(PO4)2P2O7 in highly alkaline solutions occurs along various routes and provokes the generation of 2D Ni(OH)2 nanosheets or stable core(phosphate)-shell(Ni(OH)2) particles, respectively. In both cases, in the carbon matrix (through chemical and electrochemical conversion of phosphate in situ during electrolysis in a 6 M KOH or NaOH solution) stable OER electrocatalysts with low overpotentials of 250-290 mV at a current density of 10 mA cm-2 were obtained. The best candidate for the OER process is core-shell particles, which maintain overpotentials of around 250 mV in 6 M KOH for more than 3 days. The activity enhancement can be attributed to the formation of abundant NiOOH nanoparticles on the shell surface due to improved lattice matching. This report discusses future prospects for the creation of core-shell particles to reduce the overpotential of durable electrocatalysts for the OER.

Scheelite-related MBi1-xV1-xMoxO4 (MII- Ca, Sr) solid solution-based photoanodes for enhanced photoelectrochemical water oxidation.

The photoelectrochemical properties of scheelite-related MBi1-xV1-xMoxO4 (MII = Ca, Sr, x = 0.1 to 0.9) solid solutions deposited on conductive glass (coated with SnO2, F-doped) have been investigated as photoanodes in photoelectrochemical (PEC) water splitting. The variation of the final annealing temperature during the preparation of the conduction electrodes as well as the value of substitution x have been shown to affect the PEC performance. The micropowders of MBi1-xV1-xMoxO4 (MII = Ca, Sr, x = 0.1 to 0.9) samples were first fabricated vi a solid-state method; they were characterised by SEM microscopy and powder and single crystal X-ray diffraction, and the band gap values were estimated using diffusive reflectance data. The value of substitution x = 0.1 in the cases of samples containing calcium and strontium affords the highest PEC performance reported for the whole range of substitution. These results demonstrate a promising approach for the beneficial utilization of BiVO4-substituted scheelite-related solid solutions in photo-electrochemical cells towards efficient and inexpensive photoanodes.

Facile Synthesis of Hierarchical Tin Oxide Nanoflowers with Ultra-High Methanol Gas Sensing at Low Working Temperature.

In this work, the hierarchical tin oxide nanoflowers have been successfully synthesized via a simple hydrothermal method followed by calcination. The as-obtained samples were investigated as a kind of gas sensing material candidate for methanol. A series of examinations has been performed to explore the structure, morphology, element composition, and gas sensing performance of as-synthesized product. The hierarchical tin oxide nanoflowers exhibit sensitivity to 100 ppm methanol and the response is 58, which is ascribed to the hierarchical structure. The response and recovery time are 4 s and 8 s, respectively. Moreover, the as-prepared sensor has a low working temperature of 200 °C which is lower than that for other gas sensors of such type has been reported elsewhere. The excellent sensitivity of the sensor is caused by its complex phase mixture of SnO, SnO2, Sn2O3, and Sn6O4 revealed by XRD analysis. The proposed hierarchical tin oxide nanoflowers gas sensing material is promising for development of methanol gas sensor. The as-obtained hierarchical tin oxide nanoflower (HTONF) gas sensor shows excellent gas-sensing performance at low working temperature (200 °C) and high annealing temperature (400 °C).