Advances in Mn-Based Electrode Materials for Aqueous Sodium-Ion Batteries.

Aqueous sodium-ion batteries have attracted extensive attention for large-scale energy storage applications, due to abundant sodium resources, low cost, intrinsic safety of aqueous electrolytes and eco-friendliness. The electrochemical performance of aqueous sodium-ion batteries is affected by the properties of electrode materials and electrolytes. Among various electrode materials, Mn-based electrode materials have attracted tremendous attention because of the abundance of Mn, low cost, nontoxicity, eco-friendliness and interesting electrochemical performance. Aqueous electrolytes having narrow electrochemical window also affect the electrochemical performance of Mn-based electrode materials. In this review, we introduce systematically Mn-based electrode materials for aqueous sodium-ion batteries from cathode and anode materials and offer a comprehensive overview about their recent development. These Mn-based materials include oxides, Prussian blue analogues and polyanion compounds. We summarize and discuss the composition, crystal structure, morphology and electrochemical properties of Mn-based electrode materials. The improvement methods based on electrolyte optimization, element doping or substitution, optimization of morphology and carbon modification are highlighted. The perspectives of Mn-based electrode materials for future studies are also provided. We believe this review is important and helpful to explore and apply Mn-based electrode materials in aqueous sodium-ion batteries.

Lowered phase transition temperature and excellent solar heat shielding properties of well-crystallized VO2 by W doping.

Monoclinic VO2 (M) is a key material for energy-efficient smart window applications. Fine crystalline VO2 particles with an ambient phase transition temperature are urgently required to achieve excellent properties including high luminous transmittance and solar heat shielding ability. Moreover, the anti-oxidation ability is regarded as a significant factor which determines the lifetime of VO2-based products. In this paper, well-crystallized W-doped VO2 with low phase transition temperature, excellent solar heat shielding ability and considerable anti-oxidation ability was synthesized by a solid-state reaction process. The phase transition temperature was reduced from 67.3 °C to 10.8 °C at 2.0% W doping with an efficiency of -28.1 °C per at%. Importantly, an excellent balance between the phase transition temperature and the latent heat was obtained at high doping levels (1.5-2.0%). Furthermore, W-doped VO2 particles exhibited a significantly longer exposure time (more than 5 h) at 300 °C in air than the previously reported 2 h in the literature, and the corresponding derived composite foils showed excellent luminous transmittance and solar heat shielding properties (Tlum = 49.9% and Tsol = 44.8% for 2.0% W doping).

VO2 thermochromic smart window for energy savings and generation.

The ability to achieve energy saving in architectures and optimal solar energy utilisation affects the sustainable development of the human race. Traditional smart windows and solar cells cannot be combined into one device for energy saving and electricity generation. A VO2 film can respond to the environmental temperature to intelligently regulate infrared transmittance while maintaining visible transparency, and can be applied as a thermochromic smart window. Herein, we report for the first time a novel VO2-based smart window that partially utilises light scattering to solar cells around the glass panel for electricity generation. This smart window combines energy-saving and generation in one device, and offers potential to intelligently regulate and utilise solar radiation in an efficient manner.

The visible transmittance and solar modulation ability of VO2 flexible foils simultaneously improved by Ti doping: an optimization and first principle study.

The Mott phase transition compound vanadium dioxide (VO2) shows promise as a thermochromic smart material for the improvement of energy efficiency and comfort in a number of applications. However, the use of VO2 has been restricted by its low visible transmittance (Tvis) and limited solar modulation ability (ΔTsol). Many efforts have been made to improve both of these limitations, but progress towards the optimization of one aspect has always come at the expense of the other. This paper reports that Ti doping results in the improvement of both the Tvis and ΔTsol of VO2-nanoparticle-derived flexible foils to the best levels yet reported. Compared with an undoped VO2 foil, a 15% increase (from 46.1% to 53%) in Tvis and a 28% increase (from 13.4% to 17.2%) in ΔTsol are achieved at a Ti doping level of 1.1%, representing the best performance reported for similar foils or films prepared using various methods. Only a defined doping level of less than 3% is beneficial for simultaneous improvement in Tvis and ΔTsol. First principle calculations suggest that an increase in the intrinsic band gap of VO2 (M) and the reduced electron density at Fermi level of VO2 (R) cooperate to result in the improvement of ΔTsol and that an enhancement in the optical band gap of VO2 (M) leads to the increase of Tvis.

F-doped VO2 nanoparticles for thermochromic energy-saving foils with modified color and enhanced solar-heat shielding ability.

F-doped VO2 (M1) nanoparticles were prepared via one-pot hydrothermal synthesis. The F-doping can minimise the size of the VO2 (M1) nanoparticles, induce a homogeneous size distribution and effectively decrease the phase transition temperature to 35 °C at 2.93% F in VO2. VO2 smart glass foils obtained by casting these nanoparticles exhibit excellent thermochromism in the near-infrared region, which suggests that these foils can be used for energy-efficient glass. Compared to a pure VO2 foil, the 2.93% F-doped VO2 foil exhibits an increased solar-heat shielding ability (35.1%) and a modified comfortable colour, while still retaining an excellent solar modulation ability (10.7%) and an appropriate visible transmittance (48.7%). The F-doped VO2 foils are the first to simultaneously meet the requirements of a reduced phase transition temperature, diluted colour and excellent thermochromic properties, and these properties make the further improved F-doped VO2 foils suitable for commercial applications in energy efficient glass.

Mg-doped VO2 nanoparticles: hydrothermal synthesis, enhanced visible transmittance and decreased metal-insulator transition temperature.

This paper reports the successful preparation of Mg-doped VO2 nanoparticles via hydrothermal synthesis. The metal-insulator transition temperature (T(c)) decreased by approximately 2 K per at% Mg. The Tc decreased to 54 °C with 7.0 at% dopant. The composite foils made from Mg-doped VO2 particles displayed excellent visible transmittance (up to 54.2%) and solar modulation ability (up to 10.6%). In addition, the absorption edge blue-shifted from 490 nm to 440 nm at a Mg content of 3.8 at%, representing a widened optical band gap from 2.0 eV for pure VO2 to 2.4 eV at 3.8 at% doping. As a result, the colour of the Mg-doped films was modified to increase their brightness and lighten the yellow colour over that of the undoped-VO2 film. A first principle calculation was conducted to understand how dopants affect the optical, Mott phase transition and structural properties of VO2.

Fabrication and temperature-dependent field-emission properties of bundlelike VO2 nanostructures.

Bundlelike VO(2)(B) nanostructures were synthesized via a hydrothermal method, and VO(2)(M(1)/R) nanobundles were obtained after a heat-treatment process. Structural characterization shows that these nanobundles are self-assembled by VO(2) nanowires, and VO(2)(M(1)/R) nanobundles have better crystallinity. Temperature-dependent field-emission (FE) measurement indicates that FE properties of these two phases of nanobundles can both be improved by increasing the ambient temperature. Moreover, for the VO(2)(M(1)/R) nanobundles, their FE properties are also strongly dependent on the temperature-induced metal-insulator transitions process. Compared with poor FE properties found in the insulating phase, FE properties were significantly improved by increasing the temperature, and about a three-orders-of-magnitude increasing of the emission current density has been observed at a fixed field of 6 V/µm. Work function measurement and density-functional theory calculations indicated that the decrease of work function with temperature is the main reason that caused the improvement of FE properties. These characteristics make VO(2)(M(1)/R) a candidate material for application of new type of temperature-controlled field emitters, whose emission density can be adjusted by ambient temperature.

Highly crystalline spindle-shaped mesoporous anatase titania particles: solution-phase synthesis, characterization, and photocatalytic properties.

Spindlelike mesoporous anatase titania particles were directly synthesized at a low temperature (95 degrees C) by using an aqueous peroxotitanium solution with polyacrylamide (PAM). The mesoporous titania had a BET-specific surface area of 89.6 m(2) g(-1) and showed high crystallinity, thermal stability, and good photocatalytic activity in the degradation of rhodamine B. PAM, as an additive, was confirmed to be crucial in the evolution of the specific structure, morphology, and crystalline phase, and a possible formation mechanism was suggested.

Thermochromic VO2 thin films: solution-based processing, improved optical properties, and lowered phase transformation temperature.

This paper describes a solution-phase synthesis of high-quality vanadium dioxide thermochromic thin films. The films obtained showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal-insulator phase transition (MIPT). For a 59 nm thick single-layer VO(2) thin film, the integral values of visible transmittance (T(int)) for metallic (M) and semiconductive (S) states were 54.1% and 49.1%, respectively, while the NIR switching efficiencies (DeltaT) were as high as 50% at 2000 nm. Thinner films can provide much higher transmittance of visible light, but they suffer from an attenuation of the switching efficiency in the near-infrared region. By varying the film thickness, ultrahigh T(int) values of 75.2% and 75.7% for the M and S states, respectively, were obtained, while the DeltaT at 2000 nm remained high. These results represent the best data for VO(2) to date. Thicker films in an optimized range can give enhanced NIR switching efficiencies and excellent NIR blocking abilities; in a particularly impressive experiment, one film provided near-zero NIR transmittance in the switched state. The thickness-dependent performance suggests that VO(2) will be of great use in the objective-specific applications. The reflectance and emissivity at the wavelength range of 2.5-25 microm before and after the MIPT were dependent on the film thickness; large contrasts were observed for relatively thick films. This work also showed that the MIPT temperature can be reduced simply by selecting the annealing temperature that induces local nonstoichiometry; a MIPT temperature as low as 42.7 degrees C was obtained by annealing the film at 440 degrees C. These properties (the high visible transmittance, the large change in infrared transmittance, and the near room-temperature MIPT) suggest that the current method is a landmark in the development of this interesting material toward applications in energy-saving smart windows.