1. A light absorbing material characterized by: the material has a spinel crystal structure and the chemical general formula of the material is CuMn_{2- y}RE_yO₄Wherein RE is Ce or La, and y is more than or equal to 0 and less than or equal to 0.20.

2. A method of making a light absorbing material according to claim 1, wherein: first, CuO and MnO are added₂、REO_xThe powder is prepared by the following steps of 1: 2-y: weighing the molar ratio of the metal elements of y, and then performing ball milling, mixing, drying and grinding to obtain mixture powder; the mixture powder is prepared by high-temperature calcination, cooling and grinding in the air atmosphere until the particle size is less than or equal to 700 nm; the REO_xRefers to CeO₂Or La₂O₃(ii) a The value range of y is 0-0.20.

3. A method of making a light absorbing material according to claim 2, wherein: the ball milling conditions are that a planetary ball mill is adopted, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-12 hours, and the mass ratio of ball material to water is 2-5: 1: 3.

4. a method of making a light absorbing material according to claim 2, wherein: the drying condition is that the temperature is 75-85 ℃ and the time is 10-14 h.

5. A method of making a light absorbing material according to claim 2, wherein: the high-temperature calcination condition is that the calcination temperature is 800-1200 ℃, the heating rate is 3-10 ℃/min, and the calcination time is 2-6 hours.

6. A method of making a light absorbing material according to claim 2, wherein: the cooling mode is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.

Background

With the progress and development of industry and science and technology, the demand of human beings on energy is increasing day by day, the shortage of energy is a major problem facing the world at present, and the utilization of new energy-saving and environment-friendly materials and new renewable energy sources is the fundamental way to solve the problems, which will become a new direction for the development of future materials. The light absorption material has high absorption rate on radiation in an ultraviolet-visible light-near infrared range (0.3-2.5 microns), is a core material for realizing photo-thermal conversion, can convert solar radiation into heat energy for utilization, and is applied to solar collectors and solar heat accumulators.

Spinel type transition metal oxide is an important solar heat absorbing material, the spinel type light absorbing material has high solar energy absorption rate and thermal stability, and Chinese invention patent (publication No. CN 102286243B) applied to Liu gang, Gunn Genfen and the like, namely a method for preparing solar selective heat absorbing paint by taking spinel type pigment as light absorbing agent, takes metal nitrate, citric acid and the like as raw materials, adopts a gel-gel self-propagating combustion method to prepare fluffy powder, and then calcinates the fluffy powder for 1 to 2 hours at 500 ℃, and then cools the fluffy powder to obtain the spinel type transition oxide powder. However, the spinel-type transition oxide powder prepared by the method has the defects of high cost, complex preparation process, difficulty in control and the like.

Disclosure of Invention

The invention aims to provide a light absorption material with stable structure and good thermal stability.

The invention also provides a preparation method of the light absorption material.

In order to solve the above problems, the present invention provides a light absorbing material, comprising: the material has a spinel crystal structure and the chemical general formula of the material is CuMn_2-yRE_yO₄Wherein RE is Ce or La, and y is more than or equal to 0 and less than or equal to 0.20.

The preparation method of the light absorption material is characterized by comprising the following steps: first, CuO and MnO are added₂、REO_xThe powder is prepared by the following steps of 1: 2-y: weighing the molar ratio of the metal elements of y, and then performing ball milling, mixing, drying and grinding to obtain mixture powder; calcining the mixture powder at high temperature in the air atmosphere, cooling and grinding the mixture powder until the particle size is less than or equal to 700nm to obtain the powder; the REO_xRefers to CeO₂Or La₂O₃(ii) a The value range of y is 0-0.20.

The ball milling conditions are that a planetary ball mill is adopted, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-12 hours, and the mass ratio of ball material to water is 2-5: 1: 3.

the drying condition is that the temperature is 75-85 ℃ and the time is 10-14 h.

The high-temperature calcination condition is that the calcination temperature is 800-1200 ℃, the heating rate is 3-10 ℃/min, and the calcination time is 2-6 hours.

The cooling mode is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.

Compared with the prior art, the invention has the following advantages:

1. the invention uses rare earth element Ce⁴⁺Or La³⁺The doping of the alloy changes the original CuMn₂O₄The crystal crystallization condition and the lattice distortion are caused, the original lattice vibration period is destroyed, and the lattice vibration is increased, so that the light absorption performance of the material is improved, and the segregation of the traditional spinel is avoided.

2. The invention adopts mechanical wet grinding method mixing and solid phase synthesis method sintering, can ensure that the prepared material metal elements are fully and uniformly mixed, and has the advantages of simple operation, short production period, no need of complex post-treatment, realization of industrial production and the like.

3. The solar energy absorption rate of the material prepared by the invention in a wave band of 0.3-2.5 mu m is more than or equal to 0.90, and a thermal stability experiment is carried out in 1000 ℃ air for 100h, and the result shows that the crystal structure is stable, which indicates that the material has good thermal stability.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 is a schematic representation of CuMn prepared in example 2 of the present invention_1.99Ce_0.01O₄XRD pattern of (a).

FIG. 2 is a graph of CuMn prepared in example 3 of the present invention_1.99La_0.01O₄XRD pattern of (a).

FIG. 3 is a graph of CuMn prepared in example 3 of the present invention_1.99La_0.01O₄SEM image of (d).

Detailed Description

A light absorbing material having a spinel crystal structureThe chemical formula is CuMn_2-yRE_yO₄Wherein RE is Ce or La, and y is more than or equal to 0 and less than or equal to 0.20.

The preparation method comprises the following steps: first, CuO and MnO are added₂、REO_xThe powder is prepared by the following steps of 1: 2-y: weighing the molar ratio of the metal elements of y, and then performing ball milling, mixing, drying and grinding to obtain mixture powder; calcining the mixture powder at high temperature in air atmosphere, cooling, and grinding until the particle size is less than or equal to 700 nm.

Wherein: REO_xRefers to CeO₂Or La₂O₃(ii) a The value range of y is 0-0.20.

The ball milling conditions are that a planetary ball mill is adopted, the ball milling rotating speed is 300-500 r/min, the ball milling time is 5-12 hours, and the mass ratio of ball material to water is 2-5: 1: 3.

the drying condition is that the temperature is 75-85 ℃ and the time is 10-14 h.

The high-temperature calcination condition is that the calcination temperature is 800-1200 ℃, the heating rate is 3-10 ℃/min, and the calcination time is 2-6 hours.

The cooling mode is one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.

Example 1A light-absorbing Material having the chemical composition formula CuMn₂O₄. The preparation process comprises the following steps:

according to the molar ratio of metal elements of 1: 2 CuO (15.910 g) and MnO were weighed respectively₂(34.776 g) powder; pressing a ball: material preparation: mass ratio of water (g/g) 2: 1: 3, respectively pouring the ball milling beads, the raw materials and ultrapure water into a ball milling tank; placing the ball milling tank on a ball milling machine station, firstly carrying out ball milling for 1 hour at the rotating speed of 300r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, carrying out ball milling for 1 hour after 10 minutes, and carrying out ball milling at the rotating speed of 300r/min for 5 hours in total to obtain mixture powder; then drying and grinding the mixture powder obtained after ball milling; then heating the ground mixture powder to 800 ℃ in the air atmosphere of a box-type resistance furnace for calcination, wherein the heating rate is 3 ℃/min, the calcination time is 2 hours, and cooling the calcined mixture powder to room temperature along with the furnace to obtain CuMn₂O₄A light absorbing material.

0.2g of the CuMn is taken₂O₄The light absorbing material is evaluated for solar absorption rate by a Lambda 950 type ultraviolet/visible/near infrared spectrophotometer (equipped with a 150mm integrating sphere) manufactured by Perkinelmer company, and then the solar absorption rate is calculated according to a calculation formula in International Standard ISO 9845-1 (1992), and the solar absorption rate in a 0.3-2.5 μm band is measured to be 0.90.

Example 2A light-absorbing Material having the chemical composition formula CuMn_1.99Ce_0.01O₄. The preparation process comprises the following steps:

according to the molar ratio of metal elements of 1: 1.99: 0.01 weight of CuO (15.910 g) and MnO, respectively₂（34.602g）、CeO₂(0.344 g) powder; pressing a ball: material preparation: mass ratio of water (g/g) 4: 1: 3, respectively pouring the ball milling beads, the raw materials and ultrapure water into a ball milling tank; placing a ball milling tank on a ball milling machine station, firstly carrying out ball milling for 1 hour at the rotation speed of 450r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, carrying out ball milling for 1 hour after 10 minutes, and carrying out ball milling for 7 hours at the rotation speed of 450r/min to obtain mixed powder; then drying and grinding the mixture powder obtained after ball milling; then heating the ground mixture powder to 1100 ℃ in the air atmosphere of a box-type resistance furnace for calcination at the heating rate of 5 ℃/min for 5 hours, and carrying out air quenching and cooling to room temperature after calcination to obtain CuMn_1.99Ce_0.01O₄A light absorbing material.

For the CuMn_1.99Ce_0.01O₄X-ray diffraction test of the light absorption material shows that the obtained material has CuMn₂O₄Spinel structure, and good crystal structure and growth state (as shown in figure 1).

0.2g of the CuMn is taken_1.99Ce_0.01O₄The solar energy absorptivity of the light absorption material is tested by the same test method as that of the example 1, and the result shows that the solar energy absorptivity of the material in a wave band of 0.3-2.5 mu m is 0.93.

Example 3A light-absorbing Material having the chemical composition formula CuMn_1.99La_0.01O₄. The preparation process comprises the following steps:

according to the molar ratio of metal elements of 1: 1.99: 0.01 weight of CuO (15.910 g) and MnO, respectively₂（34.602g）、La₂O₃(0.326 g) powder; pressing a ball: material preparation: mass ratio of water (g/g) 4: 1: 3, respectively pouring the ball milling beads, the raw materials and ultrapure water into a ball milling tank; placing a ball milling tank on a ball milling machine station, performing ball milling for 1 hour at the rotation speed of 350r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10 minutes, and performing ball milling for 12 hours at the rotation speed of 350r/min to obtain mixed powder; then drying and grinding the mixture powder obtained after ball milling; heating the ground mixture powder to 1100 ℃ in the air atmosphere of a box-type resistance furnace for calcination at the heating rate of 3 ℃/min for 6 hours, and cooling the calcined mixture powder to room temperature along with the furnace to obtain CuMn_1.99La_0.01O₄A light absorbing material.

For the CuMn_1.99La_0.01O₄X-ray diffraction test of the light absorption material shows that the obtained material has CuMn₂O₄Spinel structure, and good crystal structure and growth state (as shown in figure 2).

0.2g of the CuMn is taken_1.99La_0.01O₄The solar energy absorptivity of the light absorption material is tested by the same test method as that of the example 1, and the result shows that the solar energy absorptivity of the material in a wave band of 0.3-2.5 mu m is 0.92.

For the CuMn_1.99La_0.01O₄The light absorption material is subjected to electron microscope scanning, and the result shows that the particle size is 50-700 nm (shown in figure 3).

Example 4A light-absorbing Material having the chemical composition formula CuMn_1.8Ce_0.2O₄. The preparation process comprises the following steps:

according to the molar ratio of metal elements of 1: 1.8: 0.2 separately weighed CuO (15.910 g) and MnO₂（31.298g）、CeO₂(6.884 g) powder; pressing a ball: material preparation: mass ratio of water (g/g) 5: 1: 3, respectively pouring the ball milling beads, the raw materials and ultrapure water into a ball milling tank; placing a ball milling tank on a ball milling station, firstlyPerforming ball milling for 1 hour at the rotation speed of 500r/min, then pausing for 10min, taking the ball milling period as one ball milling period, performing ball milling for 1 hour after 10min, and performing ball milling for 12 hours to obtain mixed powder; then drying and grinding the mixture powder obtained after ball milling; then heating the ground mixture powder to 1200 ℃ in the air atmosphere of a box-type resistance furnace for calcination, wherein the heating rate is 7 ℃/min, the calcination time is 6 hours, and air quenching and cooling are carried out after calcination to room temperature, thus obtaining the CuMn_1.8Ce_0.2O₄A light absorbing material.

0.2g of the CuMn is taken_1.8Ce_0.2O₄The solar energy absorptivity of the light absorption material is tested by the same test method as that of the example 1, and the result shows that the solar energy absorptivity of the material in a wave band of 0.3-2.5 mu m is 0.92.

Example 5A light-absorbing Material having the chemical composition formula CuMn_1.8La_0.2O₄. The preparation process comprises the following steps:

according to the molar ratio of metal elements of 1: 1.8: 0.2 separately weighed CuO (15.910 g) and MnO₂（31.298g）、La₂O₃(6.517 g) powder; pressing a ball: material preparation: mass ratio of water (g/g) 5: 1: 3, respectively pouring the ball milling beads, the raw materials and ultrapure water into a ball milling tank; placing a ball milling tank on a ball milling machine station, firstly carrying out ball milling for 1 hour at the rotation speed of 500r/min, then pausing for 10 minutes, taking the ball milling period as one ball milling period, carrying out ball milling for 1 hour after 10 minutes, and carrying out ball milling at the rotation speed of 500r/min for 12 hours in total to obtain mixed powder; then drying and grinding the mixture powder obtained after ball milling; heating the ground mixture powder to 1200 ℃ in the air atmosphere of a box-type resistance furnace for calcination at the heating rate of 10 ℃/min for 6 hours, and cooling the calcined mixture powder to room temperature along with the furnace to obtain CuMn_1.8La_0.2O₄A light absorbing material.

0.2g of the CuMn is taken_1.8La_0.2O₄The solar energy absorptivity of the light absorption material is tested by the same test method as that of the example 1, and the result shows that the solar energy absorptivity of the material in a wave band of 0.3-2.5 mu m is 0.92.