CN116855234A - Solar full-spectrum photo-thermal conversion heat storage material with high thermal conductivity and preparation method thereof - Google Patents
Solar full-spectrum photo-thermal conversion heat storage material with high thermal conductivity and preparation method thereof Download PDFInfo
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- CN116855234A CN116855234A CN202310823427.0A CN202310823427A CN116855234A CN 116855234 A CN116855234 A CN 116855234A CN 202310823427 A CN202310823427 A CN 202310823427A CN 116855234 A CN116855234 A CN 116855234A
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- 238000005338 heat storage Methods 0.000 title claims abstract description 101
- 239000011232 storage material Substances 0.000 title claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 238000001228 spectrum Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 64
- 239000000126 substance Substances 0.000 claims abstract description 32
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 230000003595 spectral effect Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000012546 transfer Methods 0.000 claims abstract description 12
- 230000002708 enhancing effect Effects 0.000 claims abstract description 8
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 67
- 239000002002 slurry Substances 0.000 claims description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 18
- 229910052791 calcium Inorganic materials 0.000 description 18
- 239000011575 calcium Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003349 gelling agent Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000000655 anti-hydrolysis Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Abstract
The invention discloses a solar full-spectrum photo-thermal conversion heat storage material with high thermal conductivity and a preparation method thereof, wherein the composite heat storage material contains a thermochemical heat storage substance, a porous ceramic skeleton and a spectrum absorption enhancement substance, and the preparation method comprises the following steps: (1) Preparing a precursor solution, wherein a solute consists of a solute a and a solute b, the solute a is a substance capable of generating thermochemical heat storage, and the solute b is a substance capable of enhancing spectral absorption; (2) preparing a high thermal conductivity ceramic skeleton; (3) Loading a precursor material on the porous ceramic skeleton by adopting a vacuum impregnation method; (4) The resulting material was calcined, carbonated and then annealed to room temperature. Compared with pure heat storage materials, the thermal conductivity of the composite heat storage material is greatly improved, full spectrum photo-thermal conversion within the range of 300nm-2500nm of solar wave bands can be realized, heat and mass transfer channels are increased through pore formation, and the composite heat storage material is combined with thermochemical heat storage, so that a heat collection and heat storage system is optimized.
Description
Technical Field
The invention relates to a heat storage material and a preparation method thereof, in particular to a solar full-spectrum photo-thermal conversion heat storage material with high heat conductivity and a preparation method thereof.
Background
Solar energy is clean, abundant, inexhaustible and considered as a promising energy source for replacing the traditional fossil energy source. However, it is difficult to provide continuous and stable energy output due to limitations such as intermittent and fluctuating solar energy. The energy storage technology can store solar radiation energy first and release the solar radiation energy when needed, solves the problem of mismatching of energy supply and demand in time, space and intensity, and improves the energy utilization efficiency of the system to the maximum extent. Therefore, efficient storage of solar energy is a trend in the future. The thermochemical heat storage technology has the advantages of high energy storage density, long energy storage time, high energy storage speed, suitability for large-scale energy storage systems and the like, and becomes the most promising heat storage technology at present. However, the existing thermochemical heat storage materials have the problems of low heat conductivity, low spectral absorptivity, serious attenuation of circulating heat storage and the like, and severely restrict the development of heat storage technology. From the perspective of improving heat storage rate, spectral absorptivity and circulation stability, development of a thermochemical heat storage material combining high heat conductivity, high spectral absorptivity and high circulation stability is needed.
Disclosure of Invention
The invention aims to: the invention aims to provide a solar full-spectrum photo-thermal conversion heat storage composite material with high heat conductivity, which has the function of combining high heat conductivity, high spectrum absorptivity and high cycle stability, and can realize the application of cross-quantity-level high heat conductivity in a thermo-chemical heat storage technology for the first time, and can perform rapid photo-thermal conversion and heat storage; the invention also aims to provide a preparation method of the composite heat storage material.
The technical scheme is as follows: the invention relates to a solar full-spectrum photo-thermal conversion heat storage material with high thermal conductivity, which comprises a thermochemical heat storage substance, a porous ceramic skeleton and a spectrum absorption enhancement substance. The thermochemical heat storage material converts high-temperature heat energy into chemical energy by utilizing reversible chemical reaction, stores the chemical energy in a chemical bond of the heat storage material, converts the chemical energy into heat energy by reverse thermochemical reaction when the thermochemical heat storage material is needed to be used, and releases the heat energy; the porous ceramic skeleton has a porous structure, is used as a heat transfer channel, can alleviate the problem of high-temperature sintering of the traditional heat storage material, and the heat conduction theoretical model of the coupling of the skeleton and the thermochemical heat storage material is close to the Maxwell model in state. The coupling morphology created by the material enables scattering between phonons to be inhibited, reduces heat transfer obstruction, and can enhance the heat conductivity of the composite material; the spectrum absorption enhancement substance has high spectrum absorption characteristic, and can enhance the solar full spectrum absorption rate of the heat storage composite material; furthermore, under the synergistic effect of the high-heat conductivity ceramic skeleton and the spectrum absorption enhancement substance, an additional driving force can be provided in the chemical reaction, so that the chemical reaction rate is increased, and the method is an effective way for improving the thermochemical heat storage/release of the composite material.
Preferably, the thermochemical heat storage substance has a thermochemical heat storage function, and can be calcium carbonate and calcium oxide, or magnesium carbonate and magnesium oxide and other materials.
Preferably, the porous ceramic skeleton can be aluminum nitride, silicon carbide and other substances, and the porosity of the skeleton is 50-80%.
Preferably, the spectrum absorption enhancing substance has the function of full spectrum solar energy high-efficiency photo-thermal conversion, and can be manganese oxide, chromium oxide and other metal oxides or a mixture of a plurality of metal oxides.
Preferably, the thermochemical heat storage material, the high thermal conductivity ceramic skeleton and the absorption enhancement material in the composite heat storage material are in direct contact to synthesize the composite heat storage material with a porous foam structure, and the composite heat storage material has the function of optimizing heat and mass transfer so as to solve the efficiency problem caused by low thermal conductivity of the traditional heat storage material.
Preferably, the preparation method of the porous ceramic skeleton comprises the following steps:
(1) Performing hydrolysis resistance treatment on aluminum nitride or silicon carbide powder;
(2) Mixing the treated aluminum nitride or silicon carbide powder, a solvent, ib-104 as a gelling agent and a dispersing agent;
(3) Adding a foaming agent, and mechanically stirring to form a slurry into a required porous structure;
(4) Drying the slurry to obtain a porous aluminum nitride or silicon carbide blank, and calcining to remove all residual reagents and impurities;
(5) Calcining the burned aluminum nitride or silicon carbide blank, and annealing to obtain the sintered aluminum nitride or silicon carbide framework.
The preparation method of the high-thermal conductivity solar full-spectrum photo-thermal conversion heat storage material comprises the following steps: (1) Preparing a precursor solution, wherein a solvent is deionized water, and a solute consists of a solute a and a solute b, wherein the solute a in the solution is a substance capable of generating thermochemical heat storage after the preparation step is finished, and the solute b in the solution is a substance capable of enhancing spectral absorption after the preparation step is finished; (2) Preparing a porous ceramic skeleton, wherein the porosity of the skeleton is 50-80%; (3) Loading a precursor material on the porous ceramic skeleton by adopting a vacuum impregnation method; (4) The resulting material was calcined, carbonated and then annealed to room temperature.
Preferably, solute a may be calcium nitrate, calcium hydroxide or magnesium nitrate during the preparation process; solute b may be ferric nitrate, chromium nitrate, manganese nitrate or cobalt nitrate. Wherein the mole fraction of solute b is 1% -20% of solute a.
Preferably, steps (3) and (4) can be repeated multiple times to increase the loading of the thermochemical heat storage substance and the spectral absorption enhancing substance.
Preferably, the calcination temperature of the material in the step (4) is 700-900 ℃, the calcination time is 10-40min, the carbonization temperature is 600-800 ℃ and the carbonization time is 10-40min.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: compared with the heat conductivity of a pure heat storage substance, the heat conductivity of the composite heat storage material is greatly improved, and the highest heat conductivity can reach 22.98W.m -1 K -1 The solar thermal energy heat collector can realize full spectrum photo-thermal conversion with the wavelength of solar light within the range of 300nm-2500nm, the formation of pores increases heat and mass transfer channels, the heat and mass transfer channels are combined with thermochemical heat storage, and meanwhile, under the synergistic effect of a high-thermal conductivity ceramic skeleton and a spectrum absorption enhancing substance, an extra driving force is provided in chemical reaction, so that the chemical reaction rate is increased, the thermochemical heat storage/release capability of the composite material is improved, and a heat collection and heat storage system is optimized.
Drawings
FIG. 1 is a flow chart of a method of preparing a composite heat storage material according to an embodiment of the present invention;
FIG. 2 is a schematic view of the thermal conductivity of a composite thermal storage material according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of the spectral absorptivity of a composite heat storage material according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of average spectral absorptivity of a composite heat storage material according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of the conversion rate of a composite heat storage material according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of the conversion rate versus time derivative of a composite thermal storage material according to an embodiment of the present invention;
fig. 7 is a microscopic SEM morphology of the composite thermal storage material of an embodiment of the invention.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
Example 1
(1) Preparing a precursor solution: 11.8076g of calcium nitrate tetrahydrate, 0.8003g of chromium nitrate nonahydrate and 1.4317g of manganese nitrate solution are weighed under the room temperature condition, placed in a clean beaker, deionized water is added to obtain 10mL of solution, and the mixed solution is dispersed and stirred for 60min in a magnetic stirring mode, and the stirring speed is 500rpm, so as to obtain a precursor solution;
(2) 35g of aluminum nitride powder, 1g of yttrium oxide and 30ml of absolute ethanol were weighed at room temperature, placed in a ball mill pot, placed in a ball mill and stirred at a speed of 300rpm for 30 minutes, to obtain a slurry. 0.3wt% of ethanol dispersant polyacrylic acid was added to the slurry, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes, and 1wt% of polycyanate was added, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes. The slurry in the ball mill pot was then removed to a beaker, tetraethylenepentamine of the same mass as the polycyanate was added, and the reaction was accelerated by stirring with mechanical stirring at a rate of 500rpm for 1 hour, forming a water-repellent film on the surface of the aluminum nitride powder. Then, the treated powder was put into an oven at 100 ℃ to be dried, and the temperature was kept constant for 24 hours to obtain an aluminum nitride powder having an anti-hydrolysis effect, and a predetermined amount of the treated aluminum nitride powder, deionized water, 0.35wt% of Ib-104 serving as a gelling agent and a dispersing agent were mixed, and then placed into a ball mill to be stirred at a speed of 300rpm for 30 minutes to obtain a slurry. After the slurry was removed, 1wt% of the foaming agent lauryl sulfate triethanolamine was added and stirred at a mechanical stirring rate of 1000rpm for 30 minutes so that air was sufficiently introduced into the slurry to form a desired porous structure. The foamed slurry was then poured into a removable mold and dried naturally at room temperature for 50 hours. And then placing the dried porous aluminum nitride blank into a muffle furnace, heating to 600 ℃ in air at a heating rate of 1 ℃/min, and keeping the temperature for 200min to remove all residual reagents and impurities to obtain the aluminum nitride blank. And finally, placing the burned aluminum nitride blank body into a hot pressing furnace, keeping the temperature at 2000 ℃ for 200min, and annealing to obtain the sintered aluminum nitride skeleton. Cutting the sintered aluminum nitride skeleton into a circular sheet with the diameter of 12.7mm and the thickness of 3mm by using a sampler and a wire cutting machine;
(3) Vacuum dipping an aluminum nitride framework with the diameter of 12.7mm, the thickness of 3mm and the porosity of 65% into a precursor solution by adopting a vacuum dipping method, and vacuum dipping for 5min;
(4) Calcining the aluminum nitride skeleton after vacuum impregnation in a tube furnace, heating to 800 ℃ from 20 ℃ at a speed of 10 ℃/min by a temperature control program, keeping the constant temperature for 40min, cooling to 700 ℃ at a speed of 10 ℃/min by the temperature control program, introducing carbon dioxide, carbonating for 30min in a carbon dioxide atmosphere, and annealing to room temperature. Repeating the steps (3) - (4) for 6 times to prepare the composite heat storage material A1.
Example 2
(1) Preparing a precursor solution: 11.8076g of calcium nitrate tetrahydrate, 0.4002g of chromium nitrate nonahydrate and 2.1475g of manganese nitrate solution are weighed under the room temperature condition, placed in a clean beaker, deionized water is added to obtain 10mL of solution, and the mixed solution is dispersed and stirred for 60min in a magnetic stirring mode, and the stirring speed is 500rpm, so as to obtain a precursor solution;
(2) 35g of aluminum nitride powder, 1g of yttrium oxide and 30ml of absolute ethanol were weighed at room temperature, placed in a ball mill pot, placed in a ball mill and stirred at a speed of 300rpm for 30 minutes, to obtain a slurry. 0.3wt% of ethanol dispersant polyacrylic acid was added to the slurry, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes, and 1wt% of polycyanate was added, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes. The slurry in the ball mill pot was then removed to a beaker, tetraethylenepentamine of the same mass as the polycyanate was added, and the reaction was accelerated by stirring with mechanical stirring at a rate of 500rpm for 1 hour, forming a water-repellent film on the surface of the aluminum nitride powder. Then, the treated powder was put into an oven at 100 ℃ to be dried, and the temperature was kept constant for 24 hours to obtain an aluminum nitride powder having an anti-hydrolysis effect, and a predetermined amount of the treated aluminum nitride powder, deionized water, 0.35wt% of Ib-104 serving as a gelling agent and a dispersing agent were mixed, and then placed into a ball mill to be stirred at a speed of 300rpm for 30 minutes to obtain a slurry. After the slurry was removed, 1wt% of the foaming agent lauryl sulfate triethanolamine was added and stirred at a mechanical stirring rate of 1000rpm for 30 minutes so that air was sufficiently introduced into the slurry to form a desired porous structure. The foamed slurry was then poured into a removable mold and dried naturally at room temperature for 50 hours. And then placing the dried porous aluminum nitride blank into a muffle furnace, heating to 600 ℃ in air at a heating rate of 1 ℃/min, and keeping the temperature for 200min to remove all residual reagents and impurities to obtain the aluminum nitride blank. And finally, placing the burned aluminum nitride blank body into a hot pressing furnace, keeping the temperature at 2000 ℃ for 200min, and annealing to obtain the sintered aluminum nitride skeleton. Cutting the sintered aluminum nitride skeleton into a circular sheet with the diameter of 12.7mm and the thickness of 3mm by using a sampler and a wire cutting machine;
(3) Vacuum dipping an aluminum nitride framework with the diameter of 12.7mm, the thickness of 3mm and the porosity of 65% into a precursor solution by adopting a vacuum dipping method, and vacuum dipping for 5min;
(4) Calcining the aluminum nitride skeleton after vacuum impregnation in a tube furnace, heating to 800 ℃ from 20 ℃ at a speed of 10 ℃/min by a temperature control program, keeping the constant temperature for 40min, cooling to 700 ℃ at a speed of 10 ℃/min by the temperature control program, introducing carbon dioxide, carbonating for 30min in a carbon dioxide atmosphere, and annealing to room temperature. Repeating the steps (3) - (4) for 6 times to prepare the composite heat storage material A2.
Example 3
(1) Preparing a precursor solution: 11.8076g of calcium nitrate tetrahydrate, 1.2005g of chromium nitrate nonahydrate and 0.7159g of manganese nitrate solution are weighed under the room temperature condition, placed in a clean beaker, deionized water is added to obtain 10mL of solution, and the mixed solution is dispersed and stirred for 60min in a magnetic stirring mode, and the stirring speed is 500rpm, so as to obtain a precursor solution;
(2) 35g of aluminum nitride powder, 1g of yttrium oxide and 30ml of absolute ethanol were weighed at room temperature, placed in a ball mill pot, placed in a ball mill and stirred at a speed of 300rpm for 30 minutes, to obtain a slurry. 0.3wt% of ethanol dispersant polyacrylic acid was added to the slurry, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes, and 1wt% of polycyanate was added, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes. The slurry in the ball mill pot was then removed to a beaker, tetraethylenepentamine of the same mass as the polycyanate was added, and the reaction was accelerated by stirring with mechanical stirring at a rate of 500rpm for 1 hour, forming a water-repellent film on the surface of the aluminum nitride powder. Then, the treated powder was put into an oven at 100 ℃ to be dried, and the temperature was kept constant for 24 hours to obtain an aluminum nitride powder having an anti-hydrolysis effect, and a predetermined amount of the treated aluminum nitride powder, deionized water, 0.35wt% of Ib-104 serving as a gelling agent and a dispersing agent were mixed, and then placed into a ball mill to be stirred at a speed of 300rpm for 30 minutes to obtain a slurry. After the slurry was removed, 1wt% of the foaming agent lauryl sulfate triethanolamine was added and stirred at a mechanical stirring rate of 1000rpm for 30 minutes so that air was sufficiently introduced into the slurry to form a desired porous structure. The foamed slurry was then poured into a removable mold and dried naturally at room temperature for 50 hours. And then placing the dried porous aluminum nitride blank into a muffle furnace, heating to 600 ℃ in air at a heating rate of 1 ℃/min, and keeping the temperature for 200min to remove all residual reagents and impurities to obtain the aluminum nitride blank. And finally, placing the burned aluminum nitride blank body into a hot pressing furnace, keeping the temperature at 2000 ℃ for 200min, and annealing to obtain the sintered aluminum nitride skeleton. Cutting the sintered aluminum nitride skeleton into a circular sheet with the diameter of 12.7mm and the thickness of 3mm by using a sampler and a wire cutting machine;
(3) Vacuum dipping an aluminum nitride framework with the diameter of 12.7mm, the thickness of 3mm and the porosity of 65% into a precursor solution by adopting a vacuum dipping method, and vacuum dipping for 5min;
(4) Calcining the aluminum nitride skeleton after vacuum impregnation in a tube furnace, heating to 800 ℃ from 20 ℃ at a speed of 10 ℃/min by a temperature control program, keeping the constant temperature for 40min, cooling to 700 ℃ at a speed of 10 ℃/min by the temperature control program, introducing carbon dioxide, carbonating for 30min in a carbon dioxide atmosphere, and annealing to room temperature. Repeating the steps (3) - (4) for 6 times to prepare the composite heat storage material A3.
Comparative example
(1) Preparing a precursor solution: weighing 11.8076g of calcium nitrate tetrahydrate at room temperature, placing the calcium nitrate tetrahydrate in a clean beaker, adding deionized water to obtain 10mL of solution, dispersing and stirring the mixed solution for 60min in a magnetic stirring mode, and stirring at 500rpm to obtain a precursor solution;
(2) 35g of aluminum nitride powder, 1g of yttrium oxide and 30ml of absolute ethanol were weighed at room temperature, placed in a ball mill pot, placed in a ball mill and stirred at a speed of 300rpm for 30 minutes, to obtain a slurry. 0.3wt% of ethanol dispersant polyacrylic acid was added to the slurry, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes, and 1wt% of polycyanate was added, and the slurry was placed in a ball mill and stirred at 300rpm for 30 minutes. The slurry in the ball mill pot was then removed to a beaker, tetraethylenepentamine of the same mass as the polycyanate was added, and the reaction was accelerated by stirring with mechanical stirring at a rate of 500rpm for 1 hour, forming a water-repellent film on the surface of the aluminum nitride powder. Then, the treated powder was put into an oven at 100 ℃ to be dried, and the temperature was kept constant for 24 hours to obtain an aluminum nitride powder having an anti-hydrolysis effect, and a predetermined amount of the treated aluminum nitride powder, deionized water, 0.35wt% of Ib-104 serving as a gelling agent and a dispersing agent were mixed, and then placed into a ball mill to be stirred at a speed of 300rpm for 30 minutes to obtain a slurry. After the slurry was removed, 1wt% of the foaming agent lauryl sulfate triethanolamine was added and stirred at a mechanical stirring rate of 1000rpm for 30 minutes so that air was sufficiently introduced into the slurry to form a desired porous structure. The foamed slurry was then poured into a removable mold and dried naturally at room temperature for 50 hours. And then placing the dried porous aluminum nitride blank into a muffle furnace, heating to 600 ℃ in air at a heating rate of 1 ℃/min, and keeping the temperature for 200min to remove all residual reagents and impurities to obtain the aluminum nitride blank. And finally, placing the burned aluminum nitride blank body into a hot pressing furnace, keeping the temperature at 2000 ℃ for 200min, and annealing to obtain the sintered aluminum nitride skeleton. Cutting the sintered aluminum nitride skeleton into a circular sheet with the diameter of 12.7mm and the thickness of 3mm by using a sampler and a wire cutting machine;
(3) Vacuum dipping an aluminum nitride framework with the diameter of 12.7mm, the thickness of 3mm and the porosity of 65% into a precursor solution by adopting a vacuum dipping method, and vacuum dipping for 5min;
(4) Calcining the aluminum nitride skeleton after vacuum impregnation in a tube furnace, heating to 800 ℃ from 20 ℃ at a speed of 10 ℃/min by a temperature control program, keeping the constant temperature for 40min, cooling to 700 ℃ at a speed of 10 ℃/min by the temperature control program, introducing carbon dioxide, carbonating for 30min in a carbon dioxide atmosphere, and annealing to room temperature. Repeating the steps (3) - (4) for 6 times to prepare the composite heat storage material B1.
As shown in fig. 1, the calcium-based composite material with compact structure can be obtained through the operation in the above embodiment, and since the aluminum nitride ceramic skeleton has a porous foam structure, the structure is conducive to the full filling of the calcium precursor solution in the pores of the skeleton, so that the state of the coupled heat conduction theoretical model of the aluminum nitride skeleton and the calcium-based material is close to that of the maxwell model, unlike other compounding methods, the calcium-based composite material obtained by the method can maintain high mechanical strength and high adhesiveness, and the possibility of material breakage and leakage is avoided.
Meanwhile, the ion doping ensures that the sample has higher material uniformity, manganese and chromium oxides at Gao Daman temperature space calcium carbonate crystals apart, and strengthen the structure of the composite material, which can effectively inhibit migration of the calcium carbonate crystals and resist thermal movement of calcium carbonate molecules, thereby inhibiting sintering of the calcium carbonate molecules.
The obtained composite heat storage material A1, the composite heat storage material A2 and the composite heat storage material A3 are subjected to heat conductivity test, the heat conductivity measurement results are shown in figure 2, and the heat conductivities of the three materials are 19.66 W.m respectively -1 K -1 、16.40W·m -1 K -1 And 22.98 W.m -1 K -1 . It can be seen that the other three composite heat storage materials have two orders of magnitude higher thermal conductivity than pure calcium carbonate without aluminum nitride backbone. The aluminum nitride framework with high thermal conductivity provides an excellent heat transfer channel, and the aluminum nitride framework is taken as a substrate to load the composite material, so that the aluminum nitride framework is effective in improving the thermal conductivity of the calcium-based composite materialThe way makes great contribution to improving the heat storage efficiency.
The obtained composite heat storage material A1, the composite heat storage material A2, the composite heat storage material A3 and the composite heat storage material B1 are subjected to optical absorption test to obtain optical absorption curves of four samples shown in FIG. 3, and compared with the composite heat storage material B1 without the spectrum absorption enhancement substance, the absorption rate of the other three composite heat storage materials in the range of 300nm-2500nm is higher, and the absorption wave band range is wider.
The calculation results are shown in fig. 4, wherein the solar average absorptivity of the composite heat storage material A1 is 82.09%, the solar average absorptivity of the composite heat storage material A2 is 82.56%, the solar average absorptivity of the composite heat storage material A3 is 81.87%, and the solar average absorptivity of the composite heat storage material B1 is 22.36% in the wave band of 300nm-2500 nm. The results clearly demonstrate that the light absorption of the calcium-based composite material is significantly enhanced due to the synergistic effect of the doping of the manganese and chromium metal oxides, and is an effective way to improve the light absorption performance of the calcium-based composite material.
As shown in fig. 5, the obtained composite heat storage material A1, composite heat storage material A2, composite heat storage material A3 and composite heat storage material B1 are subjected to reaction kinetic analysis to obtain decomposition conversion rate curves of pure calcium carbonate and four samples, and the results show that compared with pure calcium carbonate, the four calcium-based composite materials prepared by the aluminum nitride framework have higher conversion rates; meanwhile, compared with the composite heat storage material B1 without the spectrum absorption enhancement substance, the conversion rate of other three composite heat storage materials is higher.
Fig. 6 shows more clearly the superiority of the calcium-based composite material prepared in the embodiment in improving the reaction rate, which illustrates that the aluminum nitride skeleton provides additional driving force for improving the chemical reaction rate of the calcium-based composite material, and the synergistic effect of the doping of the manganese and chromium metal oxides can further improve the chemical reaction rate of the calcium-based composite material, and under the combined action of the two, the aluminum nitride skeleton is an effective way for improving the thermochemical heat storage/release of the calcium-based composite material.
The polycrystal structure of the calcium-based composite material prepared by the invention mainly depends on phonon heat transfer, and in the heat transfer process, defects, crystal boundaries, pores, electrons and phonons in the pure calcium carbonate crystal can generate phonon scattering, so that the heat transfer is not facilitated. From the SEM image of fig. 7, the morphology of the calcium-based composite material is represented, the coupling heat conduction theoretical model of the aluminum nitride framework and the calcium-based material is close to the maxwell model, and the continuous structure of the aluminum nitride framework can be used as a continuous heat conduction path in the heat transfer process. The morphology created by coupling of the calcium-based composite material prepared by the invention enables scattering between phonons to be inhibited, the mean free path of phonons is increased along with the reduction of scattering between phonons through lattice solid vibration analysis, the heat transmission driving force of the calcium-based material is greatly improved, and the calcium-based composite material is combined with thermochemical heat storage to optimize a heat collection and heat storage system.
From the perspective of improving the heat storage rate, the spectral absorptivity and the circulation stability, the invention realizes the preparation of the multifunctional thermochemical heat storage material combining the high heat conductivity, the high spectral absorptivity and the high circulation stability.
Claims (10)
1. The solar full-spectrum photo-thermal conversion heat storage material with high heat conductivity is characterized in that the composite heat storage material contains a thermochemical heat storage substance, a porous ceramic skeleton and a spectrum absorption enhancing substance, can effectively inhibit scattering between phonons of a thermochemical heat storage system, and has the function of optimizing heat and mass transfer.
2. The high thermal conductivity solar full spectrum photothermal conversion heat storage material of claim 1, wherein said thermochemical heat storage substance is calcium carbonate and calcium oxide, or magnesium carbonate and magnesium oxide.
3. The high thermal conductivity solar full spectrum photo-thermal conversion heat storage material according to claim 1, wherein the porous ceramic skeleton is aluminum nitride or silicon carbide, and the porosity is 50-80%.
4. The high thermal conductivity solar full spectrum photo-thermal conversion heat storage material according to claim 3, wherein the preparation method of the porous ceramic skeleton comprises the following steps:
(1) Performing hydrolysis resistance treatment on aluminum nitride or silicon carbide powder;
(2) Mixing predetermined amounts of the treated aluminum nitride or silicon carbide powder, a solvent, and Ib-104;
(3) Adding a foaming agent, and mechanically stirring to form a slurry into a required porous structure;
(4) Drying the slurry to obtain a porous aluminum nitride or silicon carbide blank, and calcining to remove all residual reagents and impurities;
(5) Calcining the burned aluminum nitride or silicon carbide blank, and annealing to obtain the sintered aluminum nitride skeleton.
5. The high thermal conductivity solar full spectrum photothermal conversion heat storage material of claim 1, wherein said spectral absorption enhancement material is at least one metal oxide.
6. The high-thermal-conductivity solar full-spectrum photo-thermal conversion heat storage material according to claim 1, wherein the thermo-chemical heat storage material, the porous ceramic skeleton and the spectrum absorption enhancement material are in direct contact to synthesize the composite heat storage material.
7. The high thermal conductivity solar full spectrum photothermal conversion heat storage material of claim 1, wherein said composite heat storage material has a porous foam structure.
8. A method for preparing the high thermal conductivity solar full spectrum photo-thermal conversion heat storage material according to any one of claims 1-7, comprising the following steps:
(1) Preparing a precursor solution, wherein a solute consists of a solute a and a solute b, the solute a is a substance capable of generating thermochemical heat storage, and the solute b in the solution is a substance capable of enhancing spectral absorption;
(2) Preparing a porous ceramic skeleton;
(3) Loading a precursor material on the porous ceramic skeleton by adopting a vacuum impregnation method;
(4) The resulting material is calcined, carbonated and then annealed.
9. The method of claim 8, wherein steps (3) and (4) are repeated a plurality of times to increase the loading of the thermochemical heat storage substance and the spectral absorption enhancing substance to synthesize the composite heat storage material.
10. The method for preparing a high thermal conductivity solar full spectrum photothermal conversion heat storage material according to claim 8, wherein the mole fraction of solute b in step (1) is 1% -20% of solute a; in the step (4), the calcining temperature of the material is 700-900 ℃, the calcining time is 10-40min, the carbonizing temperature is 600-800 ℃ and the carbonizing time is 10-40min.
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