CN108517209B - Light conversion fluorescent powder and preparation method thereof - Google Patents
Light conversion fluorescent powder and preparation method thereof Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention provides a light conversion fluorescent powder and a preparation method thereof. The light conversion fluorescent powder is prepared by a high-temperature solid-phase sintering method, and the chemical general formula is as follows: m3‑yGa2‑xGeO8：xCr3+，yRE3+Wherein M is selected from one or a combination of more of Zn, Ba, Ca and Sr, RE is selected from one or a combination of more of Yb, Nd and Ho, x is 0-0.50, preferably 0.15-0.30, and y is 0.001-0.05, preferably 0.005-0.02. The light conversion fluorescent powder is formed by doping Cr in a matrix of the light conversion fluorescent powder3+And near infrared emitting rare earth ions RE3+(Yb3+，Nd3+，Ho3+And combinations thereof) with Cr3+As a sensitizer, the material can efficiently absorb 250-650nm wide spectrum ultraviolet-visible light and transfer energy to an activator RE3+Exciting high intensity near infrared light due to Cr3+Is a non-rare earth element, rare earth ion RE3+The doping amount is low, and the production cost is reduced to a certain extent; and the fluorescent powder has good matching with the spectral response of the silicon-based solar cell, and can be used for the spectral conversion fluorescent powder of the silicon-based solar cell.
Description
Technical Field
The invention relates to the field of spectrum conversion luminescence, in particular to light conversion fluorescent powder and a preparation method thereof.
Background
Sunlight contains light with various wavelengths, and only part of the sunlight can be utilized by the current single-junction solar cell. Taking the most widely used silicon-based solar cell in the prior art as an example, the Eg (band gap) of a silicon semiconductor is 1.12eV, that is, only sunlight with a wavelength less than 1100nm can pass through the silicon-based solar cell for photoelectric conversion, and infrared light with a wavelength greater than 1100nm passes through the cell and cannot be utilized; while for higher energy photons in the short wavelength range, electrons and holes (carriers) are excited to higher energy states, which lose excess energy by heat exchange with the lattice before current flow through the P-N junction occurs. In addition, the silicon solar cell has different light responses to different wavelengths, particularly has poor light response to ultraviolet to red light bands, and has the highest spectral response to 800-1100nm near infrared bands. Therefore, the local response of the silicon-based solar cell to the solar spectrum causes a great deal of sunlight waste, which also limits an important factor for further improving the energy conversion efficiency of the silicon-based solar cell. Based on the characteristic of poor corresponding property to short-wavelength high-energy photons, a light conversion layer doped with light conversion fluorescent powder is introduced on the surface of a cell panel, and the incident spectrum of sunlight is adjusted, so that the modulated emission spectrum is more matched with the highly-efficient utilization waveband of the solar cell, and the photoelectric conversion efficiency of the solar cell is improved, which becomes a hotspot in the field of researching and improving the photoelectric conversion efficiency of the solar cell at present.
At present, the solar spectrum is modulated mainly in two main types of three ways, (1) Up-conversion (Up-conversion), a process of converting two photons (E < Eg) with energy lower than the band gap of a silicon-based solar cell into a photon (E > Eg) with energy higher than the band gap; (2) down-conversion (DC), in particular, is divided into two forms: near infrared down conversion (NIR DC), namely converting one high-energy photon (E >2Eg) into two low-energy near infrared photons (E is approximately equal to Eg) with energy near the forbidden bandwidth of a silicon-based solar cell; ② a process of Down-shifting (DS) to convert a short wavelength high-energy photon into a longer wavelength low-energy photon with higher response. Compared with a down-conversion process, the up-conversion spectrum modulation has the defects of weak luminescence, low conversion efficiency and the like, so that the modulation research on the sunlight spectrum is mainly focused on the aspect of down-conversion materials, and the utilization rate of the solar cell on the high-energy spectrum and the photoelectric conversion efficiency of the cell can be effectively improved by two modes of down-conversion luminescence.
Fig. 1 shows the principle of applying the light conversion phosphor to a solar cell: sunlight is directly irradiated on the light conversion layer 1' doped with the light conversion fluorescent powder (the lower transfer DS or the near infrared lower conversion NIR DC fluorescent powder), and then Ce in the light conversion fluorescent powder3+，Tb3+，Pr3+，Tm3+The plasma sensitizer ions or substrates (such as vanadate and niobate) can absorb high-energy UV-visible light and transfer energy to equal Yb with near infrared emission3+，Nd3+Or Ho3+When the activator ions are activated, the activator ions emit near infrared light which can be efficiently utilized by the track solar cell 2 ', so that energy loss is reduced, and the photoelectric conversion efficiency of the solar cell 2' is effectively improved. For example, in patent CN201310143254.4, in LaBO3Passage of Ce in the matrix3+And Yb3+Combined to realize Yb under the excitation of ultraviolet light3+(ii) near infrared emission; in patent CN201010292983.2, Yb is incorporated in alkaline earth molybdates3+Ions, adsorption and Yb by molybdate matrix3+The sensitization of the ions realizes the near infrared luminescence.
Firstly, in order to improve the luminous intensity of the down-conversion luminescent material, a relatively high concentration of rare earth ions, including a sensitizer or an activator, is generally doped into a matrix, and as a common knowledge, the rare earth ions are high in cost, and the relatively high concentration of doping causes high production cost of the down-conversion luminescent material; secondly, the existing down-converting luminescent materials mainly belong to the rare earth donors (sensitizers, such as Tb)3+,Tm3+Or Pr3+) And receptors (activators, e.g. Yb)3+，Nd3+Or Ho3+) The synergistic luminescence of ion pairs, the 4f-4f transition of trivalent rare earth ions as sensitizer is an electric dipole transition of steric forbidden resistance, corresponding to a series of sharp and narrow excitation spectral lines, because the absorption capacity of photons in the near ultraviolet-red light region is very low, which leads to weak near infrared emission intensity of activator ions, thereby limiting further practical application of the existing solar spectrum conversion materials.
Therefore, it is a problem to be urgently needed by those skilled in the art to find a light conversion phosphor that can be excited in a wide band, has high near-infrared emission intensity and is low in cost, and adjusts the incident spectrum of sunlight to improve the spectral responsiveness of a solar cell and further increase the photoelectric conversion efficiency of the solar cell.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, an object of the present invention is to provide a light conversion phosphor and a method for preparing the same, which are used to solve the problems of narrow excitation band, low near infrared emission intensity and high cost of the light conversion phosphor in the prior art.
To achieve the above and other related objects, the present invention provides a light-converting phosphor having a chemical formula as follows:
M3-yGa2-xGeO8：xCr3+，yRE3+
wherein,
m is selected from one or a combination of more of Zn, Ba, Ca and Sr;
RE is selected from one or a combination of Yb, Nd and Ho;
0＜x≤0.50，0.001≤y≤0.05。
as a preferable mode of the light conversion phosphor of the present invention, the M contains Zn; the RE comprises Yb.
As a preferable embodiment of the light conversion phosphor of the present invention, x satisfies the following condition: x is more than or equal to 0.1 and less than or equal to 0.3.
As a preferable embodiment of the light conversion phosphor of the present invention, y satisfies the following condition: y is more than or equal to 0.005 and less than or equal to 0.04.
As a preferable embodiment of the light conversion phosphor of the present invention, x satisfies the following condition: x is more than or equal to 0.15 and less than or equal to 0.30.
As a preferable embodiment of the light conversion phosphor of the present invention, x satisfies the following condition: x is more than or equal to 0.2 and less than or equal to 0.30.
As a preferable embodiment of the light conversion phosphor of the present invention, y satisfies the following condition: y is more than or equal to 0.005 and less than or equal to 0.02.
In order to achieve the above and other related objects, the present invention provides a method for preparing a light-converting phosphor, the method at least comprising the steps of:
s10, according to the formula M3-yGa2-xGeO8：xCr3+，yRE3+The raw materials of each component are respectively weighed according to the molar ratio;
s20, fully grinding and uniformly mixing the raw materials of the components weighed in the step S10;
s30, sintering the raw materials which are fully ground and uniformly mixed in the step S20 at high temperature in an air atmosphere, and then cooling to room temperature;
s40, grinding the high-temperature sintered product in the step S30 into powder.
In order to promote the phase formation of the light conversion phosphor, a certain amount of flux may be added to the raw material.
As a preferable scheme of the preparation method of the light conversion fluorescent powder, the temperature of the high-temperature sintering is 1300-1500 ℃, and the time is 3-10 h.
As a preferable scheme of the preparation method of the light conversion fluorescent powder, the temperature of the high-temperature sintering is 1350-1450 ℃, and the time is 5-7 h.
As described above, the light conversion phosphor and the preparation method thereof of the present invention have the following beneficial effects:
1. the light conversion fluorescent powder of the invention uses Cr3+As sensitizer, Yb emitted in the near infrared3+，Nd3+，Ho3+As an activator, the solar cell realizes the spectrum conversion of broadband absorption (250 nm-650 nm) in the ultraviolet to visible light region and near infrared emission, increases the emission integral area of the near infrared, and improves the absorption and utilization efficiency of the solar cell to sunlight.
2. The light conversion fluorescent powder of the invention is applied to Cr3+High doping concentration and rare earth ion RE3+(Yb3+，Nd3+，Ho3+And combination thereof) has strong near infrared emission when the doping concentration is very low, the main emission peak is positioned at a wave band which can be efficiently utilized by the silicon-based solar cell, the energy of the main emission peak is matched with the forbidden band width of silicon, and the photoelectric conversion efficiency of the silicon-based solar cell can be effectively improved.
Cr as perThe transition metal element, compared with rare earth compound, Cr compound has lower price, and the rare earth ion RE in the light conversion fluorescent powder of the invention3+(Yb3+，Nd3+，Ho3+And combinations thereof) is less than or equal to 5 mol%, the production cost of the light conversion phosphor of the present invention is lower.
Drawings
Fig. 1 is a schematic diagram illustrating a principle of applying a light conversion phosphor to a solar cell in the prior art.
FIG. 2 is a flow chart of the preparation method of the light conversion phosphor of the present invention.
FIG. 3 shows an XRD spectrum of a light-converting phosphor of example 2 of the present invention, ZnCa2O4Standard diffraction Pattern (JCPDS No.38-1240) and Zn2Ce2O4Standard diffraction Pattern (JCPDS No. 25-1018).
FIG. 4 shows an emission spectrum (PL) of a light-converting phosphor in example 2 of the present invention, which has an emission peak in the range of 950-1150 nm under 408nm excitation and is attributed to Yb3+Is/are as follows2F5/2-2F7/2The energy level transition, wherein, at 972nm, 1007nm, there are two sharp peaks.
FIG. 5 shows the excitation spectrum of the light-converting phosphor of example 2 of the present invention when monitored at 1007 nm; three peaks in the range of 250-650nm, which are respectively attributed to Cr3+Is/are as follows4A2(4F)→4T1(4P)、4A2(4F)→4T1(4F)、4A2(4F)→4T2(4F) A transition in energy level.
Fig. 6 is a graph showing the emission spectrum and the excitation spectrum of the solar spectrum and the light conversion phosphor of example 2 of the present invention, and a graph corresponding to the spectrum of the silicon-based solar cell. The light conversion fluorescent powder disclosed by the invention can be well matched with the spectral response of the silicon-based solar cell, and can be used as the spectral conversion fluorescent powder of the silicon-based solar cell.
Description of the element reference numerals
| 1’ | Light conversion layer |
| 2’ | Solar cell |
| S10～S40 | Step (ii) of |
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 2-6. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
As shown in FIG. 2, the present invention provides a light-converting phosphor prepared by a high-temperature solid-phase synthesis method of the prior artThe chemical general formula is M3-yGa2-xGeO8：xCr3+，yRE3+Wherein, M is selected from one or a combination of more of Zn, Ba, Ca and Sr; RE is selected from one or a combination of Yb, Nd and Ho; the value of x is 0-0.50 (excluding 0), preferably 0.15-0.30, and more preferably 0.15-0.30; preferably 0.2-0.30; the value of y is 0.001-0.05, preferably 0.005-0.04, and more preferably 0.005-0.02.
The light-emitting principle of the light-converting fluorescent powder is that Cr is doped into a matrix of the light-converting fluorescent powder3+And near infrared emitting rare earth ions RE3+(Yb3+，Nd3+，Ho3+And combinations thereof) with Cr3+As a sensitizer to transfer energy efficiently to rare earth ions RE3+And exciting high-intensity near infrared light.
In a specific embodiment, said M is selected from Zn; and the RE is Yb.
The preparation method of the light conversion fluorescent powder comprises the following steps:
step S10 is executed according to the chemical formula M3-yGa2-xGeO8：xCr3+，yRE3+The raw materials of each component are weighed respectively according to the molar ratio.
S20, fully grinding and uniformly mixing the raw materials of the components weighed in the step S10.
In a specific embodiment, the weighed raw materials of the components are put into an agate mortar and added with absolute ethyl alcohol for grinding for 30min, so that the raw materials are uniformly mixed, and the method is suitable for the invention as long as the method can achieve the purpose.
And S30, sintering the raw materials which are fully ground and uniformly mixed in the step S20 at a high temperature in an air atmosphere, and then cooling to room temperature.
In one embodiment, the fully ground and uniformly mixed raw materials are placed in a corundum crucible and subjected to high-temperature sintering in an air atmosphere in a resistance furnace; the heating rate is 2-10 ℃/min, preferably 4-8 ℃/min, more preferably 5 ℃/min; the high temperature is kept at 1300-1500 ℃, preferably at 1350-; the heat preservation time is 3-10h, preferably 5-7h, and more preferably 6 h; then cooled to room temperature.
And S40, grinding the product sintered at high temperature in the step S30 into powder, and grinding the powder to obtain the required fluorescent powder.
The test method of the data in the embodiment of the invention is as follows:
the X-ray diffraction (XRD) test was performed on a D2PHASER table-top X-ray diffractometer manufactured by Bruker, germany. Using Cu target Ka radiation
The working voltage is 30kV and the current is 10 mA. The mode adopted in the test is step scanning, the step length is 0.02 degrees, and the scanning range is 5-80 degrees.
The luminescence characteristics and quantum efficiency of the samples under excitation in the near ultraviolet region were measured using an FLS-980 fluorescence spectrometer manufactured by Edinburgh, England.
Preferred embodiments within the scope of the present invention are further described and demonstrated below in conjunction with the specific examples. These examples are given for illustrative purposes only and are not to be construed as limiting the invention.
It should be noted that, in examples 1 to 7, the raw materials of the respective components used are oxides of the respective components, and in the actual production process, other compounds corresponding to the respective components may be used based on experimental conditions or other considerations, as long as the compound of the component (such as carbonate, bicarbonate, nitrate, etc.) can generate its corresponding oxide during the sintering process as the raw material.
Example 1
Light conversion phosphor Zn3Ga2GeO8:0.3Cr3+，0.01Yb3+The preparation of (1): weighing 0.2458g ZnO (analytically pure) and Yb2O3(analytical grade) 0.002g of Cr2O3(analytical purity) 0.023g Ga2O3(analytical grade) 0.1593g, GeO2(analytical purity) 0.1046 g. Mixing the above materials, placing into mortar, adding anhydrous ethanol, and grindingAfter grinding, the mixture is put into a corundum crucible and then high-temperature solid-phase synthesis is carried out in the air atmosphere. The calcination temperature was set to 1400 ℃ and the calcination time was 6 hours in this example. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 2
Light conversion phosphor Zn3Ga2GeO8:0.25Cr3+，0.01Yb3+The preparation of (1): weighing 0.2458g ZnO (analytically pure) and Yb2O3(analytical grade) 0.002g of Cr2O3(analytical purity) 0.0192g of Ga2O3(analytically pure) 0.1640g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature was 1380 ℃ and the calcination time was 8 hours in this example. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 3
Light conversion phosphor Zn3Ga2GeO8:0.20Cr3+，0.01Yb3+The preparation of (1): weighing 0.2458g ZnO (analytically pure) and Yb2O3(analytical grade) 0.002g of Cr2O3(analytical purity) 0.0154g, Ga2O3(analytical grade) 0.1687g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature in this example was set to 1420 ℃ and the calcination time was 7 hours. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 4
Light conversion phosphor Zn3Ga2GeO8:0.15Cr3+，0.01Yb3+The preparation of (1): weighing 0.2458g ZnO (analytically pure) and Yb2O3(analytical grade) 0.002g of Cr2O3(analytical purity) 0.0115g、Ga2O3(analytical grade) 0.1734g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature was set to 1370 ℃ and the calcination time was 9 hours in this example. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 5
Light conversion phosphor Zn3Ga2GeO8:0.02Cr3+，0.01Yb3+The preparation of (1): weighing 0.2458g ZnO (analytically pure) and Yb2O3(analytical grade) 0.002g of Cr2O3(analytical purity) 0.0015g, Ga2O3(analytical grade) 0.1734g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature in this example was set at 1390 ℃ and the calcination time was 5 hours. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 6
Light conversion phosphor Zn3Ga2GeO8:0.15Cr3+，0.005Yb3+The preparation of (1): weighing 0.2462g ZnO (analytically pure) and Yb2O3(analytical grade) 0.001g, Cr2O3(analytically pure) 0.0115g, Ga2O3(analytical grade) 0.1734g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature was set to 1430 ℃ and the calcination time was 4 hours in this example. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
Example 7
Light conversion phosphor Zn3Ga2GeO8:0.15Cr3+，0.02Yb3+The preparation of (1): weighing ZnO (analytically pure) 0.245g and Yb2O3(analytical grade) 0.003g of Cr2O3(analytically pure) 0.0115g, Ga2O3(analytical grade) 0.1734g, GeO2(analytical purity) 0.1046 g. The raw materials are uniformly mixed and put into a mortar, absolute ethyl alcohol is added for full grinding, then the mixture is put into a corundum crucible, and then high-temperature solid-phase synthesis is carried out under the air atmosphere. The calcination temperature in this example was set at 1440 ℃ and the calcination time was 9.5 hours. And (3) cooling the resistance furnace to room temperature, taking out the sample, and fully grinding to obtain the light conversion fluorescent powder sample.
The phase structure of the photoconversion phosphors of examples 1-7 was characterized using a Bruker D2PHASER X-ray diffractometer, and the XRD patterns of the photoconversion phosphor samples of examples 1-7 were all consistent with Zn3Ga2GeO8Matched with the standard X-ray diffraction patterns (JCPDS No.38-1240, JCPDS No.25-1018), the light-converting phosphor samples of the above examples 1-7 all retained their matrix Zn3Ga2GeO8Crystal structure of (2), Cr3+And Yb3+Without altering the matrix Zn3Ga2GeO8The lattice structure of (1).
In summary, the light conversion phosphor of the present invention is formed by doping Cr into the matrix3+And near infrared emitted Yb3 +，Nd3+Or Ho3+Using Cr3+As a sensitizer for efficient energy transfer to Yb3+Exciting high intensity near infrared light due to Cr3+The alloy is non-rare earth elements, so that the production cost is reduced; and the fluorescent powder has good matching with the spectral response of the silicon-based solar cell, and can be used for the spectral conversion fluorescent powder of the silicon-based solar cell.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A light conversion phosphor, characterized in that the chemical formula of the light conversion phosphor is as follows:
M3-yGa2-xGeO8：xCr3+，yRE3+
wherein,
the M is Zn; the RE is Yb;
0＜x≤0.50，0.001≤y≤0.05。
2. the light-converting phosphor according to claim 1, wherein x is 0.1 to 0.3.
3. The light-converting phosphor according to claim 2, wherein x is 0.15 to 0.30.
4. The light-converting phosphor according to claim 3, wherein x is 0.2 to 0.30.
5. The light-converting phosphor according to claim 1, wherein y is 0.005 to 0.04.
6. The light-converting phosphor according to claim 5, wherein y is 0.005 to 0.02.
7. A method for preparing a light-converting phosphor according to any of claims 1 to 6, wherein the method comprises at least the steps of:
s10, according to the formula M3-yGa2-xGeO8：xCr3+，yRE3+The raw materials of each component are respectively weighed according to the molar ratio;
s20, fully grinding and uniformly mixing the raw materials of the components weighed in the step S10;
s30, sintering the raw materials which are fully ground and uniformly mixed in the step S20 at high temperature in an air atmosphere, and then cooling to room temperature;
s40, grinding the high-temperature sintered product in the step S30 into powder.
8. The method for preparing light-converting phosphor according to claim 7, wherein the temperature of the high-temperature sintering is 1300-1500 ℃ for 3-10 hours.
9. The method for preparing light-converting phosphor according to claim 8, wherein the temperature of the high-temperature sintering is 1350-1450 ℃ for 5-7 hours.
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| CN107286932A (en) * | 2017-07-21 | 2017-10-24 | 山东大学 | Long after glow luminous material and preparation method thereof is changed on a kind of near-infrared |
| CN107936963A (en) * | 2017-11-02 | 2018-04-20 | 杭州显庆科技有限公司 | A kind of green tribo-luminescence fluorescent powder and preparation method thereof |
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| CN107286932A (en) * | 2017-07-21 | 2017-10-24 | 山东大学 | Long after glow luminous material and preparation method thereof is changed on a kind of near-infrared |
| CN107936963A (en) * | 2017-11-02 | 2018-04-20 | 杭州显庆科技有限公司 | A kind of green tribo-luminescence fluorescent powder and preparation method thereof |
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