CN115044352A - Phase-change energy storage material and preparation method thereof - Google Patents
Phase-change energy storage material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011232 storage material Substances 0.000 title claims abstract description 15
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 230000008859 change Effects 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000012782 phase change material Substances 0.000 claims abstract description 23
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- 238000003825 pressing Methods 0.000 claims abstract description 18
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
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- 239000000243 solution Substances 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Abstract
The invention provides a phase change energy storage material and a preparation method thereof. The preparation method provided by the invention comprises the following steps: a) mixing Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder, water and a chelating agent, and then heating to react to form nickel metal organic framework modified expandable graphite powder; b) performing thermal expansion treatment on the nickel metal organic framework modified expandable graphite powder in a protective atmosphere to obtain nickel metal organic framework modified expandable graphite powder; c) alternately laminating and paving the nickel metal organic framework modified expanded graphite powder and the phase-change wax, and then carrying out heat treatment to obtain a composite material; d) and pressing the composite material to obtain the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material. The phase change energy storage material prepared by the invention improves the thermal conductivity and the cycle stability of the material on the basis of ensuring high phase change latent heat.
Description
Technical Field
The invention relates to the field of phase change energy storage, in particular to a phase change energy storage material and a preparation method thereof.
Background
The peak-valley time-of-use electricity price mechanism is characterized in that a day is divided into periods of high peak, flat section and low valley according to the operation characteristics of the power system, different electricity price levels are formulated for the periods of time, the time-of-use electricity price level is closer to the power supply cost of the power system, people are guided to cut peaks and fill valleys of power, and therefore the utilization efficiency of the whole power system is improved. However, at present, the trend of peak clipping and valley leveling tends to be gentle, and when the period of high peak power utilization of people is difficult to change, how to better realize storage of low valley power energy is an important research direction. Phase change material can be fine realize thermal absorption and release, if use for warm up in, store the heat through the low ebb electricity at night, later release the heat when daytime temperature reduces, realize the peak of low ebb electricity and use.
Phase change wax is as the phase change material that phase change wax modified and obtained, and it has high phase change latent heat, is greater than 200J/g, and temperature phase transition is invariable during the use, carries out energy storage and release through its phase change process, and the problem of the intermittence and the mismatch of solution energy supply and demand that can be better can show the utilization ratio that improves the energy. In the prior art, phase-change wax and expanded graphite are combined to prepare the phase-change energy storage material. However, these phase change materials have problems of easy leakage (difficult to use for many times, poor stability), poor thermal conductivity, and even poor latent heat of phase change.
Disclosure of Invention
In view of the above, the present invention provides a phase change energy storage material and a preparation method thereof. The phase change energy storage material prepared by the invention improves the heat conductivity and the cycle stability of the material on the basis of ensuring high phase change latent heat.
The invention provides a preparation method of a phase change energy storage material, which comprises the following steps:
a) mixing Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder, water and a chelating agent, and then heating for reaction to form nickel metal organic framework modified expandable graphite powder;
b) performing thermal expansion treatment on the nickel metal organic framework modified expandable graphite powder in a protective atmosphere to obtain nickel metal organic framework modified expandable graphite powder;
c) alternately laminating and paving the nickel metal organic framework modified expanded graphite powder and the phase-change wax, and then carrying out heat treatment to obtain a composite material;
d) and pressing the composite material to obtain the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material.
Preferably, in the step a), the chelating agent is at least one selected from terephthalic acid, trimesic acid and phthalic acid.
Preferably, in step a):
the Ni (NO) 3 ) 2 ·6H 2 The mass ratio of the O to the expandable graphite powder is (0.2-0.8) to 0.5;
the mixing temperature is 50-55 ℃;
ni (NO) as chelating agent 3 ) 2 ·6H 2 The mass ratio of O is 0.2 to (0.2-0.8);
the temperature of the temperature-raising reaction is 150 ℃.
Preferably, in the step b), the temperature of the thermal expansion treatment is 700-900 ℃, and the heat preservation time is 1-2 hours.
Preferably, in step c):
the mass ratio of the nickel metal organic framework modified expanded graphite powder to the total amount of the phase-change wax is 5-20%;
the temperature of the heat treatment is 60-70 ℃, and the time is 1-2 hours.
Preferably, in the step d), the conditions of the pressing treatment are as follows: the pressure is 20-30 MPa, and the pressure maintaining time is 5-10 min.
Preferably, in the step a), the particle size of the expandable graphite powder is 80-100 meshes, and the carbon content is more than or equal to 99 wt%;
in the step c), the phase change temperature of the phase change wax is 20-45 ℃, and the phase change latent heat is more than 200J/g.
Preferably, in the step a), the expandable graphite powder is subjected to impurity removal;
the impurity-removed expandable graphite powder is prepared by the following method:
soaking the expandable graphite powder raw material in a strong alkaline solution, washing with water, and freeze-drying to obtain the impurity-removed expandable graphite powder;
in the step a), after the temperature-raising reaction, the method further includes: washing and drying;
the step d) further comprises, before and after the pressing treatment: and carrying out ball milling on the composite material.
Preferably, the strong alkaline solution is a NaOH solution and/or a KOH solution;
the temperature of the freeze drying is-45 ℃ to-40 ℃;
the rotation speed of the ball milling is 300-350 rpm, and the time is 3-5 h.
The invention also provides the phase change energy storage material prepared by the preparation method in the technical scheme.
The preparation method provided by the invention firstly prepares Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder and water, introducing a chelating agent, carrying out a heating reaction, carrying out surface treatment on the expandable graphite powder to generate nickel metal organic framework modified expandable graphite powder, wherein the nickel metal framework has a pore structure with a high specific surface area and a nanoscale, and is mutually combined with expanded graphite with a micron pore structure to form a specific modified structure complex; then carrying out thermal expansion treatment to obtain nickel metal organic framework modified expanded graphite; the composite phase-change material is combined with phase-change wax for heat treatment, and due to the fact that the nickel metal organic framework modifies the expanded graphite and the nickel metal organic framework has a mesopore size and a macropore structure, the composite phase-change wax can achieve a good adsorption effect, and the leakage problem of the phase-change wax in the use process of the composite material can be well reduced, so that the leakage amount of phase-change components is small in the multiple use process of the composite phase-change material, and the circulation stability is improved; in addition, the excellent adsorption effect increases the mass fraction of the phase-change wax in the composite phase-change material, so that the composite phase-change material product has higher energy storage density. Finally, ball milling refinement and pressing are carried out, the problem that the final composite material is low in density due to the fact that the volume of the expanded graphite is too large is solved to a certain extent, the density of the composite phase-change material is increased, and further the composite phase-change material has larger phase-change potential under the same volume in actual useHeating; in addition, the nickel metal organic framework modified expanded graphite is used as an adsorption structure material, has high heat conductivity coefficient, and forms a heat conduction path of the composite material, so that the composite material has high heat conductivity. Therefore, the material obtained by the invention has high phase change latent heat, excellent heat conductivity and good cycle stability, and can be well used for storing and releasing energy.
Experimental results show that the material obtained by the invention has the endothermic phase change temperature of over 36.3 ℃, the endothermic phase change latent heat of over 160J/g, the exothermic phase change temperature of over 36.1 ℃, the exothermic phase change latent heat of over 161J/g, the thermal conductivity of over 5.0W/(m.K), and the leakage rate of less than 0.45 percent after 50 times of circulation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a DSC chart of the product obtained in example 1;
FIG. 2 is a DSC chart of the product obtained in example 2;
FIG. 3 is a DSC chart of the product obtained in example 3.
Detailed Description
The invention provides a preparation method of a phase change energy storage material, which comprises the following steps:
a) mixing Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder, water and a chelating agent, and then heating for reaction to form nickel metal organic framework modified expandable graphite powder;
b) performing thermal expansion treatment on the nickel metal organic framework modified expandable graphite powder in a protective atmosphere to obtain nickel metal organic framework modified expandable graphite powder;
c) alternately laminating and paving the nickel metal organic framework modified expanded graphite powder and the phase-change wax, and then carrying out heat treatment to obtain a composite material;
d) and pressing the composite material to obtain the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material.
The invention utilizes the loose and porous worm structure of the expanded graphite as an adsorption material, uses phase-change wax as a phase-change energy storage component, and prepares the expanded graphite powder modified by the nickel metal organic framework by surface treatment of the expandable graphite. And then the expanded graphite is subjected to heat treatment to realize the adsorption of the liquid phase-change wax, the powder obtained by mixing is further refined by planetary ball milling, and finally the powder is subjected to cold press molding. The finally obtained phase change energy storage material improves the thermal conductivity and the cycle stability of the material on the basis of ensuring high phase change latent heat.
[ with respect to step a ]:
a) mixing Ni (NO) 3 ) 2 ·6H 2 And O, expandable graphite powder, water and a chelating agent are mixed, and then the mixture is heated to react to form the nickel metal organic framework modified expandable graphite powder.
In the present invention, the Ni (NO) is 3 ) 2 ·6H 2 The source of O is not particularly limited, and may be a commercially available product.
In the invention, the expandable graphite powder is preferably subjected to impurity removal. In the invention, the impurity-removed expandable graphite powder is preferably prepared by the following method: soaking the expandable graphite powder raw material in a strong alkaline solution, washing with water, and freeze-drying to obtain the impurity-removed expandable graphite powder. Wherein, the strong alkaline solution is preferably NaOH solution and/or KOH solution, and both are aqueous solutions. The concentration of the strong alkaline solution is preferably 0.5-1 mol/L, and specifically may be 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8 mol/L. The temperature of the soaking is not particularly limited, and may be performed at room temperature. The soaking time is preferably 20-50 min, specifically 20min, 30min, 40min and 50 min; acid impurities remained in the production process of the expandable graphite by the chemical oxidation method are removed by soaking. After soaking, washing with water, preferably deionized water, is performed. After washing, freeze-drying was performed. The temperature of the freeze drying is preferably-45 ℃ to-40 ℃. After the treatment, the expandable graphite powder after impurity removal is obtained. In the invention, the granularity of the expandable graphite powder (i.e. the expandable graphite powder after impurity removal) is preferably 80-100 meshes, more preferably 80 meshes, and the carbon content is more than or equal to 99 wt%.
In the present invention, the Ni (NO) is 3 ) 2 ·6H 2 The mass ratio of O to expandable graphite powder is preferably (0.2-0.8) to 0.5, and specifically may be 0.2: 0.5, 0.3: 0.5, 0.4: 0.5, 0.5: 0.5, 0.6: 0.5, 0.7: 0.5, 0.8: 0.5.
In the present invention, the water is preferably deionized water. In the present invention, the Ni (NO) is 3 ) 2 ·6H 2 The preferable dosage ratio of O to water is (0.2-0.8) g to 70mL, and the dosage ratio of the matrix can be 0.2g to 70mL, 0.3g to 70mL, 0.4g to 70mL, 0.5g to 70mL, 0.6g to 70mL, 0.7g to 70mL, 0.8g to 70 mL.
In the present invention, the chelating agent is preferably at least one of terephthalic acid, trimesic acid and phthalic acid, and the chelating agent can chelate metal ions. In the present invention, the chelating agent is Ni (NO) 3 ) 2 ·6H 2 The mass ratio of O is preferably 0.2: 0.2-0.8, and specifically may be 0.2: 0.2, 0.2: 0.3, 0.2: 0.4, 0.2: 0.5, 0.2: 0.6, 0.2: 0.7, 0.2: 0.8.
In the invention, the mixing is preferably magnetic stirring mixing; the rotating speed of the stirring is preferably 800-1000 rpm. In the present invention, the mixing temperature is preferably 50 to 55 ℃, and the mixture can be heated by a water bath, specifically 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃ and 55 ℃. In the present invention, the order of mixing is preferably: firstly, Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder and water, adding a chelating agent, and continuously mixing. The mixing time of the first three materials is preferably 1-2 h, and specifically can be 1h, 1.5h and 2 h. The time for mixing after adding the chelating agent is preferably 20-50 min, specifically 20min, 30min, 40min, 50min, and more preferably 30 min.
In the present invention, after the above-mentioned mixing, a temperature-raising reaction is carried out. In the present invention, the target temperature of the temperature-increasing reaction is preferably 150 ℃. The incubation time for the temperature-rising reaction is preferably 3 hours.
In the present invention, after the above reaction, the following post-treatment is preferably further performed: and (4) washing and drying. Wherein, the washing is preferably washing with deionized water and ethanol in sequence. The drying is preferably freeze drying. The freeze drying temperature is preferably-45 to-40 ℃, and specifically can be-45 ℃, -44 ℃, -43 ℃, -42 ℃, -41 ℃ and-40 ℃. And (3) obtaining the expandable graphite powder modified by a nickel metal organic framework (Ni-MOF) after the treatment.
According to the invention, through the reaction of the step a), the nickel metal organic framework modified expandable graphite powder is generated in the system, the nickel metal framework has a pore structure with a high specific surface area and a nano-scale, and is combined with the expanded graphite with a micro-pore structure to form a specific modified structure complex, so that the subsequent phase-change wax can be better adsorbed, and the leakage of the phase-change wax in the phase-change process in the product application process can be prevented.
[ regarding step b ]:
b) and carrying out thermal expansion treatment on the nickel metal organic framework modified expandable graphite powder in a protective atmosphere to obtain the nickel metal organic framework modified expandable graphite powder.
In the present invention, the kind of the gas for providing the protective atmosphere is not particularly limited, and may be an inert gas which is conventional in the art, such as nitrogen, helium, argon, or the like.
In the present invention, the temperature of the thermal expansion treatment is preferably 700 to 900 ℃, and specifically 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃ and 900 ℃. The rate of temperature rise in the thermal expansion treatment is preferably 3 ℃/min. The heat preservation time of the thermal expansion treatment is preferably 1-2 h, and specifically can be 1 h. 1.5h and 2 h. And (3) performing high-temperature expansion on the material through the heat treatment to obtain the nickel metal organic framework modified expanded graphite powder.
[ with respect to step c ]:
c) and alternately laminating and paving the nickel metal organic framework modified expanded graphite powder and the phase-change wax, and then carrying out heat treatment to obtain the composite material.
In the present invention, the type of the phase-change wax is preferably: the phase-change wax has the phase-change temperature of 20-45 ℃ and the phase-change latent heat of more than 200J/g.
In the invention, the nickel metal organic framework modified expanded graphite powder and the phase-change wax are alternately paved, for example, a layer of nickel metal organic framework modified expanded graphite powder is paved first, and then a layer of phase-change wax is paved on the surface of the nickel metal organic framework modified expanded graphite powder. In the invention, the mass ratio of the nickel metal organic framework modified expanded graphite powder to the total amount of the phase-change wax is preferably 5-20%, and specifically may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, and more preferably 15-20%.
In the present invention, the heat treatment temperature is preferably 60 to 70 ℃, and specifically 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃. The time of the heat treatment is preferably 1-2 h, and specifically can be 1h, 1.5h and 2 h. In the heat treatment process, the nickel metal organic framework modified expanded graphite powder adsorbs the liquid phase-change paraffin, and the phase-change paraffin fully enters the nickel metal organic framework modified expanded graphite structure to obtain the composite material.
[ with respect to step d ]:
d) and pressing the composite material to obtain the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material.
In the present invention, it is preferable to perform a ball milling process before the pressing process. In the present invention, the ball milling is preferably planetary ball milling. In the invention, the rotation speed of the ball mill is preferably 300-350 rpm, and specifically can be 300rpm, 310rpm, 320rpm, 330rpm, 340rpm and 350 rpm. The ball milling time is preferably 3-5 h, and specifically can be 3h, 4h and 5 h. Through the ball milling, the powder can be refined, the problem that the final composite material is low in density due to the fact that the volume of the expanded graphite is too large is solved to a certain extent, the density of the composite phase-change material is increased, and further the composite phase-change material is large in phase-change latent heat under the same volume in actual use.
In the present invention, the pressing treatment is preferably cold press molding. The pressure of the pressing treatment is preferably 20 to 30MPa, and specifically may be 20MPa, 21MPa, 22MPa, 23MPa, 24MPa, 25MPa, 26MPa, 27MPa, 28MPa, 29MPa, or 30 MPa. The pressure maintaining time of the pressing treatment is preferably 5-10 min, and specifically can be 5min, 6min, 7min, 8min, 9min and 10 min. And obtaining the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material after the treatment.
The invention also provides the phase change energy storage material prepared by the preparation method in the technical scheme.
The preparation method provided by the invention firstly prepares Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder and water, introducing a chelating agent, carrying out a heating reaction, carrying out surface treatment on the expandable graphite powder to generate nickel metal organic framework modified expandable graphite powder, wherein the nickel metal framework has a pore structure with a high specific surface area and a nanoscale, and is mutually combined with expanded graphite with a micron pore structure to form a specific modified structure complex; then carrying out thermal expansion treatment to obtain nickel metal organic framework modified expanded graphite; the composite phase-change material is combined with phase-change wax for heat treatment, and due to the fact that the nickel metal organic framework modifies the expanded graphite and the nickel metal organic framework has a mesopore size and a macropore structure, the composite phase-change wax can achieve a good adsorption effect, and the leakage problem of the phase-change wax in the use process of the composite material can be well reduced, so that the leakage amount of phase-change components is small in the multiple use process of the composite phase-change material, and the circulation stability is improved; in addition, the excellent adsorption effect increases the mass fraction of the phase-change wax in the composite phase-change material, so that the composite phase-change material product has higher energy storage density. Finally, ball milling refinement and pressing are carried out, so that the problem that the final composite material is low in density due to the fact that the volume of the expanded graphite is too large is solved to a certain extent, the density of the composite phase-change material is increased, and further the composite phase-change material has larger phase-change latent heat under the same volume in actual use; moreover, the nickel metal organic framework modified expanded graphite is used as an adsorption structure material, has high heat conductivity coefficient, and forms a heat conduction path of the composite material, so that the composite material hasHigh thermal conductivity. Therefore, the material obtained by the invention has high phase change latent heat, excellent heat conductivity and good cycle stability, and can be well used for storing and releasing energy. Moreover, the phase change temperature of the floor is adjustable between 18 ℃ and 48 ℃, and the floor can be used in a phase change heat storage floor. In addition, the raw materials of the invention are cheap and easily available, nontoxic and environment-friendly, the preparation method is simple, and the invention can be used for industrial mass production.
Experimental results show that the material obtained by the invention has the advantages that the heat absorption phase change latent heat is more than 160J/g, the thermal conductivity is more than 5.0W/(m.K), and the leakage rate after 50 times of circulation is less than 0.45%.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, the starting materials used were commercially available ones unless otherwise specified. Wherein the phase-change wax has the phase-change temperature of 37 ℃ and the phase-change latent heat of 210J/g, and is purchased from Shanghai Joule wax industry.
Example 1
S1, placing the expandable graphite raw material in NaOH solution (with the concentration of 1mol/L), soaking for 30min at room temperature, washing with deionized water, and freeze-drying at-45 ℃ to obtain the expanded graphite powder with the particle size of 80 meshes and the carbon content of more than or equal to 99 wt% after impurity removal.
S2, 0.5 (NO) 0.5gNi 3 ) 2 ·6H 2 O and 0.5g of the expandable graphite powder after impurity removal are soaked in 70mL of deionized water, and are magnetically stirred for 1h at 53 ℃, then 0.2g of terephthalic acid is added, and the stirring is continued for 0.5 h. Thereafter, the resulting solution was transferred to an autoclave and reacted at 150 ℃ for 3 hours. Then, washing the sample with deionized water and ethanol in sequence, and finally, freeze-drying at-45 ℃ to obtain the nickel metal organic framework modified expandable graphite powder.
S3, heating the expandable graphite powder modified by the nickel metal organic framework to 900 ℃ at a speed of 3 ℃/min in an argon atmosphere, and preserving heat for 1h to obtain the expandable graphite powder modified by the nickel metal organic framework.
S4, firstly paving a layer of nickel metal organic framework modified expanded graphite powder in a beaker, and then paving a layer of phase-change wax on the surface of the beaker, wherein the mass ratio of the nickel metal organic framework modified expanded graphite powder to the phase-change wax is 15% to 85%, and then heating, mixing and adsorbing for 2h in a water bath environment at 60 ℃ to obtain the composite material.
And S5, placing the composite material in a steel die, and pressing for 5min under the pressure of 30MPa to obtain a round block sample.
Example 2
The procedure of example 1 was repeated, except that in step S4, the mass ratio of the nickel metal organic skeleton-modified expanded graphite powder to the phase-change wax was 20% to 80%.
Example 3
The procedure of example 1 was repeated, except that in step S4, the mass ratio of the nickel metal organic skeleton-modified expanded graphite powder to the phase-change wax was 25% to 75%.
Example 4
Performed as in example 1, except that: in step S2, Ni (NO) is added 3 ) 2 ·6H 2 The dosage of O is 0.8g, the temperature for magnetic stirring and mixing is 50 ℃, and terephthalic acid is replaced by trimesic acid; in step S3, the heat treatment temperature is 800 ℃, and the heat preservation time is 1.5 h; in step S5, the pressing pressure is 25MPa, and the dwell time is 8 min.
Example 5
Performed as in example 1, except that: in step S2, Ni (NO) is added 3 ) 2 ·6H 2 Reducing O to 0.2g, and replacing terephthalic acid with phthalic acid at the temperature of 55 ℃ for magnetic stirring and mixing; in step S3, the heat treatment temperature is 700 ℃, and the heat preservation time is 2 h; in step S5, the pressing pressure is 20MPa, and the dwell time is 10 min.
Example 6
The process was carried out as in example 1, except that in step S5, a ball milling operation was added at a ball milling speed of 350rpm for 4 hours before pressing.
Comparative example 1
The procedure was as in example 3 except that step S2 was not performed, i.e., the nickel metal organic framework modification was not performed.
Comparative example 2
Was conducted as in example 3 except that in step S2, Ni (NO) was added 3 ) 2 ·6H 2 Replacement of O by Cr (NO) 3 ) 3 ·9H 2 O。
Example 7: product testing
The products obtained in the above examples and comparative examples were subjected to performance tests, and the results are shown in Table 1. Wherein, the leakage rate is tested as follows: and (3) placing the sample in a constant-temperature drying oven at 60 ℃ for 20min, taking out the sample, placing the sample at room temperature for 20min, repeating the cycle for 50 times, weighing the mass change of the block sample, and calculating to obtain the leakage rate of the material. Specific leakage rate (m) 1 -m 2 )/m 1 Wherein m is 1 Mass of bulk sample, m, before 50 cycles 2 Is the sample mass after 50 cycles.
Table 1: results of Performance testing of samples
Wherein, DSC curves of the samples obtained in examples 1 to 3 are shown in FIGS. 1 to 3, respectively.
The test results in table 1 show that the materials obtained in examples 1 to 6 of the present invention have an endothermic phase transition temperature of 36.3 ℃ or higher, an endothermic phase transition latent heat of 160J/g or higher, an exothermic phase transition temperature of 36.1 ℃ or higher, an exothermic phase transition latent heat of 161J/g or higher, a thermal conductivity of 5.0W/(m · K) or higher, and a leakage rate after 50 cycles of 0.45% or lower, which proves that the materials obtained in the present invention have a high phase transition latent heat, a high thermal conductivity, and good cycle stability. The cycle stability of the materials obtained in comparative examples 1-2 is obviously poor, and the fact that the performance of the materials can be effectively improved only by carrying out metal organic framework modification and nickel metal organic framework modification is proved.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The preparation method of the phase change energy storage material is characterized by comprising the following steps of:
a) mixing Ni (NO) 3 ) 2 ·6H 2 Mixing O, expandable graphite powder, water and a chelating agent, and then heating for reaction to form nickel metal organic framework modified expandable graphite powder;
b) carrying out thermal expansion treatment on the nickel metal organic framework modified expandable graphite powder in a protective atmosphere to obtain nickel metal organic framework modified expandable graphite powder;
c) alternately laminating and paving the nickel metal organic framework modified expanded graphite powder and the phase-change wax, and then carrying out heat treatment to obtain a composite material;
d) and pressing the composite material to obtain the phase-change wax/nickel metal organic framework modified expanded graphite composite phase-change material.
2. The method according to claim 1, wherein the chelating agent is at least one selected from the group consisting of terephthalic acid, trimesic acid and phthalic acid in the step a).
3. The method of claim 1, wherein in step a):
the Ni (NO) 3 ) 2 ·6H 2 The mass ratio of the O to the expandable graphite powder is (0.2-0.8) to 0.5;
the mixing temperature is 50-55 ℃;
ni (NO) as chelating agent 3 ) 2 ·6H 2 The mass ratio of O is 0.2 to (0.2-0.8);
the temperature of the temperature-raising reaction is 150 ℃.
4. The preparation method according to claim 1, wherein in the step b), the temperature of the thermal expansion treatment is 700-900 ℃, and the holding time is 1-2 h.
5. The method of claim 1, wherein in step c):
the mass ratio of the nickel metal organic framework modified expanded graphite powder to the total amount of the phase-change wax is 5-20%;
the temperature of the heat treatment is 60-70 ℃, and the time is 1-2 hours.
6. The method according to claim 1, wherein in the step d), the conditions of the press treatment are: the pressure is 20-30 MPa, and the pressure maintaining time is 5-10 min.
7. The preparation method according to claim 1, characterized in that in the step a), the particle size of the expandable graphite powder is 80-100 meshes, and the carbon content is more than or equal to 99 wt%;
in the step c), the phase change temperature of the phase change wax is 20-45 ℃, and the phase change latent heat is more than 200J/g.
8. The preparation method according to claim 1, wherein in the step a), the expandable graphite powder is impurity-removed expandable graphite powder;
the impurity-removed expandable graphite powder is prepared by the following method:
soaking the expandable graphite powder raw material in a strong alkaline solution, washing with water, and freeze-drying to obtain the impurity-removed expandable graphite powder;
in the step a), after the temperature-raising reaction, the method further includes: washing and drying;
the step d) further comprises, before and after the pressing treatment: and carrying out ball milling on the composite material.
9. The production method according to claim 8, wherein the strongly alkaline solution is a NaOH solution and/or a KOH solution;
the temperature of the freeze drying is-45 ℃ to-40 ℃;
the rotation speed of the ball milling is 300-350 rpm, and the time is 3-5 h.
10. The phase change energy storage material prepared by the preparation method of any one of claims 1-9.
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