CN103113892B - A kind of tungstate rare earth light conversion material, preparation method and application - Google Patents

Abstract

The invention discloses a kind of tungstate rare earth light conversion material, preparation method and application.The chemical general formula of the light-converting material provided is M ₅r _1-xyb _x(WO ₄) ₄, wherein, R is Er ³⁺, Eu ³⁺, La ³⁺, Y ³⁺, Ce ³⁺, Tm ³⁺, Pr ³⁺, Nd ³⁺, Sm ³⁺, Gd ³⁺, Tb ³⁺, Dy ³⁺, Ho ³⁺and Lu ³⁺in one; M is Na ⁺, Li ⁺and K ⁺in one; <i>x</iGreatT.Gr eaT.GT is Yb ³⁺the molecular fraction of doping, 0.0001≤x & lt; 1.0.The present invention adopts high temperature solid-state method or chemical synthesis; protect without the need to reducing atmosphere in preparation process; technique is simple; production cost is low, pollution-free, environmentally friendly; the light-converting material obtained has strong absorption in 250 ~ 450nm wavelength region; and launch the near infrared light of high strength within the scope of 900 ~ 1100nm, the luminous energy of this wave band is absorbed by silica-based solar cell effectively, can be used for preparing light-converting material used for solar batteries.

Description

A kind of tungstate rare earth light conversion material, preparation method and application

technical field

The invention relates to a luminescent material, a preparation method and an application thereof, in particular to a tungstate rare earth light conversion material, a preparation method and an application thereof, and belongs to the technical field of luminescent materials.

Background technique

In contemporary society and economy, the impact of massive consumption of fossil energy on the ecological environment has become increasingly prominent, and energy issues have gradually become a bottleneck restricting the development of the international society and economy. Therefore, it is urgent to develop and apply new and renewable energy. As an inexhaustible and renewable clean energy, solar energy has attracted widespread attention from all walks of life. Among them, the most prominent development is the field of silicon solar cells, which is considered to be the most promising new energy technology in the world today.

The bandgap width of crystalline silicon is about 1.12ev, which is equivalent to 1100nm. The effective response spectrum range of silicon solar cells to incident light is 400-1100nm. Only the incident light in this band contributes to the photoelectric conversion of silicon cells, and the rest The energy will be converted into heat and dissipated, so the natural sunlight energy cannot be completely absorbed and converted, resulting in great waste. At present, the crystalline silicon solar cells available on the market can only achieve a maximum light conversion rate of 25% by improving the material treatment process. By adjusting the solar spectrum, visible light is converted into infrared light that can be efficiently absorbed by solar cells, thereby effectively improving the efficiency of solar cells.

The spectral response range of solar cells can be broadened by using down-conversion luminescent materials to absorb ultraviolet light and emit near-infrared light. At present, the rare earth light conversion materials for silicon-based solar cells that have been studied more mainly adopt the method of doping trivalent rare earth ions (such as: Tb ³⁺ , Pr ³⁺ , Er ³⁺ , etc.) The absorption to the visible light region, such as the luminescent material research experts represented by A.Meijerink of Utrecht University in the Netherlands, designed Tb ³⁺ -Yb ³⁺ , Pr ³⁺ -Yb ³⁺ and Tm ³⁺ -Yb ³⁺ , etc. Rare earth ions produce quantum tailoring luminescence (PhysicalReviewB: CondensedMatterandMaterialsPhysics, 2005, 71(1), 014119/1-014119/11), and have made many pioneering works in the field of near-infrared quantum tailoring luminescence; Li Kaiyu and others have also successfully prepared The YPO ₄ powder co-doped with Pr ³⁺ and Yb ³⁺ realizes down-conversion near-infrared luminescence under 450nm light excitation (Luminescence Journal, May 2012, Volume 33, Issue 5). However, although these sensitizing ions have absorption in the ultraviolet to visible region, their absorption is linear and the absorption intensity is relatively weak.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art and provide a tungstate with simple preparation process, low production cost, strong absorption in the wavelength range of 250-450nm, and high-intensity near-infrared light emission of 900-1100nm Rare earth light conversion materials, preparation methods and applications.

In order to achieve the above object, the technical solution adopted by the present invention is to provide a tungstate rare earth light conversion material, its chemical formula is M ₅ R _1-x Yb _x (WO ₄ ) ₄ , wherein, R is a rare earth erbium ion Er ³⁺ , europium ion Eu ³⁺ , lanthanum ion La ³⁺ , yttrium ion Y ³⁺ , cerium ion Ce ³⁺ , thulium ion Tm ³⁺ , praseodymium ion Pr ³⁺ , neodymium ion Nd ³⁺ , samarium ion Sm ^{3 +} , one of gadolinium ion Gd ³⁺ , terbium ion Tb ³⁺ , dysprosium ion Dy ³⁺ , holmium ion Ho ³⁺ , lutetium ion Lu ³⁺ ; M is alkaline earth metal ion sodium ion Na ⁺ , lithium ion Li ⁺ and one of potassium ions K ⁺ ; x is the mole percentage of Yb ³⁺ doping, 0.0001≤x<1.0; the photo-conversion material emits near-infrared light of 900-1100nm under the excitation of 250-450nm ultraviolet light Light.

The technical solution of the present invention also provides a method for preparing the above-mentioned tungstate rare earth light conversion material, that is, using a high-temperature solid-phase method, which specifically includes the following steps:

1. According to the stoichiometric ratio of each element in the chemical formula M ₅ R _1-x Yb _x (WO ₄ ) ₄ , where 0.0001≤x<1.0, weigh the compound containing ytterbium ion Yb ³⁺ , the compound containing ion R, Compounds containing ions M and compounds containing tungsten ions W ⁶⁺ are ground and mixed uniformly to obtain a mixture; the ions R are rare earth erbium ions Er ³⁺ , europium ions Eu ³⁺ , lanthanum ions La ³⁺ , yttrium ions Y ³⁺ , cerium ion Ce ³⁺ , thulium ion Tm ³⁺ , praseodymium ion Pr ³⁺ , neodymium ion Nd ³⁺ , samarium ion Sm ³⁺ , gadolinium ion Gd ³⁺ , terbium ion Tb ³⁺ , dysprosium ion Dy ^{3 +} , one of holmium ion Ho ³⁺ , lutetium ion Lu ³⁺ ; the ion M is one of alkaline earth metal ion sodium ion Na ⁺ , lithium ion Li ⁺ and potassium ion K ⁺ ;

2. Calcining the mixture obtained in step 1 in an air atmosphere for 1 to 2 times; the calcination temperature is 200-500°C, and the calcination time is 1-10 hours;

3. Cool the obtained mixture naturally, grind and mix it evenly, then calcinate in the air atmosphere, the calcining temperature is 500-850°C, the calcining time is 1-10 hours, and naturally cool to room temperature to obtain a tungstate rare earth light Convert material.

A preferred scheme of the present invention is: when using the high-temperature solid-phase method, the calcination temperature of step 2 is 250-450°C, and the calcination time is 2-9 hours; the calcination temperature of step 3 is 550-800°C, and the calcination time is 2-9 hours. 9 hours.

The technical solution of the present invention also includes another method for preparing the above-mentioned tungstate rare earth light conversion material, that is, using a chemical synthesis method, which specifically includes the following steps:

1. According to the stoichiometric ratio of each element in the chemical formula M ₅ R _1-x Yb _x (WO ₄ ) ₄ , wherein 0.0001≤x<1.0, weigh the compound containing ytterbium ion Yb ³⁺ , the compound containing ion R, the compound containing Compounds of ion M are dissolved in dilute nitric acid solution to obtain various transparent solutions; complexing agent citric acid or oxalic acid is added according to 0.5-2.0wt% of the mass of each reactant, and the temperature is 50-80°C The ion R is rare earth erbium ion Er ³⁺ , europium ion Eu ³⁺ , lanthanum ion La ³⁺ , yttrium ion Y ³⁺ , cerium ion Ce ³⁺ , thulium ion Tm ³⁺ , and praseodymium ion Pr ^{3 +} , one of neodymium ions Nd ³⁺ , samarium ions Sm ³⁺ , gadolinium ions Gd ³⁺ , terbium ions Tb ³⁺ , dysprosium ions Dy ³⁺ , holmium ions Ho ³⁺ , and lutetium ions Lu ³⁺ ; The ion M is one of alkaline earth metal ion sodium ion Na ⁺ , lithium ion Li ⁺ and potassium ion K ⁺ ;

2. According to the stoichiometric ratio of each element in the chemical formula M ₅ R _1-x Yb _x (WO ₄ ) ₄ , where 0.0001≤x<1.0, weigh the compound containing tungsten ion W ⁶⁺ and dissolve it in deionized water or ethanol In the solution, add complexing agent citric acid or oxalic acid according to 0.5-2.0wt% of the reactant mass, and stir at a temperature of 50-80°C;

3. Slowly mix the various solutions obtained in steps 1 and 2, stir at a temperature of 50-80°C for 1-2 hours, let stand, and dry to obtain a fluffy precursor;

4. The precursor is calcined in a muffle furnace at a temperature of 550-800° C. for 2-15 hours, and naturally cooled to room temperature to obtain a tungstate rare earth light conversion material.

The compound containing ion R described in the present invention is one of oxides, fluorides, and nitrates of R; the compound containing ytterbium ion Yb ³⁺ is one of ytterbium oxide and ytterbium nitrate; the compound containing ion M It is one of the oxides, fluorides, carbonates, sulfates, and nitrates of M; the compound containing tungsten ions W ⁶⁺ is one of tungsten oxide and ammonium tungstate.

The tungstate rare earth light conversion material described in the invention has strong absorption in the wavelength range of 250-450nm, and emits high-intensity near-infrared light in the range of 900-1100nm, and can be used as a light conversion material for silicon-based solar cells.

The principle of the present invention is: using the infrared emission of Yb ³⁺ ions, its 1000nm emission is just in the best response range of the silicon solar cell to the incident light, and then absorbs a 250-450nm short-wave photon through the co-operation energy transfer between the ions, and emits Two 575nm and 1000nm long-wavelength photons realize the efficient utilization of ultraviolet light and at the same time reduce the thermal effect of silicon-based solar cells, so they can be used as potential materials for improving the efficiency of silicon-based solar cells.

Compared with the prior art, the present invention has the following beneficial effects:

1. The tungstate rare earth light conversion material of the present invention uses a tungstate matrix material that is non-toxic, free from any pollution, and environmentally friendly, and does not require a reducing atmosphere protection during the preparation process, so the requirements for equipment are relatively low.

2. The tungstate rare earth light conversion material of the present invention has a main emission peak at 900-1100nm, and its energy perfectly matches the forbidden band width of silicon, which can effectively improve the photoelectric conversion efficiency of silicon-based solar cells, and is a potential silicon-based solar energy Rare earth light conversion materials for batteries.

3. The ultraviolet light conversion and emission near-infrared light material of the present invention has strong absorption in the ultraviolet region (250-450nm), which can improve the utilization rate of solar energy and at the same time reduce the thermal effect of solar cells.

Description of drawings

Fig. 1 is the X-ray powder diffraction pattern of the sample Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄ prepared in Example 1 of the present invention;

Fig. 2 is the excitation spectrum of the sample Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄ prepared in Example 1 of the present invention monitored at a wavelength of 1000 nm;

Fig. 3 is a fluorescence spectrum diagram of the sample Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄ prepared in Example 1 of the present invention under excitation at a wavelength of 355 nm;

Fig. 4 is the luminescence attenuation curve of the sample Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄ prepared in Example 1 of the present invention monitored at a wavelength of 1000 nm.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Example 1:

Preparation of Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula Na ₅ Dy _0.65 Yb _0.35 (WO ₄ ) ₄ , weigh sodium carbonate Na ₂ CO ₃ : 1.33 grams, dysprosium oxide Dy ₂ O ₃ : 0.61 grams, ytterbium oxide Yb ₂ O ₃ : 0.35 g, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 g, ground in an agate mortar and mixed evenly, then select the air atmosphere for the first calcination, the temperature is 250 ° C, the calcination time is 4 hours, and then Cool to room temperature and remove the sample. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly again, and the second sintering is carried out at 650°C in the air atmosphere. The sintering time is 8 hours, cooled to room temperature, taken out and fully ground to obtain powder. Tungstate Rare Earth Photoconversion Materials.

Referring to accompanying drawing 1, it is the X-ray powder diffraction spectrum of the sample prepared by the technical scheme of this embodiment, the position and relative intensity of the diffraction peaks show that the crystalline substance is all Na ₅ Dy(WO ₄ ) ₄ pure phase, without any other impurities Phases exist.

Referring to accompanying drawing 2, it is the excitation spectrum under 1000nm wavelength monitoring of the sample prepared according to the technical scheme of this embodiment; See accompanying drawing 3, it is the emission spectrum figure under the excitation of 355nm wavelength of the sample prepared according to the technical scheme of this embodiment , as can be seen from the figure, the emission spectrum appears near-infrared luminescence in the 900-1100nm band, and the prepared material effectively converts ultraviolet light into near-infrared luminescence; see accompanying drawing 4, which is the sample prepared according to the technical scheme of this embodiment at 1000nm Luminescence decay curve under wavelength monitoring, the calculated decay time is 0.034ns.

Example 2:

Preparation of Na ₅ Lu _0.65 Yb _0.35 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula Na ₅ Lu _0.65 Yb _0.35 (WO ₄ ) ₄ , weigh sodium carbonate Na ₂ CO ₃ : 1.33 grams, lutetium oxide Lu ₂ O ₃ : 0.65 grams, ytterbium oxide Yb ₂ O ₃ : 0.35 g, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 g, ground in an agate mortar and mixed evenly, and then calcined for the first time in an air atmosphere at a temperature of 350°C for 2 hours, and then Cool to room temperature and remove the sample. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly again, and the second sintering is carried out at 600°C in an air atmosphere. The sintering time is 7 hours, cooled to room temperature, taken out and fully ground to obtain powder Tungstate Rare Earth Photoconversion Materials.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of accompanying drawing 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Example 3:

Preparation of Li ₅ Gd _0.7 Yb _0.3 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula Li ₅ Gd _0.7 Yb _0.3 (WO ₄ ) ₄ , weigh lithium carbonate Li ₂ CO ₃ : 0.93 g, gadolinium oxide Gd ₂ O ₃ : 0.54 g, ytterbium oxide Yb ₂ O ₃ : 0.29 g, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 g, ground in an agate mortar and mixed evenly, then choose the air atmosphere for the first calcination, the temperature is 300 ° C, the calcination time is 5 hours, and then Cool to room temperature and remove the sample. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly again, and the second sintering is carried out at 550°C in an air atmosphere. The sintering time is 9 hours, cooled to room temperature, taken out and fully ground to obtain powder. Tungstate Rare Earth Photoconversion Materials.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of the sample prepared in Example 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Example 4:

Preparation of K ₅ Y _0.8 Yb _0.2 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula K ₅ Y _0.8 Yb _0.2 (WO ₄ ) ₄ , respectively weigh potassium carbonate K ₂ CO ₃ : 1.73 grams, yttrium oxide Y ₂ O ₃ : 0.45 grams, ytterbium nitrate Yb (NO ₃ ) ₃ : 0.36 g, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 g, ground in an agate mortar and mixed evenly, then select the air atmosphere for the first calcination, the temperature is 400 ℃, and the calcination time is 9 hours , then cooled to room temperature, and the samples were taken out. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly again, and the second sintering is carried out at 700°C in the air atmosphere. The sintering time is 8 hours, cooled to room temperature, taken out and fully ground to obtain powder Tungstate Rare Earth Photoconversion Materials.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of the sample prepared in Example 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Example 5:

Preparation of K ₅ La _0.85 Yb _0.15 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula K ₅ La _0.85 Yb _0.15 (WO ₄ ) ₄ , we weigh potassium carbonate K ₂ CO ₃ : 1.73 grams, lanthanum oxide La ₂ O ₃ : 0.69 grams, ytterbium oxide Yb ₂ O ₃ : 0.15 g, tungsten oxide WO ₃ : 4.637 g, ground in an agate mortar and mixed evenly, then calcined for the first time in an air atmosphere at a temperature of 450°C for 5 hours, then cooled to room temperature, and took out the sample. After the first calcination of the raw materials, the mixture is fully mixed and ground evenly again, and the second sintering is carried out at 800°C in an air atmosphere. The sintering time is 7 hours, cooled to room temperature, taken out and fully ground to obtain powder. Tungstate Rare Earth Photoconversion Materials.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of the sample prepared in Example 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Embodiment 6:

Preparation of Na ₅ Gd _0.9 Yb _0.1 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula Na ₅ Gd _0.9 Yb _0.1 (WO ₄ ) ₄ , weigh sodium carbonate Na ₂ CO ₃ : 1.33 grams, gadolinium oxide Gd ₂ O ₃ : 0.82 grams, ytterbium oxide Yb ₂ O ₃ : 0.098 grams, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 grams, the weighed sodium carbonate Na ₂ CO ₃ , gadolinium oxide Gd ₂ O ₃ and ytterbium oxide Yb ₂ O ₃ were dissolved in dilute nitric acid solution Dissolve the weighed ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ in deionized water or ethanol solution, and then add 2.0wt% citric acid of the above-mentioned medicines to each solution, and stir at 80°C ; Then slowly mix the above solution and stir continuously for 2 hours; let it stand and dry to obtain a fluffy precursor; place the precursor in a muffle furnace for calcination, the sintering temperature is 800 ° C, the calcination time is 2 hours, and cool to room temperature, taken out and fully ground to obtain a powdery tungstate rare earth light conversion material.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of the sample prepared in Example 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Embodiment 7:

Preparation of K ₅ Tm _0.95 Yb _0.05 (WO ₄ ) ₄

According to the stoichiometric ratio of each element in the chemical formula K ₅ Tm _0.95 Yb _0.05 (WO ₄ ) ₄ , respectively weigh potassium carbonate K ₂ CO ₃ : 1.73 grams, thulium oxide Tm ₂ O ₃ : 0.92 grams, ytterbium oxide Yb ₂ O ₃ : 0.049 grams, ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ : 5.07 grams, the weighed potassium carbonate K ₂ CO ₃ , thulium oxide Tm ₂ O ₃ and ytterbium oxide Yb ₂ O ₃ were dissolved in dilute nitric acid solution Dissolve the weighed ammonium tungstate (NH ₄ ) ₁₀ W ₁₂ O ₄₁ in deionized water or ethanol solution, add 0.5wt% oxalic acid of the above drug quality to each solution, and stir at 50°C ; then slowly mix the above solution and stir continuously for 1 hour; let it stand and dry to obtain a fluffy precursor; place the precursor in a muffle furnace for calcination, the sintering temperature is 550 ° C, the calcination time is 15 hours, and cool to room temperature, taken out and fully ground to obtain a powdery tungstate rare earth light conversion material.

The X-ray powder diffraction pattern of the sample prepared by the technical scheme of this embodiment is consistent with that of the sample prepared in Example 1. Its excitation spectrum and emission spectrum are similar to accompanying drawings 2 and 3 respectively, and the decay time is consistent with the sample prepared in Example 1.

Claims (8)

1. a tungstate rare earth light conversion material, is characterized in that: its chemical general formula is M ₅r _1-xyb _x(WO ₄) ₄, wherein, R is lanthanum ion La ³⁺, ruthenium ion Y ³⁺, thulium ion Tm ³⁺, gadolinium ion Gd ³⁺, dysprosium ion Dy ³⁺, lutetium ion Lu ³⁺in one; M is alkaline-earth metal ions sodium ion Na ⁺, lithium ion Li ⁺with potassium ion K ⁺in one; xfor Yb ³⁺the molecular fraction of doping, 0.0001≤x<1.0; Described light-converting material, under the ultraviolet excitation of 250 ~ 450nm, launches the near infrared light of 900 ~ 1100nm.

2. a preparation method for tungstate rare earth light conversion material as claimed in claim 1, adopts high temperature solid-state method, it is characterized in that comprising the steps:

(1) by chemical formula M ₅r _1-xyb _x(WO ₄) ₄in the stoichiometric ratio of each element, wherein 0.0001≤x<1.0, takes respectively containing ytterbium ion Yb ³⁺compound, the compound containing ion R, the compound containing ion M, containing tungsten ion W ⁶⁺compound, grind and mix, obtaining mixture; Described ion R is lanthanum ion La ³⁺, ruthenium ion Y ³⁺, thulium ion Tm ³⁺, gadolinium ion Gd ³⁺, dysprosium ion Dy ³⁺, lutetium ion Lu ³⁺in one; Described ion M is alkaline-earth metal ions sodium ion Na ⁺, lithium ion Li ⁺with potassium ion K ⁺in one;

(2) mixture that step (1) obtains is calcined 1 ~ 2 time in air atmosphere; Calcining temperature is 200 ~ 500 DEG C, and calcination time is 1 ~ 10 hour;

(3) the mixture naturally cooling will obtained, grinds and after mixing, calcine in air atmosphere, calcining temperature is 500 ~ 850 DEG C, and calcination time is 1 ~ 10 hour, naturally cools to room temperature, obtains a kind of tungstate rare earth light conversion material.

3. the preparation method of a kind of tungstate rare earth light conversion material according to claims 2, is characterized in that: the calcining temperature of step (2) is 250 ~ 450 DEG C, and calcination time is 2 ~ 9 hours.

4. the preparation method of a kind of tungstate rare earth light conversion material according to claims 2, is characterized in that: the calcining temperature of step (3) is 550 ~ 800 DEG C, and calcination time is 2 ~ 9 hours.

5. the preparation method of a kind of tungstate rare earth light conversion material according to claims 2, is characterized in that: the described compound containing ion R is the one in the oxide compound of R, fluorochemical, nitrate; Containing ytterbium ion Yb ³⁺compound be one in ytterbium oxide, ytterbium nitrate; Compound containing ion M is the one in the oxide compound of M, fluorochemical, carbonate, vitriol, nitrate; Containing tungsten ion W ⁶⁺compound be one in Tungsten oxide 99.999, ammonium tungstate.

6. a preparation method for tungstate rare earth light conversion material as claimed in claim 1, adopts chemical synthesis, it is characterized in that comprising the steps:

(1) by chemical formula M ₅r _1-xyb _x(WO ₄) ₄in the stoichiometric ratio of each element, wherein 0.0001≤x<1.0, takes containing ytterbium ion Yb ³⁺compound, the compound containing ion R, the compound containing ion M, they are dissolved in dilute nitric acid solution respectively, obtain various clear solution; Add complexing agent citric acid or oxalic acid respectively by 0.5 ~ 2.0wt% of each reactant quality, stir under the temperature condition of 50 ~ 80 DEG C; Described ion R is lanthanum ion La ³⁺, ruthenium ion Y ³⁺, thulium ion Tm ³⁺, gadolinium ion Gd ³⁺, dysprosium ion Dy ³⁺, lutetium ion Lu ³⁺in one; Described ion M is alkaline-earth metal ions sodium ion Na ⁺, lithium ion Li ⁺with potassium ion K ⁺in one;

(2) by chemical formula M ₅r _1-xyb _x(WO ₄) ₄in the stoichiometric ratio of each element, wherein 0.0001≤x<1.0, takes containing tungsten ion W ⁶⁺compound, be dissolved in deionized water or ethanolic soln, add complexing agent citric acid or oxalic acid by 0.5 ~ 2.0wt% of reactant quality, stir under the temperature condition of 50 ~ 80 DEG C;

(3) the various solution that step (1) and (2) obtain slowly are mixed, stir after 1 ~ 2 hour under the temperature condition of 50 ~ 80 DEG C, leave standstill, dry, obtain fluffy presoma;

(4) presoma is placed in retort furnace to calcine, temperature is 550 ~ 800 DEG C, and the time is 2 ~ 15 hours, naturally cools to room temperature, obtains a kind of tungstate rare earth light conversion material.

7. the preparation method of a kind of tungstate rare earth light conversion material according to claims 6, is characterized in that: the described compound containing ion R is the one in the oxide compound of R, fluorochemical, nitrate; Containing ytterbium ion Yb ³⁺compound be one in ytterbium oxide, ytterbium nitrate; Compound containing ion M is the one in the oxide compound of M, fluorochemical, carbonate, vitriol, nitrate; Containing tungsten ion W ⁶⁺compound be one in Tungsten oxide 99.999, ammonium tungstate.

8. an application for tungstate rare earth light conversion material as claimed in claim 1, is characterized in that: for the light-converting material of silica-based solar cell.