阅读说明：本技术 一种稀土掺杂钨钼酸盐及其制备方法、应用 (Rare earth doped tungsten molybdate and preparation method and application thereof ) 是由 程继海 李萌 田长安 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种稀土掺杂钨钼酸盐,其化学式为Sr<Sub>1-x</Sub>Sm<Sub>x</Sub>(MoO<Sub>4</Sub>)<Sub>0.5</Sub>(WO<Sub>4</Sub>)<Sub>0.5</Sub>,其中,0.05≤x≤0.25。本发明还公开了上述稀土掺杂钨钼酸盐的制备方法,包括如下步骤：S1、根据化学式Sr<Sub>1-</Sub><Sub>x</Sub>Sm<Sub>x</Sub>(MoO<Sub>4</Sub>)<Sub>0.5</Sub>(WO<Sub>4</Sub>)<Sub>0.5</Sub>,按化学计量比分别称取钐盐、锶盐、钨酸盐和钼酸盐；S2、向水中加入钐盐和锶盐溶解,再加入钨酸盐和钼酸盐溶解混匀,然后调节pH≥9,水热反应,冷却至室温,离心取沉淀,洗涤,烘干得到稀土掺杂钨钼酸盐。本发明还公开了上述稀土掺杂钨钼酸盐在固体电解质中的应用。本发明具有良好的导电性能和烧结致密性能,且烧结温度低,烧结体导电性好,可用于固体电解质。(The invention discloses a rare earth doped tungsten molybdate with a chemical formula of Sr 1‑x Sm x (MoO 4 ) 0.5 (WO 4 ) 0.5 Wherein x is more than or equal to 0.05 and less than or equal to 0.25. The invention also discloses a preparation method of the rare earth doped tungsten molybdate, which comprises the following steps: s1, according to formula Sr 1‑ x Sm x (MoO 4 ) 0.5 (WO 4 ) 0.5 Respectively weighing samarium salt, strontium salt, tungstate and molybdate according to the stoichiometric ratio; s2, adding samarium salt and strontium salt into water to dissolve, adding tungstate and molybdate to dissolve and mix uniformly, then adjusting the pH to be more than or equal to 9, carrying out hydrothermal reaction, cooling to room temperature, centrifuging to obtain precipitate, washing and drying to obtain the rare earth doped tungsten molybdate. The invention also discloses application of the rare earth doped tungsten molybdate in solid electrolyte. The invention has good conductive performance and sintering compactness, low sintering temperature and good sintered body conductivity, and can be used for solid electrolyte.)

1. A rare earth doped tungsten molybdate is characterized in that the chemical formula is Sr_1-xSm_x(MoO₄)_0.5(WO₄)_0.5Wherein x is more than or equal to 0.05 and less than or equal to 0.25.

2. The rare earth doped tungsten molybdate according to claim 1, wherein x is 0.1.

3. A method for preparing a rare earth doped tungsten molybdate according to claim 1 or 2, comprising the steps of:

s1, according to formula Sr_1-xSm_x(MoO₄)_0.5(WO₄)_0.5Respectively weighing samarium salt, strontium salt, tungstate and molybdate according to the stoichiometric ratio;

s2, adding samarium salt and strontium salt into water to dissolve, adding tungstate and molybdate to dissolve and mix uniformly, then adjusting the pH to be more than or equal to 9, carrying out hydrothermal reaction, cooling to room temperature, centrifuging to obtain precipitate, washing and drying to obtain the rare earth doped tungsten molybdate.

4. The method of claim 3, wherein the pH is 9-11; preferably, the pH is 9.

5. The method for preparing rare earth-doped tungstomolybdate as claimed in claim 3 or 4, characterized in that the temperature of hydrothermal reaction is 160-200 ℃, and the time of hydrothermal reaction is 20-28 h.

6. The method for preparing rare earth-doped tungstomolybdate according to any one of claims 3 to 5, characterized in that the temperature of the hydrothermal reaction is 180 ℃ and the time of the hydrothermal reaction is 24 h.

7. The method for preparing rare earth-doped tungstomolybdate in accordance with any one of claims 3 to 6 wherein the samarium salt is at least one of samarium nitrate and samarium nitrate hydrate; preferably, the strontium salt is at least one of strontium nitrate and strontium nitrate hydrate.

8. The method for preparing rare earth doped tungsten molybdate according to any one of claims 3 to 7, wherein the tungstate is at least one of ammonium tungstate and ammonium tungstate hydrate; preferably, the molybdate is at least one of ammonium molybdate and ammonium molybdate hydrate.

9. The method for preparing rare earth doped tungsten molybdate according to any one of claims 3 to 8, characterized in that the pH is adjusted with ammonia or nitric acid.

10. Use of a rare earth doped tungsten molybdate according to claim 1 or 2 in a solid electrolyte.

Technical Field

The invention relates to the technical field of self-activating luminescent materials, in particular to rare earth doped tungsten molybdate and a preparation method and application thereof.

Background

The tungsten molybdate powder is not doped with some rare earth ions for activation, and can generate highly efficient fluorescence under the excitation of some special light rays, so that the fact that other active ions are doped into a matrix can be obtainedThe luminescent property of the substrate can be improved very obviously; the tungsten molybdate also has the properties of good stability, excellent ionic conductivity and the like under the condition of high temperature. Having ABO₄Tungsten molybdate oxide of type scheelite (a ═ Ca, Sr, Ba, etc.; B ═ W, Mo) is a typical oxygen ion conductor. The tungsten molybdate is very suitable for being used as a luminescent material and has very important application in the fields of laser devices, ion conductors of oxides and the like.

At present, the preparation of tungsten molybdic acid powder mainly focuses on the traditional solid phase reaction method. However, the powder prepared by the method is easy to agglomerate and needs higher sintering temperature (generally 1150-. In order to improve the performance of the materials, the hydrothermal method, the sol-gel method and other soft chemical methods are being searched for preparing the materials, but at present, the tungsten molybdic acid powder prepared by the hydrothermal method is commonly used in the field of luminescent materials and is rarely used in electrolyte materials.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides the rare earth doped tungsten molybdate and the preparation method and the application thereof, and the rare earth doped tungsten molybdate has good conductive performance and sintering compactness; the invention has smaller grain diameter, regular crystal appearance, uniform size and reasonable grain distribution, and the material pressed and densely formed can be sintered into a sintered body with compact structure, and the required sintering temperature is low, thus reducing the sintering energy consumption; and the prepared sintered body has good conductivity and can be used for solid electrolyte.

The invention provides a rare earth doped tungsten molybdate with a chemical formula of Sr_1-xSm_x(MoO₄)_0.5(WO₄)_0.5Wherein x is more than or equal to 0.05 and less than or equal to 0.25.

Preferably, x is 0.1.

The invention also provides a preparation method of the rare earth doped tungsten molybdate, which comprises the following steps:

s1, according to formula Sr_1-xSm_x(MoO₄)_0.5(WO₄)_0.5Respectively weighing samarium salt, strontium salt and tungstic acid according to stoichiometric ratioSalts and molybdates;

s2, adding samarium salt and strontium salt into water to dissolve, adding tungstate and molybdate to dissolve and mix uniformly, then adjusting the pH to be more than or equal to 9, carrying out hydrothermal reaction, cooling to room temperature, centrifuging to obtain precipitate, washing and drying to obtain the rare earth doped tungsten molybdate.

Preferably, the pH is 9-11.

Preferably, the pH may be 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11.

Preferably, the pH is 9.

Preferably, the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 20-28 h.

Preferably, the temperature of the hydrothermal reaction is 180 ℃ and the time of the hydrothermal reaction is 24 h.

Preferably, the samarium salt is at least one of samarium nitrate and samarium nitrate hydrate.

Preferably, the strontium salt is at least one of strontium nitrate and strontium nitrate hydrate.

Preferably, the tungstate is at least one of ammonium tungstate and ammonium tungstate hydrate.

Preferably, the molybdate is at least one of ammonium molybdate and ammonium molybdate hydrate.

Preferably, the pH is adjusted with ammonia or nitric acid.

The invention also provides the application of the rare earth doped tungsten molybdate in the solid electrolyte.

According to the invention, Sm and Sr are adopted to dope tungsten molybdate, and proper doping amount is selected, so that the conductive material has good conductivity and sintering compactness; the rare earth doped tungsten molybdate is prepared by a hydrothermal method, and has a pure-phase scheelite structure and no other heterocrystal phase by adjusting the proper pH; the rare earth doped tungsten molybdate has smaller particle size, regular crystal morphology, uniform size and reasonable grain distribution through proper pH and hydrothermal reaction conditions, and the pressed and densely formed material can be sintered into a sintered body with compact structure, and the required sintering temperature is low, so that the sintering energy consumption can be reduced; and the prepared sintered body has good conductivity and can be used for solid electrolyte.

Drawings

FIG. 1 is a TG plot of rare earth doped tungsten molybdate.

FIG. 2 is an XRD diffraction pattern of rare earth doped tungsten molybdate obtained at different pH values.

FIG. 3 is a SME picture of a section of a rare earth doped tungsten molybdate sintered body obtained at different pH values.

FIG. 4 is a graph of conductivity versus temperature for tungsten molybdate doped with varying amounts Sm.

FIG. 5 is an Arrhenius plot of the ionic conductivity of tungsten molybdates doped with varying amounts of Sm.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to specific examples.