AlF3-modified LiCoPO4 for an advanced cathode towards high energy lithium-ion battery

Surface-interface reaction between the electrode and electrolyte plays a key role in lithium-ion storage properties, especially for high voltage cathode such as LiCoPO₄ and Ni-riched cathode. Generally, surface modification is an effective method to improve the electrochemical performance of electrode materials. Herein, in order to revise the LiCoPO₄ cathode with desirable properties, uniform AlF₃-modified LiCoPO₄ (LiCoPO₄@AlF₃) cathode materials in nano-sized distribution are synthesized. XRD result indicates that there is no structural transformation observed after AlF₃ coating. TEM characterization and XPS analysis reveal that the surface of LiCoPO₄ particle is coated by a nano-sized uniform AlF₃ layer. Further, the electrochemical results indicate that AlF₃ layer significantly improves the cycling and rate performances of LiCoPO₄ cathode within the voltage range of 3.0–5.0 V. After a series of optimization, 4 mol% AlF₃-coated LiCoPO₄ material exhibits the best properties including an initial discharge capacity of 159 mA h g^?1 at 0.1 C with 91% capacity retention after 50 cycles, especially a discharge capacity of 90 mA h g^?1 can be obtained at 1 C rate. CV curves indicate that the polarization of cathode is reduced by AlF₃ layer and EIS curves reveal that AlF₃ layer relieves the increase of resistance to facilitate Li-ion transfer at the interface between electrode and electrolyte during the cycling process. The enhanced electrochemical performances are attributed to that the AlF₃ layer can stabilize the interface between the cathode and electrolyte, form steady SEI film and suppress the electrolyte continuous decomposition at 5 V high voltages. This feasible strategy and novel characteristics of LiCoPO₄@AlF₃ could promise the prospective applications in the stat-art of special lithium-ion battery with high energy and/or power density.     

Plasmonic-excitonic multi-hybrid glass-based nanocomposites incorporating Ag plus core-shell CdSe/CdS and alloyed CdSxSe1−x nanoparticles

Successful fabrication of glass-based hybrid nanocomposites (GHNCs) incorporating Ag, core-shell CdSe/CdS and CdS_xSe_1?x nanoparticles (NPs) is herein reported. Both metallic (Ag) and semiconductor (CdSe/CdS) NPs were pre-synthesized, suspended in colloids and added into the sol-gel reaction medium which was used to fabricate the GHNCs. During fabrication of the nanocomposites a fraction (20–60%) of core-shell CdSe/CdS NPs was alloyed into CdS_xSe_1?x (0.20 < x < 0.35) NPs without changing morphology. Modulation of in situ alloying is possible via the relative content of organics added into the sol-gel protocol. Within colloids Ag (core-shell CdSe/CdS) NPs presented average diameter and polydispersity index of 49.5 nm (4.2 nm) and 0.41 (0.21), respectively. On the other hand, the Ag (core-shell CdSe/CdS) NPs’ average diameter and polydispersity index assessed from the GHNCs were respectively 51.5 nm (4.1 nm) and 0.43 (0.25), revealing negligible aggregation of the nanophases within the glass template. The new GHNCs herein introduced presented two independent excitonic transitions associated to homogenously dispersed semiconductor NPs, peaking around 420 nm (core-shell CdSe/CdS) and 650 nm (CdS_xSe_1?x) and matching the plasmonic resonance (Ag NPs) in the 400–500 nm range. We envisage that the new GHNCs represent very promising candidates for superior light manipulation while illuminated with multiple laser beams in quantum interference-based devices.     

Critical roles of the rhombohedral-phase inducers in morphotropic NaNbO3-BaTiO3-ABO3 quasi-ternary lead-free piezoelectric ceramics

A morphotropic phase boundary (MPB) between rhombohedral (R) and tetragonal (T) phases was identified in a few (0.9-x)NaNbO₃-0.1BaTiO₃-xABO₃ (x?=?0–0.05) lead-free systems. Critical roles of R-phase inducers were specially evaluated in terms of phase boundary position, microstructure and piezoelectric responses. The results indicate not only the tolerance factor of the ABO₃ additive but also its ferroelectricity and corresponding volume change would influence the formation of phase boundary and further determine dielectric and ferroelectric responses. The piezoelectric coefficient d₃₃ of MPB compositions was compared with theoretically-calculated d_33-cal according to d₃₃?=?2P_r·ε₃₃·Q₃₃, demonstrating that the piezoelectric response of these systems should be determined by combined effects of the phase coexistence, nano-scale domains and particularly enhanced dielectric responses. The largest d₃₃ ～305 pC/N, the highest ε₃₃^T/ε_o ～2815 and the lowest P_r ～14.7 μC/cm² were achieved in the MPB composition with 3.75% SrZrO₃. These experimental results provide a valuable reference for designing new NaNbO₃-based lead-free piezoelectric materials.     

Boron-containing bioactive glasses in bone and soft tissue engineering

Boron is considered to influence the performance of several metabolic enzymes and boron deficiency is associated with impaired growth and abnormal bone development. As such, boron is a beneficial bioactive element for animals and humans. It is also well known that boron stimulates wound healing and improves bone health. The addition of boron in different proportions to bioactive glasses has significant effects on glass structure, glass processing parameters, biodegradability, biocompatibility, bioactivity and cytotoxicity. Different compositions of bioactive glasses (BGs) containing boron, including boron-doped, borosilicate and borate glasses, are being investigated for bone and soft tissue engineering under the premise that these BGs are suitable carriers of boron, indicating controlled release of B species in the biological environment. This paper reviews up to date research and applications of borate, borosilicate, and boron doped silicate and phosphate BGs focussing on their physical, structural, degradation and biological properties for hard and soft tissue regeneration.     

Effects of deformation rate on properties of Nd,Y-codoped CaF2 transparent ceramics

Different deformation rates of Nd,Y-codoped CaF₂ transparent ceramics were prepared by ceramization of single crystals. The deformation rate effects on the crystallization behaviors, microstructures, mechanical properties, and optical performances were investigated for the first time. The results indicate that the comprehensive performances of Nd,Y-codoped CaF₂ ceramic (△a?=?62%) are the most optimal compared with other ceramics having different deformation rates (△a?=?34%, 40%, 50%, and 75%). In further investigations of the optical properties, the Nd,Y-codoped CaF₂ ceramic (△a?=?62%) sample exhibited a high transparency (T_a?>?91%, 3-mm thick，250?～?1200?nm), low light scattering, superior fracture toughness (K_1c?～?0.71?MPa·m^1/2), strong fluorescence emission, long lifetime (τ?=?348.72?μs), and broad FWHM (29.2?nm), promising a good candidate for high-power laser material.     

Ferroelastic domain structure and phase transition in single-crystalline [PbZn1/3Nb2/3O3]1-x[PbTiO3]x observed via in situ x-ray microbeam

(1-x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃ ((1-x)PZN-xPT in short) is one of the most important piezoelectric materials. In this work, we extensively investigated (1-x)PZN-xPT (x = 0.07–0.11) ferroelectric single crystals using in-situ synchrotron μXRD, complemented by TEM and PFM, to correlate microstructures with phase transitions. The results reveal that (i) at 25 °C, the equilibrium state of (1-x)PZN-xPT is a metastable orthorhombic phase for x = 0.07 and 0.08, while it shows coexistence of orthorhombic and tetragonal phases for x = 0.09 and x = 0.11, with all ferroelectric phases accompanied by ferroelastic domains; (ii) upon heating, the phase transformation in x = 0.07 is Orthorhombic → Monoclinic → Tetragonal → Cubic. The coexistence of ferroelectric tetragonal and paraelectric cubic phases was in-situ observed in x = 0.08 above Curie temperature (T_C), and (iii) phase transition can be explained by the evolution of the ferroelectric and ferroelastic domains. These results disclose that (1-x)PZN-xPT are in an unstable regime, which is possible factor for its anomalous dielectric response and high piezoelectric coefficient.     

Enhanced energy storage properties of Ba0.4Sr0.6TiO3 lead-free ceramics with Bi2O3-B2O3-SiO2 glass addition

In this study, we present an effective strategy to enhance the energy storage properties of Ba_0.4Sr_0.6TiO₃ (BST) lead-free ceramics by the addition of Bi₂O₃-B₂O₃-SiO₂ (BBS) glass, which were prepared by the conventional solid state sintering method. The phase structure, microstructure and energy storage properties were investigated in detail. It can be found that the Ba_0.4Sr_0.6TiO₃-x wt%(Bi₂O₃-B₂O₃-SiO₂) (BST- x wt%BBS, 0 ≤ x ≤ 12) ceramics possess large maximum polarization (P_max), low remanent polarization (P_r) and slim polarization electric field (P-E) hysteresis loops. The breakdown strength (BDS), recoverable energy storage density (W_rec) and energy storage efficiency (η) are enhanced obviously with the addition of BBS glass. The BST-9 wt%BBS ceramic is found to exhibit excellent energy storage properties with a W_rec of 1.98 J/cm³ and a η of 90.57% at 279 kV/cm. These results indicate that the BST-x wt%BBS ceramics might be good candidates for high energy storage applications.