High light-heat conversion performance composite material and preparation method thereof

Abstract

This invention discloses a high photothermal conversion performance composite material and a direct mixing method and a core-shell structure method for preparing the material. The high photothermal conversion performance composite material includes a photothermal matrix material and a downconversion fluorescent material; the photothermal matrix material includes nano-tungsten bronze and / or nano-rare earth hexaborides; the downconversion fluorescent material includes Cr-doped materials. 3+ / Yb 3+ / Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 and / or doped with Cr 3+ / Yb 3+ / Nd 3+ Li2Mg 0.99 Zr 1.985 O4. This invention uses a direct mixing method and a core-shell structure method to create a composite material from a photothermal matrix material and a downconversion fluorescent material. This composite material can convert visible light into near-infrared light, which is absorbed by the photothermal matrix material through localized surface plasmon resonance and efficiently converted into heat energy output. This expands the spectral response range, breaks through the limitation of traditional photothermal materials that only utilize near-infrared light, improves the utilization rate of visible light, significantly improves the photothermal conversion efficiency of the material, and also reduces costs, showing good application prospects.

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;

[0013] 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%;

[0014] The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Cr 3+ ,Nd 3+ It is 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%;

[0015] The Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Yb 3+ ,Nd 3+ It is 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%;

[0016] 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 :Cr 3+ Cr 3+ ≤10%;

[0017] 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 :Yb 3+ Yb 3+ ≤20%;

[0018] Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ Gd 2.4 Lu 0.6-x Ga 4-y AlO 12 :Nd 3+ Nd 3+ ≤20%;

[0019] Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Yb 3+ ,Nd 3+ Cr 3+ ≤10%,Yb 3+ ≤20%,Nd 3+ ≤20%; 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ ;

[0020] Li2Mg 1-x Zr2-y O4:Cr 3+ ,Yb 3+ It is in Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ Yb 3+ The Cr 3+ The doping ratio of Yb is ≤10%. 3+ The doping ratio is ≤20%;

[0021] The Li2Mg 1-x Zr 2-y O4:Cr 3+ ,Nd 3+ It is in Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ 、Nd 3+ The Cr 3+ The doping ratio is ≤10%, the Nd 3+ The doping ratio is ≤20%;

[0022] The Li2Mg 1-x Zr 2-y O4:Yb 3+ ,Nd 3+ It is in Li2Mg 1-x Zr 2-y Yb doped in O4 3+ 、Nd 3+ The Yb 3+ The doping ratio is ≤20%, the Nd 3+ The doping ratio is ≤20%;

[0023] The Li2Mg 1-x Zr 2-y O4:Cr 3+ It is in Li2Mg 1-x Zr 2-y O4 doped with Cr 3+ The Cr 3+ The doping ratio is ≤10%;

[0024] 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%;

[0025] The Li2Mg 1-x Zr 2-yO4:Nd 3+ is Li2Mg 1-x Zr 2-y O4 doped with Nd 3+ , the doping ratio of the Nd 3+ ≤20%.

[0026] by doping one or more of Gd 2.4 Lu 0.6 Ga4AlO 12 , Li2MgZr2O4 doped with Cr 3+ , Yb 3+ , Nd 3+ , one or more of the ion-doped down-conversion fluorescent materials.

[0027] The second object of the application is implemented by the following technical solutions.

[0028] A direct mixing method for preparing a high light-heat conversion performance composite material, comprising the following steps:

[0029] 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;

[0030] S2, adding a down-conversion fluorescent material to the matrix dispersion liquid, and obtaining a mixed liquid I after magnetic stirring;

[0031] S3, drying the mixed liquid I to obtain a high light-heat conversion performance composite material powder.

[0032] The direct mixing method is suitable for rapid preparation, has simple steps and low cost, and can be rapidly mass-produced.

[0033] 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; 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.

[0034] 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+ 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-yO4: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 1.985O4:Cr 3+ Li2Mg 0.99 Zr 1.985 O4:Yb 3+ Li2Mg 0.99 Zr 1.985 O4:Nd 3+ The mass ratio of the photothermal matrix material to the down-conversion fluorescent material is ≥ 1:1, preferably 1:0.1~1:0.5. When the amount of the down-conversion fluorescent material is less than one-tenth, the synergistic effect is not obvious, and when the amount of the down-conversion fluorescent material is too much and exceeds the mass of the photothermal matrix material, fluorescence quenching is prone to occur.

[0035] The third object of the application is implemented by the following technical scheme.

[0036] The high photothermal conversion performance composite material is 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.

[0037] A core-shell structure preparation method of a high photothermal conversion performance composite material, comprising the following steps:

[0038] P1, preparing down-conversion fluorescent powder: adding raw materials of down-conversion fluorescent material into anhydrous ethanol for 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-yAlO 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 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 Lu0.45 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 following: a gadolinium source, a lutetium source, a gallium source, an aluminum source, an oxygen source, a lithium source, a magnesium source, a zirconium source, a chromium source, a ytterbium source, a neodymium source;

[0039] P2, preparing a photothermal matrix liquid: dispersing raw materials of a photothermal matrix material in benzyl alcohol to obtain a photothermal matrix liquid; the photothermal matrix material includes nanometer tungsten bronze and / or nanometer rare earth hexaboride; the nanometer 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 nanometer rare earth hexaboride includes LaB 6、 CeB6, PrB6, NdB6; the raw material of the photothermal matrix material is selected according to the chemical formula of the photothermal matrix material, wherein the raw material of the nanometer tungsten bronze includes one of cesium source, sodium source, lithium source, ammonium source, barium source, lanthanum source and tungsten source, and the raw material of the nanometer rare earth hexaboride is a purchased rare earth hexaboride;

[0040] P3, the down-conversion fluorescent powder prepared by the P1 is put into the photothermal matrix liquid prepared by the P2 and is fully stirred to obtain a mixed liquid II;

[0041] P4, the mixed liquid II is subjected to microwave reaction at 180-220°C for 12-24 h, and the product obtained after the reaction is completed is subjected to centrifugation;

[0042] P5, the precipitate obtained after the centrifugation is sequentially cleaned with pure water, dilute sulfuric acid and anhydrous ethanol, and is dried after the cleaning to obtain a high photothermal conversion performance composite core-shell powder.

[0043] The core-shell structure method is suitable for a scene with high requirement on material performance, and the tungsten bronze is coated on the down-conversion fluorescent material to form a core-shell structure, the interface is strongly combined, the dispersibility 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.

[0044] Further, in the P3, the mass ratio of the photothermal matrix material to the down-conversion fluorescent powder is ≥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.

[0045] The high photothermal conversion performance composite material prepared by the above 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 μm) of the down-conversion fluorescent powder by in-situ deposition of the coating layer by the solvothermal method, and constructs an ordered structure with clear layering of the inner core and the outer shell. The advantage is that the strong synergistic effect and functional integration between components can be realized, the energy transfer efficiency is improved by the chemical bonding of the core-shell interface, the light scattering loss of physical mixing is avoided, and thus a new performance beyond simple addition is generated, and the photothermal conversion efficiency is higher.

[0046] Beneficial effects: the application provides a high-efficiency light-heat conversion composite material based on nano-tungsten bronze and rare earth hexaboride, which is made of a light-heat matrix material and a down-conversion fluorescent material, can convert visible light into near-infrared light, and can be absorbed by the light-heat matrix material through local surface plasmon resonance and converted into heat energy output with high efficiency, expand the spectral response range, break through the limitation of traditional light-heat materials only using near-infrared, improve the visible light utilization rate, significantly improve the light-heat conversion efficiency of the material, and reduce the cost, and has good application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0047] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0048] Figure 1 Cs 0.32 Thermal image of WO3 nanoparticles;

[0049] Figure 2 Thermal image of GLGA:Cr, Yb nanoparticles;

[0050] Figure 3 Cs 0.32 Thermal image of WO3@GLGA:Cr, Yb composite material;

[0051] Figure 4 Thermal image of LaB6 nanoparticles;

[0052] Figure 5 Thermal image of LaB6@GLGA:Cr, Yb composite material in Example 2;

[0053] Figure 6 Ba 0.2 Thermal image of WO3 nanoparticles;

[0054] Figure 7 Ba 0.2 Thermal image of WO3@GLGA:Cr, Yb composite material;

[0055] Figure 8 La 0.1 Thermal image of WO3 nanoparticles;

[0056] Figure 9 La 0.1 Thermal image of WO3@GLGA:Cr, Yb composite material;

[0057] Figure 10 Thermal image of LMZO:Cr,Yb nanoparticles;

[0058] Figure 11 Cs 0.32 Thermal image of WO3@LMZO:Cr,Yb composite material;

[0059] Figure 12 Cs 0.32 Thermal image of WO3@GLGA:Cr,Yb composite material core-shell powder;

[0060] Figure 13 Thermal image of LaB6@GLGA:Cr,Yb composite material core-shell powder in Example 7;

[0061] Figure 14 Ba 0.2 Thermal image of WO3@GLGA:Cr,Yb composite material core-shell powder;

[0062] Figure 15 La 0.1 Thermal image of WO3@GLGA:Cr,Yb composite material core-shell powder;

[0063] Figure 16 Cs 0.32 Thermal image of WO3@LMZO:Cr,Yb composite material core-shell powder;

[0064] Figure 17 Cs 0.32 Thermal image of WO3@LaB6@GLGA:Cr,Yb composite material core-shell powder;

[0065] Figure 18 Cs 0.32 Thermal image of WO3@LaB6@GLGA:Cr,Yb@LMZO:Cr,Yb composite material core-shell powder. DETAILED DESCRIPTION

[0066] The technical solutions in the embodiments of the present application will be apparently 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 of the present application. In addition, the terms “I” and “II” are only used for the purpose of description, and cannot be understood as indicating or implying relative importance. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0067] In one specific embodiment of the present application, a high light-heat conversion performance composite material comprises a light-heat matrix material and a down-conversion fluorescent material, and the mass ratio of the light-heat matrix material to the down-conversion fluorescent material is ≥ 1:1. The light-heat matrix 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 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 :Cr 3+ ,Nd 3+ (hereinafter abbreviated as GLGA:Cr,Nd), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ ,Nd 3+ (hereinafter abbreviated as GLGA:Yb,Nd), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ (hereinafter abbreviated as GLGA:Cr), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ (hereinafter abbreviated as GLGA:Yb), Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Nd 3+ (hereinafter abbreviated as GLGA:Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ (hereinafter abbreviated as LMZO:Cr,Yb,Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb3+ (Hereinafter abbreviated as LMZO:Cr,Yb), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Nd 3+ (Hereinafter abbreviated as LMZO:Cr,Nd), Li2Mg 0.99 Zr 1.985 O4:Yb 3+ ,Nd 3+ (Hereinafter abbreviated as LMZO:Yb,Nd), Li2Mg 0.99 Zr 1.985 O4:Cr 3+ (Hereinafter abbreviated as LMZO:Cr), Li2Mg 0.99 Zr 1.985 O4:Yb 3+ (Hereinafter abbreviated as LMZO:Yb), Li2Mg 0.99 Zr 1.985 O4:Nd 3+ At least one of (hereinafter abbreviated as LMZO:Nd).

[0068] 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.

[0069] In downconversion fluorescent materials:

[0070] 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%;

[0071] GLGA:Cr,Yb is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Cr 3+ Yb3+ Cr 3+ The doping ratio is ≤10%, Yb 3+ The doping ratio is ≤20%;

[0072] 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%;

[0073] 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%;

[0074] GLGA:Cr is Cr-doped Gd2.4Lu0.45Ga3.87AlO12. 3+ Cr 3+ The doping ratio is ≤10%;

[0075] GLGA:Yb is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Yb 3+ Yb 3+ The doping ratio is ≤20%;

[0076] GLGA:Nd is in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Medium-doped Nd 3+ Nd 3+ The doping ratio is ≤20%;

[0077] LMZO:Cr,Yb,Nd is Li2Mg 0.99 Zr 1.985 O4 doped with Cr 3+ Yb 3+ 、Nd 3+ In the middle, Cr 3+ The doping ratio is ≤10%, Yb 3+ The doping ratio is ≤20%, Nd 3+≤ 20%.

[0078] LMZO:Cr, Yb is doped with Cr 0.99 Zr 1.985 O4 doped with Cr 3+ , Yb 3+ , Cr 3+ ≤ 10%, Yb 3+ ≤ 20%.

[0079] LMZO:Cr, Nd is doped with Cr 0.99 Zr 1.985 O4 doped with Cr 3+ , Nd 3+ , Cr 3+ ≤ 10%, Nd 3+ ≤ 20%.

[0080] LMZO:Yb, Nd is doped with Yb 0.99 Zr 1.985 O4 doped with Yb 3+ , Nd 3+ , Yb 3+ ≤ 20%, Nd 3+ ≤ 20%.

[0081] LMZO:Cr is doped with Cr 0.99 Zr 1.985 O4 doped with Cr 3+ , Cr 3+ ≤ 10%.

[0082] LMZO:Yb is doped with Yb 0.99 Zr 1.985 O4 doped with Yb 3+ , Yb 3+ ≤ 20%.

[0083] LMZO:Nd is doped with Nd 0.99 Zr 1.985 O4 doped with Nd 3+ , Nd 3+ ≤ 20%.

[0084] In one specific embodiment of the present application, a high light-heat conversion performance composite material is prepared by using a direct mixing method, which includes steps S1-S3.

[0085] S1, disperse the photothermal matrix material in ethanol, and place 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 photothermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; the concentration of the nano-tungsten bronze or nano-rare earth hexaboride in the matrix dispersion liquid is 0.01-50 mg / mL, preferably 0.1-10 mg / mL, and more preferably 0.5-5 mg / mL.

[0086] S2, add the down-conversion fluorescent material to the matrix dispersion liquid, and magnetically stir (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 photothermal matrix material to the down-conversion fluorescent material is ≥1:1.

[0087] S3, dry the mixed liquid I in an oven at 60-90℃ for 6-12 h, to obtain a high photothermal conversion performance composite material powder.

[0088] The high photothermal conversion performance composite material prepared by the steps S1-S3 of the above direct mixing preparation method.

[0089] In one specific embodiment of the present application, the high photothermal conversion performance composite material is prepared by using a core-shell structure method, which comprises steps P1-P5.

[0090] P1, prepare a down-conversion fluorescent powder: prepare raw materials according to the chemical formula of each element 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, and 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, and reduce and sinter the sample. After cooling, take out and grind in the agate mortar to obtain a uniform powder with a diameter of 1-5 μm.

[0091] P2, prepare a 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 comprises nano-tungsten bronze and / or nano-rare earth hexaboride, and the raw materials are prepared according to the chemical formula of each element 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, and lanthanum source, and tungsten source, and the raw materials of the nano-rare earth hexaboride are purchased rare earth hexaboride.

[0092] 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.

[0093] P4, the mixed solution II is placed in a high-pressure reaction kettle (commonly made of Teflon (maximum 100 bar) or quartz (maximum 45 bar)), and then placed in a microwave synthesizer to microwave at 180-220°C for 12-24 h. The product obtained after the reaction is completed is placed in a high-speed centrifuge under the condition of 3000-5000 rad / min for 2-5 min;

[0094] P5, the precipitate obtained after centrifugation is sequentially washed with pure water, dilute sulfuric acid, and anhydrous ethanol, and then placed in a vacuum drying oven for drying at 40-50°C for 2-3 h to obtain a high light-heat conversion performance composite material core-shell powder.

[0095] The high light-heat conversion performance composite material prepared by the above core-shell structure preparation method.

[0096] Example 1 - Direct mixing method + Cs 0.32 WO3+ GLGA: Cr, Yb

[0097] 1, Cs 0.32 WO3nanoparticles: according to Cs 0.32 WO3element preparation raw materials, first 150 mL benzyl alcohol (C7H8O) solvent is placed in a beaker, then 0.24 g of cesium hydroxide powder is slowly added to the beaker containing benzyl alcohol, and a magnetic stirring device is used for continuous stirring; after complete dispersion, 1.98 g of tungsten hexachloride is poured into the beaker, and stirring is performed until uniform, to obtain a precursor dispersion liquid. Then the precursor dispersion liquid is injected into the inner liner of a polytetrafluoroethylene material high-pressure reaction kettle, and kept at 200°C for 8 h of reaction time. After the reaction is completed, the natural cooling program is used, and the precipitate is separated and extracted by centrifugation. Then the precipitate is washed with dilute sulfuric acid solution, deionized water and anhydrous ethanol to treat the product. Finally, a 2 h vacuum drying operation is performed at 40°C in a vacuum environment to obtain Cs 0.32 WO3nanoparticle blue powder. Figure 1 Cs 0.32 The thermal image of the WO3nanoparticle shows that it can absorb light energy and convert it into heat energy output under natural light irradiation conditions, with a center temperature of 37.6°C.

[0098] 2、Preparation of fluorescent material GLGA:Cr, Yb: According to the preparation of raw materials, 2.1750 g of gadolinium oxide, 0.4477 g of lutetium oxide, 1.8135 g of gallium oxide, 0.2549 g of aluminum oxide, 0.0494 g of chromium oxide and 0.1478 g of ytterbium oxide were weighed with an electronic balance, respectively, and then put into a agate mortar and ground for 30 min with ethanol. Then the ground raw materials were 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, and finally the obtained sample was ground into a uniform size powder in an agate mortar, and then passed through a 200 mesh sieve to obtain fluorescent material GLGA:Cr, Yb nanoparticle powder. Figure 2 The thermal image of GLGA:Cr, Yb nanoparticles is shown, with a center temperature of 31.0℃.

[0099] 3、0.25 g Cs 0.32 The WO3 nanoparticles were dispersed in 5 mL of ethanol to obtain a matrix dispersion liquid after ultrasonic treatment for 60 min.

[0100] 4、0.2 g of GLGA:Cr, Yb nanoparticle powder was added to the matrix dispersion liquid, and a mixed liquid I was 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-to-heat conversion performance composite powder was obtained. 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 the light-to-heat conversion efficiency of Cs 0.32 WO3.

[0101] Example 2 - Direct mixing method + LaB6+ GLGA:Cr, Yb

[0102] 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, with a center temperature of 37.8℃.

[0103] 2、According to the method of example 1, the fluorescent material GLGA:Cr, Yb was prepared.

[0104] 3、0.25 g of LaB6 nanoparticles were dispersed in 5 mL of ethanol to obtain a matrix dispersion liquid after ultrasonic treatment for 60 min.

[0105] 4. Add 0.2 g of GLGA:Cr,Yb nanoparticle powder to the matrix dispersion and stir magnetically at 80℃ for 1 h to obtain mixture I. Dry mixture I in an oven at 90℃ for 6 h to obtain LaB6@GLGA:Cr,Yb high photothermal conversion performance composite powder. Figure 5 Thermal images of the LaB6@GLGA:Cr,Yb composite material are shown, with a center temperature of 40.1℃, indicating that it improves the photothermal conversion efficiency of LaB6.

[0106] Example 3 - Direct Mixing Method + Ba 0.2 WO3+ GLGA:Cr,Yb

[0107] 1. Preparation of Ba 0.2 WO3 nanoparticles: based on Ba 0.2 For the preparation of WO3, 0.09867 g of barium carbonate and 0.63741 g of ammonium tungstate were weighed and added sequentially to 100 mL of deionized water. The mixture was stirred continuously for 1 h in a glass beaker to complete the mixing. The crucible was then placed in a drying oven at 180℃ for 3 h and ground to obtain a powder sample. The sample was transferred to a tube furnace purged with a nitrogen-hydrogen mixture and reduced for 2 h at 900℃. Afterward, it was allowed to cool naturally to room temperature to obtain Ba. 0.2 WO3 nanoparticles in blue powder. Figure 6 Ba was displayed 0.2 Thermal images of WO3 nanoparticles show that they can absorb light energy and convert it into heat energy output under natural light irradiation, with a core temperature of 36.9℃.

[0108] 2. The fluorescent material GLGA:Cr,Yb was prepared according to the method in Example 1.

[0109] 3. Add 0.25 g Ba 0.2 WO3 nanoparticles were dispersed in 5 mL of ethanol and sonicated for 60 min to obtain a matrix dispersion.

[0110] 4. Add 0.2 g of GLGA:Cr,Yb nanoparticle powder to the matrix dispersion, and magnetically stir at 80℃ for 1 h to obtain mixture I. Dry mixture I in an oven at 90℃ for 6 h to obtain Ba. 0.2 WO3@GLGA:Cr,Yb high photothermal conversion performance composite powder. Figure 7 Ba was displayed 0.2 The thermal image of the WO3@GLGA:Cr,Yb composite material shows a center temperature of 39.5℃, indicating that it enhances the performance of Ba. 0.2 Photothermal conversion efficiency of WO3.

[0111] Example 4 - Direct mixing method + La 0.1 WO3+ GLGA:Cr,Yb

[0112] 1、La 0.1 WO3nanoparticles: according to La 0.1 WO3elementary preparation of raw materials, weighing 0.0858 g of lanthanum aquachloride and 0.6374 g of ammonium tungstate, and then adding them into 100 mL of deionized water in a glass cup, stirring continuously for 1 h to complete the mixing. Then place the crucible in a drying oven at 180℃ for 3 h, and then grind to obtain a powder sample. Transfer the sample to a tube furnace with a mixture of nitrogen and hydrogen at 900℃, and carry out reduction operation for 2 h. Then naturally cool to room temperature to obtain La 0.1 WO3nanoparticles blue powder. Figure 8 La 0.1 Thermal image of WO3nanoparticles, which can absorb light energy and convert it into heat energy output under natural light irradiation, with a central temperature of 37.9℃.

[0113] 2、According to the method of Example 1, fluorescent material GLGA:Cr,Yb is prepared.

[0114] 3、0.25 g La 0.1 WO3nanoparticles are dispersed in 5 mL of ethanol, and after ultrasonic treatment for 60 min, a matrix dispersion liquid is obtained.

[0115] 4、0.2 g of GLGA:Cr,Yb nanoparticle powder is added to the matrix dispersion liquid, and magnetic stirring is carried out at 80℃ for 1 h to obtain a mixed solution I. After drying in an oven at 90℃ for 6 h, a high light-heat conversion performance composite material powder is obtained. Figure 9 La 0.1 Thermal image of WO3@GLGA:Cr,Yb composite material, with a central temperature of 39.4℃, indicating that it improves the light-heat conversion efficiency of La 0.1 WO3.

[0116] Example 5 - Direct mixing method + Cs 0.32 WO3+ LMZO:Cr,Yb

[0117] 1、According to the method of Example 1, Cs 0.32 WO3nanoparticles.

[0118] 2、Preparation of fluorescent material LMZO:Cr, Yb: The 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 with an electronic balance. The weighed raw materials were placed in an agate mortar and ground with ethanol for 30 min. 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 dropped 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 fluorescent material 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.

[0119] 3、0.25 g Cs 0.32 The WO3 nanoparticles were dispersed in 5 mL of ethanol, and after ultrasonic treatment for 60 min, a matrix dispersion liquid was obtained.

[0120] 4、0.2 g of LMZO:Cr, Yb nanoparticle powder was added to the matrix dispersion liquid, and a mixed liquid I was obtained by magnetic stirring at 80°C for 1 h. After drying the mixed liquid I in an oven at 90°C for 6 h, a high light-to-heat conversion performance composite powder was obtained. Figure 11 The thermal image of Cs 0.32 WO3@LMZO:Cr, Yb composite material is shown, with a center temperature of 39.7°C, indicating that it improves the light-to-heat conversion efficiency of Cs 0.32 WO3.

[0121] Example 6 - Core-shell structure method + Cs 0.32 WO3+ GLGA:Cr, Yb

[0122] 1、Solid phase reaction synthesis of micron-sized GLGA:Cr, Yb fluorescent powder: The raw materials were prepared according to the elements, and 2.1750 g of gadolinium oxide, 0.4477 g of lutetium oxide, 1.8135 g of gallium oxide, 0.2549 g of aluminum oxide, 0.0494 g of chromium oxide, and 0.1478 g of ytterbium oxide were weighed with an electronic balance. The weighed raw materials were placed in an agate mortar and ground with ethanol for 30 min. Then the ground raw materials were transferred to an alumina boat and sintered at 1450°C for 5 h under a reducing atmosphere in a tube furnace, and cooled to room temperature. Finally, the obtained sample was thoroughly ground in an agate mortar to a uniform powder with a diameter of 1-5 μm.

[0123] 2、Preparation of Cs 0.32WO3 photothermal matrix fluid: according to Cs 0.32 To prepare the raw materials for WO3, first place 150 mL of benzyl alcohol (C7H8O) solvent in a beaker. Then, slowly add 0.24 g of cesium hydroxide monohydrate (CsOH·H2O) powder to the beaker containing the benzyl alcohol solvent. Use a magnetic stirrer to continuously stir at 80°C until it is completely dispersed. Then, add 1.98 g of tungsten hexachloride (WCl6) and continue stirring until it is completely dispersed to obtain Cs. 0.32 WO3 photothermal matrix fluid.

[0124] 3. Preparation of Cs by solvothermal method 0.32 WO3@GLGA:Cr,Yb core-shell material: 0.6 g of GLGA:Cr,Yb phosphor was placed in Cs 0.32 The WO3 photothermal matrix liquid was thoroughly stirred 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 Cs. 0.32 WO3@GLGA:Cr,Yb high photothermal conversion performance composite core-shell powder. Figure 12 Cs was displayed 0.32 Thermal images of the WO3@GLGA:Cr,Yb composite core-shell powder show a center temperature of 47.5℃, significantly improving the Cs content. 0.32 Photothermal conversion efficiency of WO3.

[0125] Example 7 - Core-shell structure method + LaB6 + GLGA:Cr,Yb

[0126] 1. GLGA:Cr,Yb phosphor was prepared according to the method in Example 6.

[0127] 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.

[0128] 3. Solvothermal method for preparing LaB6@GLGA:Cr, Yb core-shell material: 0.6 g of GLGA:Cr, Yb fluorescent powder was put into LaB6 photothermal matrix liquid and stirred thoroughly to obtain mixed liquid II. The mixed liquid 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 LaB6@GLGA:Cr, Yb high photothermal conversion performance composite core-shell powder. Figure 13 A thermal image of the LaB6@GLGA:Cr, Yb composite core-shell powder is shown, with a center temperature of 46.2°C, significantly improving the photothermal conversion efficiency of LaB6.

[0129] Example 8 - Core-shell structure method + Ba 0.2 WO3+ GLGA:Cr, Yb

[0130] 1. GLGA:Cr, Yb fluorescent powder was prepared according to the method of Example 6.

[0131] 2. Preparation of Ba 0.2 WO3 photothermal matrix liquid: according to the method of Example 7, 0.6 g of GLGA:Cr, Yb fluorescent powder was put into Ba 0.2 WO3 photothermal matrix liquid, 0.0895 g of barium carbonate powder was slowly added into the beaker containing benzyl alcohol solvent, and a magnetic stirring device was used for continuous stirring at 80°C. After complete dispersion, 0.9 g of tungsten hexachloride was added for continuous stirring. After complete dispersion, Ba 0.2 WO3 photothermal matrix liquid was obtained.

[0132] 3. Solvothermal method for preparing Ba 0.2 WO3@GLGA:Cr, Yb core-shell material: 0.03 g of GLGA:Cr, Yb fluorescent powder was put into Ba 0.2 WO3 photothermal matrix liquid and stirred thoroughly to obtain mixed liquid II. The mixed liquid 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 Ba 0.2 WO3@GLGA:Cr, Yb high photothermal conversion performance composite core-shell powder. Figure 14 A thermal image of the Ba 0.2Thermal image of WO3@GLGA:Cr, Yb composite core-shell powder, the center temperature is 42.6℃, which significantly improves the Ba 0.2 Photo-thermal conversion efficiency of WO3.

[0133] Example 9 - Core-shell structure method + La 0.1 WO3+ GLGA:Cr, Yb

[0134] 1. GLGA:Cr, Yb fluorescent powder was prepared according to the method of Example 6.

[0135] 2. Preparation of La 0.1 WO3 photo-thermal matrix liquid: according to La 0.1 WO3 each element preparation raw material, first 150 mL benzyl alcohol solvent is placed in a beaker, then 0.0431 g lanthanum hydroxide powder is slowly added into the beaker with benzyl alcohol, a magnetic stirring device is used to continuously stir at 80℃, after complete dispersion, 0.9 g tungsten hexachloride is added and continue to stir, after complete dispersion, La 0.1 WO3 photo-thermal matrix liquid.

[0136] Solvent-thermal method for preparing La 0.1 WO3@GLGA:Cr, Yb core-shell material: 0.24 g GLGA:Cr, Yb fluorescent powder is placed in La 0.1 WO3 photo-thermal matrix liquid is fully stirred to obtain mixed liquid II. The mixed liquid II is placed in a high-pressure reaction kettle and then placed in a microwave synthesizer for microwave reaction at 220℃ for 12 h. After the reaction is completed, the obtained product is placed in a high-speed centrifuge for centrifugation at 5000 rad / min for 5 min. The precipitate obtained after centrifugation is sequentially washed with pure water, dilute sulfuric acid and anhydrous ethanol, and then placed in a vacuum drying box for drying at 50℃ for 3 h to obtain La 0.1 WO3@GLGA:Cr, Yb high photo-thermal conversion performance composite core-shell powder. Figure 15 La 0.1 Thermal image of WO3@GLGA:Cr, Yb composite core-shell powder, the center temperature is 43.2℃, which significantly improves La 0.1 Photo-thermal conversion efficiency of WO3.

[0137] Example 10 - Core-shell structure method + Cs 0.32 WO3+ LMZO:Cr, Yb

[0138] 1. Synthesis of micron-sized LMZO:Cr, Yb phosphor by solid-state 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 using an electronic balance. The weighed raw materials were placed in an agate mortar and ground with ethanol for 30 min. 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 under a reducing atmosphere for 5 h. The sample was cooled to room temperature and removed. Finally, the obtained sample was thoroughly ground in an agate mortar to obtain a uniform powder with a diameter of 1-5 μm.

[0139] 2. Cs 0.32 WO3 photo-thermal matrix solution.

[0140] 3. Preparation of Cs 0.32 WO3@LMZO:Cr, Yb core-shell material: 0.6 g of LMZO:Cr, Yb phosphor was placed in Cs 0.32 WO3 photo-thermal matrix solution. The mixture 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 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, respectively. After washing, it was placed in a vacuum drying box and dried at 50°C for 3 h to obtain Cs 0.32 WO3@LMZO:Cr, Yb high photo-thermal conversion performance composite core-shell powder. Figure 16 Cs 0.32 WO3@LMZO:Cr, Yb composite core-shell powder, with a center temperature of 48.3°C, significantly improving the Cs 0.32 WO3 photo-thermal conversion efficiency.

[0141] Example 11 - Core-shell structure method + Cs 0.32 WO3 + LaB6 + GLGA:Cr, Yb

[0142] 1. GLGA:Cr, Yb phosphor was prepared according to the method of Example 6.

[0143] 2. Cs 0.32 WO3 photo-thermal matrix solution.

[0144] 3. Preparation of Cs 0.32WO3@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 of 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 high photo-thermal conversion performance composite core-shell powder. Figure 17 Cs 0.32 WO3@LaB6@GLGA:Cr,Yb composite core-shell powder, with a center temperature of 49.5°C, significantly improved the photo-thermal conversion efficiency of Cs 0.32 WO3, LaB6 photo-thermal conversion efficiency.

[0145] Example 12 - Core-shell structure method + Cs 0.32 WO3 + LaB6 + GLGA:Cr,Yb + LMZO:Cr,Yb

[0146] 1. GLGA:Cr,Yb fluorescent powder was prepared according to the method of Example 6.

[0147] 2. LMZO:Cr,Yb fluorescent powder was prepared according to the method of Example 10.

[0148] 3. Cs 0.32 WO3 photo-thermal matrix solution.

[0149] 4. Solvothermal method for preparing Cs 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.

[0150] 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 0.45 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 2. The high light-to-heat conversion performance composite material according to claim 1, characterized in that, The nano-tungsten bronze includes Cs 0.32 WO3, [(NH4)2O] 0.3-0.15 • WO 2.8-3.0 , Ba 0.2 WO3, La 0.1 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 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ ,Nd 3+ Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 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%. Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ ,Yb 3+ is doped with Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 Cr 3+ ,Yb 3+ , the doping ratio of Cr 3 + ≤10%, the doping ratio of Yb 3+ ≤20%; 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 Cr 3+ ,Nd 3+ Cr 3 + ≤10%, Nd 3+ ≤20%. 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 Yb 3+ ,Nd 3+ Yb 3 + Nd 3+ ​ The Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Cr 3+ is doped with Cr 2.4 Lu 0.45 Ga 3.87 AlO 12 doped with Cr 3+ , the doping ratio of Cr 3+ ≤10%. The Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Yb 3+ is doped in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 doped with Yb 3+ , the doping ratio of Yb 3+ ≤20%. The Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 :Nd 3+ is doped in Gd 2.4 Lu 0.45 Ga 3.87 AlO 12 doped with Nd 3+ , the doping ratio of the Nd 3+ is ≤20%. The Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ ,Nd 3+ is Li2Mg 0.99 Zr 1.985 O4 doped with Cr 3+ ,Yb 3+ ,Nd 3+ Among them, the doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%, the doping ratio of Nd 3+ ≤20%. The Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Yb 3+ Is doped in Li2Mg 0.99 Zr 1.985 O4 3+ , Yb 3+ The doping ratio of Cr 3+ ≤10%, the doping ratio of Yb 3+ ≤20%. The Li2Mg 0.99 Zr 1.985 O4:Cr 3+ ,Nd 3+ Is in 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%. The Li2Mg 0.99 Zr 1.985 O4:Yb 3+ ,Nd 3+ It is in Li2Mg 0.99 Zr 1.985 Yb doped in O4 3+ 、Nd 3+ The Yb 3+ The doping ratio is ≤20%, the Nd 3+ The doping ratio is ≤20%; The Li2Mg 0.99 Zr 1.985 O4:Cr 3+ is doped with Cr in Li2Mg 0.99 Zr 1.985 O4 3+ , the doping ratio of Cr 3+ ≤10%. The Li2Mg 0.99 Zr 1.985 O4:Yb 3+ It is in Li2Mg 0.99 Zr 1.985 Yb doped in O4 3+ The Yb 3+ The doping ratio is ≤20%; The Li2Mg 0.99 Zr 1.985 O4:Nd 3+ It is in Li2Mg 0.99 Zr 1.985 O4 doped with Nd 3+ The Nd 3+ The doping ratio is ≤20%.

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 photo-thermal matrix material in ethanol, and obtaining matrix dispersion liquid after ultrasonic treatment; wherein the photo-thermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; S2, adding a down-conversion fluorescent material into the base dispersion liquid, and obtaining a mixed liquid I after magnetic stirring; the down-conversion fluorescent material comprises 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 S3, drying the mixed liquid I to obtain high photo-thermal conversion performance composite material 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 0.32 WO3, [(NH4)2O] 0.3-0.15 • WO 2.8-3.0 , Ba 0.2 WO3, La 0.1 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 mass ratio of the photo-thermal matrix material to the down-conversion fluorescent material is ≥1:

1.

7. A method for preparing a core-shell structure of a high light-to-heat conversion performance composite material, characterized by, 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 0.45 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 P2, preparing photo-thermal matrix liquid: dispersing photo-thermal matrix material raw material in benzyl alcohol to obtain photo-thermal matrix liquid; the photo-thermal matrix material comprises nano-tungsten bronze and / or nano-rare earth hexaboride; P3, putting the down-conversion fluorescent powder prepared in P1 into the photo-thermal matrix liquid prepared in P2 and stirring thoroughly to obtain mixed liquid II; P4, microwave reacting the mixed liquid II at 180-220℃ 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 high photo-thermal conversion performance composite material core-shell powder.

8. The method for preparing a core-shell structure of a high photothermal conversion performance composite material according to claim 7, characterized in that, In the P3, the mass ratio of the photo-thermal matrix material to the down-conversion fluorescent powder is ≥1:1.

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