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1.
In this study, Li6Y1–xEux(BO3)3 phosphor was successfully synthesized using a modified solid‐state diffusion method. The Eu3+ ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80‐0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the 5D07Fj transition of Eu3+ ions. Concentration quenching was observed at 0.5 mol% Eu3+ in the Li6Y1–xEux(BO3)3 host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the 5D07 F2 electric dipole transition of Eu3+ ions. The novel Li6Y1–xEux(BO3)3 phosphor may be a suitable red‐emitting component for solid‐state lighting using double‐excited wavelengths, i.e. near‐UV at 395 nm and blue light at 466 nm. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

2.
Triple whitlockite‐type structure‐based red phosphors Ca8MgBi1?x(PO4)7:xEu3+ (x = 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80 and 1.00) were synthesized by a conventional solid‐state reaction route and characterized by their X‐ray crystal structures. The X‐ray diffraction (XRD) patterns, Fourier transform infrared spectra, morphologies, photoluminescence spectra, UV/Vis reflectance spectra, decay times and the International Commission on Illumination (CIE) chromaticity coordinates of Ca8MgBi1?x(PO4)7:xEu3+ were analyzed. Eu‐doped Ca8MgBi(PO4)7 phosphors exhibited strong red luminescence with peaks at 616 nm due to the 5D07 F2 electric dipole transition of Eu3+ ions after excitation at 396 nm. The UV/Vis spectra indicated that the band gap of Ca8MgBi0.30(PO4)7:0.70Eu3+ is larger than that of Ca8MgBi(PO4)7. The phosphor developed in this study has great potential as a red‐light‐emitting phosphor for UV light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
Na‐ion technology is increasingly studied as a low‐cost solution for grid storage applications. Many positive electrode materials have been reported, mainly among layered oxides and polyanionic compounds. The vanadium oxy/flurophosphate solid solution Na3V2(PO4)2F3‐y O2y (0 ≤ y ≤ 1), in particular, has proven the ability to deliver ≈500 Wh kg‐1, operating on the V3+/V4+ (y = 0) or V4+/V5+ redox couples (y = 1). This paper reports here on a significant increase in specific energy by enabling sodium insertion into Na3V2(PO4)2FO2 to reach Na4V2(PO4)2FO2 upon discharge. This occurs at ≈1.6 V and increases the theoretical specific energy to 600 Wh kg?1, rivaling that of several Li‐ion battery cathodes. This improvement is achieved by the judicious modification of the composition either as O for F substitution, or Al for V substitution, both of which disrupt Na‐ion ordering and thereby enable insertion of the 4th Na. This paper furthermore shows from operando X‐Ray Diffraction (XRD) that this energy is obtained in the cycling range Na4V2(PO4)2FO2–NaV2(PO4)2FO2 with a very small overall volume change of 1.7%, which is one of the smallest volume changes for Na‐ion cathodes and which is a crucial requisite for stable long‐term cycling.  相似文献   

4.
Sr3(PO4)2:Dy3+,Li+ phosphors were prepared using a simple high temperature solid method for luminescence enhancement. The structures of the as‐prepared samples agreed well with the standard phase of Sr3(PO4)2, even when Dy3+ and Li+ were introduced. Under ultraviolet excitation at 350 nm, the Sr3(PO4)2:Dy3+ sample exhibited two emission peaks at 483 nm and 580 nm, which were due to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions, respectively. A white light was fabricated using these two emissions from the Sr3(PO4)2:Dy3+ phosphors. The luminescence properties of Sr3(PO4)2:Dy3+,Li+ phosphors, including emission intensity and decay time, were improved remarkably with the addition of Li+ as the charge compensator, which would promote their application in near‐ultraviolet excited white‐light‐emitting diodes.  相似文献   

5.
Sodium‐ion battery has captured much attention due to the abundant sodium resources and potentially low cost. However, it suffers from poor cycling stability and low diffusion coefficient, which seriously limit its widespread application. Here, K3V2(PO4)3/C bundled nanowires are fabricated usinga facile organic acid‐assisted method. With a highly stable framework, nanoporous structure, and conductive carbon coating, the K3V2(PO4)3/C bundled nanowires manifest excellent electrochemical performances in sodium‐ion battery. A stable capacity of 119 mAh g?1 can be achieved at 100 mA g?1. Even at a high current density of 2000 mA g?1, 96.0% of the capacity can be retained after 2000 charge–discharge cycles. Comparing with K3V2(PO4)3/C blocks, the K3V2(PO4)3/C bundled nanowires show significantly improved cycling stability. This work provides a facile and effective approach to enhance the electrochemical performance of sodium‐ion batteries.  相似文献   

6.
Mechanochemical synthesis of Cu3P in the presence of n‐dodecane results in a material with a secondary particle size distribution of 10 μm, secondary particles which consist of homogeneously agglomerated 20 nm primary particles. The electrochemical performance of Cu3P with lithium is influenced by the reaction depth, in other words by the lower potential cut‐off. During the electrochemical reaction, the displacement of copper by lithium from the Cu3P structure until the formation of Li3P and Cu deteriorates the capacity retention. Improved performance was obtained when the charge potential was limited to 0.50 V (vs. Li/Li+) and the formation of the LixCu3‐xP phase (0 ≤ × ≤ 2). In this case, when the potential is limited to 0.5 V, the capacity is stable for more than 50 cycles. Acceptable electrochemical performances in Li‐ion cells within the voltage range 0.50–2.0 V (vs. Li/Li+) were shown when Cu3P was used as an anode and Li1.2(Ni0.13Mn0.54Co0.13)O2 and LiNi0.5Mn1.5O4 as positive electrode materials.  相似文献   

7.
Na3V2(PO4)3 has attracted great attention due to its high energy density and stable structure. However, in order to boost its application, the discharge potential of 3.3–3.4 V (vs Na+/Na) still needs to be improved and substitution of vanadium with other lower cost and earth‐abundant active redox elements is imperative. Therefore, the Na superionic conductor (NASICON)‐structured Na4MnV(PO4)3 seems to be more attractive due to its lower toxicity and higher voltage platform resulting from the partial substitution of V with Mn. However, Na4MnV(PO4)3 still suffers from poor electronic conductivity, leading to unsatisfactory capacity delivering and poor high‐rate capability. In this work, a graphene aerogel–supported in situ carbon–coated Na4MnV(PO4)3 material is synthesized through a feasible solution‐route method. The elaborately designed Na4MnV(PO4)3 can reach ≈380 Wh kg?1 at 0.5 C (1 C = 110 mAh g?1) and realize superior high‐rate capability evenat 50 C (60.1 mAh g?1) with a long cycle‐life of 4000 cycles at 20 C. This impressive progress should be ascribed to the multifunctional 3D carbon framework and the distinctive structure of trigonal Na4MnV(PO4)3, which are deeply investigated by both experiments and calculations.  相似文献   

8.
In order to improve the luminescent performance of silicate blue phosphors, Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ phosphors were synthesized using one‐step calcination of a precursor prepared by chemical co‐precipitation. The crystal structure and luminescent properties of the phosphors were analyzed using X‐ray diffraction and fluorescence spectrophotometry, respectively. Because the activated ions (Eu2+) can occupy two different types of sites (Sr1 and Sr2), the emission spectrum of Eu2+ excited at 350 nm contains two single bands (EM1 and EM2) in the wavelength range 400–550 nm, centered at 463 nm, and the emission intensity first increases and then decreases with increasing concentrations of Eu2+ ions. Co‐doping of Ce3+ ions can greatly enhance the emission intensity of Eu2+ by transferring its excitation energy to Eu2+. Because of concentration quenching, a higher substitution concentration of Ce3+ can lead to a decrease in the intensity. Meanwhile, the quantum efficiency of the phosphor is improved after doping with Ce3+, and a blue shift phenomenon is observed in the CIE chromaticity diagram. The results indicate that Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ can be used as a potential new blue phosphor for white light‐emitting diodes.  相似文献   

9.
Sodium‐ion batteries may become an alternative to the widespread lithium‐ion technology due to cost and kinetic advantages provided that cyclability is improved. For this purpose, the interplay between electrochemical and structural processes is key and is demonstrated in this work for Na2.46V6O16 (NVO) and Li2.55V6O16 employing operando synchrotron X‐ray diffraction. When NVO is cycled between 4.0 and 1.6 V, Na‐ions reversibly occupy two crystallographic sites, which results in remarkable cyclability. Upon discharge to 1.0 V, however, Na‐ions occupy also interstitial sites, inducing irreversible structural change with some loss of crystallinity concomitant with a decrease in capacity. Capacity fading increases with the ionic radius of the alkali ions (K+ > Na+ > Li+), suggesting that smaller ions stabilize the structure. This correlation of structural variation and electrochemical performance suggests a route toward improving cycling stability of a sodium‐ion battery. Its essence is a minor Li+‐retention in the A2+xV6O16 structure. Even though the majority of Li‐ions are replaced by the abundant Na+, the residual Li‐ions (≈10%) are sufficient to stabilize the layered structure, diminishing the irreversible structural damage. These results pave the way for further exploitation of the role of small ions in lattice stabilization that increases cycling performance.  相似文献   

10.
The γ phase Li3VO4 which possesses higher ionic conductivity is more preferable for lithium ion batteries, but it is only stable at high temperature and would convert to low temperature β phase spontaneously when cooling down. Here, the phase control of Li3VO4 to stabilize its γ phase in room temperature is successfully mediated by introducing proper Si‐doping, and for the first time the electrochemical performances of γ‐Li3VO4 is investigated. It is found that pure γ‐Li3VO4 can be obtained in a doping ratio of x = 0.05–0.15 in Li3+xV1?xSixO4 with addition of excess Li source in synthesis design. The doping mechanism and the energy changes are investigated in detail by using the first principle calculations, it reveals that an interstitial Li+ is formed with doping of Si4+ in Li3VO4 to balance the system charge. When served as an anode, the Si‐doped γ‐Li3VO4 shows much smoothed Li+ insertion/extraction and enhanced cycle stability with only a single pair of redox peaks, which behaves much different with the complex multicouples of redox peaks in typical β‐Li3VO4. These changes in electrochemical performances implies that γ‐Li3VO4 can effectively accommodate Li+ in an easier and more facile way and relieved structure stress during the charge/discharge process.  相似文献   

11.
A NaSICON‐type Li+‐ion conductive membrane with a formula of Li1+ x Y x Zr2? x (PO4)3 (LYZP) (x = 0–0.15) has been explored as a solid‐electrolyte/separator to suppress polysulfide‐crossover in lithium‐sulfur (Li‐S) batteries. The LYZP membrane with a reasonable Li+‐ion conductivity shows both favorable chemical compatibility with the lithium polysulfide species and exhibits good electrochemical stability under the operating conditions of the Li‐S batteries. Through an integration of the LYZP solid electrolyte with the liquid electrolyte, the hybrid Li‐S batteries show greatly enhanced cyclability in contrast to the conventional Li‐S batteries with the porous polymer (e.g., Celgard) separator. At a rate of C/5, the hybrid Li ||LYZP|| Li2S6 batteries developed in this study (with a Li‐metal anode, a liquid/LYZP hybrid electrolyte, and a dissolved lithium polysulfide cathode) delivers an initial discharge capacity of ≈1000 mA h g?1 (based on the active sulfur material) and retains ≈90% of the initial capacity after 150 cycles with a low capacity fade‐rate of <0.07% per cycle.  相似文献   

12.
Sodium superionic conductor (NASICON) cathodes are attractive for Na‐ion battery applications as they exhibit both high structural stability and high sodium ion mobility. Herein, a comprehensive study is presented on the structural and electrochemical properties of the NASICON‐Na3+yV2?yMny(PO4)3 (0 ≤ y ≤ 1) series. A phase miscibility gap is observed at y = 0.5, defining two solid solution domains with low and high Mn contents. Although, members of each of these domains Na3.25V1.75Mn0.25(PO4)3 and Na3.75V1.25Mn0.75(PO4)3 reversibly exchange sodium ions with high structural integrity, the activity of the Mn3+/Mn2+ redox couple is found to be absent and present in the former and latter candidate, respectively. Galvanostatic cycling and rate studies reveal higher capacity and rate capability for the Na3.75V1.25Mn0.75(PO4)3 cathode (100 and 89 mA h g?1 at 1C and 5C rate, respectively) in the Na3+yV2?yMny(PO4)3 series. Such a remarkable performance is attributed to optimum bottleneck size (≈5 Å2) and modulated V‐ and Mn‐redox centers as deduced from Rietveld analysis and DFT calculations, respectively. This study shows how important it is to manipulate electronic and crystal structures to achieve high‐performance NASICON cathodes.  相似文献   

13.
K. N. Shinde  K. Park 《Luminescence》2013,28(5):793-796
A series of efficient Li3Al2(PO4)3:Eu2+ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li3Al2(PO4)3 phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li3Al2(PO4)3:Eu2+ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu2+ was observed in Li3Al2(PO4)3:Eu2+ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu2+ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

14.
Developing rechargeable lithium ion batteries with fast charge/discharge rate, high capacity and power, long lifespan, and broad temperature adaptability is still a significant challenge. In order to realize the fast and efficient transport of ions and electrons during the charging/discharging process, a 3D hierarchical carbon‐decorated Li3V2(PO4)3 is designed and synthesized with a nanoscale amorphous carbon coating and a microscale carbon network. The Brunauer–Emmett–Teller (BET) surface area is 65.4 m2 g?1 and the porosity allows for easy access of the electrolyte to the active material. A specific capacity of 121 mAh g?1 (91% of the theoretical capacity) can be obtained at a rate up to 30 C. When cycled at a rate of 20 C, the capacity retention is 77% after 4000 cycles, corresponding to a capacity fading of 0.0065% per cycle. More importantly, the composite cathode shows excellent temperature adaptability. The specific discharge capacities can reach 130 mAh g?1 at 20 C and 60 °C, and 106 mAh g?1 at 5 C and –20 °C. The rate performance and broad temperature adaptability demonstrate that this hierarchical carbon‐decorated Li3V2(PO4)3 is one of the most attractive cathodes for practical applications.  相似文献   

15.
Li and Mn‐rich layered oxides, xLi2MnO3·(1–x)LiMO2 (M=Ni, Mn, Co), are promising cathode materials for Li‐ion batteries because of their high specific capacity that can exceed 250 mA h g?1. However, these materials suffer from high 1st cycle irreversible capacity, gradual capacity fading, low rate capability, a substantial charge‐discharge voltage hysteresis, and a large average discharge voltage decay during cycling. The latter detrimental phenomenon is ascribed to irreversible structural transformations upon cycling of these cathodes related to potentials ≥4.5 V required for their charging. Transition metal inactivation along with impedance increase and partial layered‐to‐spinel transformation during cycling are possible reasons for the detrimental voltage fade. Doping of Li, Mn‐rich materials by Na, Mg, Al, Fe, Co, Ru, etc. is useful for stabilizing capacity and mitigating the discharge‐voltage decay of xLi2MnO3·(1–x)LiMO2 electrodes. Surface modifications by thin coatings of Al2O3, V2O5, AlF3, AlPO4, etc. or by gas treatment (for instance, by NH3) can also enhance voltage and capacity stability during cycling. This paper describes the recent literature results and ongoing efforts from our groups to improve the performance of Li, Mn‐rich materials. Focus is also on preparation of cobalt‐free cathodes, which are integrated layered‐spinel materials with high reversible capacity and stable performance.  相似文献   

16.
In this article, we report the synthesis of Na2Sr1‐x(PO4)F:Eux phosphor via a combustion method. The influence of different annealing temperatures on the photoluminescence properties was investigated. The phosphor was excited at both 254 and 393 nm. Na2Sr1‐x(PO4)F:Eux3+ phosphors emit strong orange and red color at 593 and 612 nm, respectively, under both excitation wavelengths. Na2Sr1‐x(PO4)F:Eux3+ phosphors annealed at 1050°C showed stronger emission intensity compared with 600, 900 and 1200°C. Moreover, Na2Sr1‐x(PO4)F:Eux3+ phosphor was found to be more intense when compared with commercial Y2O3:Eu3+ phosphor. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

17.
A series of single‐phase full‐color emitting Li2Sr1−x−ySiO4:xDy3+,yEu3+ phosphors were synthesized by solid‐state reaction and characterized by X‐ray diffraction and photoluminescence analyses. The samples showed emission peaks at 488 nm (blue), 572 nm (yellow), 592 nm (orange) and 617 nm (red) under 393 nm excitation. The photoluminescence excitation spectra, comprising the Eu–O charge transfer band and 4f–4f transition bands of Dy3+ and Eu3+, range from 200 to 500 nm. The Commission Internationale de I'Eclairage chromaticity coordinates for Li2Sr0.98−xSiO4:0.02Dy3+,xEu3+ phosphors were simulated. By manipulating Eu3+ and Dy3+ concentrations, the color points of Li2Sr1−x−ySiO4:xDy3+,yEu3+ were tuned from the greenish‐white region to white light and eventually to reddish‐white region, demonstrating that a tunable white light can be obtained by Li2Sr1−x−ySiO4:xDy3+,yEu3+ phosphors. Li2Sr0.98−xSiO4:0.02Dy3+, xEu3+ can serve as a white‐light‐emitting phosphor for phosphor‐converted light‐emitting diode. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

18.
Ce3+/Eu2+ co‐doped Na3Ca6(PO4)5 phosphors were prepared using a combustion‐assisted synthesis method. X‐Ray powder diffraction (XRD) analysis confirmed the formation of a Na3Ca6(PO4)5 crystal phase. Na3Ca6(PO4)5:Eu2+ phosphors have an efficient bluish‐green emission band that peaks at 489 nm, whereas Ce3+‐doped Na3Ca6(PO4)5 showed a bright emission band at 391 nm. Analysis of the experimental results suggests that enhancement of the Eu2+ emission intensity in co‐doped Na3Ca6(PO4)5:Eu2+,Ce3+ phosphors is due to a resonance‐type energy transfer from Ce3+ to Eu2+ ions, which is predominantly governed by an exchange interaction mechanism. These results indicate that Ce3+/Eu2+ co‐doped Na3Ca6(PO4)5 is potentially useful as a highly efficient, bluish‐green emitting, UV‐convertible phosphor for white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

19.
Vanadium‐based fluorophosphates are promising sodium‐ion battery cathode materials. Different phases of NaVPO4F and Na3V2(PO4)2F3 are reported in the literature. However, experiments in this work suggest that there could be confusions about the single‐phase NaVPO4F in solid‐state synthesis. Here, systematic investigation of the mechanism underlying structural and compositional evolution of solid‐state synthesis (NaF:VPO4 = 1:1) is determined by in situ and ex situ X‐ray diffraction and electrochemical measurements. Three reactions—3NaF + 3VPO4 → Na3V2(PO4)2F3 + VPO4 (up to 500 °C), Na3V2(PO4)2F3 + VPO4 → Na3V2(PO4)3 + VF3↑ (600–800 °C), and 2Na3V2(PO4)3 → 2(VO)2P2O7 + Na4P2O7 + amorphous products (above 800 °C)—are validated by in situ XRD and thermogravimetric analysis/differential scanning calorimetry. None of the products reported in this work is consistent with single‐phase NaVPO4F at any temperature. It is speculated that the assignments of I4/mmm and C2/c NaVPO4F from solid‐state synthesis are incorrect, which are instead multiphase mixtures of Le Meins' Na3V2(PO4)2F3, unreacted VPO4, and hexagonal Na3V2(PO4)3. Liquid‐electrolyte‐based electrochemical ion exchange of LiVPO4F produces a tavorite NaVPO4F structure, which is very different from Le Meins' family of Na3Al2(PO4)2F3 polymorphs.  相似文献   

20.
In this study, Eu‐doped Li2(Ba1‐xSrx)SiO4 powders (x = 0, 0.2, 0.4, and 0.6) were synthesized at 850°C in a reduction atmosphere (5% H2 + 95% N2) for a duration of 1 h using a solid‐state reaction method. The reduction atmosphere was infused as the synthesis temperature reached 850°C, and was removed as the temperature dropped to 800–500°C. Li2(Ba1‐xSrx)SiO4 (or Li2BaSiO4), (Ba,Sr)2SiO4 (or BaSiO4), and Li4SiO4 phases co‐existed in the synthesized Eu‐doped Li2(Ba1‐xSrx)SiO4 powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li2(Ba1‐xSrx)SiO4 phosphors had a large effect on their photoluminescence excitation (PLE) and PL properties. Except for the 800°C‐RAR‐treated Li2BaSiO4 phosphor, PLE spectra of all other Li2(Ba1‐xSrx)SiO4 phosphors had one broad emission band with two emission peaks centred at ~242 and ~283 nm; these PL spectra had one broad emission band with one emission peak centred at 502–514 nm. We showed that the 800°C‐RAR‐treated Li2BaSiO4 phosphor emitted a red light and all other Li2(Ba1‐xSrx)SiO4 phosphors emitted a green light. Reasons for these results are discussed thoroughly.  相似文献   

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