CN113736432B - Metal oxide heat storage material, metal oxide heat storage unit and preparation method - Google Patents
Metal oxide heat storage material, metal oxide heat storage unit and preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of heat storage materials, and provides a metal oxide heat storage material with excellent cycle performance, a metal oxide heat storage unit and a preparation method. The metal oxide heat storage material is A x B 3‑x O 4 A composite metal oxide material, wherein A x B 3‑ x O 4 The A site of the composite metal oxide material includes Cu, and the B site includes Mn. The metal oxide heat storage unit loaded by the metal oxide heat storage material has excellent reduction/oxidation activity and cycle performance, can ensure that the metal oxide heat storage unit can efficiently and repeatedly store and release heat in a cycle manner, obviously reduces the use cost of the metal oxide heat storage unit and provides guarantee for system operation.
Description
Technical Field
The invention relates to the technical field of heat storage materials, in particular to a metal oxide heat storage material with excellent cycle performance, a metal oxide heat storage unit and a preparation method.
Background
The energy storage technology is a key technical support for the continuous and robust development and large-scale utilization of renewable energy. The heat storage is an important component of energy storage, and only by taking solar thermal power generation as an example, the heat storage market of China before and after 2025 years can reach 300 billion yuan.
The heat storage mainly comprises three forms of sensible heat, latent heat and chemical heat. Chemical heat storage is to store and release energy by using the heat effect of reversible chemical reaction, and the optional heat storage temperature range is wider according to the difference of reaction substances. For high temperature application techniques, the reduction/oxidation reaction temperature of the metal oxide is high (>700 ℃ and a high energy density of (>400 kJ/kg) has very great development potential. The metal oxide systems suitable for high temperature heat storage applications are mainly: co 3 O 4 /CoO、 Mn 2 O 3 /Mn 3 O 4 、CuO/Cu 2 O and Fe 2 O 3 /Fe 3 O 4 And so on. Wherein Mn is 2 O 3 /Mn 3 O 4 The system has the advantages of wide reaction temperature range and reaction temperature lower than 1000 ℃, but the heat storage density is lower; cuO/Cu 2 The O system has high heat storage density and low price, but the reaction temperature zone is narrower.
Based on the above-mentioned CuO/Cu 2 O、Mn 2 O 3 /Mn 3 O 4 The problems of poor cyclicity, slow reaction rate and the like of the reduction/oxidation chemical reaction of the single-system high-temperature thermochemical heat storage material mean urgent need to develop a novel high-temperature metal oxide heat storage material, improve the rate of the reduction/oxidation reaction, improve the long-period cycle performance, ensure that the heat storage unit can efficiently and repeatedly store and release heat, thereby remarkably reducing the use cost of the heat storage unit and providing guarantee for the system operation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the metal oxide heat storage material, which can improve the reduction/oxidation reaction performance and the reduction/oxidation reaction rate of the material, simultaneously give consideration to the excellent cycle performance of the material, and ensure that the metal oxide heat storage unit can efficiently and repeatedly store and release heat in a cycle manner.
According to the metal oxide heat storage material provided by the invention, the metal oxide heat storage material is A x B 3-x O 4 A composite metal oxide heat storage material, wherein A x B 3-x O 4 The A site of the composite metal oxide heat storage material comprises Cu, and the B site comprises Mn. Due to A x B 3-x O 4 The main component of the composite metal oxide heat storage material is Cu x Mn 3-x O 4 By adjusting the doping ratio of Cu or Mn, the metal oxide heat storage material with excellent reduction/oxidation reaction performance and cycle performance is obtained, and the material can be ensured to be capable of storing and releasing heat in a cycle for multiple times with high efficiency.
In the preferred technical scheme of the invention, A x B 3-x O 4 The value range of x in the composite metal oxide heat storage material is 1.2-1.8.
According to this preferred embodiment, A x B 3-x O 4 The value range of x in the composite metal oxide heat storage material is 1.2-1.8, and the composite metal oxide heat storage material has stronger desorption/adsorption and oxygen transmission capacity, so that the reduction/oxidation reaction performance and the cycle performance are further improved.
In a preferred embodiment of the invention, A x B 3-x O 4 The composite metal oxide heat storage material is prepared by a hydrothermal method or a sol-gel method.
According to the preferred technical scheme, A is synthesized by a hydrothermal method x B 3-x O 4 The temperature and the cost in the process of the composite metal oxide heat storage material are low, the crystal growth rate is high, the prepared sample particles are uniform and small in size, and the preparation process is relatively simple.
According to the preferred technical scheme, raw materials used in the sol-gel method are firstly dispersed in a solvent to form a low-viscosity mixed solution, so that the raw materials used for preparing the composite metal oxide heat storage material can obtain uniformity on a molecular level in a short time, the raw materials can be uniformly mixed on the molecular level when gel is formed, and the prepared composite metal oxide heat storage material has good uniformity, high purity and fine particles.
The invention also provides a metal oxide heat storage unit which is formed by loading the metal oxide heat storage material powder on the surface of a base body.
According to the technical scheme, the metal oxide heat storage material powder is loaded on the surface of the base body through an immersion adsorption method to form the metal oxide heat storage unit, and the operation is simple, convenient and quick.
In the preferred technical scheme of the invention, the matrix is a porous inert supporting material.
According to the technical scheme, the porous inert supporting material has the advantages of high open porosity, high temperature resistance, high strength, good chemical stability, long service life, good product regeneration performance and the like. The porous inert supporting material with high porosity can increase the chemical reaction area of the composite metal oxide heat storage material, the high temperature resistance can avoid the reaction of the porous inert supporting material and the metal oxide heat storage material, the high strength can ensure the structural stability of the porous inert supporting material at high temperature, the service life is long, and the cost is reduced.
According to the better technical scheme, the porous inert supporting material has high heat conductivity, heat can be more quickly transferred to the composite metal oxide heat storage material, and the internal heat conduction effect is better. And the porosity is high, the metal oxide heat storage material loaded on the surface has larger contact area with air, the reduction/oxidation reaction rate is accelerated, the heat storage/heat release performance of the metal oxide heat storage unit with excellent cycle performance is improved, meanwhile, the load capacity of the composite metal oxide heat storage material can be increased, and the heat storage density is increased. In addition, the porous inert supporting material can be recycled, so that the production cost is saved. Specifically, the metal oxide heat storage material is loaded on the surface of a high-temperature-resistant porous inert support material such as SiC or cordierite.
The invention provides a preparation method of a metal oxide heat storage unit, which comprises the following steps:
s1, preparation A x B 3-x O 4 The composite metal oxide heat storage material is ground into powder;
s2, carrying out a pretreatment step on the matrix;
s3, mixing A formed in the step S1 x B 3-x O 4 The composite metal oxide material is prepared into turbid liquid with a certain concentration, and the metal oxide heat storage material powder is loaded on the surface of the substrate by adopting a dipping adsorption method to prepare the metal oxide heat storage unit.
According to the better technical scheme, impurities on the surface and inside of the porous inert supporting material can be effectively removed through ultrasonic cleaning in the pretreatment process, a certain acidic active center can be formed on the surface of the porous matrix material through soaking in an acid solution, the surface pore channel can be increased, and the specific surface area of the porous inert supporting material can be effectively increased.
According to the technical scheme, the metal oxide heat storage material and the metal oxide heat storage unit prepared by the method can be obtained, the crystal phase content of the crystal of the metal oxide heat storage material is high, the crystallinity is good, and the metal oxide heat storage unit formed by loading the metal oxide heat storage material on the substrate still has good circulation stability and reaction activity after multiple reduction/oxidation reactions.
In the optional technical scheme of the invention, hydrothermal method is adopted to prepare A x B 3-x O 4 The method of the composite metal oxide heat storage material comprises the following steps:
t1, stirring and dissolving copper nitrate and manganese nitrate in a certain proportion into deionized water, adding sodium hydroxide to adjust the solution to be alkaline, and continuously stirring to obtain a precursor;
t2, pouring the precursor formed in the step T1 into a reaction kettle, performing hydrothermal reaction, washing, filtering, drying and calcining to obtain A x B 3-x O 4 A composite metal oxide material.
According to the preferred technical scheme, A is synthesized by a hydrothermal method x B 3-x O 4 Oxidation of composite metalsThe temperature and the cost in the process of the material heat storage material are low, the crystal growth rate is high, the prepared sample particles are uniform and small in size, and the preparation process is relatively simple.
In the optional technical scheme of the invention, the sol-gel method is adopted to prepare the A x B 3-x O 4 The method of the composite metal oxide heat storage material comprises the following steps:
v1, stirring and dissolving copper nitrate, manganese nitrate and citric acid in a certain proportion into deionized water;
v2, adding ethylene glycol in a certain proportion into the mixed solution obtained in the step V1 and uniformly stirring;
v3, drying and calcining the gel solution obtained in the step V2 to obtain A x B 3-x O 4 A composite metal oxide material.
According to the preferred technical scheme, raw materials used in the sol-gel method are firstly dispersed in a solvent to form a low-viscosity mixed solution, so that the raw materials used for preparing the composite metal oxide heat storage material can obtain uniformity on a molecular level in a short time, the raw materials can be uniformly mixed on the molecular level when gel is formed, and the prepared composite metal oxide heat storage material has good uniformity, high purity and fine particles.
In the preferred technical scheme of the invention, the pretreatment comprises ultrasonic cleaning, acid leaching and drying of the matrix.
Drawings
FIG. 1 is a schematic flow chart of a hydrothermal method for preparing a metal oxide heat storage material according to the present invention.
FIG. 2 is a schematic flow chart of a method for preparing a metal oxide heat storage material by a sol-gel method according to the present invention.
FIG. 3 shows a metal oxide heat storage material Cu provided in the present invention x Mn 3-x O 4 The x value in (1) is a thermogravimetric curve comparison graph at different values.
Fig. 4 is a schematic thermogram of multiple reduction/oxidation reactions performed by the metal oxide heat storage material provided in the present invention.
Fig. 5 is a scanning electron microscope image of a metal oxide heat storage material provided in the present invention.
Fig. 6 is a scanning electron microscope image of the metal oxide heat storage material provided in the present invention after 140 cycles of reduction/oxidation reactions.
Fig. 7 is a scanning electron microscope image of the metal oxide heat storage material provided in the present invention, magnified 2K times after 200 cycles of reduction/oxidation reaction.
Fig. 8 is a scanning electron microscope image of a metal oxide heat storage material provided in the present invention, after 200 cycles of reduction/oxidation reaction, at 20K times magnification.
FIG. 9 shows a metal oxide heat storage material Cu prepared by different preparation methods provided in the present invention 1.5 Mn 1.5 O 4 X-ray diffraction analysis chart of (2).
FIG. 10 is a schematic flow chart of a method for preparing a metal oxide heat storage unit by using an immersion adsorption method according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The metal oxide heat storage material provided by the embodiment of the invention is A x B 3-x O 4 A composite metal oxide material, wherein A x B 3-x O 4 The A site of the composite metal oxide heat storage material comprises Cu, and the B site comprises Mn. Due to A x B 3-x O 4 The main component of the composite metal oxide heat storage material is Cu x Mn 3-x O 4 The metal oxide heat storage material with excellent reduction/oxidation reaction and cycle performance is obtained by adjusting the doping proportion of Cu or Mn, and the material can be ensured to be capable of efficiently and repeatedly storing/releasing heat in a cycle manner, so that the use cost of the material can be obviously reduced, and the material can be obviously usedAnd the system operation is guaranteed.
The invention provides a metal oxide heat storage material Cu x Mn 3-x O 4 Wherein x is constant in the range of 1.2-1.8, cu x Mn 3-x O 4 The composite metal oxide heat storage material is prepared by a hydrothermal method or a sol-gel method.
Specifically, as shown in FIG. 1, A is prepared by a hydrothermal method x B 3-x O 4 The method for preparing the composite metal oxide heat storage material comprises the following steps:
step T1: stirring and dissolving copper nitrate and manganese nitrate in a certain proportion into deionized water, adding sodium hydroxide to adjust the solution to be alkaline, and continuously stirring to obtain a precursor;
step T2: pouring the precursor formed in the step T1 into a reaction kettle for hydrothermal reaction, washing, filtering, drying and calcining to obtain the precursor A x B 3-x O 4 A composite metal oxide material.
As shown in FIG. 2, preparation A was carried out by a sol-gel method x B 3-x O 4 The method of the composite metal oxide heat storage material comprises the following steps:
v1: stirring and dissolving copper nitrate, manganese nitrate and citric acid in a certain proportion into deionized water;
v2: adding ethylene glycol in a certain proportion into the mixed solution obtained in the step V1 and uniformly stirring;
v3: drying and calcining the uniformly stirred gel solution to obtain the A x B 3-x O 4 A composite metal oxide material.
FIG. 3 shows a metal oxide heat storage material Cu according to an embodiment of the present invention x Mn 3-x O 4 In the thermogravimetric curve comparison graph, when the x value is different, the abscissa is time in seconds, the ordinate of the left column is temperature in units of degrees centigrade, and the ordinate of the right column is mass percent in units of degrees centigrade; wherein, the change of the experimental temperature is represented by a solid broken line marked as Tr, and represents three stages of temperature rise, constant temperature and temperature drop of the experimental temperature; metal oxide heat storage material at temperature rising stageReduction reaction occurs in the section, the quality is reduced, reaction does not occur in the constant temperature stage, oxidation reaction occurs in the temperature reduction stage, and the quality is increased; referring to FIG. 3, when Cu x Mn 3-x O 4 When the value of x in the reaction is 1.2-1.8, the reduction/oxidation reaction time is short, the reaction rate is high, and complete reoxidation can be realized. The reaction curves are respectively marked by CuMn 2 O 4 Double-dot chain line Cu of 1.2 Mn 1.8 O 4 Dot-dash line of (1), cu 1.5 Mn 1.5 O 4 Solid line of (1) and Cu 1.8 Mn 1.2 O 4 And Cu 2.1 Mn 0.9 O 4 Indicated by the short dotted line. Wherein when Cu x Mn 3-x O 4 When the value of x in the reaction is lower than 1.2, compared with the initial mass before reaction, the weight loss rate in the reduction process is about 3 percent, the weight gain rate in the oxidation process is only about 2 percent, the storable/exothermic heat is less, the oxidation is not completed, and the reoxidation degree is 67 percent; when Cu x Mn 3-x O 4 When the value of x in the formula is 1.2-1.8, the reduction/oxidation reaction time is shorter, about 4min, the reaction rate is higher (namely the slope is steeper), complete reoxidation can be realized, the storage/heat release reaction performance is excellent, and when Cu is used, the reaction time is shorter, and the reaction time is higher (namely the slope is steeper), so that the Cu can be completely reoxidized, and the Cu-based catalyst has excellent heat storage/release reaction performance x Mn 3-x O 4 When the value of x in the formula is 1.5, the reduction/oxidation reaction degree is more complete, and the re-oxidation degree reaches 100 percent; when Cu x Mn 3-x O 4 When the value of x in (1) is higher than 1.8, the oxidation reaction rate is slow, the reoxidation degree is only 14%, and the reaction performance is poor. Thus, A x B 3-x O 4 The value range of x in the composite metal oxide material is 1.2-1.8, and the composite metal oxide heat storage material has stronger desorption/adsorption and oxygen transmission capacity, so that the reduction/oxidation reaction is further improved. The degree of reoxidation in the present invention refers to the ratio of the change in mass of the oxidation reaction to the change in mass of the reduction reaction.
FIG. 4 is a schematic thermogravimetric plot of multiple reduction/oxidation reactions of the metal oxide heat storage material provided in the present invention, and it can be seen from FIG. 4 that when Cu is used x Mn 3-x O 4 When x in (1) is 1.5, i.e. Cu 1.5 Mn 1.5 O 4 Carry out moreAfter reduction/oxidation reaction for several times (including 1 time, 100 times, 200 times, 300 times and 400 times), no obvious attenuation occurs even after 400 reduction/oxidation reactions, and Cu 1.5 Mn 1.5 O 4 The metal oxide heat storage material has excellent cycle stability and reactivity.
FIG. 5 is a scanning electron microscope image of a metal oxide heat storage material provided in the present invention;
fig. 6 is a scanning electron microscope image at 20K times magnification after 140 cycles of reduction/oxidation reaction of the metal oxide heat storage material provided in the present invention, fig. 7 is a scanning electron microscope image at 2K times magnification after 200 cycles of reduction/oxidation reaction of the metal oxide heat storage material provided in the present invention, and fig. 8 is a scanning electron microscope image at 20K times magnification after 200 cycles of reduction/oxidation reaction of the metal oxide heat storage material provided in the present invention. As clearly seen from fig. 5, the particles before the reduction/oxidation reaction are small, as shown in fig. 7, as the reduction/oxidation reaction proceeds, the particles start to aggregate and gradually grow, as shown in fig. 6 and 8, after multiple cycles, a hollow porous tubular structure appears, which is beneficial to the transmission of oxygen, and even if the particles aggregate after multiple cycles and have the structure for 200 times, oxygen can still conveniently enter and exit in the channel, thereby further proving that the particles have excellent cycling reaction performance.
FIG. 9 shows a metal oxide heat storage material Cu prepared by different preparation methods provided in the present invention 1.5 Mn 1.5 O 4 The X-ray diffraction analysis chart in fig. 9 shows that the metal oxide heat storage materials prepared by the two methods have a plurality of independent peaks, the diffraction peak is strong, the peak width is narrow, the crystal phase content of the crystal is high, the crystallization condition is good, and the metal oxide heat storage material Cu prepared by the hydrothermal method or the sol-gel method is successful 1.5 Mn 1.5 O 4 And the crystallinity is higher.
The metal oxide heat storage unit provided by the invention is composed of Cu x Mn 3-x O 4 The composite metal oxide heat storage material is loaded on the surface of the substrate; in particular toThe matrix is porous inert supporting material, cu x Mn 3-x O 4 The composite metal oxide heat storage unit is prepared from the composite metal oxide heat storage material and the porous inert support material by an immersion adsorption method.
The metal oxide heat storage material powder is loaded on the surface of the base body through an immersion adsorption method to form a metal oxide heat storage unit, the operation is simple, convenient and quick, the obtained metal oxide heat storage unit has excellent cycle stability and reaction activity, the reduction/oxidation reaction frequency is high, and the material can be ensured to be capable of efficiently and repeatedly cyclically storing heat/releasing heat, so that the use cost of the material can be obviously reduced and the system operation is guaranteed.
The porous inert supporting material has the advantages of high open porosity, high temperature resistance, high strength, good chemical stability, long service life, good product regeneration performance and the like. The high porosity of the porous inert support material can increase the chemical reaction area of the composite metal oxide heat storage material, accelerate the reduction/oxidation reaction rate, improve the heat storage/heat release performance of the metal oxide heat storage unit with excellent cycle performance, and simultaneously increase the load capacity of the composite metal oxide heat storage material and improve the heat storage density. The high temperature resistance can avoid the reaction between the high temperature resistance and the metal oxide heat storage material, the high strength characteristic can ensure the structural stability of the high temperature heat storage material, the service life is long, and the cost is reduced.
In addition, the porous inert supporting material is high in heat conductivity, heat can be more quickly transferred to the composite metal oxide heat storage material, the internal heat conduction effect is good, and in addition, the porous inert supporting material can be recycled, so that the production cost is saved.
Specifically, the metal oxide heat storage material is loaded on the surface of a high-temperature-resistant porous inert support material such as SiC or cordierite.
Example 1
In embodiment 1 of the present invention, a preparation method of a metal oxide heat storage material, that is, a hydrothermal method, is provided, and the prepared raw materials include copper nitrate, manganese nitrate, and sodium hydroxide. The preparation method mainly comprises the following steps:
providing a molar ratio of 1:1, stirring and dissolving copper nitrate and manganese nitrate serving as main raw materials into deionized water at room temperature, adding sodium hydroxide to adjust the pH value to 12, and continuously stirring for 30min to obtain a precursor;
pouring the precursor into a polytetrafluoroethylene substrate reaction kettle, placing the reaction kettle in a drying oven for hydrothermal reaction at 160-180 ℃ for 12h, washing, filtering and drying, and calcining at 800-900 ℃ for 6h to obtain Cu 1.5 Mn 1.5 O 4 A composite metal oxide heat storage material;
in this example, when preparing the main raw materials, copper nitrate and manganese nitrate were mixed in a ratio of 1:1, so that the copper element and the manganese element are uniformly doped for subsequent reaction. Preparation of Cu 1.5 Mn 1.5 O 4 In this case, a hydrothermal method is employed. The basic principle is as follows: in a special closed reaction kettle, an aqueous solution is adopted as a reaction system, and the vapor pressure of the reaction system is increased by heating the reaction system, so that a relatively high-temperature and high-pressure reaction environment is created, and insoluble or insoluble substances are dissolved and recrystallized in the relatively high-temperature and high-pressure environment to carry out inorganic synthesis. The water solution in the reaction system not only serves as a solvent to promote the dissolution of raw materials and accelerate the reaction, but also serves as a chemical component to participate in the reaction, and the water solution can also serve as a medium for transmitting pressure, and promotes the rapid formation and growth of crystals by controlling physical and chemical factors and accelerating the reaction permeation speed. Chemical reactions are easier to perform and require lower synthesis temperatures than solid phase reactions. Compared with the sol-gel method, the process flow is simpler, the closed condition of hydro-thermal synthesis can reduce the emission of harmful and toxic gases, and the environmental pollution is reduced as much as possible.
Specifically, firstly, the molar ratio of 1:1, respectively weighing main raw materials of copper nitrate and manganese nitrate, then adding the copper nitrate, the manganese nitrate and a proper amount of deionized water into a beaker, fully stirring and dissolving the mixture in a magnetic stirrer device at room temperature, then adding sodium hydroxide to adjust the pH value of the solution to about 12, and continuously stirring the solution for 30min at room temperature by using the magnetic stirrer. Thereafter mixing the above-mentioned uniformly mixed precursorPouring the solution into a polytetrafluoroethylene substrate reaction kettle, and placing the hydrothermal reaction kettle in an air-blowing drying oven to react for 12 hours at 160-180 ℃. And taking out after the reaction is finished, washing the obtained solution with the powder by pure water for multiple times under vacuum pump equipment, repeatedly performing suction filtration, and drying the wet powder on the filter paper in a drying oven at 80 ℃ for 10 hours. After drying, the raw materials are placed in a tubular furnace with the heating rate of 10 ℃/min, the temperature is maintained at 800-900 ℃, and the calcination is carried out for 6 hours. Finally, after cooling to room temperature, taking out the powder and grinding the powder to obtain the composite metal oxide heat storage material Cu 1.5 Mn 1.5 O 4 。
Example 2
In this embodiment, another method for preparing a metal oxide heat storage material, that is, a sol-gel method, is also provided, and the raw materials for the preparation include copper nitrate, manganese nitrate, ethylene glycol, and citric acid. The preparation method mainly comprises the following steps:
providing a molar ratio of 1:1, copper nitrate and manganese nitrate as main raw materials;
mixing main raw materials, ethylene glycol and citric acid according to a molar ratio of 3 1.5 Mn 1.5 O 4 ；
Specifically, in preparing the main raw materials, copper nitrate and manganese nitrate were mixed in a ratio of 1:1, so that the copper and manganese elements are uniformly doped on a molecular level for subsequent reaction.
Preparation of Cu 1.5 Mn 1.5 O 4 Then, a sol-gel method is adopted to prepare and obtain the composite metal oxide material Cu 1.5 Mn 1.5 O 4 The basic principle of the method is as follows: dissolving metal nitrate and citric acid in a solvent, forming metal ions into a complex by using the citric acid as a complexing agent, adding ethylene glycol for polymerization, generating complex gel through sol-gel process at a certain temperature, and finally drying and calcining to obtain the composite metal oxide heat storage material.
Sol-gel processes have many unique advantages over other processes: since the raw materials used in the sol-gel method are first dispersed in a solvent to form a mixed solution having a low viscosity, the raw materials can be easily mixed to obtain uniformity at a molecular level in a short time, and the raw materials can be uniformly mixed at a molecular level when a gel is formed. Due to the solution reaction step, some trace elements can be easily and uniformly and quantitatively doped, and uniform doping on a molecular level is realized. Chemical reactions are easier to perform and require lower synthesis temperatures than solid phase reactions, which are believed to be easier to perform and lower temperatures because the diffusion of components in sol gel systems is in the nanometer range, while the diffusion of components in the micrometer range is the case in solid phase reactions.
Specifically, in the present embodiment, the main raw materials (copper nitrate, manganese nitrate in a molar ratio of 1. And taking out the raw materials after the stirring is finished twice, and placing the raw materials in a forced air drying oven, wherein the temperature of the drying oven is set to be 200 ℃, and the drying time is 3 hours. After the drying is finished, the raw materials are placed in a tubular furnace with the heating rate of 10 ℃/min, the temperature is firstly kept at 450 ℃, the calcination is carried out for 4 hours, and then the temperature is kept at 800-900 ℃, and the calcination is carried out for 4 hours. Finally, after cooling to room temperature, taking out the powder and grinding the powder into powder to obtain the composite metal oxide heat storage material Cu 1.5 Mn 1.5 O 4 。
Example 3
In the present embodiment, as shown in fig. 10, there is provided a method for producing a metal oxide heat storage unit, that is, an immersion adsorption method, by which the above-mentioned composite metal oxide material Cu is used 1.5 Mn 1.5 O 4 The metal oxide heat storage unit is prepared by loading the metal oxide heat storage unit on the surface of a matrix-porous inert support material by using the impregnation adsorption principle. The preparation method mainly comprises the following steps:
step S1, preparation A x B 3-x O 4 A composite metal oxide heat storage material, and grinding the obtained composite metal oxide heat storage material into powder; the invention adopts the composite metal oxide high-temperature heat storage material Cu prepared in the embodiment 1 or the embodiment 2 1.5 Mn 1.5 O 4 ；
Step S2: pretreating a substrate; specifically, a porous inert supporting material with high porosity and high strength is selected and pretreated; the pretreatment comprises the steps of ultrasonic cleaning, acid leaching, drying and the like; the ultrasonic cleaning can effectively remove impurities on the surface and inside of the porous inert supporting material, the immersion acid solution can form a certain acid active center on the surface of the porous base material, the surface pore channel can be increased, and the specific surface area of the porous inert supporting material can be effectively improved. The porous inert support material is dried for later use.
And step S3: a formed in step S1 x B 3-x O 4 Preparing the composite metal oxide material into turbid liquid with a certain concentration, and loading metal oxide heat storage material powder on the surface of a base body by adopting a dipping adsorption method to prepare a metal oxide heat storage unit;
in step S3, a dipping adsorption method is used to prepare the metal oxide heat storage unit. The basic principle is as follows: on one hand, when the surface and the inner pores of the porous inert supporting material are contacted with a solution made of the composite metal oxide high-temperature heat storage material, the capillary pressure is generated under the action of the surface tension of the solution, so that the solution permeates into the capillary; on the other hand, the active component, namely the composite metal oxide heat storage material is adsorbed on the surface and the inside of the porous inert supporting material. The method can select a substrate with certain shape and size, such as a cylinder, a cuboid and other shapes, various commercially available porous inert supporting material substrates are supplied at home, and physical structural characteristics of the porous inert supporting material substrates are provided, such as specific surface area, pore radius, mechanical strength, thermal conductivity and the like of the porous inert supporting material substrates.
Specifically, in the embodiment, the porous inert support material is firstly placed in deionized water for ultrasonic cleaning for 30-60min, then is soaked in 1-2mol/L dilute nitric acid solution for soaking and cleaning for 30-60min, then is taken out, is washed by deionized water, is placed in a forced air drying oven for drying at 100-120 ℃ for 2-3 h, and is taken out after being cooled to room temperature. Putting composite metal oxide powder to be loaded into a clean container, adding a proper amount of deionized water to prepare a suspension with higher concentration, immersing the porous inert supporting material into the suspension, blowing off residual liquid in a porous structure of the porous inert supporting material after the surface and the interior of the porous inert supporting material are completely adsorbed with the composite metal oxide high-temperature heat storage material, then putting the porous inert supporting material into a forced air drying oven to dry for 8-10h at 120-140 ℃, cooling to room temperature, and taking out to obtain the metal oxide heat storage unit.
So far, the technical scheme of the invention has been described with reference to the attached drawings. However, it is readily understood by those skilled in the art that the scope of the present invention is obviously not limited to the above specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (4)
1. A metal oxide material for heat storage, characterized in that the metal oxide material is Cu 1.5 Mn 1.5 O 4 Composite metal oxide material, said Cu 1.5 Mn 1.5 O 4 The composite metal oxide material is prepared by a hydrothermal method, wherein the Cu is obtained by calcining a hydrothermal reaction product at the high temperature of 800-900 ℃ in the hydrothermal method 1.5 Mn 1.5 O 4 Composite metal oxide material, said Cu 1.5 Mn 1.5 O 4 The composite metal oxide material has a hollow porous structure after multiple heat storage cycles.
2. A metal oxide heat storage unit is characterized in thatThe metal oxide heat storage unit is made of Cu as claimed in claim 1 1.5 Mn 1.5 O 4 The composite metal oxide material is loaded on the surface of a substrate, and the substrate is cordierite.
3. A method of making a metal oxide heat storage unit as claimed in claim 2, comprising the steps of:
s1, preparation of Cu 1.5 Mn 1.5 O 4 A composite metal oxide heat storage material, and grinding the obtained composite metal oxide heat storage material into powder;
s2, carrying out ultrasonic cleaning, acid leaching and drying on the matrix;
s3, mixing the Cu formed in the step S1 1.5 Mn 1.5 O 4 And adding deionized water into the composite metal oxide material to prepare a suspension, and loading metal oxide heat storage material powder on the surface of the substrate by adopting an immersion adsorption method to prepare the metal oxide heat storage unit.
4. The method of claim 3 wherein the hydrothermal Cu process is used to form the metal oxide heat storage unit 1.5 Mn 1.5 O 4 The method of the composite metal oxide heat storage material comprises the following steps:
t1, mixing the components in a molar ratio of 1:1, stirring and dissolving copper nitrate and manganese nitrate into deionized water, adding sodium hydroxide to adjust the pH of the solution to be =12, and continuously stirring to obtain a precursor;
t2, pouring the precursor formed in the step T1 into a reaction kettle, performing hydrothermal reaction, washing, filtering and drying, and calcining at the high temperature of 800-900 ℃ for 6h to obtain the Cu 1.5 Mn 1.5 O 4 A composite metal oxide material.
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