阅读说明：本技术 一种亚铜激活的荧光玻璃及其制备方法和应用 (Cuprous activated fluorescent glass and preparation method and application thereof ) 是由 阮健 程闰之 于 2019-10-18 设计创作，主要内容包括：本发明公开了一种亚铜激活的荧光玻璃及其制备方法和应用。其组成按摩尔百分比为：SiO<Sub>2</Sub> 40～66％,Al<Sub>2</Sub>O<Sub>3</Sub> 5～20％,MO 15～45％,R<Sub>2</Sub>O 0.1～15％,PO 0.01～30％,还原剂0.01～5％,掺杂物0.001～5％。本发明制备的亚铜激活荧光玻璃在波长为280nm～400nm的紫外光波激发下发出绿光到黄光到橙光,峰值在480nm～640nm之间,其最佳发射波长在360nm附近,发射峰位于580nm附近。该玻璃可作为荧光太阳能聚光器的光转换材料,将紫外光转换为可被太阳能电池吸收的可见光。(The invention discloses cuprous activated fluorescent glass and a preparation method and application thereof. The composition comprises the following components in percentage by mole: SiO 2 2 40～66％，Al 2 O 3 5～20％，MO 15～45％，R 2 0.1-15% of O, 0.01-30% of PO, 0.01-5% of reducing agent and 0.001-5% of dopant. The cuprous activated fluorescent glass prepared by the invention emits green light to yellow light to orange light under the excitation of ultraviolet light waves with the wavelength of 280 nm-400 nm, the peak value is between 480 nm-640 nm, the optimal emission wavelength is near 360nm, and the emission peak is near 580 nm. The glass can be used as a light conversion material of a fluorescent solar concentrator, and converts ultraviolet light into visible light which can be absorbed by a solar cell.)

1. The cuprous activated fluorescent glass is characterized by comprising the following components in percentage by mole:

SiO₂ 40～66％，Al₂O₃ 5～20％，MO 15～45％，R₂0.1-15% of O, 0.01-30% of PO, 0.01-5% of reducing agent and 0.001-5% of dopant;

wherein, the MO is any one or mixture of magnesium oxide, magnesium carbonate, basic magnesium carbonate, calcium oxide, calcium carbonate, strontium oxide and strontium carbonate;

the R is₂O is lithium oxide or carbonic acidAny one or mixture of lithium, sodium oxide, sodium carbonate and sodium bicarbonate;

the PO is any one or mixture of germanium oxide, lanthanum oxide, yttrium oxide and titanium oxide.

2. The cuprous-activated fluorescent glass of claim 1, wherein the reducing agent is SiC, Si₃N₄AlN, BN and aluminum powder or a mixture thereof.

3. The cuprous-activated fluorescent glass of claim 1, wherein the dopant is Cu-containing²⁺Or containing Cu⁺The compound of (1).

4. The cuprous-activated fluorescent glass of claim 3, wherein said glass comprises Cu²⁺The compound (B) is CuO or CuCl₂·2H₂O、Cu(NO₃)₂·3H₂O、CuSO₄·5H₂O、Cu(OH)₂One of (1); the Cu is contained⁺The compound of (A) is Cu₂O, CuCl.

5. The method for preparing cuprous-activated fluorescent glass as claimed in claim 1, wherein the method comprises the steps of:

1) fully mixing and grinding the raw materials uniformly;

2) presintering for 1-8 hours at 500-800 ℃ in an air atmosphere, and then melting for 0.5-6 hours at 1470-1650 ℃;

3) and pouring the mixture into a preheated mold, annealing for 2-12 hours at 450-750 ℃, cooling, cutting and polishing to obtain the cuprous activated fluorescent glass.

6. Use of the cuprous activated fluorescent glass of any of claims 1 to 4 as light conversion material in a fluorescent solar concentrator.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a cuprous-activated fluorescent glass material, and a preparation method and application thereof.

Background

A fluorescent solar concentrator (LSC) is a new type of solar concentrator based on spectrum conversion, and has attracted attention in recent years. Firstly, preparing an organic or inorganic waveguide material embedded with a fluorescence center, and emitting visible or near-infrared fluorescence with slightly smaller absorption energy and longer wavelength position through Stokes shift by utilizing the broadband absorption of the fluorescence center to ultraviolet light or visible light in a solar spectrum; then, the emitted visible or near-infrared fluorescence can be bound in the waveguide to be transmitted under the condition of total reflection, and then the visible or near-infrared fluorescence overflows from the side face to form condensed light; finally, the photovoltaic cell, which is placed on the side and has the energy band matched with the emitted light, converts the collected fluorescence into current with high efficiency, and realizes high-power concentrating solar power generation. The photovoltaic conversion device has the remarkable beneficial effects that the photoelectric conversion efficiency of the solar cell in unit area can be improved, so that the overall cost of the photovoltaic module with the same photoelectric conversion efficiency is reduced.

Currently, LSC technology still fails to achieve satisfactory light collection effect and photoelectric conversion efficiency. The conventional LSC device has two disadvantages: (1) the fluorescence quantum efficiency is low, and is caused by too narrow absorption spectrum of a fluorescence center, low absorption coefficient or serious fluorescence reabsorption effect; (2) the 'escape cone' fluorescence overflows, and the angle of the 'escape cone' is larger because the refractive index n1 of the waveguide material is not high, so that the light is easy to enter the 'escape cone' and overflow from the waveguide material, and the actual light condensation effect is far lower than the theoretical light condensation effect.

In addition, in consideration of the manufacturing cost of the LSC material and the fluorescent center dispersing process, the prior art mainly adopts a high molecular polymer as a waveguide material. For example, CN105223633A patent document proposes a fluorescent condenser with copper indium sulfide quantum dot material as fluorescent material and high molecular polymer as optical waveguide material, and its preparation method. The CN109244183A patent document proposes that quantum dots and polymer solution are mixed and coated on the surface of the optical waveguide carrier to form a quantum dot thin film condenser. Therefore, the LSC material has low stability and a service life much shorter than that of a solar cell.

Disclosure of Invention

Aiming at the technical current situation, the invention aims to provide cuprous-activated fluorescent glass as an LSC material, which has the characteristics of wide absorption spectrum, unobvious fluorescent reabsorption effect, high quantum efficiency, wide source and low cost. The refractive index of the fluorescent glass provided by the invention is not less than 1.60, the formed escape cone angle is small, the overflow of light condensation from the waveguide material can be obviously reduced, and the actual light condensation effect is obviously improved. In addition, compared with organic materials, the silicate glass matrix provided by the invention also has the characteristics of excellent stability and long service life. The invention also provides a preparation method and application of the material.

In order to achieve the purpose, the technical scheme is as follows:

the cuprous activated fluorescent glass comprises the following components in percentage by mole:

SiO ₂40～66％，Al₂O₃5～20％，MO15～45％，R₂0.1-15% of O, 0.01-30% of PO, 0.01-5% of reducing agent and 0.001-5% of dopant;

wherein, the MO is any one or mixture of magnesium oxide, magnesium carbonate, basic magnesium carbonate, calcium oxide, calcium carbonate, strontium oxide and strontium carbonate;

the R is₂O is any one or mixture of lithium oxide, lithium carbonate, sodium oxide, sodium carbonate and sodium bicarbonate;

the PO is any one or mixture of germanium oxide, lanthanum oxide, yttrium oxide and titanium oxide.

According to the scheme, the reducing agent is SiC or Si₃N₄AlN, BN and aluminum powder or a mixture thereof.

According to the scheme, the dopant is Cu-containing²⁺Or containing Cu⁺The compound of (1).

According to the scheme, the Cu is contained²⁺The compound (B) is CuO or CuCl₂·2H₂O、Cu(NO₃)₂·3H₂O、CuSO₄·5H₂O、 Cu(OH)₂One of (1); the Cu is contained⁺The compound of (A) is Cu₂O, CuCl.

The preparation method of the cuprous-activated fluorescent glass comprises the following steps:

1) fully mixing and grinding the raw materials uniformly;

2) presintering for 1-8 hours at 500-800 ℃ in an air atmosphere, and then melting for 0.5-6 hours at 1470-1650 ℃;

3) and pouring the mixture into a preheated mold, annealing for 2-12 hours at 450-750 ℃, cooling, cutting and polishing to obtain the cuprous activated fluorescent glass.

The cuprous activated fluorescent glass is applied as a light conversion material of a fluorescent solar concentrator.

Compared with the prior art, the invention has the beneficial effects that:

the alloy is prepared by adopting a traditional melting quenching method, the preparation process is simple, and the technology is mature.

By doping copper ions with different concentrations, silicate glass with a series of concentration ratios is obtained. The glass has excellent physical and chemical properties, good thermal stability and high transmittance, emits green light to yellow light to orange light under the excitation of light waves of 280-400 nm, has weak self-absorption, and is suitable for the field of solar fluorescent condensers.

The cuprous activated fluorescent glass prepared by the invention emits green light to yellow light to orange light under the excitation of ultraviolet light waves with the wavelength of 280 nm-400 nm, the peak value is between 480 nm-640 nm, the optimal emission wavelength is near 360nm, and the emission peak is near 580 nm. The glass can be used as a light conversion material of a fluorescent solar concentrator, and converts ultraviolet light into visible light which can be absorbed by a solar cell.

Drawings

FIG. 1: the transmission spectrum of the glass obtained in example 3;

FIG. 2: the emission spectrum of the glass prepared in the example 3 is excited by 360nm light;

FIG. 3: emission spectra of the glass prepared in example 3 under excitation of different excitation light wavelengths of 280nm to 400 nm.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

In the following examples, all reagents used are commercially available chemical reagents unless otherwise specified.