Patent Application
20240191123
The present application claims the rights and interests of the Chinese patent application 202110355151.9 submitted on Mar. 31, 2021 with the title of “heat storage graphite having low degree of orientation, composition for preparing heat storage graphite having low degree of orientation, and method therefor”, the content of this application is incorporated herein by reference.
The present invention relates to the technical field of heat storage materials, in particular to a heat storage graphite having a low degree of orientation, a composition for preparing the heat storage graphite having a low degree of orientation, and a preparation method for the heat storage graphite having a low degree of orientation.
Existing heat storage carbon materials are generally made by sintering binders (such as pitch) and fillers (such as natural graphite) after molding. Since natural graphite itself has an oriented structure, after compression process, the orientation of natural graphite increases, and the obtained bulk material often has strong anisotropy, resulting in high thermal conductivity. However, high orientation will also cause a large difference between the vertical thermal conductivity and the plane-oriented thermal conductivity, and the ratio of the two is generally less than 0.2. Larger anisotropy is not conducive to the temperature transfer and temperature uniformity of the heat storage and heat release process.
Therefore, it is urgent to provide a heat storage carbon material having a low degree of orientation and a high thermal conductivity.
The purpose of the present invention is to overcome the problem of strong anisotropy of heat storage carbon materials in the prior art, and provide a heat storage graphite having a low degree of orientation, a composition for preparing the heat storage graphite and a preparation method thereof. The heat storage graphite has the advantages of low degree of orientation, high thermal conductivity and high compressive strength.
In order to achieve the above purpose, the first aspect of the present invention provides a heat storage graphite having a low degree of orientation, the heat storage graphite comprises, based on the total mass of the heat storage graphite, 65-85 wt % dispersed-phase graphite and 15-35 wt % continuous-phase graphite; wherein the dispersed-phase graphite is spherical graphite, and the sphericity of the spherical graphite is 0.5-1; the ratio of vertical thermal conductivity/plane-oriented thermal conductivity of the heat storage graphite is 0.4-0.8, and the plane-oriented thermal conductivity of the heat storage graphite is 50-150 W/mK.
The second aspect of the present invention provides a composition for preparing a heat storage graphite having a low degree of orientation, the composition comprises 60-80 parts by weight of spherical graphite and 20-40 parts by weight of pitch, wherein the sphericity of the spherical graphite is 0.5-1.
The third aspect of the present invention provides a method for preparing a heat storage graphite having a low degree of orientation, the method includes the following steps:
Through the above technical scheme, the beneficial technical effects obtained by the present invention are as follows:
Neither the endpoints of the ranges nor any values disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values close to these ranges or values. For value ranges, between the endpoints of the ranges, between the endpoints of the ranges and individual point values, and between individual point values can be combined with each other to obtain one or more new value ranges, these value ranges should be considered as specifically disclosed herein.
The first aspect of the present invention provides a heat storage graphite having a low degree of orientation, the heat storage graphite comprises, based on the total mass of the heat storage graphite, 65-85 wt % dispersed-phase graphite and 15-35 wt % continuous-phase graphite; wherein the dispersed-phase graphite is spherical graphite, and the sphericity of the spherical graphite is 0.5-1; the ratio of vertical thermal conductivity/plane-oriented thermal conductivity of the heat storage graphite is 0.4-0.8, and the plane-oriented thermal conductivity of the heat storage graphite is 50-150 W/mK.
Through research, the inventors of the present invention have found that the spherical graphite with a sphericity of 0.5-1 is uniformly dispersed in the continuous-phase graphite, which can reduce the degree of orientation of the heat storage graphite and increase the ratio of vertical thermal conductivity/plane-oriented thermal conductivity(λ⊥∥), thus making the temperature transfer of heat storage materials more stable during the heat storage and heat release process.
In a preferred embodiment, based on the total mass of the heat storage graphite, the heat storage graphite includes 75-85 wt % dispersed-phase graphite and 15-25 wt % continuous-phase graphite.
In a preferred embodiment, the sphericity of the spherical graphite is 0.8-1.
In a preferred embodiment, the ratio of vertical thermal conductivity/plane-oriented thermal conductivity of the heat storage graphite is 0.6-0.8.
In a preferred embodiment, the plane-oriented thermal conductivity of the heat storage graphite is 80-120 W/mK.
In a preferred embodiment, the density of the heat storage graphite is 1.6-2.1 g/cm3, preferably 1.8-2.1 g/cm3; the compressive strength of the heat storage graphite is 10-50 MPa, preferably 20-40 MPa.
The second aspect of the present invention provides a composition for preparing a heat storage graphite having a low degree of orientation, the composition comprises 60-80 parts by weight of spherical graphite and 20-40 parts by weight of pitch, wherein the sphericity of the spherical graphite is 0.5-1.
In a preferred embodiment, the composition comprises 70-80 parts by weight of spherical graphite and 20-30 parts by weight of pitch, wherein the sphericity of the spherical graphite is 0.8-1.
In a preferred embodiment, the average particle size of the spherical graphite is 25-2000 μm.
In a further preferred embodiment, the spherical graphite is at least two kinds of spherical graphite selected from spherical graphite with an average particle size of 10-25 μm, spherical graphite with an average particle size of 25-50 μm, spherical graphite with an average particle size of 50-100 μm, spherical graphite with an average particle size of 100-300 μm, spherical graphite with an average particle size of 300-600 μm, and spherical graphite with an average particle size of 600-1000 μm.
In the present invention, 25-50 μm, 50-100 μm, 100-300 μm, and 300-600 μm refer to the range including the minimum value but not including the maximum value, 600-1000 μm refers to the range including the minimum value and the maximum value.
In a more preferred embodiment, the spherical graphite is at least three kinds of spherical graphite selected from spherical graphite with an average particle size of 10-25 μm, spherical graphite with an average particle size of 25-50 μm, spherical graphite with an average particle size of 50-100 μm, spherical graphite with an average particle size of 100-300 μm, spherical graphite with an average particle size of 300-600 μm, and spherical graphite with an average particle size of 600-1000 μm.
In a further more preferred embodiment, the spherical graphite is at least three kinds of spherical graphite selected from spherical graphite with an average particle size of 10-25 μm, spherical graphite with an average particle size of 25-50 μm, spherical graphite with an average particle size of 50-100 μm, spherical graphite with an average particle size of 100-300 μm, spherical graphite with an average particle size of 300-600 μm, and spherical graphite with an average particle size of 600-1000 μm, wherein the mass ratio of spherical graphite with small-range particle size, medium-range particle size and large-range particle size is 1:0.1-15:0.1-30, preferably 1:0.5-10:1-15, more preferably 1: 1-4:2-8. Wherein, the small-range particle size, medium-range particle size and large-range particle size are distinguished according to the numerical values of the particle size ranges of the three kinds of spherical graphite. Preferably, the spherical graphite with small-range particle size is selected from spherical graphite with an average particle size of 10-25 μm and/or spherical graphite with an average particle size of 25-50 μm; the spherical graphite with medium-range particle size is selected from spherical graphite with an average particle size of 50-100 μm and/or spherical graphite with an average particle size of 100-300 μm; the spherical graphite with large-range particle size is selected from spherical graphite with an average particle size of 300-600 μm and/or spherical graphite with an average particle size of 600-1000 μm.
In a preferred embodiment, the carbon content of the spherical graphite is ≥95 wt %, preferably 97 wt %, and the graphitization degree of the spherical graphite is 85%, preferably 90%.
In the present invention, the spherical graphite can be obtained commercially. For example, the spherical graphite has a sphericity of 0.9, a carbon content of 99.5%, a graphitization degree of 99%, and an average particle size of 25-50 μm, 100-300 μm, 600-1000 μm and other parameters. When its sphericity does not meet the use requirements, the materials can be screened by ball milling and screening.
In a preferred embodiment, the pitch is non-mesophase pitch or mesophase pitch. Wherein, the mesophase content of the non-mesophase pitch is 0, the softening point of the non-mesophase pitch is 130-250° C., preferably 140-200° C., and the carbon residue rate of the non-mesophase pitch is ≥60 wt %, preferably 65 wt %. The mesophase content of the mesophase pitch is 50-100 wt %, preferably 75-100 wt %; the H/C molar ratio of the mesophase pitch is 0.5-0.7, preferably 0.55-0.65; the softening point of the mesophase pitch is 200-350° C., preferably 230-325° C.; the carbon residue rate of the mesophase pitch is 70 wt %, preferably 75 wt %.
In the present invention, the non-mesophase pitch and the mesophase pitch can be obtained commercially. For example, the non-mesophase pitch has a mesophase content of 0, a softening point of 165° C., and a carbon residue rate of 65 wt % and other parameters; the mesophase pitch has a mesophase content of 100 wt %, an H/C molar ratio of 0.64, a softening point of 285° C., a carbon residue rate of 75 wt % and other parameters.
The third aspect of the present invention provides a method for preparing a heat storage graphite, the method includes the following steps:
In a preferred embodiment, the conditions of the thermo-compression molding comprise a molding temperature of 250-600° C., preferably 300-550° C., a molding pressure of 10-100 MPa, preferably 20-80 MPa, and a molding time of 1-5 h, preferably 1.5-2 h.
In a preferred embodiment, the conditions of the carbonization treatment comprise a carbonization temperature of 800-1600° C., preferably 1200-1600° C., and a carbonization time of 0.5-3 h, preferably 0.5-1 h.
In a preferred embodiment, the graphitization treatment is performed at 2700-3200° C. for 0.5-2 h; further preferably, the graphitization treatment is performed at 2800-3200° C. for 0.5-1 h.
In a preferred embodiment, the carbonization treatment and graphitization treatment are performed under the protection of an inert gas, wherein the inert gas can be nitrogen and/or argon.
Hereinafter, the present invention will be described in detail through examples. Wherein, the sphericity of spherical graphite is measured by BT-2800 dynamic image particle size and particle shape analysis system. The vertical thermal conductivity and plane-oriented thermal conductivity in the examples and comparative examples are tested according to ASTME1461, the vertical thermal conductivity refers to the lowest thermal conductivity in the three directions of x, y, and z, and the plane-oriented thermal conductivity refers to the highest thermal conductivity in the three directions of x, y, and z; the porosity is tested by mercury porosimetry, the compressive strength is tested according to GBT1431-2019, and the bulk density is tested according to GB/T24528-2009. The content of the dispersed-phase (spherical graphite) in the heat storage graphite is calculated by the formula: the content of the dispersed-phase (spherical graphite) in the heat storage graphite=the mass of spherical graphite in the raw material/(the mass of spherical graphite in the raw material+the mass of pitch*the carbon residue rate of pitch).
In the following examples and comparative examples, the spherical graphite, mesophase pitch, and non-mesophase pitch are all commercially available products, and the parameters of the products meet the parameters in the examples and comparative examples.
Similar to Example 1, the difference is that the mesophase pitch in Example 1 is replaced by non-mesophase pitch (with a mesophase content of 0, a softening point of 165° C., and a carbon residue rate of 65 wt %).
Similar to Example 1, the difference is that the sphericity of the spherical graphite is 0.6.
Similar to Example 1, the difference is that the molding pressure is 25 MPa.
Similar to Example 1, the difference is that the addition amount of spherical graphite is 60 g, the addition amount of mesophase pitch (with a mesophase content of 50 wt %, a H/C molar ratio of 0.6, a softening point of 245° C., and a residual carbon rate of 70 wt %) is 40 g; the molding temperature is 400° C., the pressure is 50 MPa, and the graphitization temperature is 2800° C.
Similar to Example 1, the difference is that the addition amount of spherical graphite (with a sphericity of 0.9, a carbon content of 99.5%, and a graphitization degree of 99%, wherein the spherical graphite with an average particle size of 10-25 μm is 20 g, and the spherical graphite with an average particle size of 25-50 μm is 25 g, the spherical graphite with an average particle size of 50-100 μm is 25 g) is 75 g and the addition amount of mesophase pitch is 25 g.
Similar to Example 1, the difference is that the spherical graphite in Example 1 is replaced by natural flake graphite (with an average particle size of 500 μm, a carbon content of 99.5%, and a graphitization degree of 99%).
Similar to Example 1, the difference is that the spherical graphite in Example 1 is replaced by the spherical graphite with a sphericity of 0.3, a carbon content of 99.5%, a graphitization degree of 99%, and an average particle size of 600-1000 μm.
Similar to Example 1, the difference is that the addition amount of spherical graphite is 90 g, and the addition amount of mesophase pitch is 10 g.
The heat storage materials prepared in Examples 1-6 and Comparative Examples 1-3 were tested for vertical thermal conductivity, plane-oriented thermal conductivity, compressive strength and density, the test results are shown in Table 1:
It can be seen from the results of Examples 1-6 in Table 1 that the heat storage graphite prepared by the present invention has the advantages of low degree of orientation, high thermal conductivity and high compressive strength. By comparing Example 1 and Comparative Example 1, Comparative Example 2, it can be seen that when the sphericity of flake graphite or spherical graphite is relatively small, the obtained heat storage graphite has large plane-oriented thermal conductivity, but high degree of orientation and low vertical thermal conductivity, which is not conducive to the temperature transfer and temperature uniformity during the heat storage and heat release process.
By comparing Example 1 and Comparative Example 3, it can be seen that when the amount of pitch is too small, effective bonding cannot be achieved, and the obtained heat storage graphite has poor compressive strength and low thermal conductivity.
The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, these simple modifications and combinations should also be regarded as the content disclosed by the present invention, and all belong to the protection scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110355151.9 | Mar 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2021/133577 | 11/26/2021 | WO |
