CN114806515B - Copper-based composite metal oxide heat storage material and preparation method thereof - Google Patents
Copper-based composite metal oxide heat storage material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a copper-based composite metal oxide heat storage material and a preparation method thereof, which can solve the problem of particle agglomeration and sintering of copper oxide particles under a high-temperature reaction condition through zirconium dioxide attached to the surfaces of the copper oxide particles. The copper-based composite metal oxide heat storage material is formed by compounding copper oxide particles and zirconium dioxide, and the zirconium dioxide is attached to the surfaces of the copper oxide particles. The copper-based composite metal oxide heat storage material provided by the invention comprises: step S1, providing copper oxide particles and zirconium dioxide particles; and S2, fully and uniformly mixing copper oxide and the zirconium dioxide particles, and synthesizing the copper-based composite metal oxide heat storage material by a high-temperature solid-phase method.
Description
Technical Field
The invention relates to the technical field of heat storage materials, in particular to a zirconium dioxide surface coating modified copper-based composite metal oxide heat storage material and a preparation method thereof.
Background
Energy storage is one of important support technologies for realizing the aim of 'double carbon', and the development and maturation of the energy storage industry are the key points for the continuous and steady development and large-scale utilization of renewable energy. Heat storage is one of large-scale energy storage, and is an effective means for realizing efficient utilization of renewable energy.
The heat storage mainly comprises three forms of sensible heat, latent heat of phase change and chemical reaction heat. Sensible heat storage (such as fused salt, heat conduction oil, water/steam and the like) mainly realizes the storage and release of heat by utilizing the rise and fall of the temperature of a medium, has simpler process and the widest application, but the heat storage temperature is generally not more than 570 ℃, the heat storage energy density is smaller, the temperature fluctuation range is large, and the requirement (more than 700 ℃) of the next generation high-temperature application technology is difficult to meet; latent heat storage is to store and release heat by utilizing latent heat in a phase change process of a medium, but the heat conductivity coefficient is low, heat exchange is difficult to control in the phase change process, and a phase change material generally needs to be packaged, so that the process is complex and the cost is high. The chemical heat storage is to store and release energy by using the heat effect of reversible chemical reaction, the range of selectable reaction substances is wider according to application scenes and different storage/heat release requirements, and in addition, the energy storage density is higher by one order of magnitude than sensible heat, so that the long-time storage or long-distance transportation is facilitated. The high-temperature thermochemical energy storage technology based on metal oxides (such as cobalt/manganese/copper/iron and the like) realizes the storage/release of energy through reduction/oxidation reaction among metal oxides with different valence states, the heat storage temperature can reach over 800 ℃, and the energy storage density can reach 300-1000kJ/kg within a small temperature variation range; a typical reaction formula thereof is as follows,
M x O y+z +△H＝＝M x O y +z/2*O 2
the copper oxide system has the advantages of high energy density, no toxicity, no harm, high reduction rate, small temperature difference between heat storage/release reactions and high energy taste, but because the reaction temperature of the iron oxide system during heat storage/release is close to the self melting point, the iron oxide system can be sintered seriously in the reaction process, namely, copper oxide particles are agglomerated and grown under the high-temperature condition, the surface area is reduced, so that the reoxidation reaction degree of the material is lower, the oxidation reaction rate is slow, the copper oxide particles are obviously agglomerated and enlarged and densified after multiple heat storage/release reaction circulation reactions, the circulation life is short, and the scale multi-scene application of the copper oxide system as a heat storage material is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the copper-based composite metal oxide heat storage material and the preparation method thereof, which can solve the problem of particle agglomeration and sintering of copper oxide particles under high-temperature reaction conditions by using zirconium dioxide attached to the surfaces of the copper oxide particles.
The invention provides a copper-based composite metal oxide heat storage material, which is a heat storage material formed by compounding copper oxide particles and zirconium dioxide, wherein the zirconium dioxide is attached to the surfaces of the copper oxide particles.
According to the technical scheme, firstly, as the zirconium dioxide has stable crystal form, firm structure, higher use temperature than other refractory materials such as aluminum oxide, mullite, aluminum silicate and the like and stable chemical property, the zirconium dioxide in the copper-based composite metal oxide heat storage material provided by the invention does not change the biological phase at high temperature or chemically change with copper oxide or oxygen and the like under the high-temperature reaction condition, and can stably exist in multiple heat storage/release cycles while the content of a main reaction substance (copper oxide) is reduced.
Secondly, through the experimental research of the applicant, the zirconium dioxide and the copper oxide particles have stronger interaction, the zirconium dioxide can be attached to the surfaces of the copper oxide particles, and the zirconium dioxide is not easy to fall off in the process of multiple heat storage/heat release circulation reactions.
Finally, the zirconium dioxide can be attached to the surfaces of the copper oxide particles, so that the contact between the copper oxide particles can be effectively blocked, the agglomeration and sintering of the copper oxide particles in a high-temperature reaction condition are avoided, and the zirconium dioxide can stably exist on the surfaces of the copper oxide particles in a plurality of cycles of heat storage/heat release reactions.
In the preferable technical scheme of the invention, the mass fraction of the zirconium dioxide is not less than 10 percent of the mass of the copper-based composite metal oxide heat storage material.
According to the technical scheme, the copper oxide particles can be agglomerated and sintered under the high-temperature reaction condition, and too little zirconium dioxide can not effectively obstruct the copper oxide particles, so that part of the copper oxide particles can still be agglomerated and sintered, more than 10% of the zirconium dioxide can effectively obstruct most of the copper oxide particles, wherein the higher the mass fraction of the zirconium dioxide is, the more uniform the distribution is, the better the obstruction effect of agglomeration among the copper oxide particles is.
In the preferred technical scheme of the invention, the mass fraction of the copper oxide is 1-x, the mass fraction of the zirconium dioxide is x, and the value range of x is 30-50%.
According to the technical scheme, when the mass fraction of the zirconium dioxide is more than 30%, the copper oxide particles can be effectively blocked, the phenomenon that the copper oxide particles are agglomerated and sintered under a high-temperature reaction condition is avoided, the reoxidation degree of the heat storage material reaches 99%, but the higher the mass fraction of the zirconium dioxide is, the lower the mass fraction of the copper oxide particles is, the main reaction substance of the copper-based composite metal oxide heat storage material is the copper oxide particles, the lower the content of the copper oxide particles is, the energy density of the heat storage/heat release reaction of the material under the same mass condition is reduced, in addition, excessive zirconium dioxide is attached to the surfaces of the copper oxide particles, the contact reaction area of the copper oxide particles and air is easy to be insufficient, and therefore when the mass fraction of the zirconium dioxide is 30-50%, the heat storage/heat release density and the cycle performance of the copper-based composite metal oxide heat storage material can be considered at the same time.
In a preferred embodiment of the invention, the zirconium dioxide is in the form of particles. According to the technical scheme, when the granular zirconium dioxide is attached to the surface of the copper oxide particles and is in point contact with the surface points of the copper oxide particles, the copper oxide particles are guaranteed to generate a blocking effect, and meanwhile, the copper oxide particles and air have a large reaction contact area, so that in the circulation of multiple heat storage/heat release reactions, the copper-based composite metal oxide heat storage material provided by the invention has a large reaction area, and the reoxidation degree and the reaction rate of the copper-based composite metal oxide heat storage material in the circulation of the heat storage/heat release reactions are further improved.
In a preferred embodiment of the present invention, the surface of the copper oxide particles is uniformly coated with the particulate zirconium dioxide.
According to the technical scheme, the zirconium dioxide with the smaller particle size is uniformly attached to the surface of the copper oxide particles with the larger particle size, so that the agglomeration among the copper oxide particles can be blocked by the zirconium dioxide particles uniformly distributed on the surface of the copper oxide particles under the condition that the reaction area of the copper oxide particles and air is not influenced, and the blocking effect of the zirconium dioxide with the same mass ratio on the agglomeration among the copper oxide particles is improved to the greatest extent.
The invention also provides a preparation method of the copper-based composite metal oxide heat storage material in the technical scheme, which comprises the following steps:
step S1, providing copper oxide particles and zirconium dioxide particles;
and S2, fully and uniformly mixing the copper oxide and the zirconium dioxide particles, and synthesizing the copper-based composite metal oxide heat storage material by a high-temperature solid-phase method.
According to the technical scheme, the zirconium dioxide and the copper oxide particles which are uniformly mixed are compounded at high temperature by a high-temperature solid phase method, and under the high-temperature condition, a composite substance is finally obtained through contact, reaction, nucleation and crystal growth reaction between solid interfaces.
In a preferred embodiment of the present invention, step S2 further includes the following substeps:
step S21: grinding and mixing copper oxide and zirconium dioxide by using a ball mill;
step S22: and calcining the mixed copper oxide powder and zirconium dioxide powder at high temperature, cooling to obtain a calcined product, and grinding the calcined product into powder to obtain the copper-based composite metal oxide heat storage material.
According to the technical scheme, during the high-temperature calcination of the uniformly mixed powdery copper oxide and zirconium dioxide in the step S22, the zirconium dioxide powder can be uniformly and firmly attached to the surface of the copper oxide powder, so that the agglomeration sintering phenomenon of the copper oxide powder under the high-temperature reaction condition is effectively improved, and the copper-based composite metal oxide heat storage material with excellent circulating heat storage/heat release performance can be obtained.
Drawings
Fig. 1 is a flowchart of a method for producing a copper-based composite metal oxide heat storage material according to an embodiment of the present invention.
Fig. 2 is a flowchart of step S2 of a method for producing a copper-based composite metal oxide heat storage material according to an embodiment of the present invention.
Fig. 3 is an SEM image of copper oxide at different cycle numbers.
Fig. 4 is an SEM image of the copper-based composite metal oxide heat storage material provided by the embodiment of the present invention at different cycle times.
Fig. 5 is an X-ray diffraction analysis (XRD) pattern of the copper-based composite metal oxide heat storage material provided in the embodiment of the present invention.
Fig. 6 is a schematic thermogravimetric curve of the copper-based composite metal oxide heat storage material provided by the embodiment of the invention under different cycle numbers.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood 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, fall within the scope of the present invention.
1. Preparation of materials
The copper-based composite metal oxide heat storage material provided by the embodiment is prepared by a high-temperature solid-phase method, and fig. 1 is a flowchart of the preparation method of the copper-based composite metal oxide heat storage material provided by the embodiment of the invention. As shown in fig. 1, the method comprises the following steps:
step S1, providing copper oxide particles and zirconium dioxide particles;
and S2, fully and uniformly mixing the copper oxide and the zirconium dioxide particles, and synthesizing the copper-based composite metal oxide heat storage material by a high-temperature solid-phase method.
Preferably, the zirconium dioxide and copper oxide chemical reagents for preparing the copper-based composite metal oxide heat storage material have the purity levels of analytical purity, higher purity and less interference impurities. The influence of impurities on the heat storage/release chemical reaction of the copper-based composite heat storage material can be reduced as much as possible, and the heat storage/release reaction characteristic and the cycle performance of the heat storage material are prevented from being damaged.
In step S2, first, copper oxide and zirconium dioxide need to be fully and uniformly mixed, a specific mixing manner is not limited herein, in some embodiments, copper oxide and zirconium dioxide may be placed in a solvent to be mixed, and then dried to obtain a homogeneous mixture, in other embodiments, copper oxide powder and zirconium dioxide powder may also be placed in a ball mill to be ground and mixed; and then, compounding the uniformly mixed powder by a high-temperature solid-phase method, wherein the synthesis by the high-temperature solid-phase method refers to the steps of contact, reaction, nucleation and crystal growth reaction between solid interfaces under a high-temperature condition to finally obtain the composite substance. The preparation method has the advantages of low cost, high yield, simple equipment and preparation process, high production efficiency and the like, is suitable for large-scale industrial production, and in addition, compared with zirconium dioxide which is slightly burnt or is not burnt, the zirconium dioxide which is burnt at high temperature has more stable chemical properties, and the circulation stability of the heat storage material can be further improved.
Preferably, as shown in fig. 2, the step S2 further includes the following sub-steps:
step S21: grinding and mixing copper oxide and zirconium dioxide by using a ball mill;
step S22: and calcining the mixed copper oxide powder and zirconium dioxide powder at high temperature, cooling to obtain a calcined product, and grinding the calcined product into powder to obtain the copper-based composite metal oxide heat storage material.
In the present embodiment, the main raw materials (zirconia and copper oxide particles) are first weighed according to a mass ratio of 3. And finally, after the temperature is cooled to room temperature, taking out the calcined product, and grinding the calcined product taken out into powder to obtain the copper-based composite metal oxide heat storage material formed by compounding zirconium dioxide and copper oxide.
2. Material characterization
The following experiments were used to determine the material characterization of the copper-based composite metal oxide heat storage material. The thermogravimetric analysis was carried out using a synchronous thermal analyzer model STA-449F3 manufactured by Nasicon, germany, and X-ray diffraction (XRD) analysis was carried out using an X-pert Powder X-ray diffractometer manufactured by Pasacaceae, the Netherlands. The redox ratio of the sample is measured by thermogravimetric analysis (TG), about 10mg of the sample is put into an alumina crucible with a capacity of 50ul, the temperature control program is that the temperature is directly reduced to 400 ℃ after being increased from room temperature to 1000 ℃, the temperature increase and decrease rate is 20 ℃/min, and the air flow is 30ml/min (pO) 2 ＝0.21)。
Fig. 3 is an SEM image of copper oxide at different cycle numbers. As can be seen from fig. 3, in the cycle of the heat storage/heat release reaction, along with the increasing of the cycle times, the copper oxide particles are agglomerated and grown, and finally, a very serious agglomeration and sintering phenomenon occurs, so that the copper oxide particles are fused together, and along with the increasing of the reaction times, the densification condition is more serious, and as the copper oxide particles are fused, the specific surface area of the copper oxide is reduced, a large amount of copper oxide material cannot contact with air, so that the reoxidation reaction cannot be performed, and therefore, the cycle heat storage/heat release performance of the pure copper oxide heat storage material is not good.
FIG. 4 is SEM images of the copper-based composite metal oxide heat storage material prepared by the preparation method under different cycle times. Referring to fig. 4, in the present embodiment, the copper-based composite metal oxide heat storage material is copper oxide particles and zirconium dioxide (ZrO) 2 ) The zirconium dioxide is attached to the surface of the copper oxide particles.
As can be seen from fig. 4, as the heat storage/release reaction cycles are performed for 1-300 times, due to the surface energy difference driving of different grain sizes (Ostwald ripening theory), the aggregation of small grains and large grains is merged, and the grain size is rapidly increased, but after 300 cycles, the grain size of the heat storage material formed by compounding zirconium dioxide and copper oxide particles tends to be unchanged, which indicates that the zirconium dioxide on the surface of the copper oxide particles effectively inhibits the aggregation between the copper oxide particles; and even after 600 cycles, the zirconium dioxide still adheres to the surface of the copper oxide particles, further proving that even if the cycle of heat storage/heat release reaction is carried out for many times under the high-temperature condition, the zirconium dioxide and the copper oxide particles still have stronger interaction force and are not easy to fall off, so that the copper oxide particles can be prevented from agglomeration and sintering under the high-temperature condition, and the cycle heat storage performance is improved.
Among them, preferably, as shown in fig. 4, zirconium dioxide is in the form of particles. When the granular zirconium dioxide is attached to the surface of the copper oxide particles, the granular zirconium dioxide is in point contact with the surface points of the copper oxide particles, so that the copper oxide particles and air have more reaction contact areas while the barrier effect on the copper oxide particles is ensured, and therefore, in the circulation of multiple heat storage/heat release reactions, the copper-based composite metal oxide heat storage material provided by the embodiment has a larger reaction area, and the reoxidation degree and the reaction rate of the copper-based composite metal oxide heat storage material in the circulation of the heat storage/heat release reactions are further improved.
Among them, preferably, as shown in fig. 4, the particulate zirconium dioxide is uniformly coated on the surface of the copper oxide particles. The zirconium dioxide with the smaller particle size is uniformly attached to the surface of the copper oxide particles with the larger particle size, so that the zirconium dioxide particles uniformly distributed on the surface of the copper oxide particles can block the agglomeration among the copper oxide particles under the condition of not influencing the reaction area of the copper oxide particles and air, and the blocking effect of the zirconium dioxide with the same mass ratio on the agglomeration among the copper oxide particles is improved to the greatest extent.
FIG. 5 is an X-ray diffraction analysis (XRD) pattern of the copper-based composite metal oxide heat storage material prepared by the above-mentioned preparation method. Referring to fig. 5, the phases of the copper-based composite metal oxide heat storage material prepared by the preparation method at room temperature are mainly two crystal phases of copper oxide and zirconium dioxide, and no new phase is generated, which indicates that zirconium dioxide does not react with copper oxide particles to form a new substance, thereby avoiding reducing the content of a main reaction substance (copper oxide) of the copper-based composite metal oxide heat storage material and damaging the reaction activity of the copper oxide metal oxide, and ensuring that the copper-based composite metal oxide heat storage material has higher heat storage/release density.
FIG. 6 is a schematic thermogravimetric curve of the copper-based composite metal oxide heat storage material prepared by the above preparation method under different cycle times. As shown in fig. 6, in the process of multiple heat storage/release (the temperature of the sample copper-based composite metal oxide is raised from room temperature to 1100 ℃, then the temperature is directly lowered to 700 ℃, the temperature raising and lowering rate is 20 ℃/min, and one complete temperature raising and lowering is one cycle), compared with the first cycle, the copper-based composite metal oxide heat storage material compounded by zirconium dioxide and copper oxide particles has the advantages that the change rate of the mass is not large after 600 cycles, and the reoxidation degree can still reach more than 97%, so that the copper-based composite metal oxide heat storage material provided by the embodiment can still keep a high reoxidation degree after multiple cycles, and has better cycle heat storage/release performance.
Further, the embodiment also provides a heat storage performance test result of the copper-based composite metal oxide heat storage material prepared from copper oxide and zirconium dioxide in different proportions by the preparation method. Experiments show that the mass fraction of the zirconium dioxide is not too low, the zirconium dioxide with too low mass fraction cannot have good barrier effect on copper oxide particles, and particularly the mass fraction of the zirconium dioxide is not less than 10% of the mass of the copper-based composite metal oxide heat storage material. Further, the mass fraction of the zirconium dioxide is not too high, and too much zirconium dioxide affects the content of the main reaction substance (copper oxide) of the heat storage material, so that the heat storage density of the heat storage material is reduced, specifically, the mass fraction of the copper oxide is 1-x, the mass fraction of the zirconium dioxide is x, and the value range of x is 30-50%.
Table 1 shows the weight loss rate of the copper-based composite metal oxide heat storage material obtained by the above preparation method for copper oxide and zirconium dioxide in different proportions during heat storage and the weight gain rate during heat release.
TABLE 1
As shown in table 1, when the mass fraction of the zirconium dioxide is higher than 10%, the ratio of the weight gain to the weight loss is increased, which means that the degree of reoxidation of the heat storage material formed by compounding the copper oxide particles and the zirconium dioxide is continuously increased, so that the zirconium dioxide with the mass ratio of more than 10% can effectively block the copper oxide particles, and the copper oxide particles are prevented from agglomeration and sintering under the high-temperature reaction condition, when the mass ratio of the zirconium dioxide to the copper oxide reaches 3/7, the ratio of the weight gain to the weight loss reaches 99%, i.e., when the mass fraction x of the zirconium dioxide is in the range of 30% to 50%, the degree of reoxidation of the copper-based composite metal oxide material can reach 99%, but when the mass fraction of the heat storage is continuously increased, the mass fraction of the copper oxide particles is continuously decreased, the weight loss of the heat storage material is also decreased, the energy density of the heat storage/heat release reaction of the material under the same mass condition is decreased, and too much zirconium dioxide is attached to the surface of the copper oxide particles, which easily causes insufficient contact reaction area of the copper oxide particles with air, so that the heat storage material preferably, when the mass ratio of the copper-based composite metal oxide is 30%, the heat storage material can achieve heat storage and heat release performance.
In the present embodiment, firstly, because the zirconium dioxide has a stable crystal form, a firm structure, a high melting point and stable chemical properties, the zirconium dioxide in the copper-based composite metal oxide heat storage material provided in the present invention does not react with the copper oxide particles under a high temperature reaction condition, thereby preventing the content of the main reaction substance (copper oxide) from decreasing.
Secondly, zirconium dioxide and copper oxide particles have strong interaction, so that zirconium dioxide can be attached to the surfaces of the copper oxide particles and is not easy to fall off in the process of multiple heat storage/heat release circulation reactions.
And finally, uniformly attaching 30-50% of zirconium dioxide particles to the surfaces of the copper oxide particles, so that the contact between the copper oxide particles can be effectively blocked under the condition that the reaction area of the copper oxide particles in contact with air is basically not influenced, the agglomeration and sintering of the copper oxide particles in a high-temperature reaction condition are avoided, the reaction rate and the reaction degree of the copper-based composite metal oxide heat storage material in heat storage/heat release reaction are improved, and the higher heat storage/heat release density and the cyclic reaction performance of the copper-based composite metal oxide are considered.
So far, the technical scheme of the invention has been described with reference to the attached drawings. However, it is to be understood by those skilled in the art that the scope of the present invention is not limited to the above 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 (5)
1. The copper-based composite metal oxide heat storage material is characterized by being prepared by polishing and mixing copper oxide particles and zirconium dioxide through a high-temperature solid-phase method, wherein the zirconium dioxide with a small particle size is attached to the surface of the copper oxide particles with a large particle size, and the mass fraction of the zirconium dioxide is not less than 10% of the mass of the copper-based composite metal oxide heat storage material.
2. The copper-based composite metal oxide heat storage material as claimed in claim 1, wherein the mass fraction of copper oxide is 1-x, the mass fraction of zirconium dioxide is x, and the value range of x is 30% -50%.
3. Copper-based composite metal oxide heat storage material according to claim 1 or 2, wherein the zirconium dioxide is in the form of particles.
4. The heat storage material of claim 3, wherein the particulate zirconium dioxide is uniformly coated on the surface of the copper oxide particles.
5. A method for producing a copper-based composite metal oxide heat storage material according to any one of claims 1 to 4, comprising the steps of:
step S1, providing copper oxide particles and zirconium dioxide particles;
s2, fully and uniformly mixing copper oxide and the zirconium dioxide particles, synthesizing the copper-based composite metal oxide heat storage material by a high-temperature solid phase method,
the step S2 further comprises the following substeps:
step S21: grinding and mixing the copper oxide and the zirconium dioxide by using a ball mill;
step S22: and calcining the mixed copper oxide powder and zirconium dioxide powder at high temperature, cooling to obtain a calcined product, and grinding the calcined product into powder to obtain the copper-based composite metal oxide heat storage material.
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