Composite material with high photothermal conversion performance and preparation method thereof

Abstract

The invention discloses a composite material with high photothermal conversion performance and a direct mixing method and a core-shell structure method for preparing the material. The composite material with high photothermal conversion performance comprises a photothermal matrix material and a down-conversion fluorescent material, the photo-thermal base material comprises nano tungsten bronze and / or nano rare earth hexaboride; the down-conversion fluorescent material comprises Gd < 2.4 > Lu < 0.45 > Ga < 3.87 > AlO12 doped with Cr < 3 + > / Yb < 3 + > / Nd < 3 + > and / or Li2Mg < 0.99 > Zr < 1.985 > O4 doped with Cr < 3 + > / Yb < 3 + > / Nd < 3 + >. The composite material is prepared from the photo-thermal base material and the down-conversion fluorescent material through a direct mixing method and a core-shell structure method, visible light can be converted into near-infrared light, the near-infrared light is absorbed by the photo-thermal base material through local surface plasmon resonance and efficiently converted into heat energy to be output, the spectral response range is expanded, and the conversion efficiency is improved. The limitation that a traditional photo-thermal material only utilizes near infrared rays is broken through, the visible light utilization rate is increased, the photo-thermal conversion efficiency of the material is remarkably improved, meanwhile, the cost is reduced, and good application prospects are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photothermal conversion materials, and particularly relates to a high photothermal conversion performance composite material and a preparation method thereof. BACKGROUND

[0002] Photothermal conversion materials exhibit wide application potential in many fields, including thermal insulation coatings, photothermal therapy, seawater desalination and thermal clothing, etc. Such materials usually include nano noble metal particles, semiconductor materials, carbon-based materials and polymer organic matters. Among them, nano noble metal materials are widely used due to their unique localized surface plasmon resonance effect, especially nano gold, nano silver and nano aluminum, etc. However, the high cost of nano gold and its strong dependence of photothermal conversion efficiency on morphology make experimental control very harsh, so there is an urgent need for new, efficient, stable and low-cost photothermal conversion materials in the market.

[0003] In recent years, materials with localized surface plasmon resonance (LSPR) effect such as tungsten bronze and rare earth hexaboride nanoparticles have attracted much attention due to their excellent optical properties, especially in the absorption of near-infrared light. When these nanoparticles are exposed to specific wavelength light irradiation, the absorbed photon energy can be converted into heat, improving the photothermal conversion efficiency of the material. The above-mentioned materials developed at present mainly absorb near-infrared light and then convert it into heat energy, but these materials have low absorption of visible light and cannot utilize this band.

[0004] Therefore, exploring new composite materials that can absorb the visible light band not only can solve the limitations of traditional photothermal conversion materials, but also can provide an important technical foundation for achieving more efficient energy utilization and heat management. SUMMARY

[0005] The first object of the present application is to provide a high photothermal conversion performance composite material, which can convert visible light into near-infrared light and then reabsorb it, thereby enhancing the absorption and photothermal conversion capacity of tungsten bronze and rare earth hexaboride nanoparticles in the visible and near-infrared light bands.

[0006] The second object of the present application is to provide a preparation method of the high photothermal conversion performance composite material, which includes a direct mixing preparation method and a core-shell structure preparation method.

[0007] The third object of the present application is to provide the high photothermal conversion performance composite material prepared by the direct mixing preparation method and the core-shell structure preparation method.

[0008] The first object of the present application is implemented by the following technical solutions.

[0009] A high light-heat conversion performance composite material, comprising a photothermal matrix material and a down-conversion fluorescent material, the mass ratio of the photothermal matrix material to the down-conversion fluorescent material is greater than or equal to 1:1; the photothermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; the down-conversion fluorescent material comprises Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3 + ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ 、Li2Mg 1- x Zr 2-yO4:Yb 3+ ,Nd 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ Li2Mg 1-x Zr 2-y O4:Yb 3+ Li2Mg 1-x Zr 2-y O4:Nd 3+ At least one of them, preferably, the downconversion fluorescent material includes Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3 + ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Yb 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ Li2Mg 0.99 Zr 1.985 O4:Yb 3+ Li2Mg 0.99 Zr 1.985 O4:Nd 3+ at least one of them.

[0010] The combination of the above photothermal matrix material and down-conversion fluorescent material produces a synergistic effect, producing a down-conversion + localized surface plasmon resonance effect, the down-conversion fluorescent material converts 400~700 nm visible light into 700~1500 nm near-infrared light, and the photothermal matrix material absorbs near-infrared light through localized surface plasmon resonance (LSPR) and efficiently converts it into heat energy, expanding the spectral response range, breaking through the limitation of traditional photothermal materials only using near-infrared, and improving the utilization rate of visible light.

[0011] Further, the nano-tungsten bronze includes Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 ·WO 2.8-3.0 , Ba x WO3, La x WO3, tungsten bronze is a kind of non-stoichiometric compound, its chemical formula is MxWO3, wherein x value is between 0 and 1, M is usually alkali metal, alkaline earth metal, ammonium ion and rare earth metal ion etc.;The nano-rare earth hexaboride includes LaB6, CeB6, PrB6, NdB6.

[0012] Further, the Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ is doped in Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Cr 3+ ,Yb 3+、Nd 3+ The Cr 3+ The doping ratio of Yb is ≤10%. 3+ The doping ratio is ≤20%, the Nd 3+ The doping ratio is ≤20%; preferably, in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium doping; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Cr 3+ Yb 3+ The Cr 3+ The doping ratio of Yb is ≤10%. 3+ The doping ratio is ≤20%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Cr 3+ 、Nd 3+ The Cr 3+ The doping ratio is ≤10%, the Nd 3+ The doping ratio is ≤20%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Yb 3+ 、Nd 3+ The Yb 3+ The doping ratio of Nd is ≤20%, 3+ The doping ratio is ≤20%; The Gd 2.4 Lu 0.6-x Ga4-y AlO 12 :Cr 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Cr 3+ The Cr 3+ The doping ratio is ≤10%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Yb 3+ The Yb 3+ The doping ratio is ≤20%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ In Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Nd 3+ The Nd 3+ The doping ratio is ≤20%; The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ It is Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ Yb 3+ 、Nd 3+ In, the Cr 3+ The doping ratio of Yb is ≤10%. 3+ The doping ratio is ≤20%, the Nd 3+ The doping ratio is ≤20%; preferably, in Li2Mg 0.99 Zr 1.985 Doping in O4; The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ It is in Li2Mg 1-x Zr 2-y O4 doped with Cr 3+, Yb 3+ , the doping ratio of the Cr 3+ is ≤10%, the doping ratio of the Yb 3+ is ≤20%; The Li2Mg 1-x Zr 2-y O4:Cr 3+ , Nd 3+ is Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ , Nd 3+ , the doping ratio of the Cr 3+ is ≤10%, the doping ratio of the Nd 3+ is ≤20%; The Li2Mg 1-x Zr 2-y O4:Yb 3+ , Nd 3+ is Li2Mg 1-x Zr 2-y O4 doped with Yb 3+ , Nd 3+ , the doping ratio of the Yb 3+ is ≤20%, the doping ratio of the Nd 3+ is ≤20%; The Li2Mg 1-x Zr 2-y O4:Cr 3+ is Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ , the doping ratio of the Cr 3+ is ≤10%; The Li2Mg 1-x Zr 2-y O4:Yb 3+ is Li2Mg 1-x Zr 2-y O4 doped with Yb 3+ , the doping ratio of the Yb 3+ is ≤20%; The Li2Mg 1-x Zr 2-y O4:Nd 3+ is Li2Mg 1-x Zr 2-y O4 doped with Nd 3+ , the doping ratio of the Nd 3+ is ≤20%.

[0013] The Gd 2.4 Lu 0.6 Ga4AlO12 doped with one or more of Cr, Yb 3+ doped with one or more of Cr, Yb 3+ doped with one or more of Cr, Yb 3+ doped with one or more of Cr, Yb

[0014] The second object of the present application is implemented by the following technical solutions.

[0015] A direct mixing method for preparing a high light-heat conversion performance composite material, comprising the following steps: S1, dispersing a light-heat matrix material in ethanol, and obtaining a matrix dispersion liquid after ultrasonic treatment; wherein the light-heat matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; S2, adding a down-conversion fluorescent material to the matrix dispersion liquid, and obtaining a mixed liquid I after magnetic stirring; S3, drying the mixed liquid I to obtain a high light-heat conversion performance composite material powder.

[0016] The direct mixing method is suitable for rapid preparation, has simple steps and low cost, and can be rapidly mass-produced.

[0017] Further, in S1, the nano-tungsten bronze comprises Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 ·WO 2.8-3.0 , Ba x WO3, La x WO3, and the nano-rare earth hexaboride is LaB6, CeB6, PrB6, or NdB6; the concentration of the nano-tungsten bronze and / or the nano-rare earth hexaboride in the matrix dispersion liquid is 0.01-50 mg / mL.

[0018] Further, in S2, the down-conversion fluorescent material comprises Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+N d 3+ Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Yb 3+ N d 3+ Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 N d 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ Yb 3+ N d 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ Yb 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ N d 3+ Li2Mg 1-x Zr 2-y O4:Yb 3+ N d 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ Li2Mg 1-x Zr 2-y O4:Yb 3+ Li2Mg 1-x Zr 2-y O4:N d 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ Yb 3+ N d 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO12 :Cr 3+ ,Yb 3+ 、Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Nd 3+ 、Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3 + ,Nd 3+ 、Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ 、Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ 、Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Nd 3+ 、Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ 、Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ 、Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Nd 3+ 、Li2Mg 0.99 Zr 1.985 O4:Yb 3+ ,Nd 3+ 、Li2Mg 0.99 Zr 1.985 O4:Cr 3+ 、Li2Mg 0.99 Zr 1.985 O4:Yb 3+ 、Li2Mg 0.99 Zr 1.985 O4:Nd 3+At least one of the above-mentioned elements; the mass ratio of the photothermal matrix material to the down-conversion fluorescent material is greater than or equal to 1:1, preferably 1:0.1 to 1:0.5. When the amount of down-conversion fluorescent material is less than one-tenth, the synergistic effect is not obvious, and when the amount of down-conversion fluorescent material is too much, the mass of the photothermal matrix material, the fluorescence quenching is prone to occur.

[0019] The third object of the application is implemented by the following technical scheme.

[0020] The high light-heat conversion performance composite material prepared by the direct mixing preparation method. The direct mixing preparation method mixes different components to form a disordered mixture, which has the advantages of simple process, rapid realization of the combination of component basic functions, realization of visible light and near-infrared light conversion into heat energy, low cost and good effect.

[0021] A core-shell structure preparation method of a high light-heat conversion performance composite material, comprising the following steps: P1, preparing down-conversion fluorescent powder: adding raw materials of down-conversion fluorescent material into anhydrous ethanol and grinding, then reducing and sintering, and grinding into uniform powder with a diameter of 1-5 μm after cooling, which is the down-conversion fluorescent powder; the down-conversion fluorescent material comprises Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Cr 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ 、Gd 2.4 Lu 0.6- x Ga 4-y AlO 12 :Yb 3+ 、Gd2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ Li2Mg 1-x Zr 2-y O4:Yb 3+ ,Nd 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ Li2Mg 1- x Zr 2-y O4:Yb 3+ Li2Mg 1-x Zr 2-y O4:Nd 3+ At least one of them, preferably, the downconversion fluorescent material includes Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO12 :Cr 3 + Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Yb 3+ ,Nd 3+ Li2Mg 0.99 Zr 1.985 O4:Cr 3+ Li2Mg 0.99 Zr 1.985 O4:Yb 3+ Li2Mg 0.99 Zr 1.985 O4:Nd 3+ At least one of them; the raw materials for the downconversion fluorescent material are selected according to the chemical formula of the downconversion fluorescent material, including gadolinium source, lutetium source, gallium source, aluminum source, oxygen source, lithium source, magnesium source, zirconium source, chromium source, ytterbium source, and neodymium source; P2. Preparation of photothermal matrix liquid: The raw materials of the photothermal matrix material are dispersed with benzyl alcohol to obtain the photothermal matrix liquid; the photothermal matrix material includes nano-tungsten bronze and / or nano-rare earth hexaborides; the nano-tungsten bronze includes Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 ·WO 2.8-3.0 Ba x WO3, La x WO3; the nano-rare earth hexaborides include LaB 6、CeB6, PrB6, NdB6; the raw materials of the photothermal matrix material are selected according to the chemical formula of the photothermal matrix material, wherein the raw materials of the nano-tungsten bronze include one of cesium sources, sodium sources, lithium sources, ammonium sources, barium sources, lanthanum sources and tungsten sources, and the raw materials of the nano-rare earth hexaboride are purchased rare earth hexaboride; P3, the down-conversion fluorescent powder prepared in P1 is put into the photothermal matrix liquid prepared in P2 for sufficient stirring to obtain a mixed liquid II; P4, the mixed liquid II is subjected to microwave reaction at 180-220 DEG C for 12-24 h, and the product obtained after the reaction is completed is subjected to centrifugation; P5, the precipitate obtained after centrifugation is sequentially washed with pure water, dilute sulfuric acid and anhydrous ethanol, and is dried after washing to obtain a high photothermal conversion performance composite material core-shell powder.

[0022] The core-shell structure method is suitable for scenes with high requirements for material performance, the tungsten bronze is coated on the down-conversion fluorescent material to form a core-shell structure, the interface is strongly combined, the dispersity is improved, the energy transfer efficiency is improved by the chemical bonding of the core-shell interface, the light scattering loss of physical mixing is avoided, the fluorescence quenching is reduced, the selective fluorescence enhancement is realized, the signal-to-noise ratio is significantly improved, and the stability is strong.

[0023] Further, in the P3, the mass ratio of the photothermal matrix material to the down-conversion fluorescent powder is greater than or equal to 1:1. The parameter range ensures the uniformity of the coating layer and the crystallization quality. If the mass of the down-conversion fluorescent powder exceeds the mass of the photothermal matrix material, the coating is not complete or agglomeration occurs.

[0024] The high photothermal conversion performance composite material prepared by the above-mentioned core-shell structure preparation method can realize the coating of small particles (thickness 100-500 nm) of the photothermal matrix material on the surface of large particles (diameter 1-5 mu m) of the down-conversion fluorescent powder by in-situ deposition of a solvothermal method, and an ordered structure with clear layered core and shell is constructed. The advantage is that it can realize strong synergistic effect and function integration between components, the energy transfer efficiency is improved by the chemical bonding of the core-shell interface, the light scattering loss of physical mixing is avoided, thereby producing new performance beyond simple addition, and the photothermal conversion efficiency is higher.

[0025] Beneficial effects: The application provides a high-efficiency photothermal conversion composite material based on nano-tungsten bronze and rare earth hexaboride, which is prepared by mixing the photothermal matrix material and the down-conversion fluorescent material. The visible light can be converted into near-infrared light, which is absorbed by the photothermal matrix material through local surface plasmon resonance and converted into heat energy output, the spectral response range is expanded, the limitation of traditional photothermal materials using only near-infrared is broken, the visible light utilization rate is improved, the photothermal conversion efficiency of the material is significantly improved, the cost is reduced, and the application prospect is good. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the accompanying drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the accompanying drawings in the following description only only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained based on these drawings without creative labor.

[0027] Figure 1 Cs 0.32 Thermal image of WO3nanoparticles; Figure 2 Thermal image of GLGA:Cr,Yb nanoparticles; Figure 3 Cs 0.32 Thermal image of WO3@GLGA:Cr,Yb composite material; Figure 4 Thermal image of LaB6nanoparticles; Figure 5 Thermal image of LaB6@GLGA:Cr,Yb composite material in Example 2; Figure 6 Ba 0.2 Thermal image of WO3nanoparticles; Figure 7 Ba 0.2 Thermal image of WO3@GLGA:Cr,Yb composite material in Example 3; Figure 8 La 0.1 Thermal image of WO3nanoparticles; Figure 9 La 0.1 Thermal image of WO3@GLGA:Cr,Yb composite material in Example 4; Figure 10 Thermal image of LMZO:Cr,Yb nanoparticles; Figure 11 Cs 0.32 Thermal image of WO3@LMZO:Cr,Yb composite material in Example 5; Figure 12 Cs 0.32 Thermal image of WO3@GLGA:Cr,Yb composite material core-shell powder in Example 6; Figure 13 Thermal image of LaB6@GLGA:Cr,Yb composite material core-shell powder in Example 7; Figure 14 Ba 0.2Thermal image of WO3@GLGA:Cr, Yb composite core-shell powder; Figure 15 La for example 9 0.1 Thermal image of WO3@GLGA:Cr, Yb composite core-shell powder; Figure 16 Cs for example 10 0.32 Thermal image of WO3@LMZO:Cr, Yb composite core-shell powder; Figure 17 Cs for example 11 0.32 Thermal image of WO3@LaB6@GLGA:Cr, Yb composite core-shell powder; Figure 18 Cs for example 12 0.32 Thermal image of WO3@LaB6@GLGA:Cr, Yb@LMZO:Cr, Yb composite core-shell powder. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. In addition, the terms "I" and "II" are only used for description purposes, and cannot be understood as indicating or implying relative importance. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0029] In one specific embodiment of the present application, a high photo-thermal conversion performance composite material includes a photo-thermal matrix material and a down-conversion fluorescent material, and the mass ratio of the photo-thermal matrix material to the down-conversion fluorescent material is ≥1:1. The photo-thermal matrix material includes nano-tungsten bronze and / or nano-rare earth hexaboride; the down-conversion fluorescent material includes Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ (hereinafter abbreviated as GLGA:Cr, Yb, Nd), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ (hereinafter abbreviated as GLGA:Cr, Yb), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr3+ Nd 3+ (abbreviated as GLGA:Cr, Nd), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ Nd 3+ (abbreviated as GLGA:Yb, Nd), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ (abbreviated as GLGA:Cr), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ (abbreviated as GLGA:Yb), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Nd 3+ (abbreviated as GLGA:Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ Yb 3+ Nd 3+ (abbreviated as LMZO:Cr, Yb, Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ Yb 3+ (abbreviated as LMZO:Cr, Yb), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ Nd 3+ (abbreviated as LMZO:Cr, Nd), Li2Mg 0.99 Zr 1.985 O4:Yb 3+ Nd 3+ (abbreviated as LMZO:Yb, Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ (abbreviated as LMZO:Cr), Li2Mg 0.99 Zr 1.985 O4:Yb 3+ (abbreviated as LMZO:Yb), Li2Mg 0.99 Zr 1.985 O4:Nd 3+ (abbreviated as LMZO:Nd).

[0030] Photothermal matrix materials: Nano-tungsten bronze includes Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 ·WO 2.8-3.0 Ba x WO3, La x WO3; Nano-rare earth hexaborides include LaB6, CeB6, PrB6, and NdB6.

[0031] In downconversion fluorescent materials: GLGA:Cr,Yb,Nd is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Cr 3+ Yb 3+ 、Nd 3+ Cr 3+ The doping ratio is ≤10%, Yb 3+ The doping ratio is ≤20%, Nd 3+ The doping ratio is ≤20%; GLGA:Cr,Yb is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Cr 3+ Yb 3+ Cr 3+ The doping ratio is ≤10%, Yb 3+ The doping ratio is ≤20%; GLGA:Cr,Nd is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Cr 3+ 、Nd 3+ Cr 3+ The doping ratio is ≤10%, Nd 3+ The doping ratio is ≤20%; GLGA:Yb,Nd is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Yb 3+ 、Nd 3+ Yb 3+ The doping ratio is ≤20%, Nd 3+ The doping ratio is ≤20%; GLGA:Cr is Gd2.4Lu0.45Ga3.87AlO12 doped with Cr 3+ , the doping ratio of Cr 3+ ≤10%; GLGA:Yb is Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 doped with Yb 3+ , the doping ratio of Yb 3+ ≤20%; GLGA:Nd is Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 doped with Nd 3+ , the doping ratio of Nd 3+ ≤20%; LMZO:Cr,Yb,Nd is Li2Mg 0.99 Zr 1.985 O4 doped with Cr 3+ , Yb 3+ , Nd 3+ , the doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%, the doping ratio of Nd 3+ ≤20%.

[0032] LMZO:Cr,Yb is Li2Mg 0.99 Zr 1.985 O4 doped with Cr 3+ , Yb 3+ , the doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%; LMZO:Cr,Nd is Li2Mg 0.99 Zr 1.985 O4 doped with Cr 3+ , Nd 3+ , the doping ratio of Cr 3+ ≤10%, the doping ratio of Nd 3+ ≤20%; LMZO:Yb,Nd is Li2Mg 0.99 Zr 1.985 O4 doped with Yb 3+ , Nd 3+ , the doping ratio of Yb 3+ ≤20%, the doping ratio of Nd 3+ ≤20%; LMZO:Cr is Li2Mg0.99 Zr 1.985 Doping Cr in O4 3+ , Cr 3+ The doping ratio of is ≤10%; LMZO:Yb is in Li2Mg 0.99 Zr 1.985 Doping Yb in O4 3+ , Yb 3+ The doping ratio of is ≤20%; LMZO:Nd is in Li2Mg 0.99 Zr 1.985 Doping Nd in O4 3+ , Nd 3+ The doping ratio of is ≤20%.

[0033] In one specific embodiment of the present application, a high photo-thermal conversion performance composite material is prepared by using a direct mixing method, which comprises steps S1-S3.

[0034] S1, dispersing a photo-thermal matrix material in ethanol, and placing it in a dual-frequency liquid crystal ultrasonic cleaner (ultrasonic power 100 W, frequency 45 / 80 kHz) for ultrasonic treatment for 30-120 min, to obtain a matrix dispersion liquid after ultrasonic treatment; the photo-thermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; in the matrix dispersion liquid, the concentration of the nano-tungsten bronze or the nano-rare earth hexaboride is 0.01-50 mg / mL, preferably 0.1-10 mg / mL, and more preferably 0.5-5 mg / mL.

[0035] S2, adding a down-conversion fluorescent material to the matrix dispersion liquid, and magnetically stirring (stirring temperature 40-80℃, stirring speed 200-700 rad / min, time length 1-4 h) to obtain a mixed liquid I; the mass ratio of the photo-thermal matrix material to the down-conversion fluorescent material is ≥1:1.

[0036] S3, drying the mixed liquid I in an oven at 60-90℃ for 6-12 h to obtain a high photo-thermal conversion performance composite material powder.

[0037] The high photo-thermal conversion performance composite material prepared by the steps S1-S3 of the above direct mixing preparation method.

[0038] In one specific embodiment of the present application, a high photo-thermal conversion performance composite material is prepared by using a core-shell structure method, which comprises steps P1-P5.

[0039] P1, preparation of down-conversion fluorescent powder: prepare raw materials according to each element of the chemical formula of the down-conversion fluorescent material, including gadolinium source, lutetium source, gallium source, aluminum source, oxygen source, lithium source, magnesium source, zirconium source, chromium source, ytterbium source, neodymium source; put the raw materials of the down-conversion fluorescent material into an agate mortar, add anhydrous ethanol and grind for 30-120 min, pour into an alumina boat and place in a high-temperature tube furnace to reduce and sinter the sample. After cooling, take out and grind thoroughly in the agate mortar to obtain a uniform powder with a diameter of 1-5 μm.

[0040] P2, preparation of photothermal matrix liquid: disperse the raw materials of the photothermal matrix material with benzyl alcohol to obtain a photothermal matrix liquid; the photothermal matrix material includes nano-tungsten bronze and / or nano-rare earth hexaboride, and the raw materials are prepared according to each element of the chemical formula of the photothermal matrix material, wherein the raw materials of the nano-tungsten bronze include one of cesium source, sodium source, lithium source, ammonium source, barium source, lanthanum source and tungsten source, and the raw materials of the nano-rare earth hexaboride are purchased rare earth hexaboride.

[0041] P3, put the down-conversion fluorescent powder prepared in P1 into the photothermal matrix liquid prepared in P2 and stir thoroughly to obtain a mixed liquid II; wherein the mass ratio of the photothermal matrix material to the down-conversion fluorescent powder is ≥1:1.

[0042] P4, place the mixed liquid II in a high-pressure reaction kettle (commonly made of Teflon material (maximum 100 bar) or quartz material (maximum 45 bar)) and then place it in a microwave synthesizer for microwave reaction at 180-220°C for 12-24 h; after the reaction is completed, the obtained product is placed in a high-speed centrifuge and centrifuged at 3000-5000 rad / min for 2-5 min. P5, sequentially wash the precipitate obtained after centrifugation with pure water, dilute sulfuric acid and anhydrous ethanol, and then place it in a vacuum drying box for drying at 40-50°C for 2-3 h to obtain a high photothermal conversion performance composite material core-shell powder.

[0043] The high photothermal conversion performance composite material prepared by the above core-shell structure preparation method.

[0044] Example 1-direct mixing method + Cs 0.32 WO3+ GLGA:Cr,Yb 1, preparation of Cs 0.32 WO3 nanoparticles: according to Cs 0.32WO3each element preparation raw material, first 150 mL benzyl alcohol (C7H8O) solvent is placed in a beaker, then 0.24 g cesium hydroxide powder is slowly added to the beaker with benzyl alcohol, a magnetic stirring device is used for continuous stirring; after it is completely dispersed, 1.98 g tungsten hexachloride is poured into the beaker, and stirring is mixed uniformly to obtain a precursor dispersion liquid. Then the precursor dispersion liquid is injected into the inner liner of a high-pressure reaction kettle made of polytetrafluoroethylene, and kept at 200℃ for 8 h. After the reaction is completed, the natural cooling program is used, and the precipitate is separated and extracted by a centrifuge. Then the precipitate is washed with dilute sulfuric acid solution, deionized water and anhydrous ethanol alternately to treat the product. Finally, vacuum drying operation is carried out at 40℃ in a vacuum environment for 2 h, and Cs 0.32 WO3nanoparticle blue powder. Figure 1 The thermal image of Cs 0.32 WO3nanoparticles is shown, which can absorb light energy and convert it into heat energy output under natural light irradiation conditions, with a center temperature of 37.6℃.

[0045] 2, the fluorescent material GLGA:Cr, Yb is prepared. According to the preparation of raw materials of each element, 2.1750 g gadolinium oxide, 0.4477 g lutetium oxide, 1.8135 g gallium oxide, 0.2549 g aluminum oxide, 0.0494 g chromium oxide and 0.1478 g ytterbium oxide are weighed by an electronic balance, and the weighed raw materials are put into an agate mortar and ground for 30 min with ethanol. Then the ground raw materials are transferred to an alumina boat and sintered in a tube furnace at 1450℃ for 5 h under a reducing atmosphere, cooled to room temperature and taken out. Finally, the obtained sample is ground into a uniform size powder in an agate mortar, and the GLGA:Cr, Yb nanoparticle powder is obtained after being sieved through a 200 mesh sieve. Figure 2 The thermal image of GLGA:Cr, Yb nanoparticles is shown, with a center temperature of 31.0℃.

[0046] 3, 0.25 g Cs 0.32 WO3nanoparticles are dispersed in 5 mL ethanol, and a matrix dispersion liquid is obtained after ultrasonic treatment for 60 min.

[0047] 4, 0.2 g GLGA:Cr, Yb nanoparticle powder is added to the matrix dispersion liquid, and a mixed liquid I is obtained by magnetic stirring at 80℃ for 1 h. After drying the mixed liquid I in an oven at 90℃ for 6 h, Cs 0.32 WO3@GLGA:Cr, Yb high light-heat conversion performance composite material powder. Figure 3 The thermal image of Cs 0.32 WO3@GLGA:Cr, Yb composite material is shown, with a center temperature of 39.8℃, indicating that it improves Cs0.32 Photo-thermal conversion efficiency of WO3.

[0048] Example 2 - Direct mixing method + LaB6+ GLGA:Cr,Yb 1. Purchase LaB6 finished product. Figure 4 The thermal image of LaB6 nanoparticles is shown, which can absorb light energy and convert it into heat energy output under natural light irradiation conditions, with a center temperature of 37.8℃.

[0049] 2. Prepare the fluorescent material GLGA:Cr,Yb according to the method of Example 1.

[0050] 3. Disperse 0.25 g of LaB6 nanoparticles in 5 mL of ethanol, and after ultrasonic treatment for 60 min, obtain the matrix dispersion liquid.

[0051] 4. Add 0.2 g of GLGA:Cr,Yb nanoparticle powder to the matrix dispersion liquid, and magnetically stir at 80℃ for 1 h to obtain mixture I. After drying mixture I in an oven at 90℃ for 6 h, obtain LaB6@GLGA:Cr,Yb high photo-thermal conversion performance composite powder. Figure 5 The thermal image of LaB6@GLGA:Cr,Yb composite material is shown, with a center temperature of 40.1℃, indicating that it improves the photo-thermal conversion efficiency of LaB6.

[0052] Example 3 - Direct mixing method + Ba 0.2 WO3+ GLGA:Cr,Yb 1. Prepare Ba 0.2 WO3nanoparticles: According to the preparation method of Ba 0.2 WO3, weigh 0.09867 g of barium carbonate and 0.63741 g of ammonium tungstate into 100 mL of deionized water, and continuously stir in a glass beaker for 1 h to complete the mixing. Then place the crucible in a drying oven at 180℃ and dry for 3 h, then grind to obtain a powder sample. Transfer the sample to a tube furnace with nitrogen and hydrogen mixed gas, and carry out reduction operation at 900℃ for 2 h. Then naturally cool to room temperature to obtain Ba 0.2 WO3nanoparticles blue powder. Figure 6 The thermal image of Ba 0.2 WO3nanoparticles is shown, which can absorb light energy and convert it into heat energy output under natural light irradiation conditions, with a center temperature of 36.9℃.

[0053] 2. Prepare the fluorescent material GLGA:Cr,Yb according to the method of Example 1.

[0054] 3. Disperse 0.25 g of Ba 0.2The WO3nanoparticles were dispersed in 5 mL ethanol to obtain a matrix dispersion liquid after ultrasonic treatment for 60 min.

[0055] 4. 0.2 g of GLGA:Cr, Yb nanoparticle powder was added into the matrix dispersion liquid, and a mixed liquid I was obtained after magnetic stirring at 80 °C for 1 h. After drying the mixed liquid I in an oven at 90 °C for 6 h, a Ba 0.2 WO3@GLGA:Cr, Yb high light-heat conversion performance composite powder. Figure 7 The Ba 0.2 The thermal image of the WO3@GLGA:Cr, Yb composite material, with a center temperature of 39.5 °C, indicates that it improves the Ba 0.2 The light-heat conversion efficiency of WO3.

[0056] Example 4 - Direct mixing method + La 0.1 WO3+ GLGA:Cr, Yb 1. La 0.1 WO3nanoparticles: According to the preparation method of La 0.1 WO3element preparation raw materials, 0.0858 g of lanthanum hydrochloride and 0.6374 g of ammonium tungstate were weighed and added into 100 mL of deionized water in a glass cup, and continuously stirred for 1 h to complete the mixing. Then the crucible was placed in a drying oven at 180 °C for 3 h and ground to obtain a powder sample. The sample was transferred to a tube furnace with a nitrogen-hydrogen mixture at 900 °C, and the material was reduced for 2 h. Then it was naturally cooled to room temperature to obtain La 0.1 WO3nanoparticle blue powder. Figure 8 The La 0.1 The thermal image of the WO3nanoparticle shows that it can absorb light energy and convert it into heat energy output under natural light irradiation, with a center temperature of 37.9 °C.

[0057] 2. The fluorescent material GLGA:Cr, Yb was prepared according to the method of Example 1.

[0058] 3. 0.25 g of La 0.1 The WO3nanoparticles were dispersed in 5 mL ethanol to obtain a matrix dispersion liquid after ultrasonic treatment for 60 min.

[0059] 4. 0.2 g of GLGA:Cr, Yb nanoparticle powder was added into the matrix dispersion liquid, and a mixed liquid I was obtained after magnetic stirring at 80 °C for 1 h. After drying the mixed liquid I in an oven at 90 °C for 6 h, a Ba Figure 9 The La 0.1The thermal image of WO3@GLGA:Cr, Yb composite material shows that the center temperature is 39.4°C, indicating that it improves the Cs 0.1 The photo-thermal conversion efficiency of WO3.

[0060] Example 5 - Direct mixing method + Cs 0.32 WO3+ LMZO:Cr, Yb 1. Cs was prepared according to the method of Example 1 0.32 WO3nanoparticles.

[0061] 2. The fluorescent material LMZO:Cr, Yb was prepared: raw materials were prepared according to the elements, and 0.7389 g of lithium carbonate, 0.3990 g of magnesium oxide, 2.4460 g of zirconium oxide, 0.0076 g of chromium oxide, and 0.0296 g of ytterbium oxide were weighed separately using an electronic balance. The weighed raw materials were placed in an agate mortar and ground for 30 min with ethanol. Then, the ground raw materials were transferred to an alumina boat and pre-sintered at 650°C for 6 h in a tube furnace. After grinding the pre-sintered sample for 30 min, the sample was sintered at 1250°C for 5 h under a reducing atmosphere. After the furnace temperature decreased to room temperature, the sintered sample was taken out and ground. Finally, the obtained sample was thoroughly ground into a uniform size powder in an agate mortar, and the LMZO:Cr, Yb nanoparticle powder was obtained after passing through a 200 mesh sieve. Figure 10 The thermal image of LMZO:Cr, Yb nanoparticles is shown, with a center temperature of 30.2°C.

[0062] 3. 0.25 g of Cs 0.32 The WO3nanoparticles were dispersed in 5 mL of ethanol, and after ultrasonic treatment for 60 min, the matrix dispersion solution was obtained.

[0063] 4. 0.2 g of LMZO:Cr, Yb nanoparticle powder was added to the matrix dispersion solution, and magnetic stirring was carried out at 80°C for 1 h to obtain a mixed solution I. After drying the mixed solution I in an oven at 90°C for 6 h, the high photo-thermal conversion performance composite material powder was obtained. Figure 11 The thermal image of Cs 0.32 The thermal image of WO3@LMZO:Cr, Yb composite material shows that the center temperature is 39.7°C, indicating that it improves the Cs 0.32 The photo-thermal conversion efficiency of WO3.

[0064] Example 6 - Core-shell structure method + Cs 0.32 WO3+ GLGA:Cr, Yb 1. Synthesis of micron-sized GLGA:Cr, Yb phosphor by solid state reaction: The raw materials of each element were weighed by an electronic balance, 2.1750 g gadolinium oxide, 0.4477 g lutetium oxide, 1.8135 g gallium oxide, 0.2549 g aluminum oxide, 0.0494 g chromium oxide and 0.1478 g ytterbium oxide were weighed, and the weighed raw materials were put into an agate mortar and ground for 30 min with ethanol. Then the ground raw materials were transferred to an alumina boat and the sample was sintered in a tube furnace at 1450°C for 5 h under a reducing atmosphere, cooled to room temperature and taken out, and finally the obtained sample was ground in an agate mortar to a uniform powder with a diameter of 1-5 μm.

[0065] 2. Preparation of Cs 0.32 WO3 photo-thermal matrix solution: According to Cs 0.32 WO3, the raw materials of each element were prepared, 150 mL of benzyl alcohol (C7H8O) solvent was first placed in a beaker, then 0.24 g of cesium hydroxide monohydrate (CsOH·H2O) powder was slowly added to the beaker containing benzyl alcohol solvent, and a magnetic stirring device was used to continuously stir at 80°C, after complete dispersion, 1.98 g of tungsten hexachloride (WCl6) was added and continued to stir, and after complete dispersion, Cs 0.32 WO3 photo-thermal matrix solution was obtained.

[0066] 3. Preparation of Cs 0.32 WO3@GLGA:Cr, Yb core-shell material: 0.6 g of GLGA:Cr, Yb phosphor was put into Cs 0.32 WO3 photo-thermal matrix solution was stirred well to obtain mixed solution II. The mixed solution II was placed in a high-pressure reaction kettle and then placed in a microwave synthesizer and subjected to microwave reaction at 220°C for 12 h. After the reaction was completed, the obtained product was placed in a high-speed centrifuge and centrifuged at 5000 rad / min for 5 min. The precipitate obtained after centrifugation was washed with pure water, dilute sulfuric acid and anhydrous ethanol in turn, and then placed in a vacuum drying oven and dried at 50°C for 3 h to obtain Cs 0.32 WO3@GLGA:Cr, Yb high photo-thermal conversion performance composite core-shell powder. Figure 12 The thermal image of Cs 0.32 WO3@GLGA:Cr, Yb composite core-shell powder is shown, with a center temperature of 47.5°C, which significantly improves the photo-thermal conversion efficiency of Cs 0.32 WO3.

[0067] Example 7 - Core-shell structure method + LaB6+ GLGA:Cr, Yb 1. GLGA:Cr, Yb phosphor was prepared according to the method of Example 6.

[0068] 2. Preparation of LaB6 photothermal matrix liquid: First, place 150 mL of benzyl alcohol solvent in a beaker, then slowly add 0.6 g of LaB6 powder to the beaker containing benzyl alcohol. Use a magnetic stirrer to continuously stir at 80°C until completely dispersed to obtain LaB6 photothermal matrix liquid.

[0069] 3. Preparation of LaB6@GLGA:Cr,Yb core-shell material by solvothermal method: 0.6 g of GLGA:Cr,Yb phosphor was added to the LaB6 photothermal matrix liquid and stirred thoroughly to obtain mixture II. Mixture II was placed in a high-pressure reactor and then placed in a microwave synthesizer for microwave reaction at 220℃ for 12 h. After the reaction was completed, the product was centrifuged at 5000 rad / min for 5 min. The precipitate obtained after centrifugation was washed successively with pure water, dilute sulfuric acid, and anhydrous ethanol. After washing, it was placed in a vacuum drying oven and dried at 50℃ for 3 h to obtain LaB6@GLGA:Cr,Yb high photothermal conversion performance composite core-shell powder. Figure 13 Thermal images of the core-shell powder of LaB6@GLGA:Cr,Yb composite material are shown, with a center temperature of 46.2℃, which significantly improves the photothermal conversion efficiency of LaB6.

[0070] Example 8 - Core-shell structure method + Ba 0.2 WO3+ GLGA:Cr,Yb 1. GLGA:Cr,Yb phosphor was prepared according to the method in Example 6.

[0071] 2. Preparation of Ba 0.2 WO3 photothermal matrix fluid: according to Ba 0.2 To prepare the raw materials for WO3, first place 150 mL of benzyl alcohol solvent in a beaker, then slowly add 0.0895 g of barium carbonate powder to the beaker containing benzyl alcohol. Use a magnetic stirrer to continuously stir at 80°C until completely dispersed. Then add 0.9 g of tungsten hexachloride and continue stirring until completely dispersed to obtain Ba. 0.2 WO3 photothermal matrix fluid.

[0072] 3. Preparation of Ba by solvothermal method 0.2 WO3@GLGA:Cr,Yb core-shell material: 0.03 g of GLGA:Cr,Yb phosphor was placed in Ba... 0.2The WO3 photo-thermal matrix liquid was fully stirred to obtain a mixed liquid II. The mixed liquid II was placed in a high-pressure reaction kettle and then placed in a microwave synthesizer for microwave reaction at 220°C for 12 hours. After the reaction was completed, the obtained product was placed in a high-speed centrifuge for centrifugation at 5000 rad / min for 5 minutes. The precipitate obtained after centrifugation was sequentially washed with pure water, dilute sulfuric acid, and anhydrous ethanol, and then placed in a vacuum drying box for drying at 50°C for 3 hours to obtain La 0.2 WO3@GLGA:Cr,Yb high photo-thermal conversion performance composite material core-shell powder. Figure 14 The thermal image of the Ba 0.2 WO3@GLGA:Cr,Yb composite material core-shell powder, with a center temperature of 42.6°C, significantly improves the photo-thermal conversion efficiency of Ba 0.2 The photo-thermal conversion efficiency of WO3.

[0073] Example 9 - Core-shell structure method + La 0.1 WO3 + GLGA:Cr,Yb 1. The GLGA:Cr,Yb fluorescent powder was prepared according to the method of Example 6.

[0074] 2. Preparation of La 0.1 WO3 photo-thermal matrix liquid: according to the preparation method of La 0.1 Preparation of raw materials of each element of WO3. First, 150 mL of benzyl alcohol solvent was placed in a beaker, then 0.0431 g of lanthanum hydroxide powder was slowly added to the beaker containing benzyl alcohol, and a magnetic stirring device was used for continuous stirring at 80°C. After complete dispersion, 0.9 g of tungsten hexachloride was added and continued to be stirred. After complete dispersion, La 0.1 WO3 photo-thermal matrix liquid.

[0075] Solvent thermal method for preparing La 0.1 WO3@GLGA:Cr,Yb core-shell material: 0.24 g of GLGA:Cr,Yb fluorescent powder was placed in La 0.1 The WO3 photo-thermal matrix liquid was fully stirred to obtain a mixed liquid II. The mixed liquid II was placed in a high-pressure reaction kettle and then placed in a microwave synthesizer for microwave reaction at 220°C for 12 hours. After the reaction was completed, the obtained product was placed in a high-speed centrifuge for centrifugation at 5000 rad / min for 5 minutes. The precipitate obtained after centrifugation was sequentially washed with pure water, dilute sulfuric acid, and anhydrous ethanol, and then placed in a vacuum drying box for drying at 50°C for 3 hours to obtain La 0.1 WO3@GLGA:Cr,Yb high photo-thermal conversion performance composite material core-shell powder. Figure 15 The thermal image of the La 0.1Thermal image of WO3@GLGA:Cr,Yb composite core-shell powder, the center temperature is 43.2℃, which significantly improves the La 0.1 Photo-thermal conversion efficiency of WO3.

[0076] Example 10 - Core-shell structure method + Cs 0.32 WO3+ LMZO:Cr,Yb 1. Synthesis of micron-sized LMZO:Cr,Yb fluorescent powder by solid phase reaction: according to the preparation of raw materials, 0.7389 g of lithium carbonate, 0.3990 g of magnesium oxide, 2.4460 g of zirconium oxide, 0.0076 g of chromium oxide, and 0.0296 g of ytterbium oxide were weighed with an electronic balance, respectively. The weighed raw materials were put into an agate mortar and ground for 30 min with ethanol. Then the ground raw materials were transferred to an alumina boat and pre-sintered at 650℃ for 6 h in a tube furnace. The pre-sintered sample was ground for 30 min, and then sintered at 1250℃ for 5 h under a reducing atmosphere. The sample was cooled to room temperature and taken out. Finally, the obtained sample was thoroughly ground in an agate mortar to a uniform powder with a diameter of 1-5 μm.

[0077] 2. Cs 0.32 WO3 photo-thermal matrix solution was prepared according to the method of Example 6.

[0078] 3. Solvothermal method for preparing Cs 0.32 WO3@LMZO:Cr,Yb core-shell material: 0.6 g of LMZO:Cr,Yb fluorescent powder was put into Cs 0.32 WO3 photo-thermal matrix solution was prepared according to the method of Example 6. 0.32 WO3@LMZO:Cr,Yb high photo-thermal conversion performance composite core-shell powder. Figure 16 Cs 0.32 Thermal image of WO3@LMZO:Cr,Yb composite core-shell powder, the center temperature is 48.3℃, which significantly improves the Cs 0.32 Photo-thermal conversion efficiency of WO3.

[0079] Example 11 - Core-shell structure method + Cs 0.32 WO3+LaB6+ GLGA:Cr,Yb 1. GLGA:Cr,Yb fluorescent powder was prepared according to the method of Example 6.

[0080] 2. Cs was prepared according to the method of Example 6. 0.32 WO3 photo-thermal matrix solution.

[0081] 3. Cs was prepared by solvothermal method. 0.32 WO3@LaB6@GLGA:Cr,Yb core-shell material: 0.6 g LaB6 powder was added to Cs 0.32 WO3 photo-thermal matrix solution was stirred, and 1.2 g GLGA:Cr,Yb fluorescent powder was added and stirred thoroughly to obtain mixed solution II. Mixed solution II was placed in a high-pressure reaction kettle and then in a microwave synthesizer for microwave reaction at 220°C for 12 h. After the reaction was completed, the obtained product was placed in a high-speed centrifuge for centrifugation at 5000 rad / min for 5 min. The precipitate obtained after centrifugation was washed with pure water, dilute sulfuric acid and anhydrous ethanol in sequence, and then placed in a vacuum drying box for drying at 50°C for 3 h to obtain Cs 0.32 WO3@LaB6@GLGA:Cr,Yb core-shell powder with high photo-thermal conversion performance. Figure 17 Cs 0.32 WO3@LaB6@GLGA:Cr,Yb core-shell powder, and the center temperature was 49.5°C, which significantly improved Cs 0.32 WO3, LaB6 photo-thermal conversion efficiency.

[0082] Example 12 - Core-shell structure method + Cs 0.32 WO3 + LaB6 + GLGA:Cr,Yb + LMZO:Cr,Yb 1. GLGA:Cr,Yb fluorescent powder was prepared according to the method of Example 6.

[0083] 2. LMZO:Cr,Yb fluorescent powder was prepared according to the method of Example 10.

[0084] 3. Cs was prepared according to the method of Example 6. 0.32 WO3 photo-thermal matrix solution.

[0085] 4. Cs was prepared by solvothermal method. 0.32 WO3@LaB6@GLGA:Cr,Yb@LMZO:Cr,Yb core-shell material: 0.6 g LaB6 powder was added to Cs 0.32The WO3 photo-thermal matrix liquid was stirred, 0.6 g of GLGA:Cr, Yb fluorescent powder was added and stirred until completely dispersed, then 0.6 g of LMZO:Cr, Yb fluorescent powder was added and stirred until completely dispersed, to obtain mixed liquid II. The mixed liquid II was placed in a high-pressure reaction kettle, then placed in a microwave synthesizer and reacted at 220°C for 12 h. After the reaction was completed, the obtained product was placed in a high-speed centrifuge and centrifuged at 5000 rad / min for 5 min. The precipitate obtained after centrifugation was washed with pure water, dilute sulfuric acid and anhydrous ethanol in sequence, and then placed in a vacuum drying box and dried at 50°C for 3 h, to obtain Cs 0.32 WO3@LaB6@GLGA:Cr, Yb@LMZO:Cr, Yb high photo-thermal conversion performance composite material core-shell powder. Figure 18 Cs 0.32 The thermal image of the WO3@LaB6@GLGA:Cr, Yb@LMZO:Cr, Yb composite material core-shell powder is shown, with a center temperature of 50.8°C, which significantly improves Cs 0.32 Photo-thermal conversion efficiency of WO3 and LaB6.

[0086] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A high light-to-heat conversion performance composite material, characterized by, It includes a photothermal matrix material and a down-conversion fluorescent material, the mass ratio of the photothermal matrix material to the down-conversion fluorescent material is greater than or equal to 1:1; the photothermal matrix material includes nano-tungsten bronze and / or nano-rare earth hexaboride; the down-conversion fluorescent material includes Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Yb 3+ , Nd 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ , Li2Mg 1-x Zr 2-y O4:Yb 3+ , Li2Mg 1-x Zr 2-y O4:Nd 3+ at least one of 2. The high light-to-heat conversion performance composite material according to claim 1, characterized in that, The nano-tungsten bronze includes Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 • WO 2.8-3.0 , Ba x WO3, La x WO3; the nano-rare earth hexaboride includes LaB 6、 CeB6, PrB6, NdB6.

3. The high light-to-heat conversion performance composite material of claim 1, wherein, Gd 2.4 Lu 0.6- x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ is doped with Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Cr 3+ , Yb 3+ , Nd 3+ , the doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%, the doping ratio of Nd 3+ ≤20%; Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ is doped with Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 doped with Cr 3+ ,Yb 3+ , the doping ratio of Cr 3 + ≤10%, the doping ratio of Yb 3+ ≤20%. Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ is doped with Cr 2.4 Lu 0.6-x Ga 4-y AlO 12 doped with Cr 3+ ,Nd 3+ , the doping ratio of Cr 3 + ≤ 10%, the doping ratio of Nd 3+ ≤ 20%; Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ in Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 doped with Yb 3+ ,Nd 3+ , the doping ratio of Yb 3 + ≤ 20%, the doping ratio of Nd 3+ ≤ 20%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ is doped with Cr 2.4 in Gd 0.6-x Lu 4-y Ga 12 AlO 3+ , the doping ratio of Cr 3+ ≤10%. The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ It is in Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 Medium-doped Yb 3+ The Yb 3+ The doping ratio is ≤20%; The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ is doped in Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 doped with Nd 3+ , the doping ratio of the Nd 3+ is ≤20%. The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ The Li2Mg 1-x Zr 2-y O4 is doped with Cr 3+ ,Yb 3+ ,Nd 3+ Among them, the doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%, and the doping ratio of Nd 3+ ≤20%. The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ In Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ ,Yb 3+ The doping ratio of Cr 3+ ≤10%, and the doping ratio of Yb 3+ ≤20%. The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ Is in Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ ,Nd 3+ The doping ratio of Cr 3+ ≤10%, the doping ratio of Nd 3+ ≤20%. The Li2Mg 1-x Zr 2-y O4:Yb 3+ ,Nd 3+ is doped in Li2Mg 1-x Zr 2-y O4, the doping ratio of Yb 3+ , Nd 3+ is ≤20%, the doping ratio of Yb 3+ is ≤20%, and the doping ratio of Nd 3+ is ≤20%. The Li2Mg 1-x Zr 2-y O4:Cr 3+ In Li2Mg 1-x Zr 2-y Cr-doped in O4 3+ The doping ratio of Cr 3+ ≤10%. The Li2Mg 1-x Zr 2-y O4:Yb 3+ It is in Li2Mg 1-x Zr 2-y Yb doped in O4 3+ The Yb 3+ The doping ratio is ≤20%; The Li2Mg 1-x Zr 2-y O4:Nd 3+ is doped in Li2Mg 1-x Zr 2-y O4, and the doping ratio of the Nd 3+ is ≤20%. 3+ ​ 4. A direct mixing method for preparing a high light-to-heat conversion performance composite material, characterized in that, It comprises the following steps: S1, dispersing the photothermal matrix material in ethanol, and obtaining a matrix dispersion liquid after ultrasonic treatment; wherein the photothermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; S2, adding a down-conversion fluorescent material to the matrix dispersion liquid, and obtaining a mixed liquid I after magnetic stirring; S3, drying the mixed liquid I to obtain a high photothermal conversion performance composite powder.

5. The direct mixing method for preparing a high light-to-heat conversion performance composite material according to claim 4, characterized in that, In the S1, The nano-tungsten bronze includes Cs x WO3, Na x WO3, Li x WO3, [(NH4)2O] 0.3-0.15 • WO 2.8-3.0 , Ba x WO3, La x WO3; the nano-rare earth hexaboride includes LaB 6、 CeB6, PrB6, NdB6; In the matrix dispersion liquid, the concentration of the nano-tungsten bronze and / or the nano-rare earth hexaboride is 0.01-50 mg / mL.

6. The direct mixing method for preparing a high light-heat conversion performance composite material according to claim 4, characterized in that, In the S2, The down-conversion fluorescent material includes Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ , Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Cr 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ , Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3 + ,Nd 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ , Li2Mg 1-x Zr 2-y O4:Yb 3+ ,Nd 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ , Li2Mg 1-x Zr 2-y O4:Yb 3+ , Li2Mg 1-x Zr 2-y O4:Nd 3+ at least one of The mass ratio of the photothermal matrix material to the down-conversion fluorescent material is ≥1:

1.

7. A high photothermal conversion performance composite material prepared by the direct mixing preparation method of any one of claims 4-6.

8. A method for preparing a core-shell structure of a high light-to-heat conversion performance composite material, characterized in that, It comprises the following steps: P1, preparation of down-conversion fluorescent powder: raw materials of down-conversion fluorescent material are added to anhydrous ethanol and ground, then reduced and sintered, and after cooling, ground into uniform powder with a diameter of 1-5 μm, which is the down-conversion fluorescent powder; the down-conversion fluorescent material comprises Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4- y AlO 12 :Cr 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ 、Gd 2.4 Lu 0.6- x Ga 4-y AlO 12 :Yb 3+ 、Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ 、Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ 、Li2Mg 1-x Zr 2-y O4:Yb 3+ , Nd 3+ , Li2Mg 1-x Zr 2-y O4:Cr 3+ , Li2Mg 1- x Zr 2-y O4:Yb 3+ , Li2Mg 1-x Zr 2-y O4:Nd 3+ at least one of P2, preparing a photothermal matrix liquid: dispersing a photothermal matrix material raw material in benzyl alcohol to obtain a photothermal matrix liquid; the photothermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; P3, putting the down-conversion fluorescent powder prepared in P1 into the photothermal matrix liquid prepared in P2 and stirring thoroughly to obtain a mixed liquid II; P4, microwave reacting the mixed liquid II at 180-220°C for 12-24 h, and centrifuging the product obtained after the reaction is completed; P5, sequentially washing the precipitate obtained after centrifugation with pure water, dilute sulfuric acid, and anhydrous ethanol, drying after washing, and obtaining a high photothermal conversion performance composite core-shell powder.

9. The method for preparing a core-shell structure of a high photothermal conversion performance composite material according to claim 8, characterized in that, In the P3, the mass ratio of the photothermal matrix material to the down-conversion fluorescent powder is ≥1:

1.

10. A high photothermal conversion performance composite material prepared by the core-shell structure preparation method of any one of claims 8 or 9.

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