CN114395374A - High-performance carbon/carbonate heat transfer and storage medium, phase-change heat storage composite material and preparation method thereof - Google Patents
High-performance carbon/carbonate heat transfer and storage medium, phase-change heat storage composite material and preparation method thereof Download PDFInfo
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 121
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000003860 storage Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000005338 heat storage Methods 0.000 title claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 33
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 46
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000012530 fluid Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000010248 power generation Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention provides a high-performance carbon/carbonate heat transfer and storage medium and a preparation method thereof. The preparation method comprises the step of adding a carbon material with high dispersibility into a carbonate system, wherein the carbon material with high dispersibility is prepared from CO2Electrochemical conversion is carried out to obtain; the carbon material is dispersed into the molten carbonate system to form a uniform heat transfer and storage medium. The invention also provides a carbon/carbonate phase-change heat storage composite material and a preparation method thereof. The preparation method comprises the steps of taking mixed carbonate of lithium carbonate, sodium carbonate and potassium carbonate as a molten salt system, adding a carbon material with high wettability with the molten carbonate, wherein the carbon material is prepared from CO2Electrochemical conversion is carried out to obtain; the carbon material is added into a molten carbonate system to be compounded to form the phase-change heat storage composite material. The prepared heat transfer and storage medium material is uniform, has ultrahigh specific heat capacity and thermal conductivity, and is suitable for being used as a heat transfer and storage fluid for solar photo-thermal power generation. The prepared phase-change heat storage composite material is uniform, and has high heat conductivity and cycle stability.
Description
Technical Field
The invention belongs to the technical field of heat energy storage and transfer, particularly relates to a heat transfer and storage composite medium, and particularly relates to a high-performance carbon/carbonate heat transfer and storage medium, a phase-change heat storage composite material and a preparation method thereof.
Background
In a solar photo-thermal power station, the energy conversion efficiency of a heat engine reaches 50%, and the stable working upper limit temperature of a heat transfer and storage medium of the heat engine needs to reach above 850 ℃. Molten carbonates with high upper operating temperature, low corrosion, low saturated steam pressure and low cost are ideal molten salt systems meeting this series of requirements.
However, molten carbonate has low thermal conductivity and specific heat capacity, limiting its energy efficiency in the endothermic-exothermic cycle. Chinese patent application No. 201310731910.2 discloses a method for adding a certain proportion of nano particles (SiO) to molten carbonate2、ZnO、Al2O3、TiO2MgO and CaO) can effectively improve the heat conductivity and specific heat capacity of the molten salt. Carbon materials have higher specific surface area and thermal conductivity than the above nanoparticles, and theoretically doped carbon materials have more advantages in enhancing the thermal conductivity and specific heat capacity of molten carbonate. However, the conventional nanocarbon materials are not uniformly dispersed in the molten carbonate, and the carbon nanotubes and graphite powder are significantly phase-separated after being added to the molten carbonate.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a high performance carbon/carbonate heat transfer and storage medium and a preparation method thereof.
The technical scheme provided by the invention is as follows.
The invention provides a preparation method of a high-performance carbon/carbonate heat transfer and storage medium, which comprises the following steps:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, and heating and melting;
(3) and (3) introducing inert gas into the molten carbonate for protection, adding the molten cathode salt-carbon mixture obtained in the step (2), and continuously introducing the inert gas until a uniform carbon/carbonate heat transfer and storage medium is formed.
The second aspect of the invention provides a preparation method of a carbon/carbonate phase-change heat storage composite material, which comprises the following steps:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, washing and drying;
(3) adding the cathode salt-carbon mixture powder into molten carbonate, performing ball milling, and tabletting;
(4) and sintering the sheet product in an inert atmosphere to obtain the carbon/carbonate phase-change heat storage composite material.
The preparation method of the two materials comprises the following steps:
specifically, the molten carbonate is a mixed molten salt of lithium carbonate, sodium carbonate and potassium carbonate.
More specifically, in the preparation method of the high-performance carbon/carbonate heat transfer and storage medium, the prepared carbon/carbonate heat transfer and storage medium comprises the following components in percentage by mass: 5-40 wt.% lithium carbonate; 10-50 wt.% sodium carbonate; 10-50 wt.% potassium carbonate; 0.01-0.15 wt.% of a carbon material.
More specifically, in the preparation method of the carbon/carbonate phase-change heat storage composite material, the mass fractions of the components in the prepared carbon/carbonate phase-change heat storage composite material are as follows: 5-40 wt.% lithium carbonate; 10-50 wt.% sodium carbonate; 10-50 wt.% potassium carbonate; 5-20 wt.% of carbon material.
Specifically, the flow rate of the carbon dioxide explosion is 20-200 mL/min-1。
Specifically, the aeration head for aeration is a high-temperature resistant aeration head, and the materials comprise nickel, titanium, stainless steel and the like. The aperture of the aeration head is 20-200 μm.
Specifically, the electrolysis temperature in the step (1) is 450-750 ℃.
Specifically, the electrolysis mode in the step (1) is constant cell pressure electrolysis or constant current electrolysis.
More specifically, the steps(1) If constant-cell-pressure electrolysis is adopted, the voltage range is 1.2-5.5V; if constant current electrolysis is adopted, the current density range is 5-500 mA-cm-2。
Specifically, in the step (1), the cathode is platinized titanium, graphite flake, tin dioxide or stainless steel; the cathode is a nickel sheet, a stainless steel sheet or a copper sheet.
Specifically, the inert gas is nitrogen or argon, and the like. Preferably, the aeration flow rate is 50 to 500 mL/min-1。
Specifically, in the preparation method of the carbon/carbonate phase-change heat storage composite material, the temperature range of the mixing system in the step (3) is 450-850 ℃, and the reaction time is 60-120 min.
A third aspect of the invention provides a carbon/carbonate heat transfer and storage medium prepared by the method of the first aspect.
In a fourth aspect, the invention provides a carbon/carbonate phase-change heat storage composite material prepared by the method of the second aspect.
The invention has the following beneficial effects:
(1) according to the invention, the carbon dioxide is captured by adopting the molten salt and combining electrolysis, so that the uniformity of the carbon material in the molten salt is improved;
(2) the prepared carbon/carbonate heat transfer and storage medium, molten salt CO2The carbon/molten carbonate solid-liquid interface has good wettability due to the characteristics that the surface of the carbon material for trapping and electrochemical conversion has a large amount of oxygen-containing functional groups and is 'native' to molten carbonate, so that the carbon material is uniformly dispersed in the molten carbonate. The prepared carbon/carbonate composite fluid has ultrahigh specific heat capacity and thermal conductivity, and is very suitable for being used as a heat transfer and storage fluid for solar photo-thermal power generation.
(3) When a large amount of oxygen-containing functional groups exist on the surface of the carbon material, the carbon/molten carbonate can quickly reach a complete wetting state, and the phase separation degree is reduced. Fused salt CO2The carbon/molten carbonate solid-liquid interface has good wettability because the surface of the carbon material for trapping and electrochemical conversion contains a large amount of oxygen-containing functional groups, so that the carbon material is in molten carbonic acidThe salt can be used as a carbon skeleton to absorb molten carbonate and enhance the thermal conductivity of the molten salt. The prepared carbon/carbonate phase-change heat storage composite material has high heat conductivity and circulation stability, and is very suitable for industrial waste heat recovery and heat energy storage in solar photo-thermal power stations.
(4) The preparation method has the advantages of simple process, easily obtained raw materials and great industrial application potential.
Drawings
FIG. 1 is a flow chart of the preparation process of the carbon/carbonate heat transfer and storage medium;
FIG. 2 is a DSC curve of carbon/carbonate heat transfer and storage media prepared by different formulations; in the figure: MTC represents ternary carbonate, 0.05% EC-450-50-MTC represents 0.05% by mass added at 450 deg.C with current density of 50mA cm-2Heat transfer and storage fluid prepared from carbon material prepared by electrolysis.
FIG. 3 is a flow chart of a process for preparing a carbon/carbonate phase change heat storage composite;
FIG. 4 is a DSC curve of carbon/carbonate heat transfer and storage media prepared by different formulations, wherein (a) different proportions of carbon material are added (b) different types of carbon material are added; in the figure, MTC represents ternary carbonate, 5% EC-550-50-MTC represents 5% by mass of ternary carbonate added at 550 ℃ in a concentration of 50mA cm -210% of EC-P-450-50-MTC represents the phase-change heat storage composite material prepared by adding the electrolytic carbon material prepared by electrolysis of a pilot plant at 450 ℃ and 50mA cm & lt-2 & gt in a mass fraction of 10%.
Detailed Description
In order to more clearly illustrate the high heat transfer and storage performance of the carbon/carbonate heat transfer and storage medium, the following examples are further provided for illustrative purposes only and should not be construed as limiting the present invention.
Molten salt CO in all examples2The molten salt electrolyte in the process of preparing carbon by electrochemical conversion is Li2CO3-Na2CO3-K2CO3Minimum eutectic point mixing ofFused salt, the mass percentage of each component is Li2CO3(32.1wt.％)；Na2CO3(33.4wt.％)；K2CO3(34.5 wt.%); the molten salt system of the carbon/carbonate heat transfer and storage medium is Li2CO3-Na2CO3-K2CO3The lowest eutectic point mixed molten salt. The anode used in the electrolysis process is a platinum-plated titanium anode, and the cathode is a nickel sheet. Determination of the lowest eutectic ratio of Li2CO3-Na2CO3-K2CO3The specific heat capacity of the ternary carbonate at 450 ℃, 475 ℃ and 500 ℃ is 1.76 J.g respectively-1·K-1、1.65J·g-1·K-1And 1.60 J.g-1·K-1Average of 1.67J · g-1·K-1(ii) a The thermal conductivity is 0.51 W.m-1·K-1、0.63W·m-1·K-1And 0.68 W.m-1·K-1Average value of 0.61 W.m-1·K-1。
Example 1
The preparation method of the carbon/carbonate heat transfer and storage medium comprises the following steps:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, and heating and melting;
(3) and (3) introducing inert gas into the molten carbonate for protection, adding the molten cathode salt-carbon mixture obtained in the step (2), and continuously introducing the inert gas until a uniform carbon/carbonate heat transfer and storage medium is formed.
This example was carried out at 450 ℃ at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 2.25%. Accurately weighing 2.22g of cathode salt-carbon mixed product prepared under the condition at 100 mL/min-1Uniformly dispersing the mixture in 97.78g of molten ternary carbonate under Ar flow, and continuously uniformly mixing for 60min to obtain a uniformly dispersed carbon/carbonate heat transfer and storage medium with the mass of the carbon material of 0.05%.
Specific heat capacity and thermal conductivity testing:
the specific heat capacity of the product of this example was measured to be 3.36 J.g at 450 deg.C, 475 deg.C and 500 deg.C, respectively-1·K-1、3.14J·g-1·K-1And 3.00 J.g-1·K-1Average value of 3.17J · g-1·K-1An increase of 89.82% compared to pure molten carbonate; the thermal conductivity is 1.38 W.m-1·K-1、1.55W·m-1·K-1And 2.20 W.m-1·K-1Average value of 1.71 W.m-1·K-1An increase of 180.33% compared to pure molten carbonate.
Example 2
The carbon/carbonate heat transfer and storage medium is prepared by the same method as the example 1, and the method comprises the following specific steps:
at 450 deg.C, at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 2.25%. Accurately weighing 4.44g of cathode salt-carbon mixed product prepared under the condition at 100 mL/min-1Uniformly dispersing the mixture in 95.56g of molten ternary carbonate under Ar flow, and continuously uniformly mixing for 60min to obtain the uniformly dispersed carbon/carbonate heat transfer and storage medium with the mass fraction of the carbon material of 0.10%.
Specific heat capacity and conductivity test:
the specific heat capacity of the product of this example was measured to be 2.36 J.g at 450 deg.C, 475 deg.C and 500 deg.C, respectively-1·K-1、2.20J·g-1·K-1And 2.01 J.g-1·K-1Average value of 2.19J · g-1·K-1An increase of 31.14% compared to pure molten carbonate; the thermal conductivity is 1.00 W.m-1·K-1、0.97W·m-1·K-1And 1.01 W.m-1·K-1Average value of 0.99 W.m-1·K-1An increase of 62.30% compared to pure molten carbonate.
Example 3
The carbon/carbonate heat transfer and storage medium is prepared by the same method as the example 1, and the method comprises the following specific steps:
at 450 ℃ to50mA·cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 2.25%. The cathode salt-carbon mixture (6.67 g) prepared under the above conditions was weighed accurately at 100 mL. min-1Uniformly dispersing in 93.33g of molten ternary carbonate under Ar flow, and continuously uniformly mixing for 60min to obtain the uniformly dispersed carbon/carbonate heat transfer and storage medium with the mass fraction of the carbon material of 0.15%.
Specific heat capacity and conductivity test:
the specific heat capacity of the product of this example was measured to be 2.25 J.g at 450 deg.C, 475 deg.C and 500 deg.C, respectively-1·K-1、2.12J·g-1·K-1And 2.08 J.g-1·K-1Average value of 2.15J · g-1·K-1An increase of 28.74% compared to pure molten carbonate; the thermal conductivity is respectively 0.72 W.m-1·K-1、0.77W·m-1·K-1And 0.77 W.m-1·K-1Average value of 0.75 W.m-1·K-1An increase of 22.95% compared to pure molten carbonate.
Example 4
The carbon/carbonate heat transfer and storage medium is prepared by the same method as the example 1, and the method comprises the following specific steps:
at 550 ℃, at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 3.50%. Accurately weighing 1.42g of cathode salt-carbon mixed product prepared under the condition at 100 mL/min-1Uniformly dispersing the mixture in 98.58g of molten ternary carbonate under Ar flow, and continuously uniformly mixing for 60min to obtain the uniformly dispersed carbon/carbonate heat transfer and storage medium with the mass fraction of the carbon material of 0.05%.
Specific heat capacity and conductivity test:
the specific heat capacity of the product of this example was measured to be 2.79 J.g at 450 deg.C, 475 deg.C and 500 deg.C, respectively-1·K-1、2.50J·g-1·K-1And 2.30 J.g-1·K-1Average value of 2.53J · g-1·K-151.50% increase compared to pure molten carbonate; the thermal conductivity is 1.07 W.m-1·K-1、1.08W·m-1·K-1And 1.00 W.m-1·K-1Average value of 1.05 W.m-1·K-1An increase of 73.13% compared to pure molten carbonate.
Example 5
The carbon/carbonate heat transfer and storage medium is prepared by the same method as the example 1, and the method comprises the following specific steps:
at 650 ℃ at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 7.00%. Accurately weighing 0.72g of cathode salt-carbon mixed product prepared under the condition at 100 mL/min-1Uniformly dispersing the mixture in 99.28g of molten ternary carbonate under Ar flow, and continuously uniformly mixing for 60min to obtain the uniformly dispersed carbon/carbonate heat transfer and storage medium with the mass fraction of the carbon material of 0.05%.
Specific heat capacity and conductivity test:
the specific heat capacity of the product of this example was measured to be 1.81 J.g at 450 deg.C, 475 deg.C and 500 deg.C, respectively-1·K-1、1.72J·g-1·K-1And 1.70 J.g-1·K-1Average value of 1.74J · g-1·K-1An increase of 4.19% compared to pure molten carbonate; the thermal conductivity is 0.76 W.m-1·K-1、0.80W·m-1·K-1And 0.85 W.m-1·K-1Average value of 0.80 W.m-1·K-1An increase of 31.15% compared to pure molten carbonate.
Example 6
The preparation method of the carbon/carbonate phase-change heat storage composite material comprises the following steps:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, washing and drying;
(3) adding the cathode salt-carbon mixture powder into molten carbonate, performing ball milling, and tabletting;
(4) and sintering the sheet product in an inert atmosphere to obtain the carbon/carbonate phase-change heat storage composite material.
This example was carried out at 550 ℃ at 50mA · cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 3.50%. Accurately weighing 1.50g of electrolytic carbon material prepared under the condition and 28.50g of ternary carbonate, placing the electrolytic carbon material and the ternary carbonate in a ball milling tank at the rotating speed of 200 r-min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over the test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 5.00 percent, measuring the melting point of the composite material to be 396.54 ℃ and the phase-change heat to be-251.59J g-1·K-1. Thermal conductivity at 450 ℃ of 1.21 W.m-1·K-1Compared with pure ternary carbonate, the yield is improved by 137.3 percent.
Example 7
The method for preparing the carbon/carbonate phase-change heat storage composite material is the same as the embodiment 6, and comprises the following specific steps:
at 550 ℃, at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 3.50%. 3.00g of the electrolytic carbon material prepared under the condition and 27.00g of ternary carbonate are accurately weighed and placed in a ball milling tank at the rotating speed of 200 r.min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over the test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 10.00 percent, measuring the melting point of the composite material to be 396.20 ℃ and the phase-change heat to be-205.52 J.g-1·K-1. Thermal conductivity at 450 ℃ of 1.32 W.m-1·K-1Compared with pure ternary carbonate, the yield is improved by 158.8 percent.
Example 8
The method for preparing the carbon/carbonate phase-change heat storage composite material is the same as the embodiment 6, and comprises the following specific steps:
at 550 ℃, at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 3.50%. Accurately weighing 4.50g of electrolytic carbon material prepared under the condition and 25.50g of ternary carbonate, placing the electrolytic carbon material and the ternary carbonate in a ball milling tank at the rotating speed of 200 r-min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over the test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 15.00 percent, measuring the melting point of the composite material to be 395.48 ℃ and the phase-change heat to be-185.20J g-1·K-1. Thermal conductivity at 450 deg.C of 1.45 W.m-1·K-1Compared with pure ternary carbonate, the yield is improved by 184.3 percent.
Example 9
The method for preparing the carbon/carbonate phase-change heat storage composite material is the same as the embodiment 6, and comprises the following specific steps:
at 550 ℃, at 50mA cm-2The mass fraction of the electrolytic carbon material in the cathode salt-carbon mixture prepared by electrolysis was 3.50%. Accurately weighing 1.50g of electrolytic carbon material prepared under the condition and 28.5g of ternary carbonate, placing the electrolytic carbon material and the ternary carbonate in a ball milling tank at the rotating speed of 200 r-min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over a test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 20.00 percent, measuring the melting point of the composite material to be 395.18 ℃ and the phase-change heat to be-159.67J g-1·K-1. Thermal conductivity at 450 deg.C of 1.45 W.m-1·K-1Compared with pure ternary carbonate, the yield is improved by 184.3 percent.
Example 10
The method for preparing the carbon/carbonate phase-change heat storage composite material is the same as the embodiment 6, and comprises the following specific steps:
at 450 deg.C, at 50mA cm-2And electrolyzing to prepare a cathode salt-carbon mixture, wherein the mass fraction of the electrolytic carbon material is 2.25%. Accurate and accurate3.00g of the electrolytic carbon material prepared under the conditions and 27.00g of ternary carbonate were weighed in a ball mill jar at a rotation speed of 200 r.min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over the test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 10.00 percent, measuring the melting point of the composite material to be 395.62 ℃ and the phase-change heat to be-215.15 J.g-1·K-1. Thermal conductivity at 450 ℃ of 1.23 W.m-1·K-1Compared with pure ternary carbonate, the content of the carbonate is improved by 141.2 percent.
Example 11
The method for preparing the carbon/carbonate phase-change heat storage composite material is the same as the embodiment 6, and comprises the following specific steps:
at 650 ℃ at 50mA cm-2Electrolyzing to prepare cathode salt-carbon mixture, wherein the electrolytic carbon material accounts for 7.00 wt%, accurately weighing 3.00g of the electrolytic carbon material prepared under the condition and 27.00g of ternary carbonate, placing the electrolytic carbon material and the ternary carbonate in a ball milling tank, and rotating at 200 r.min-1Ball-milling for 120min, taking out and accurately weighing 6.00g of mixture, placing the mixture on a tablet press, pressing the mixture into a wafer at 35.0MPa, placing the wafer in an electric furnace under Ar atmosphere, sintering for 90min at 450 ℃, slowly cooling to room temperature, turning over the test piece, repeating the sintering process for 4 times to prepare the uniformly dispersed carbon/carbonate phase-change heat storage composite material with the mass fraction of 10.00 percent, measuring the melting point of the composite material to be 395.90 ℃ and the phase-change heat to be-250.18 J.g-1·K-1. Thermal conductivity at 450 ℃ of 1.25 W.m-1·K-1Compared with pure ternary carbonate, the yield is improved by 145.1 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the carbon/carbonate heat transfer and storage medium is characterized by comprising the following steps of:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, and heating and melting;
(3) and (3) introducing inert gas into the molten carbonate for protection, adding the molten cathode salt-carbon mixture obtained in the step (2), and continuously introducing the inert gas until a uniform carbon/carbonate heat transfer and storage medium is formed.
2. The preparation method of the carbon/carbonate phase-change heat storage composite material is characterized by comprising the following steps of:
(1) preparation of molten salt electrochemical preparation of cathode salt-carbon mixture: aerating carbon dioxide into molten carbonate electrolyte, inserting a cathode and an anode simultaneously, and electrifying and electrolyzing to obtain a cathode salt-carbon mixture;
(2) crushing the cathode salt-carbon mixture into powder, washing and drying;
(3) adding the cathode salt-carbon mixture powder into molten carbonate, performing ball milling, and tabletting;
(4) and sintering the sheet product in an inert atmosphere to obtain the carbon/carbonate phase-change heat storage composite material.
3. The method according to claim 1 or 2, characterized in that: the molten carbonate is mixed molten salt of lithium carbonate, sodium carbonate and potassium carbonate.
4. The method according to claim 1 or 2, characterized in that: the electrolysis temperature in the step (1) is 450-750 ℃.
5. The method according to claim 1 or 2, characterized in that: the electrolysis mode in the step (1) is constant cell pressure electrolysis or constant current electrolysis.
6. The method of claim 5, wherein: in the step (1), if constant-cell-pressure electrolysis is adopted, the voltage range is 1.2-5.5V; if constant current electrolysis is adopted, the current density range is 5-500 mA-cm-2。
7. The method according to claim 1 or 2, characterized in that: in the step (1), the cathode is platinized titanium, graphite flake, stannic oxide or stainless steel; the cathode is a nickel sheet, a stainless steel sheet or a copper sheet.
8. The method of claim 2, wherein: the temperature range of the mixing system in the step (3) is 450-850 ℃.
9. A carbon/carbonate heat transfer and storage medium is characterized in that: prepared by the method of claim 1.
10. A carbon/carbonate phase-change heat storage composite material is characterized in that: prepared by the process of claim 2.
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