CN112960702B - Preparation method of cobaltosic oxide with thermochemical energy storage performance and product - Google Patents
Preparation method of cobaltosic oxide with thermochemical energy storage performance and product Download PDFInfo
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Abstract
The invention discloses a preparation method of cobaltosic oxide with thermochemical energy storage performance and a product. The method specifically comprises the following steps: mixing cobalt acetate, urea and a dispersing agent, adding water to obtain a mixed solution, carrying out hydrothermal reaction for 10-12h at the temperature of 180 ℃ under 150 ℃, centrifuging, washing and drying to obtain a pink precursor cobalt carbonate; calcining the precursor cobalt carbonate for 10-12h at the temperature of 500-600 ℃ to obtain a black substance, namely cobaltosic oxide. The cobaltosic oxide prepared by the method has a typical cubic crystal form, has a rapid reoxidation rate and complete redox reversibility, and has a small thermal hysteresis temperature difference.
Description
Technical Field
The invention belongs to the field of development of thermochemical energy storage materials, and particularly relates to a preparation method of cobaltosic oxide with thermochemical energy storage performance and a product.
Background
Under the background of climate change and increasingly reduced fossil energy supply, the utilization of renewable energy is in line with the trend of the times and rapidly develops into a global revolutionary tide. Solar energy is a renewable energy source with development potential, but solar energy has the defects of intermittence, low density, instability and the like, and the thermochemical energy storage technology realizes the release and storage of energy by means of the breakage and recombination of chemical bonds, is one of heat storage modes which are concerned at present, and is expected to realize the peak shaving operation of a solar power plant. The thermochemical energy storage system comprises: hydrides, carbonates, hydroxides, ammonia, organics, metal oxides. The metal oxide stores heat, the oxidation-reduction reaction between the metal oxides with different valence states is used for storing and releasing heat, the metal oxide can directly use air as a heat transfer fluid, and reactants do not have phase change, so that the heat is not consumed due to the phase change, and products after the reaction are not required to be separated, so that the metal oxide is paid attention to by a plurality of scholars as a thermochemical energy storage material.
The cobalt oxide has good reaction reversibility and larger heat storage density, the theoretical enthalpy value of the cobalt oxide is 844kJ/kg, the theoretical enthalpy value is about 4 times of that of the manganese oxide, the thermal hysteresis temperature difference is about 0-50 ℃, and the thermal hysteresis temperature difference of the manganese oxide is about 200 ℃, so the cobalt oxide is a very potential thermochemical energy storage material. However, like other oxides, after undergoing a long-term energy charging and releasing cycle, cobalt oxide is sintered at a high temperature, which further affects the reoxidation rate and the redox reversibility of the material, so that increasing the reoxidation rate, reducing the thermal hysteresis phenomenon and improving the redox reversibility are the main methods for improving the application of cobalt oxide in the aspect of thermochemical energy storage.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of cobaltosic oxide with thermochemical energy storage performance and a product thereof.
In order to achieve the technical purpose, the invention provides the following technical scheme:
a preparation method of cobaltosic oxide with thermochemical energy storage performance comprises the following steps:
mixing cobalt acetate, urea and a dispersing agent, adding water to obtain a mixed solution, carrying out hydrothermal reaction for 10-12h at the temperature of 180 ℃ under 150 ℃, centrifuging, washing and drying to obtain a pink precursor cobalt carbonate;
urea provides carbonate, so the urea needs to be used in excess, and the reaction equation is as follows:
Co2++4CO(NH2)2+5H2O→CoCO3↓+3CO2↑+6NH3↑+2NH4+ (1)
the hydrothermal reaction temperature is lower than 150 ℃, the reaction can not be completely carried out, and the urea decomposition is not complete enough; the temperature higher than 180 ℃ can cause the particle size of the obtained cobalt carbonate particles to grow too large;
calcining the precursor cobalt carbonate for 10-12h at the temperature of 500-600 ℃ to obtain a black substance, namely cobaltosic oxide.
The calcination reaction equation of the precursor cobalt carbonate is as follows:
further, the concentration of the cobalt acetate in the mixed solution is 0.1mol/L-0.4 mol/L.
Furthermore, the dosage of the urea is 1-2 times of the mass of the cobalt acetate.
Furthermore, the dosage of the dispersing agent is 1-2 times of the mass of the cobalt acetate.
Further, the dispersing agent is triethanolamine and diethylene glycol.
Further, the mass ratio of the triethanolamine to the diethylene glycol is 1: (1-9). The grain size can be controlled between 1-10 μm by controlling the ratio of triethanolamine to diethylene glycol additive.
Furthermore, the heating rate of the hydrothermal reaction is 5 ℃/min, and the cubic morphology cannot be formed due to the excessively high heating rate.
Furthermore, the calcining temperature rise rate is less than or equal to 10 ℃/min, the morphology of cobaltosic oxide particles with too high temperature rise rate is damaged, and the cubic morphology of the precursor cannot be inherited.
The invention also provides cobaltosic oxide prepared according to the method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, cobalt acetate is used as a raw material, urea is used for providing carbonate, the use amount of triethanolamine and diethylene glycol is strictly controlled, so that a cobalt carbonate precursor with a higher specific surface area and a large particle size is obtained, the cobalt carbonate is decomposed at a high temperature by utilizing a calcination reaction to release carbon dioxide, and cobaltosic oxide is generated, has a porous structure and inherits the appearance of the cobalt carbonate, so that the cobaltosic oxide with a cubic crystal form is obtained, the heat transfer rate and the oxygen diffusion rate of the material are faster, and the redox performance of the material is further improved.
The cobaltosic oxide prepared by the invention has the following characteristics that (1) the cobaltosic oxide has higher specific surface area and pore volume, and is more beneficial to the diffusion of oxygen in particles; (2) due to the regular micro-nano structure and the high specific surface area, the oxygen diffusion rate is accelerated, so that the reoxidation rate of the material is accelerated; (3) the thermal hysteresis temperature difference is reduced: the initial temperature of the reduction reaction is similar to that of materials synthesized by other technologies, while the initial temperature of the oxidation reaction is increased, thereby reducing the thermal hysteresis temperature difference. (4) The sintering resistance is improved, the morphological characteristics of the alloy can be still maintained after thirty cycles, and the alloy has stable reoxidation rate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an XRD pattern of tricobalt tetroxide prepared in example 1 (FIG. 1a) and example 2 (FIG. 1 b);
FIG. 2 is a time-mass-temperature plot of the cobaltosic oxide prepared in example 1 (FIG. 2a) and example 2 (FIG. 2 b);
FIG. 3 is a graph of the reoxidation rate of tricobalt tetraoxide prepared in example 1 (FIG. 3a) and example 2 (FIG. 3 b);
FIG. 4 is a graph showing the thermal hysteresis temperature difference of cobaltosic oxide prepared in example 1 (FIG. 4a) and example 2 (FIG. 4 b);
fig. 5 is an electron micrograph of the tricobalt tetroxide prepared in example 1 (left) and example 2 (right).
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Weighing 1.77g of cobalt acetate, 0.2g of triethanolamine, 1.8g of diethylene glycol and 3.0g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL polytetrafluoroethylene-lined reaction kettle after the substances are fully dissolved, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the temperature to 180 ℃ (the temperature rise rate is 5 ℃/min), reacting for 12h at the constant temperature of 180 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, and finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace to be calcined for 12h at the temperature of 600 ℃ (the heating rate is 10 ℃/min), and obtaining black cobaltosic oxide after the calcination is finished, wherein the name of the black cobaltosic oxide is Co 19.
Example 2
The procedure is as in example 1 except that cobaltosic oxide, named Co11, is prepared by weighing 1.77g of cobalt acetate, 1.0g of triethanolamine, 1.0g of diethylene glycol and 3.0g of urea.
Test example:
1. fig. 1 is XRD diffractograms of Co19 in example 1 and Co11 in example 2, and it can be seen that cobaltosic oxide synthesized by controlling different dispersant ratios is pure and free of impurity phase.
2. The BET specific surface area and pore volume tests were carried out on Co19 in example 1 and Co11 in example 2, the results of which are shown in table 1.
TABLE 1
It can be seen that a difference in the ratio of triethanolamine to diethylene glycol results in a difference in the size of the particles.
3. The reaction equation of cobaltosic oxide in thermochemical energy storage cycle is as follows:
the energy charging process corresponds to the forward reaction of the reaction, cobaltosic oxide is converted into cobaltosic oxide and oxygen is released at the same time, the energy releasing process corresponds to the reverse reaction of the reaction, cobaltosic oxide is oxidized into cobaltosic oxide by reacting with oxygen in the air, and the theoretical weight increase/loss corresponding to the weight increase/loss process is about 6.64 percent.
The cobaltosic oxide prepared in examples 1-2 was subjected to 30 charge and discharge cycles of heat storage performance test using a thermogravimetric analyzer (STA 449F5 tolerating). Fig. 2 is a time-mass-temperature curve for the twentieth to thirty cycles of two tricobalt tetroxide (Co19 and Co 11). The upper curve represents the temperature and the lower curve represents the mass change, and it can be seen that the mass change of both cobaltosic oxides can be close to the theoretical mass change (6.64%). However, as the circulation progresses, the conversion rates of Co19 and Co11 are reduced to a certain degree, while Co11 is reduced to 98% from 100%, and Co19 is reduced to 96% from 100%, and it can be seen from the figure that there is a smooth transition section after the mass increase is finished, namely, the transition section of reduction reaction after the oxidation reaction is finished, and the mass curve a is not as smooth as that of the b figure, which shows that as the circulation progresses, the material is sintered, the thermal stability is poor, and the sintering resistance of Co19 is weaker than that of Co 11.
4. The reoxidation rate calculations were performed for the thermogravimetric results of thirty cycles for the two samples prepared in examples 1-2, and FIG. 3 is a plot of the reoxidation rate for thirty cycles of Co19 and Co 11. It can be seen that the reoxidation rates for both samples were greatly reduced during the first five cycles, but the oxidation rates for the two cobalt oxides were not much different, with the rate of Co11 being only slightly higher than that of Co 19. However, during subsequent cycles, Co11 remained stable at the oxidation rate (175. mu. mol/min/g), Co19 continued to show a significant drop, down to 100. mu. mol/min/g for the thirtieth cycle.
5. The initial temperature at which the material undergoes redox is also one of the important characteristics of whether the material is suitable as an energy storage material. Fig. 4 is a plot of mass versus time for thirty cycles of two tricobalt tetroxide (Co19 and Co11) prepared in examples 1-2 versus the initial temperature difference for the tricobalt tetroxide redox reaction. The reduction temperatures of Co11 and Co19 were 909.1 ℃ and 909.3 ℃ respectively, and the reduction initiation temperatures were the same because the reduction reaction rate was determined by heat conduction and the oxidation reaction rate was determined by oxygen diffusion when the charge-discharge cycle was performed, the oxidation reaction initiation temperature of Co11 was 899.3 ℃ and the oxidation reaction initiation temperature of Co19 was 898.0 ℃. The thermal hysteresis temperature differences of Co19 and Co11 were 11.1 ℃ and 10.0 ℃, respectively.
6. Fig. 5 is an electron microscope scanning image of the cobaltosic oxide prepared in example 1-2, and it can be seen that the cobaltosic oxide prepared by the present invention is in a tetragonal form.
Example 3
Weighing 1.77g of cobalt acetate, 0.5g of triethanolamine, 1.6g of diethylene glycol and 3.2g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL polytetrafluoroethylene-lined reaction kettle after the substances are fully dissolved, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the temperature of the room to 165 ℃ (the temperature rise rate is 5 ℃/min), reacting for 11h at the constant temperature of 165 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace to be calcined for 11h at 550 ℃ (the heating rate is 5 ℃/min), and obtaining black cobaltosic oxide after the calcination is finished. After 30 energy charging and releasing cycles of heat storage performance tests are carried out on the cobaltosic oxide in a circulating manner, the conversion rate is reduced to 97%, and the oxidation rate is reduced to 150 mu mol/min/g.
Example 4
Weighing 1.77g of cobalt acetate, 0.5g of triethanolamine, 2.0g of diethylene glycol and 3.5g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL reaction kettle with a lining of polytetrafluoroethylene, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the temperature of the room to 150 ℃ (the temperature rise rate is 5 ℃/min), reacting for 10h at the constant temperature of 150 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace to calcine for 10h at 500 ℃ (the heating rate is 1 ℃/min), and obtaining black cobaltosic oxide after the calcination is finished. After 30 energy charging and releasing cycles of heat storage performance tests are carried out on the cobaltosic oxide in a circulating manner, the conversion rate is reduced to 98 percent, and the oxidation rate is reduced to 162 mu mol/min/g.
Example 5
Weighing 1.77g of cobalt acetate, 0.3g of triethanolamine, 1.9g of diethylene glycol and 3.4g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL polytetrafluoroethylene-lined reaction kettle after the substances are fully dissolved, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the temperature of the room to 170 ℃ (the temperature rise rate is 5 ℃/min), reacting for 11.5h at the constant temperature of 170 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace to calcine for 10h at 500 ℃ (the heating rate is 1 ℃/min), and obtaining black cobaltosic oxide after the calcination is finished. After 30 energy charging and releasing cycles of heat storage performance tests are carried out on the cobaltosic oxide in a circulating manner, the conversion rate is reduced to 96%, and the oxidation rate is reduced to 120 mu mol/min/g.
Example 6
Weighing 1.77g of cobalt acetate, 1.0g of triethanolamine, 2.0g of diethylene glycol and 3.3g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL polytetrafluoroethylene-lined reaction kettle after the substances are fully dissolved, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the temperature of the room to 170 ℃ (the temperature rise rate is 5 ℃/min), reacting for 12h at the constant temperature of 170 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace at 580 ℃ for calcining for 12h (the heating rate is 4 ℃/min), and obtaining black cobaltosic oxide after the calcining is finished. After 30 energy charging and releasing cycles of heat storage performance tests are carried out on the cobaltosic oxide in a circulating manner, the conversion rate is reduced to 97%, and the oxidation rate is reduced to 165 mu mol/min/g.
Example 7
The same as example 1 except that 1.77g of cobalt acetate, 0.75g of triethanolamine, 1.25g of diethylene glycol and 3.0g of urea were weighed out.
As a result, cobaltosic oxide having different particle sizes was obtained.
Example 8
The difference from example 1 is that the amount of urea added is 1.77 g.
As a result, it was found that the amount of urea was insufficient, carbonate was insufficient, and the reaction was incomplete.
Example 9
The difference from example 1 is that the hydrothermal reaction temperature was 150 ℃.
As a result, it was found that: the particle size of the obtained cobaltosic oxide is reduced.
Example 10
The difference from example 1 is that the temperature increase rate in calcination was 5 ℃/min.
As a result, it was found that: the particle size of the obtained cobaltosic oxide is reduced.
Comparative example 1
The same as example 1 except that 1.77g of cobalt acetate, 3g of diethylene glycol and 3.0g of urea were weighed out.
As a result, it was found that: the particle size of the obtained cobaltosic oxide particles is much smaller than that of the cobaltosic oxide particles obtained in example 1.
Comparative example 2
The difference from example 1 is that cobalt acetate is replaced by cobalt sulphate.
As a result, it was found that: after 30 heat storage performance tests of energy charging and releasing cycles are carried out on the obtained cobaltosic oxide, the conversion rate is reduced to 90 percent.
Comparative example 3
The difference from example 1 is that the calcination temperature is 400 ℃.
As a result, it was found that: after 30 heat storage performance tests of energy charging and releasing cycles are carried out on the obtained cobaltosic oxide, the thermal hysteresis temperature difference is obviously increased.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. A preparation method of cobaltosic oxide with thermochemical energy storage performance is characterized by comprising the following steps:
weighing 1.77g of cobalt acetate, 1.0g of triethanolamine, 1.0g of diethylene glycol and 3.0g of urea, dissolving the substances in 100mL of deionized water, stirring for 30min, transferring the solution to a 180mL polytetrafluoroethylene lined reaction kettle after the substances are fully dissolved, putting the reaction kettle into a muffle furnace, setting a temperature rise program to raise the room temperature to 180 ℃, and raising the temperature rate to 5 ℃/min, reacting for 12h at the constant temperature of 180 ℃, after the reaction is finished, centrifugally washing the obtained mixture by using ethanol and deionized water, and finally putting the precipitate into an 80 ℃ forced air drying oven for drying to obtain a pink precursor; and putting the precursor into a muffle furnace to be calcined for 12 hours at the temperature of 600 ℃, wherein the heating rate is 10 ℃/min, and after the calcination is finished, black cobaltosic oxide is obtained and is named as Co 11.
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