CN115140724B - Heat storage carbon material, preparation method and application thereof, and composition for preparing heat storage carbon material - Google Patents
Heat storage carbon material, preparation method and application thereof, and composition for preparing heat storage carbon material Download PDFInfo
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- CN115140724B CN115140724B CN202110349338.8A CN202110349338A CN115140724B CN 115140724 B CN115140724 B CN 115140724B CN 202110349338 A CN202110349338 A CN 202110349338A CN 115140724 B CN115140724 B CN 115140724B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 149
- 238000005338 heat storage Methods 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000465 moulding Methods 0.000 claims abstract description 40
- 238000005087 graphitization Methods 0.000 claims abstract description 39
- 239000011232 storage material Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 66
- 239000011230 binding agent Substances 0.000 claims description 51
- 238000003860 storage Methods 0.000 claims description 40
- 239000010426 asphalt Substances 0.000 claims description 39
- 239000012752 auxiliary agent Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 18
- 239000011231 conductive filler Substances 0.000 claims description 16
- 239000000945 filler Substances 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000000748 compression moulding Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012778 molding material Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007770 graphite material Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 230000017525 heat dissipation Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000000463 material Substances 0.000 description 22
- 238000003763 carbonization Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000011302 mesophase pitch Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011300 coal pitch Substances 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000007431 microscopic evaluation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
- 244000146553 Ceiba pentandra Species 0.000 description 1
- RSNKHMHUYALIHE-UHFFFAOYSA-N [Mo].[Si].[Ti] Chemical compound [Mo].[Si].[Ti] RSNKHMHUYALIHE-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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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
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention relates to the technical field of heat storage materials, and discloses a heat storage carbon material, a preparation method and application thereof, and a composition for preparing the heat storage carbon material. The graphitization degree of the heat storage carbon material is more than or equal to 92%; the integral orientation degree D (x)/D (z) of the heat storage carbon material is 500-900; the z-plane orientation degree D (z)/E (z) of the high-strength heat storage carbon material is 0.2-8; the compressive strength of the heat storage carbon material is 20-60MPa, and the thermal conductivity is 200-500W/mK. The heat storage carbon material has high graphitization degree, specific overall orientation degree and z-plane orientation degree, and therefore, the heat storage carbon material has high molding density, heat conductivity and compressive strength.
Description
Technical Field
The invention relates to the technical field of heat storage materials, in particular to a heat storage carbon material, a preparation method and application thereof, and a composition for preparing the heat storage carbon material.
Background
The common heat storage carbon material is prepared by mixing, molding, dipping roasting and graphitizing graphite filler or asphalt coke, petroleum coke products and asphalt binder.
CN112110730a discloses a composition for heat storage material and preparation method thereof, the composition comprises asphalt material, graphite and inorganic mineral material, wherein the asphalt material is selected from coal-based asphalt and/or coal-based modified asphalt, the C/H of the asphalt material is 1.3-1.7, the softening point is more than or equal to 130 ℃, and the carbon residue after carbonization is more than or equal to 66%; based on the total weight of the composition for the heat storage material, the content of the asphalt material is 10-40wt%, the content of the graphite is 20-80 wt%, and the content of the inorganic mineral material is 10-70 wt%, and the prepared heat storage material has higher heat conductivity, compressive strength and volume density.
CN112111310a discloses a composition for heat-storage carbon material, heat-storage carbon material and preparation method thereof, the composition comprises asphalt material and graphite, wherein the asphalt material is selected from coal-based asphalt and/or coal-based modified asphalt, the C/H of the asphalt material is 1.3-1.7, the softening point is more than or equal to 130 ℃, and the carbon residue after carbonization is more than or equal to 66%; the asphalt material is 10-40wt% and the graphite is 60-90wt% based on the total weight of the composition for heat storage material. The heat storage carbon material has high heat conductivity, compressive strength and volume density.
CN110550955a discloses a graphite block material with ultrahigh heat conductivity and high strength and a preparation method thereof, belongs to the technical field of graphite block materials and preparation processes thereof, and solves the problem of low mechanical properties of the existing high heat conductivity graphite block materials. Adopts high-purity natural graphite powder as a heat transfer enhancement body, high-quality mesophase pitch as a binder and silicon-titanium-molybdenum three-component as a catalytic graphitization auxiliary agent, is sintered by high temperature hot pressing. The graphite block material provided by the invention has the thermal conductivity of more than 600W/mK and the bending strength of more than 50MPa, and is expected to play a significant role in the fields of high heat flow multiple chemical engineering such as thermal protection of aerospace vehicles, nuclear fusion first walls, high power density electronic devices and the like. The preparation method is simple, short in preparation period, high in yield, good in repeatability and stability, and suitable for large-scale production.
However, the heat storage materials disclosed in the above prior arts are each formed by compression molding and sintering an adhesive (asphalts) and a powder (graphite, petroleum coke, etc.). Asphalt materials (especially mesophase asphalt) must undergo a high temperature process of carbonization graphitization to achieve higher thermal conductivity, and the high temperature process increases process links and energy consumption. The adhesive dosage in the existing raw material formula is generally between 10 and 40 weight percent. The binder content in the raw materials is reduced, and the heat storage material with high graphite content can be directly obtained, so that the high-energy consumption process link such as graphitization can be avoided. However, the adhesive is an important factor for molding, and too low an amount of the adhesive directly causes non-molding or low molding strength, and further lowers thermal conductivity.
Disclosure of Invention
The invention aims to solve the problem that the thermal conductivity and the molding strength of the thermal storage carbon material which are required to meet the actual demands can be met through carbonization and/or graphitization high-temperature treatment after the thermal storage carbon material is molded in the prior art, and provides a preparation method and application thereof, a composition for preparing the high-strength thermal storage carbon material and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a thermal storage carbon material, characterized in that the graphitization degree of the thermal storage carbon material is equal to or more than 92%; the integral orientation degree D (x)/D (z) of the heat storage carbon material is 500-900; the z-plane orientation degree D (z)/E (z) of the high-strength heat storage carbon material is 0.2-8;
wherein D (x) refers to the diffraction peak intensity of a (002) crystal face of an x plane perpendicular to the stress direction in the high-strength heat storage carbon material; d (z) is the diffraction peak intensity of the (002) crystal plane of the z-plane parallel to the stress direction in the high-strength heat storage carbon material; e (z) is the diffraction peak intensity of a (110) crystal face of a z-plane parallel to the stress direction in the high-intensity heat storage carbon material; d (x), D (z) and E (z) were all obtained by XRD testing.
In a second aspect, the invention provides a composition for preparing a thermal storage carbon material, which is characterized in that the composition comprises a heat conducting filler, a binder and a high heat conducting auxiliary agent;
the amount of the heat conductive filler is 60 to 90wt%, the amount of the binder is 2 to 15wt%, and the amount of the high heat conductive auxiliary agent is 5 to 30wt%, based on the total weight of the composition.
The third aspect of the present invention provides a method for preparing a thermal storage carbon material, characterized in that the method comprises the steps of:
(1) Mixing the components in the heat storage carbon material composition to obtain a premix;
(2) Compression molding the premix to obtain a heat storage carbon material;
wherein the composition comprises a heat conducting filler, a binder and a high heat conducting auxiliary agent;
the amount of the heat conductive filler is 60 to 90wt%, the amount of the binder is 2 to 15wt% and the amount of the high heat conductive auxiliary agent is 5 to 30wt% based on the total weight of the composition.
The fourth aspect of the invention provides a heat storage carbon material prepared by the preparation method.
A fifth aspect of the invention provides the use of the above-described thermal storage carbon material or of the above-described composition for the preparation of a thermal storage carbon material in the solid thermal storage and/or in the heat dissipation field.
Through the technical scheme, the heat storage carbon material, the preparation method and the application thereof, the composition for preparing the heat storage carbon material and the application thereof provided by the invention have the following beneficial effects:
according to the invention, the large-size high-bulk heat conduction auxiliary agent is adopted to provide skeleton support, so that the consumption of an adhesive in the process of preparing the heat storage carbon material can be greatly reduced, and the graphite content and graphitization degree of the heat storage carbon material are remarkably improved, so that the heat storage carbon material has high molding density, high heat conductivity and high compressive strength.
The composition for preparing the heat storage carbon material provided by the invention contains a low-content binder, is matched with the high-heat-conductivity auxiliary agent, and can be used for preparing the heat storage carbon material with high molding density, high heat conductivity and high compressive strength without carbonization and/or graphitization treatment, so that the energy consumption is obviously reduced.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a heat storage carbon material, which is characterized in that the graphitization degree of the heat storage carbon material is more than or equal to 92%; the integral orientation degree D (x)/D (z) of the heat storage carbon material is 500-900; the z-plane orientation degree D (z)/E (z) of the high-strength heat storage carbon material is 0.2-8;
wherein D (x) refers to the diffraction peak intensity of a (002) crystal face of an x plane perpendicular to the stress direction in the high-strength heat storage carbon material; d (z) is the diffraction peak intensity of the (002) crystal plane of the z-plane parallel to the stress direction in the high-strength heat storage carbon material; e (z) is the diffraction peak intensity of a (110) crystal face of a z-plane parallel to the stress direction in the high-intensity heat storage carbon material; d (x), D (z) and E (z) were all obtained by XRD testing.
In the invention, the stress direction refers to a method for applying pressure to the high-strength heat storage carbon material in the forming process.
The heat storage carbon material provided by the invention has high graphitization degree, and has specific overall orientation degree and z-plane orientation degree, so that the heat storage carbon material has high molding density, high thermal conductivity and high compressive strength.
In the invention, the graphitization degree of the high-strength heat storage carbon material is measured according to an XRD method.
Further, the graphitization degree of the heat storage carbon material is more than or equal to 95%; the overall orientation degree D (x)/D (z) of the heat storage carbon material is 600-900; the z-plane orientation degree D (z)/E (z) of the heat storage carbon material is 0.2-2.
According to the invention, the compressive strength of the heat storage carbon material is 20-60MPa, the thermal conductivity is 200-500W/mK, and the volume density is 1.8-2.2g/cm 3 。
In the invention, the compressive strength of the heat storage carbon material is measured according to the GBT1431-2019 method; thermal conductivity is measured according to ASTM E1461; the bulk density of the heat storage carbon material was measured according to the method of GB/T24528-2009.
Further, the compressive strength of the heat storage carbon material is 30-50MPa, the thermal conductivity is 300-450W/mK, and the volume density is 1.9-2.1g/cm 3 。
In a second aspect, the invention provides a composition for preparing a thermal storage carbon material, which is characterized in that the composition comprises a heat conducting filler, a binder and a high heat conducting auxiliary agent;
the amount of the heat conductive filler is 60 to 90wt%, the amount of the binder is 2 to 15wt%, and the amount of the high heat conductive auxiliary agent is 5 to 30wt%, based on the total weight of the composition.
The composition for preparing the heat storage carbon material provided by the invention contains a low-content binder and is matched with the high-heat-conductivity auxiliary agent, so that the prepared heat storage carbon material has high molding density, high heat conductivity and high compressive strength, and more importantly, carbonization or graphitization treatment is not required in the preparation process, and the energy consumption is obviously reduced.
In the invention, the total amount of the heat conducting filler, the binder and the high heat conducting auxiliary agent is 100wt%.
It is further preferred that the thermally conductive filler is used in an amount of 70 to 80wt%, the binder is used in an amount of 3 to 7wt%, and the high thermal conductivity auxiliary is used in an amount of 5 to 20wt%, based on the total weight of the composition.
According to the invention, the binder is asphalt.
In the invention, the softening point of the asphalt is 130-350 ℃, and the carbon residue rate is more than or equal to 60wt%.
In the invention, asphalt with the softening point and the carbon residue rate is used as a binder, so that the compressive strength, the molding density and the thermal conductivity of the prepared heat storage carbon material can be remarkably improved.
In the invention, the softening point of asphalt is measured by using a GBT4507-2014 asphalt softening point measuring method ring-ball method; the char yield after asphalt carbonization was measured using ASTM D2416- (2009).
In the invention, the asphalt can be non-intermediate phase asphalt, such as coal asphalt, petroleum asphalt and the like, can be intermediate phase asphalt, and can be a mixture of the non-intermediate phase asphalt and the intermediate phase asphalt. In the invention, the content of the mesophase pitch is 50 to 100% by weight.
In the invention, the mesophase content of mesophase pitch is measured by using a GBT 38396-2019 coking pitch product-mesophase content measuring-light reflection microscopic analysis method.
Further, the softening point of the asphalt is 130-230 ℃, and the carbon residue rate is more than or equal to 63wt%.
According to the invention, the binder has an average particle diameter of 500. Mu.m, preferably 50. Mu.m, more preferably 20. Mu.m.
According to the invention, the high heat conduction auxiliary agent is selected from heat conduction graphite materials with the bulk degree more than or equal to 50 and the graphitization degree more than or equal to 90%; at least one of the three-dimensional sizes of the high heat conduction auxiliary agent is more than or equal to 50 mu m.
According to the invention, the heat-conducting graphite material with the structural characteristics is adopted as the high heat-conducting auxiliary agent, and is matched with the binder and the heat-conducting filler, so that the use amount of the binder in the composition for the heat-storage carbon material can be reduced, and the composition can obtain the heat-storage carbon material with high forming density, compression strength and heat conductivity under the condition of not graphitizing the composition.
In the invention, the three-dimensional size of the high heat conduction auxiliary agent refers to the respective sizes of the single particles of the high heat conduction auxiliary agent in the x, y and z directions.
In the present invention, the bulk of the adsorbent is a value of 1 ounce (28.35 grams) of material in volume (cubic inches) and is measured by: weighing 28.35 g of material, naturally loading the material into a measuring cylinder, and measuring the natural volume of the material to be AmL and the bulk degree B=A to be 0.061; the porosity of the adsorbent is measured by a mercury porosimetry method; the average pore diameter of the adsorbent is measured by a mercury porosimetry method; the three-dimensional size of the high heat conduction auxiliary agent is measured by adopting an optical microscope or a scanning electron microscope method; the graphitization degree of the high heat conduction auxiliary agent is measured according to an XRD method.
Further preferably, the high heat conduction auxiliary agent has a bulk degree of not less than 70% and a graphitization degree of not less than 95%.
According to the invention, the high heat conduction auxiliary agent is at least one selected from expanded graphite, carbon nano tubes, graphene, carbon felt, foam graphite and high heat conduction carbon fiber stone.
According to the invention, the thermally conductive filler is graphite.
According to the invention, the heat conducting filler is graphite with carbon content more than or equal to 95wt% and mesh number less than or equal to 150 mesh.
According to the invention, graphite with the structural characteristics is adopted as the heat conducting filler to be matched with the binder and the high heat conducting auxiliary agent, so that the consumption of the binder in the composition for the heat storage carbon material can be reduced, and the composition can obtain the heat storage carbon material with high forming density, compression strength and heat conductivity under the condition of not carbonizing and graphitizing.
In the invention, the carbon content of the heat conducting filler is measured according to the JB/T9141.6-2020 method.
Further, the heat conducting filler is graphite with carbon content more than or equal to 97.5wt% and mesh number of 30-80 meshes.
The third aspect of the present invention provides a method for preparing a thermal storage carbon material, characterized in that the method comprises the steps of:
(1) Mixing the components in the heat storage carbon material composition to obtain a premix;
(2) Compression molding the premix to obtain the heat storage material;
wherein the composition comprises a heat conducting filler, a binder and a high heat conducting auxiliary agent;
the amount of the heat conductive filler is 60 to 90wt%, the amount of the binder is 2 to 15wt% and the amount of the high heat conductive auxiliary agent is 5 to 30wt% based on the total weight of the composition.
The composition for preparing the heat storage carbon material provided by the invention contains a low-content binder and is matched with the high-heat-conductivity auxiliary agent, so that the prepared heat storage carbon material has high molding density, high heat conductivity and high compressive strength, and more importantly, carbonization and graphitization treatment are not required in the preparation process, and the energy consumption is obviously reduced.
In the invention, the total amount of the heat conductive filler, the binder and the high heat conductive additive is 100wt%.
According to the invention, the thermally conductive filler is used in an amount of 70 to 80wt%, the binder is used in an amount of 3 to 7wt%, and the high thermal conductivity auxiliary is used in an amount of 5 to 20wt%, based on the total weight of the composition.
In the preparation method of the present invention, the heat conductive filler, the binder and the adsorbent are as described in the second aspect of the present invention, and are not described herein.
In the present invention, in the step (1), the binder, the heat conductive filler and the high heat conductive auxiliary agent are directly mixed, and the mixing equipment may be conventional equipment in the art, such as a three-dimensional mixer.
According to the invention, step (1) comprises the steps of:
(1-1) first mixing a binder in the heat storage carbon material composition with a solvent to obtain a binder solution;
(1-2) adding the heat conduction filler and the high heat conduction auxiliary agent in the heat storage carbon material composition into the binder solution for second mixing, and removing the solvent to obtain the premix.
According to the invention, the premix is prepared according to the steps, so that the binder can be fully dispersed in the composition, and the prepared heat storage carbon material has high compressive strength and high thermal conductivity.
According to the present invention, in step (1-1), the solvent is selected from at least one of tetrahydrofuran, toluene, quinoline, and heavy oil.
In the present invention, the amount of the solvent is not particularly limited as long as the binder can be sufficiently dispersed to obtain a uniform binder solution.
According to the invention, the temperature of the first mixture is 50-250 ℃, preferably 100-200 ℃.
According to the invention, in the step (1-2), the temperature of the second mixing is 50-250 ℃, and the heat preservation time of the second mixing is 5-30min.
Further, in the step (1-2), the temperature of the second mixing is 100-200 ℃, and the heat preservation time of the second mixing is 10-20min.
According to the present invention, in the step (2), the molding conditions include: the molding temperature is 150-600 ℃, the molding pressure is 200-1000bar, and the molding heat preservation and pressure maintaining time is 0.5-5h.
According to the invention, the mixture is molded under the molding condition, so that the high heat conduction auxiliary agent can form a skeleton structure and the binder is carbonized, meanwhile, the components in the mixture are fully combined, and the high interface compatibility is realized, so that the prepared heat storage carbon material has high compression strength, high heat conductivity and high molding density.
Further preferably, the molding conditions include: the molding temperature is 250-550 ℃, the molding pressure is 500-1000bar, and the molding heat preservation and pressure maintaining time is 2-4h.
According to the preparation method of the heat storage carbon material, carbonization and graphitization steps are not needed, and the heat storage carbon material with high molding density, high heat conductivity and high compressive strength can be obtained. In order to further increase the molding density, the thermal conductivity and the compressive strength of the heat storage carbon material, preferably, the step (2) further includes:
(2-1) compression molding the premix to obtain a molding material;
(2-2) sintering and/or graphitizing the molding material in an inert atmosphere to obtain the heat storage carbon material.
In the present invention, the compression molding conditions are the same as those described above, and will not be described here again.
According to the present invention, in the step (2-2), the sintering conditions include: the sintering temperature is 800-1600 ℃ and the sintering time is 0.5-3h.
In the invention, the formed sample is baked under the above conditions, so that the adhesive can be carbonized sufficiently, and the compressive strength and the thermal conductivity of the heat storage carbon material can be further improved.
Further preferably, the conditions of the firing include: the roasting temperature is 1200-1600 ℃ and the constant temperature time is 0.5-1h.
In the present invention, in order to further improve the molding density, thermal conductivity and compressive strength of the produced thermal storage carbon material, it is preferable to further graphitize the calcined product. In particular, according to the invention, the graphitization conditions include: the graphitization temperature is 2500-3200 ℃, and the graphitization constant temperature time is 0.5-2h. The graphitization is carried out under the conditions, so that the binder can be further graphitized, the ordinary carbon is converted into graphitized carbon which is easier to conduct heat, and the compressive strength and the thermal conductivity of the prepared heat storage carbon material are further improved.
Further, the graphitizing conditions include: the graphitization temperature is 2800-3200 ℃ and the graphitization constant temperature time is 0.5-1h.
According to the invention, the inert atmosphere is selected from nitrogen and/or argon.
The fourth aspect of the invention provides a heat storage carbon material prepared by the preparation method.
A fifth aspect of the invention provides the use of the above-described thermal storage carbon material or of the above-described composition for the preparation of a thermal storage carbon material in the solid thermal storage and/or in the heat dissipation field.
The present invention will be described in detail by examples. In the following examples of the present invention,
the volume density of the heat storage carbon material is measured according to the GB/T24528-2009 method;
the thermal conductivity of the heat storage carbon material and the high thermal conductivity auxiliary agent is measured according to the method of ASTM E1461;
the compressive strength of the heat storage carbon material is measured according to the GBT1431-2019 method;
d (x), D (z) and E (z) of the heat storage carbon material are obtained by XRD;
the graphitization degree of the heat storage carbon material and the high heat conduction auxiliary agent is measured according to an XRD method;
the bulk of the high thermal conductivity additive is measured according to the following method:
weighing 28.35 g of material, naturally loading the material into a measuring cylinder, and measuring the natural volume of the material to be AmL and the bulk degree B=A to be 0.061;
the three-dimensional size of the high heat conduction auxiliary agent is measured by an optical microscope or a scanning electron microscope;
the softening point of the asphalt is measured according to the GBT4507-2014 asphalt softening point measuring method by the ring-ball method;
carbon residue after asphalt carbonization is measured according to the method of ASTM D2416- (2009);
the mesophase content of mesophase pitch is measured according to the GBT 38396-2019 coking pitch product-mesophase content measurement-light reflection microscopic analysis method;
the average particle size of the binder is measured by a laser particle sizer;
the raw materials used in the examples and comparative examples are all commercially available.
Example 1
(1-1) mixing 5 parts of coal tar pitch (softening point 140 ℃, carbon residue rate 63%, average particle size 15 microns) with tetrahydrofuran solvent for the first time at 65 ℃ to obtain coal-based pitch solution;
(1-2) adding 80 parts of graphite (with the carbon content of 99.5wt%, the mesh number of 50 meshes) and 15 parts of graphene (with the bulk degree of 300 and at least one of the three-dimensional sizes of more than or equal to 100 mu m and the graphitization degree of 99%) into the coal-based asphalt solution for secondary mixing, wherein the mixing temperature is 65 ℃, the heat preservation time is 15min, and removing the solvent to obtain a premix;
(2) And (3) carrying out compression molding on the premix, wherein the molding temperature is 550 ℃, the molding pressure is 1000bar, and the molding heat preservation and pressure maintaining time is 3h. The prepared heat storage carbon material A1. The properties of the heat storage carbon material A1 are shown in table 1.
Example 2
A thermal storage carbon material was prepared as in example 1, except that: in the step (1-1), the amount of coal tar pitch is 12 parts, the amount of graphite is 80 parts, and the amount of graphene is 8 parts. And (5) preparing the heat storage carbon material A2. The properties of the heat storage carbon material A2 are shown in table 1.
Example 3
A heat-storage carbon material was produced in the same manner as in example 1 except that expanded graphite (bulk degree 500, at least one of three-dimensional dimensions: 1000 μm or more, graphitization degree 99%) was used instead of graphene. And (5) preparing the heat storage carbon material A3. The performance of the heat storage carbon material A3 is shown in Table 1
Example 4
A thermal storage carbon material was prepared as in example 1, except that: and replacing graphene (the bulk degree is 300, at least one of the three-dimensional dimensions is more than or equal to 100 mu m, and the graphitization degree is 99%) with graphene (the bulk degree is 75, and at least one of the three-dimensional dimensions is more than or equal to 500 mu m, and the graphitization degree is 97%) to prepare the heat storage carbon material A4.
The properties of the heat storage carbon material A4 are shown in table 1.
Example 5
A thermal storage carbon material was prepared as in example 1, except that: adopting mesophase pitch (softening point 280 ℃, mesophase content 100wt%, carbon residue rate after carbonization is 75%, average particle diameter is 30 μm) to replace coal pitch; quinoline was used instead of tetrahydrofuran, and the mixing temperature was 238 ℃. And (5) preparing the heat storage carbon material A5. The properties of the heat storage carbon material A5 are shown in table 1.
Example 6
A thermal storage carbon material was prepared as in example 1, except that: in the step (2), the molding temperature is 550 ℃, the molding pressure is 300bar, and the molding heat preservation and pressure maintaining time is 3h, so that the heat storage carbon material A6 is prepared. The properties of the heat storage carbon material A6 are shown in table 1.
Example 7
A thermal storage carbon material was prepared as in example 1, except that: the step (2) comprises:
(2-1) carrying out compression molding on the premix, wherein the molding temperature is 550 ℃, the molding pressure is 1000bar, and the molding heat preservation and pressure maintaining time is 3 hours, so as to obtain a molding material;
(2-2) graphitizing the molding material at 3000 ℃ in the presence of an inert atmosphere, wherein the graphitization heat preservation time is 0.5h. And (5) preparing the heat storage carbon material A7.
Comparative example 1
A thermal storage carbon material was prepared as in example 1, except that: and does not contain graphene. The heat storage carbon material D1 is prepared.
The properties of the heat storage carbon material D1 are shown in table 1.
Comparative example 2
A thermal storage carbon material was prepared as in example 1, except that: in the step (1-1), the using amount of coal pitch is 1 part;
in the step (1-2), the amount of graphite is 98 parts and the amount of graphene is 1 part. And (5) preparing the heat storage carbon material D2. The properties of the heat storage carbon material D2 are shown in table 1.
Comparative example 3
A thermal storage carbon material was prepared as in example 1, except that: in the step (1-2), the graphene is replaced by corundum with equal parts by weight. And (5) preparing the heat storage carbon material D3. The properties of the heat storage carbon material D3 are shown in table 1.
Comparative example 4
A thermal storage carbon material was prepared as in example 1, except that: in the step (1-2), the graphene is replaced by equal parts by weight of kapok fiber (the fluffiness is 75, one of three-dimensional dimensions is more than or equal to 500 mu m, and the graphitization degree is 0%). And (5) preparing the heat storage carbon material D4. The properties of the heat storage carbon material D4 are shown in table 1.
Comparative example 5
A thermal storage carbon material was prepared as in example 1, except that: in the step (1-1), the using amount of coal tar pitch is 30 parts;
in the step (1-2), the amount of graphite is 65 parts and the amount of graphene is 5 parts. And (5) preparing the heat storage carbon material D5. The properties of the heat storage carbon material D5 are shown in table 1.
TABLE 1
As can be seen from the results of table 1, the thermal storage carbon materials prepared in examples 1 to 7 have a high graphitization degree and have a proper degree of overall orientation and z-plane orientation, relative to the thermal storage carbon materials prepared in comparative examples 1 to 5, in the present invention, and thus the thermal storage carbon materials prepared in examples 1 to 7 have higher compressive strength, thermal conductivity, and molding density.
Further, compared with the thermal storage carbon material prepared in example 7, the thermal storage carbon materials prepared in examples 1 to 6 do not need graphitization treatment, and can obtain the thermal storage carbon material having the compressive strength, the thermal conductivity and the molding density equivalent to those of the thermal storage carbon material prepared in example 7.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (25)
1. The heat storage carbon material is characterized in that the graphitization degree of the heat storage carbon material is more than or equal to 92%; the integral orientation degree D (x)/D (z) of the heat storage carbon material is 500-900; the z-plane orientation degree D (z)/E (z) of the high-strength heat storage carbon material is 0.2-8;
wherein D (x) refers to the diffraction peak intensity of a (002) crystal face of an x plane perpendicular to the stress direction in the high-strength heat storage carbon material; d (z) is the diffraction peak intensity of the (002) crystal plane of the z-plane parallel to the stress direction in the high-strength heat storage carbon material; e (z) is the diffraction peak intensity of a (110) crystal face of a z-plane parallel to the stress direction in the high-intensity heat storage carbon material; d (x), D (z) and E (z) were all obtained by XRD testing.
2. The thermal storage carbon material according to claim 1, wherein the thermal storage carbon material has a compressive strength of 20 to 60MPa, a thermal conductivity of 200 to 500W/mK, and a bulk density of 1.8 to 2.2g/cm 3 。
3. A composition for preparing the thermal storage carbon material according to claim 1 or 2, characterized in that the composition comprises a thermally conductive filler, a binder and a high thermal conductivity auxiliary agent;
the amount of the heat conductive filler is 60 to 90wt%, the amount of the binder is 2 to 15wt%, and the amount of the high heat conductive auxiliary agent is 5 to 30wt%, based on the total weight of the composition.
4. A composition according to claim 3, wherein the thermally conductive filler is present in an amount of 70-80wt%, the binder is present in an amount of 3-7wt% and the high thermal conductivity aid is present in an amount of 5-20wt%, based on the total weight of the composition.
5. A composition according to claim 3, wherein the binder is bitumen having a softening point of 130-350 ℃ and a char yield of greater than or equal to 60wt%;
and/or the average particle size of the binder is less than or equal to 500 mu m.
6. The composition of claim 5, wherein the binder has an average particle size of 50 μm or less.
7. The composition of claim 5, wherein the asphalt has a softening point of 130-230 ℃ and a char yield of 63wt% or more.
8. The composition of any of claims 3-7, wherein the high thermal conductivity additive is selected from thermally conductive graphite materials having a bulk of 50 or more and a graphitization of 90 or more; at least one of the three-dimensional sizes of the high heat conduction auxiliary agent is more than or equal to 50 mu m.
9. The composition of any of claims 3-7, wherein the high thermal conductivity additive is selected from at least one of expanded graphite, carbon nanotubes, graphene, carbon felt, graphite foam, and high thermal conductivity carbon fibers.
10. The composition of any of claims 3-7, wherein the thermally conductive filler is graphite.
11. The composition of claim 10, wherein the thermally conductive filler is graphite having a carbon content of 95wt% or more and a mesh number of 150 mesh or less.
12. A method of preparing a thermal storage carbon material according to claim 1 or 2, characterized in that the method comprises the steps of:
(1) Mixing the components in the heat storage carbon material composition to obtain a premix;
(2) Compression molding the premix to obtain a heat storage material;
wherein the composition comprises a heat conducting filler, a binder and a high heat conducting auxiliary agent;
the graphite is used in an amount of 60 to 90wt%, the binder is used in an amount of 2 to 15wt%, and the high thermal conductivity additive is used in an amount of 5 to 30wt%, based on the total weight of the composition.
13. The preparation method according to claim 12, wherein the amount of the heat conductive filler is 70 to 80wt%, the amount of the binder is 3 to 7wt%, and the amount of the high heat conductive auxiliary agent is 5 to 20wt%, based on the total weight of the composition.
14. The preparation method of claim 12, wherein the binder is asphalt, the softening point of the asphalt is 130-350 ℃, and the carbon residue rate is more than or equal to 60wt%;
and/or the average particle size of the binder is less than or equal to 500 mu m.
15. The method according to claim 14, wherein the binder has an average particle diameter of 50 μm or less.
16. The process according to claim 14, wherein the asphalt has a softening point of 130 to 230 ℃ and a char yield of 63 wt.% or more.
17. The method of any of claims 12-16, wherein the high thermal conductivity additive is selected from thermally conductive graphite materials having a bulk of 50 or more and a graphitization of 90 or more; at least one of the three-dimensional sizes of the high heat conduction auxiliary agent is more than or equal to 50 mu m.
18. The production method according to any one of claims 12 to 16, wherein the high thermal conductivity auxiliary agent is selected from at least one of expanded graphite, carbon nanotube, graphene, carbon felt, graphite foam, and high thermal conductivity carbon fiber.
19. The production method according to any one of claims 12 to 16, wherein step (1) comprises the steps of:
(1-1) first mixing a binder in the heat storage carbon material composition with a solvent to obtain a binder solution;
(1-2) adding the heat conduction filler and the high heat conduction auxiliary agent in the heat storage carbon material composition into the binder solution for second mixing, and removing the solvent to obtain the premix.
20. The production process according to claim 19, wherein in the step (1-1), the solvent is selected from at least one of tetrahydrofuran, toluene, quinoline and heavy oil;
and/or the temperature of the first mixing is 50-250 ℃.
21. The preparation method according to claim 19, wherein in the step (1-2), the temperature of the second mixture is 50-250 ℃ and the holding time of the second mixture is 5-30min.
22. The production method according to any one of claims 12 to 16, wherein in the step (2), the molding conditions include: the molding temperature is 150-600 ℃, the molding pressure is 200-1000bar, and the molding heat preservation and pressure maintaining time is 0.5-5h.
23. The production method according to any one of claims 12 to 16, wherein step (2) further comprises:
(2-1) compression molding the premix to obtain a molding material;
(2-2) sintering and graphitizing the molding material in an inert atmosphere to obtain the heat storage carbon material.
24. The production method according to claim 23, wherein in the step (2-2), the conditions of sintering include: sintering temperature is 800-1600 ℃ and constant temperature time is 0.5-3h;
and/or, the graphitizing conditions include: the graphitization temperature is 2500-3200 ℃, and the graphitization constant temperature time is 0.5-2h;
and/or the inert atmosphere is selected from nitrogen and/or argon.
25. Use of the thermal storage carbon material of claim 1 or 2 or of the composition for the preparation of thermal storage carbon material of any one of claims 3-11 in the solid thermal storage field and/or in the heat dissipation field.
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