CN113637462B - Preparation method of chemical heat storage material based on ordered porous carbon base - Google Patents
Preparation method of chemical heat storage material based on ordered porous carbon base Download PDFInfo
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Abstract
The invention discloses a preparation method of a chemical heat storage material based on ordered porous carbon base, which uses LiCl.nH 2 O is a matrix of the chemical heat storage material, and is loaded on the N-doped hydrophilic graphitized ordered porous carbon material to form the carbon-based chemical heat storage material, the preparation process is simple and less in time consumption, and the water absorption capacity of the obtained composite material can exceed 3000cm by properly adjusting the concentration of vitamin C, the concentration of LiCl solution, the activation temperature and the activation time 3 And/g. The hydrophilicity of the carbon material is derived from vitamin C, so that the hydration rate of LiCl is greatly increased, the heat conduction efficiency is increased by graphitization, the transmission isotropy of electrons and ions is enabled by an ordered porous structure, the overall heat and mass transfer efficiency of the composite material is greatly improved, and the large-scale industrial production is easy to realize.
Description
Technical field:
the invention relates to a preparation method of a chemical heat storage material based on ordered porous carbon base.
The background technology is as follows:
at present, the world energy research gradually changes from carbon-based energy to renewable energy development and utilization, and meanwhile, the improvement of the energy utilization rate also becomes a hot spot for energy conservation and environmental protection research. One of the main reasons for low energy utilization is the generation of industrial waste heat and the lack of industrial waste heat utilization, especially the utilization of low grade heat. A typical temperature range for low grade heat sources is from ambient to 250 c, with significant waste in industrial production. The low-grade energy source is widely utilized and mainly comprises sensible heat storage, latent heat storage, chemical heat storage and the like. The chemical heat storage can effectively solve the problems of time and space of energy distribution, is a technical means capable of efficiently storing and timely and rapidly releasing heat, thereby adjusting the energy and solving the problem of wave peaks and wave troughs, and can effectively improve the utilization rate of the residual heat at the present stage and promote the solar energy to become a reliable energy source.
Heat storage materials are one of the core hot spots of chemical heat storage technology research. The heat storage material has a great influence on the performance of the chemical heat storage device and its cost, and generally accounts for about 30% of the total investment cost. For material selection of specific applications, the standards often conflict with each other, a global optimal scheme needs to be found, and higher heat storage density and heat and mass transfer efficiency are main pursuits targets for material preparation at the present stage.
The invention comprises the following steps:
the invention aims to provide a preparation method of an ordered porous carbon-based chemical heat storage material, which uses LiCl.nH 2 O is a matrix of the chemical heat storage material, and is loaded on the N-doped hydrophilic graphitized ordered porous carbon material to form the carbon-based chemical heat storage material.
The invention is realized by the following technical scheme:
a process for preparing chemical heat-accumulating material based on ordered porous carbon base features that LiCl.nH is used as the raw material 2 O is a matrix of a chemical heat storage material, and is loaded on an N-doped hydrophilic graphitized ordered porous carbon material to form a carbon-based chemical heat storage material, and the method comprises the following steps:
1) Preparation of acidified phenolic resin precursor: phenol is melted, 0.05mol/L-0.5mol/L NaOH solution is slowly added dropwise under stirring, after 10min, 37wt% formaldehyde solution is slowly added dropwise, the mass ratio of the phenol, the NaOH solution and the formaldehyde solution is 1:22-26:2-3, meanwhile, the reaction mixture is heated for 0.5-3 h at 72-76 ℃, after the reaction mixture is cooled to room temperature, vitamin C solution and deionized water with different concentrations in the range of 2-12 mg/ml are slowly added dropwise into the mixture, the pH value of the solution is regulated to be about 6-7, then the mixture is stirred at normal temperature for 1-4h, and the redundant water is removed, so that the acidified phenolic resin precursor is finally obtained;
2) Preparation of hydrophilic graphitized ordered porous carbon material: fully dissolving PluronicF127 (EO 100PO65EO100, MW=12600) and deionized water at 45 ℃ according to the mass ratio of 1:60, stirring to form a partially transparent solution, cooling to room temperature, adding ethanol, mixing the obtained mixed solution with the acidified phenolic resin precursor obtained in the step a), wherein the mass ratio of the mixed solution to the acidified phenolic resin precursor is 3:1, stirring at 5-35 ℃, evaporating the ethanol in a fume hood, placing the sample in a muffle furnace, drying at 100-150 ℃, and drying at N 2 Calcining for 2 hours at 400-500 ℃ under 1.5 atmospheric pressure in the environment, then mixing with liquid melamine, wherein the mass ratio of the liquid melamine to the calcined melamine is 2:1, and adding the calcined melamine into N 2 Calcining for 3 hours at 350-550 ℃ in a protective environment, and carbonizing at 800-1000 ℃ in a muffle furnace to obtain an N-doped hydrophilic graphitized ordered porous carbon material with the aperture of 10-120 nm, which is marked as OMC-N-001;
3) Preparing a chemical heat storage composite material: drying the N-doped hydrophilic graphitized ordered porous carbon material OMC-N-001 and LiCl obtained in the step b) at 200 ℃ for 4-8 hours respectively for pretreatment, then soaking the pretreated OMC-N-001 in LiCl salt solution with the mass fraction of 10% -40%, and stirring the mixture for 1-12 hours; after stirring is completed, placing the mixture into a vacuum drying oven and drying the mixture at 200 ℃ for 4-8 hours; then the composite material is placed in a constant temperature and humidity box to be activated for 30-120min, and finally the chemical heat storage composite material is obtained and is marked as OMC-N-001/LiCl.nH 2 O。
Step 1) the NaOH solution may also be replaced by a KOH solution.
And 3) preparing the chemical heat storage composite material, wherein the N-doped hydrophilic graphitized ordered porous carbon material is compounded with LiCl by an ultrasonic method or a hydrothermal method.
The beneficial effects of the invention are as follows: the preparation process is simple and consumes less time, and the water absorption capacity of the obtained composite material can exceed 3000cm by properly adjusting the concentration of vitamin C, the concentration of LiCl solution, the activation temperature and the activation time 3 And/g. The hydrophilicity of the carbon material is derived from vitamin C, so that the hydration rate of LiCl is greatly increased, the heat conduction efficiency is increased by graphitization, the transmission isotropy of electrons and ions is enabled by an ordered porous structure, the overall heat and mass transfer efficiency of the composite material is greatly improved, and the large-scale industrial production is easy to realize.
Description of the drawings:
FIG. 1 is an SEM image of OMC-N-001 having a pore diameter of 10nm obtained in example 1;
FIG. 2 is a TEM image of OMC-N-001 having a pore diameter of 10nm obtained in example 1;
FIG. 3 shows the result of example 1 in OMC-N-001/LiCl.nH 2 A comparison graph of the atmospheric steam adsorption curve of the O composite material (A) and OMC-N-001 (B) under the condition of 30 ℃ and 60 percent;
FIG. 4 is an SEM image of an N-doped hydrophilic graphitized ordered porous carbon material of example 2 having a pore size of 100 nm;
FIG. 5 is a TEM image of an N-doped hydrophilic graphitized ordered porous carbon material with a pore diameter of 100nm obtained in example 2.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: preparation method of chemical heat storage material based on ordered porous carbon base
The method comprises the following steps:
1) Preparation of phenolic resin precursor:
firstly 2.5g of phenol are melted in a water bath at 44℃and 60g of a 0.1mol/LNaOH solution are added dropwise with slow stirring. After 10 minutes, 6.85g of 37% by weight formaldehyde solution are slowly added dropwise. After thorough mixing, the mixed solution was placed on a magnetic stirrer, stirred at a rate of 300r/min, and the resulting mixture was simultaneously heated at 75℃for 60 minutes. After the reaction mixture is cooled to room temperature, proper amounts of vitamin C solution with different concentrations (2-12 mg/ml) and deionized water are slowly dripped into the mixture, the PH value of the solution is regulated to be about 6-7, and then the mixture is stirred for 2 hours at the room temperature at the speed of 400 r/min. After stirring was completed, excess water was removed on a magnetic stirrer at a speed of 300r/min in a water bath at 44 ℃. Finally, the acidified phenolic resin precursor is obtained.
2) Preparation of hydrophilic graphitized ordered porous carbon material:
2g of PluronicF127 (EO 100PO65EO100, MW=12600) were stirred with 120g of deionized water at 45℃for 2h, after which a partially clear solution was formed, after cooling to room temperature 40g of ethanol was added. The resulting mixed solution was then mixed with the phenolic resin precursor and the mixture was placed on a magnetic stirrer at 400r/min and stirred thoroughly for 3h at 35 c to allow the individual substances within the mixture to be thoroughly linked. The mixture was placed in a fume hood for about 10 hours and the ethanol was allowed to evaporate. The sample was then kept in a muffle furnace at 100deg.C for 18h in the atmosphere. After the mixture has sufficiently dried, it is taken to be N 2 OMC-001 was obtained by calcining at 400℃for 2 hours at 1.5 atmospheres in the environment. The OMC-001 thus obtained was mixed with 3g of liquid melamine and under N 2 Calcining for 3h at 350 ℃ under the protection environment, wherein the mass ratio of OMC-001 to melamine is 2:1. Finally carbonizing at 800 ℃ in a muffle furnace to obtain the 10nm N-doped hydrophilic graphitized ordered porous carbon material OMC-N-001, wherein the SEM image is shown in figure 1, and the TEM image is shown in figure 2.
3) Preparing a chemical heat storage composite material:
first, 20g of 10nm nano OMC-N-001 and 20g LiCl were pretreated: drying at 200 ℃ for 4 hours. Then 2g OMC-N-001 was immersed in 10% LiCl salt solution, and the mixture was placed on a magnetic stirrer and mechanically stirred at 600r/min for 12h. After stirring, the mixture was dried in a vacuum oven at 200℃for 8 hours. Then the composite and the material are placed into a constant temperature and humidity box for activation, finally OMC-N-001/LiCl.nH is obtained 2 O composite material. Obtaining 10nm OMC-N-001/LiCl.nH 2 O composite material and N-doped hydrophilic graphitized ordered polymerThe comparison graph of the atmospheric steam adsorption curve of the porous carbon material OMC-N-001 at 30 ℃ and 60% is shown in FIG. 3.
Example 2:
referring to example 1, the difference is that PluronicF127 and deionized water are adjusted to have a mass ratio of 10:60, and the N-doped hydrophilic graphitized ordered porous carbon material with a pore diameter of 100nm is obtained in the step (2), wherein an SEM image is shown in FIG. 4, and a TEM image is shown in FIG. 5.
Claims (3)
1. A method for preparing chemical heat storage material based on ordered porous carbon base is characterized in that the material uses LiCl.nH 2 O is a matrix of a chemical heat storage material, and is loaded on an N-doped hydrophilic graphitized ordered porous carbon material to form a carbon-based chemical heat storage material, and the method comprises the following steps:
1) Preparation of acidified phenolic resin precursor: phenol is melted, 0.05mol/L-0.5mol/L NaOH solution is slowly added dropwise under stirring, after 10min, 37wt% formaldehyde solution is slowly added dropwise, the mass ratio of the phenol, the NaOH solution and the formaldehyde solution is 1:22-26:2-3, meanwhile, the reaction mixture is heated for 0.5-3 h at 72-76 ℃, after the reaction mixture is cooled to room temperature, vitamin C solution and deionized water with different concentrations in the range of 2-12 mg/ml are slowly added dropwise into the mixture, the pH value of the solution is regulated to be about 6-7, then the mixture is stirred at normal temperature for 1-4h, and the redundant water is removed, so that the acidified phenolic resin precursor is finally obtained;
2) Preparation of hydrophilic graphitized ordered porous carbon material: stirring PluronicF127 and deionized water according to a mass ratio of 1-10:60 at 45 ℃ to fully dissolve to form a partially transparent solution, cooling to room temperature, adding ethanol, mixing the obtained mixed solution with the acidified phenolic resin precursor obtained in the step 1), stirring the obtained mixed solution and the acidified phenolic resin precursor at 5-35 ℃ according to a mass ratio of 3:1, evaporating ethanol in a fume hood, placing a sample in a muffle furnace, drying at 100-150 ℃, and drying at N 2 Calcining for 2 hours at 400-500 ℃ under 1.5 atmospheric pressure in the environment, then mixing with liquid melamine, wherein the mass ratio of the liquid melamine to the calcined melamine is 2:1, and adding the calcined melamine into N 2 Calcining at 350-550 deg.C for 3 hr in protected environment, and finally calcining at 800 deg.C in muffle furnaceCarbonizing at 1000 ℃ to obtain an N-doped hydrophilic graphitized ordered porous carbon material with the pore diameter ranging from 10nm to 120nm, which is marked as OMC-N-001;
3) Preparing a chemical heat storage composite material: drying the N-doped hydrophilic graphitized ordered porous carbon material OMC-N-001 and LiCl obtained in the step 2) at 200 ℃ for 4-8 hours respectively for pretreatment, then soaking the pretreated OMC-N-001 in LiCl salt solution with the mass fraction of 10% -40%, and stirring the mixture for 1-12 hours; after stirring is completed, placing the mixture into a vacuum drying oven and drying the mixture at 200 ℃ for 4-8 hours; then the composite material is placed in a constant temperature and humidity box to be activated for 30-120min, and finally the chemical heat storage composite material is obtained and is marked as OMC-N-001/LiCl.nH 2 O。
2. The method for preparing an ordered porous carbon based chemical heat storage material according to claim 1, wherein step 1) NaOH solution is replaced by KOH solution.
3. The method for preparing the ordered porous carbon-based chemical heat storage material according to claim 1, wherein the preparation of the chemical heat storage composite material in the step 3) is carried out by compounding the N-doped hydrophilic graphitized ordered porous carbon material with LiCl by an ultrasonic method or a hydrothermal method.
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