CN112582593A - Preparation method of porous silicon/carbon composite material and application of porous silicon/carbon composite material as negative electrode of lithium ion battery - Google Patents
Preparation method of porous silicon/carbon composite material and application of porous silicon/carbon composite material as negative electrode of lithium ion battery Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 57
- 229910052799 carbon Inorganic materials 0.000 title claims description 53
- 239000002131 composite material Substances 0.000 title claims description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000000498 ball milling Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910021382 natural graphite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002931 mesocarbon microbead Substances 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The preparation method of the porous silicon/carbon composite material provided by the invention comprises the following steps: 1. the silica template is converted to porous silicon using metallothermic reduction. 2. And carrying out ball milling on the porous silicon and a carbon source to obtain the silicon-carbon composite material. The composite material prepared by the method integrates the advantages of silicon materials and carbon materials, and has excellent cycle performance while keeping high capacity.
Description
Technical Field
The invention relates to a preparation method of a porous silicon/carbon composite material and application of the porous silicon/carbon composite material as a negative electrode of a lithium ion battery
Background
The lithium ion battery has the advantages of high voltage, high specific energy, low weight, low volume, long service life and the like, and is one of the most excellent battery systems. However, the specific capacity of the graphite cathode material of the traditional lithium ion battery is close to the theoretical value (372m Ah g)-1) And the market demand is difficult to meet. Therefore, it is urgently needed to develop a novel cathode material with high energy density, high power density, high safety and low cost.
Compared with graphite materials, the silicon materials have extremely high theoretical specific capacity (4200m Ah g) when being used as the negative electrode of the lithium ion battery-1) More than 10 times as much as graphite, and is considered to be the most potential negative electrode material for replacing graphite. However, the silicon negative electrode forms an alloy phase after storing lithium, and expands by 400% or more in volume (by Li)22Si5Note). The huge volume change can cause material pulverization, electrode falling, SEI repeated growth and the like, and the capacity and the cycle efficiency are influenced. The design and utilization of porous structures has proven to be an effective method of mitigating volume changes. The extra free space in the lithium-ion battery can relieve large volume change in the lithium-ion releasing and inserting process, and meanwhile, stress generated in volume expansion and contraction is reduced. On the other hand, the porous silicon has rich pore channel structures and thin pore walls, the diffusion capacity of lithium ions in the silicon is improved, and the rate capability of the electrode is improved.
The introduction of the carbon material has many benefits to the silicon-based negative electrode, and the following reasons mainly exist: 1) carbon materials are good conductors of electrons, and can improve the conductivity of electrodes; 2) the carbon material has excellent mechanical and electrical properties, and can be used as a buffer matrix to inhibit the volume expansion of the silicon material; 3) carbon can avoid direct contact of silicon with the electrolyte, and a stable SEI film is constructed. Thus, the construction of the porous silicon/carbon composite material can combine the advantages of the two, and has excellent cycling stability while maintaining high capacity.
Disclosure of Invention
The invention aims to provide a preparation method of a porous silicon/carbon composite material, which comprises the following steps:
1) and converting the silicon dioxide template into porous silicon by using metallothermic reduction.
2) And carrying out ball milling on the porous silicon and a carbon source to obtain the silicon-carbon composite material.
Wherein, the silica template selected in the step 1) is one or a combination of more of quartz sand, diatomite, white carbon black and SBA-15. The selected metal is one or a combination of more of magnesium, aluminum, zinc and iron.
The mass ratio of the silicon dioxide template to the metal is (1-10): (1-10). Preferably (1-8): (1-8).
The temperature of the metal thermal reduction is 300-1800 ℃, and preferably 500-1500 ℃. The temperature is maintained for 1 to 48 hours, preferably 3 to 24 hours. The carbon source selected in the step 2) is one or a combination of a plurality of porous carbon, natural graphite, artificial graphite and mesocarbon microbeads.
The ball milling tank is made of one of polyurethane, corundum, zirconia and agate; the ball grinding ball is made of one or a combination of more of polyurethane, corundum, zirconia and agate.
The mass ratio of the porous silicon to the carbon source is (1-10): (1-30); the mass ratio of the materials to the ball grinding balls is (1-10): (1-20), preferably (1-8): (1-18).
The ball milling conditions are as follows: the rotating speed is 50-2000rpm, preferably 300-1200 rpm; the ball milling time is 10min-48 h.
It is a further object of the present invention to provide the use of said porous silicon/carbon composite.
The invention provides an application of a porous silicon/carbon composite material as a battery electrode material, in particular an application as a lithium ion battery cathode material.
Compared with the prior art, the preparation method provided by the invention is simple, easy to amplify and high in practicability. And the obtained porous silicon/carbon composite material integrates the advantages of porous silicon and carbon materials. The additional free space inside the porous silicon and the carbon material outside effectively suppress the volume expansion. The material can fully exert the high specific capacity of the silicon cathode while maintaining the stability.
Drawings
FIG. 1 is a scanning electron micrograph of the porous silicon/carbon composite obtained in example 4.
FIG. 2 is an X-ray diffraction pattern (XRD) of the porous silicon/carbon composite obtained in example 6.
FIG. 3 shows the porous Si/C composite obtained in example 7 at 60mA g-1Test data at current density.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1
Step 1) preparation of porous silicon: mixing the quartz sand and the magnesium according to the mass ratio of 1: 1. Keeping the temperature at 800 ℃ for 12 h. After cooling to room temperature, washing with hydrochloric acid and filtering to obtain porous silicon.
Step 2) preparing a porous silicon/carbon composite material: mixing the porous silicon and the mesocarbon microbeads according to the mass ratio of 3:17, and further performing ball milling. The ball milling tank is a polyurethane tank, the ball milling ball is a zirconia ball, and the mass ratio of the zirconia ball to the (porous silicon + intermediate phase carbon microspheres) is 15: 1. The rotating speed of the ball mill is 700rpm, and the ball milling time is 24 h. Finally obtaining the porous silicon/carbon composite material.
Characterization of the porous silicon/carbon composite:
the morphology of the porous silicon/carbon composite material obtained under the above conditions was examined by a Japanese Electron scanning Electron microscope (JSM-7001F).
The composition of the porous silicon/carbon composite obtained under the above conditions was examined with a philips X-ray powder diffractometer (X' Pert PRO MPD).
Electrochemical performance characterization of the porous silicon/carbon composite:
the porous silicon/carbon composite material prepared in example 1, acetylene black and sodium carboxymethylcellulose (binder) are mixed in a mass ratio of 80:10:10 to prepare slurry, and the slurry is uniformly coated on a copper foil current collector to obtain an electrode plate. 1mol L of lithium metal as a counter electrode and a polypropylene microporous membrane as a diaphragm-1LiPF of6(the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1: 1) as an electrolyte, assembling the electrolyte into a button cell in an argon-protected glove box, and carrying out charge and discharge testsThe test current density is 60mA g-1The charging and discharging voltage interval is 0.01-3.0V. The cell test results are shown in table 1.
Example 2
Example 2 differs from example 1 in that:
and step 1), mixing quartz sand, Mg and Al in a mass ratio of 10:5: 5. Keeping the temperature at 1000 ℃ for 10 h.
Step 2) preparing porous silicon: artificial graphite was mixed in a mass ratio of 5: 5. The mass ratio of the grinding balls to the powder is 10: 1. The rotation speed of the ball mill is 500 rpm.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 3
Example 3 differs from example 1 in that:
and step 1), mixing the diatomite, Mg and Al in a mass ratio of 10:5: 5. Keeping the temperature at 1200 ℃ for 20 h.
And 2) mixing the porous silicon, the porous carbon and the artificial graphite according to the mass ratio of 2:3: 5. The ball milling tank is a zirconia tank, and the ball milling ball is a zirconia ball. The mass ratio of the grinding balls to the powder is 20: 1. The ball milling time is 12 h.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 4
Example 4 differs from example 1 in that:
and step 1), mixing the diatomite, Mg and Zn in a mass ratio of 10:8: 2. Keeping the temperature at 1200 ℃ for 20 h.
And 2) mixing the porous silicon, the porous carbon and the natural graphite according to the mass ratio of 2:2: 6. The ball milling tank is a zirconia tank, and the ball milling ball is a zirconia ball. The mass ratio of the grinding balls to the powder is 5: 1. The rotating speed of the ball mill is 1000rpm, and the ball milling time is 12 h.
The porous silicon/carbon composite was characterized as in example 1 and the scanning electron micrograph is shown in figure 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 5
Example 5 differs from example 1 in that:
and step 1), mixing white carbon black, Al and Zn in a mass ratio of 10:8: 4. The temperature is kept at 1500 ℃ for 24 h.
And 2) mixing the porous silicon, the porous carbon and the artificial graphite according to the mass ratio of 1:2: 7. The ball milling tank is agate, and the ball milling balls are polyurethane balls. The mass ratio of the grinding balls to the powder is 1: 1. The rotating speed of the ball mill is 300rpm, and the ball milling time is 24 h.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 6
Example 6 differs from example 1 in that:
and step 1), mixing white carbon black, Mg and Zn in a mass ratio of 10:7: 5. Keeping the temperature at 800 ℃ for 10 h.
And 2) mixing the porous silicon, the porous carbon and the natural graphite according to the mass ratio of 1:2: 7. The ball milling tank is a polyurethane tank, and the ball milling balls are polyurethane balls. The mass ratio of the grinding balls to the powder is 2: 1. The rotating speed of the ball mill is 500rpm, and the ball milling time is 20 h.
The porous silicon/carbon composite was characterized as in example 1, and the X-ray diffraction pattern (XRD) is shown in fig. 2.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 7
Example 7 differs from example 1 in that:
and step 1), mixing white carbon black, Mg and Fe in a mass ratio of 10:8: 2. Keeping the temperature at 900 ℃ for 12 h.
And 2) mixing the porous silicon, the artificial graphite and the mesocarbon microbeads according to the mass ratio of 2:3: 5. The ball milling tank is an agate tank, and the ball milling balls are agate balls. The rotating speed of the ball mill is 800rpm, and the ball milling time is 5 h.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1.
Example 8
Example 8 differs from example 1 in that:
step 1) mixing according to the mass ratio of SBA-15, Mg and Zn of 10:5: 5. Keeping the temperature at 1200 ℃ for 15 h.
And 2) mixing the porous silicon, the natural graphite and the mesocarbon microbeads in a mass ratio of 1:2: 6. The ball milling tank is a polyurethane tank, and the ball milling ball is a corundum ball. The mass ratio of the grinding balls to the powder is 10: 1. The ball milling time is 36 h.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in table 1 and fig. 3.
Example 9
Example 9 differs from example 1 in that:
step 1) mixing according to the mass ratio of SBA-15: Zn: Fe-10: 10: 5. The temperature is kept at 1500 ℃ for 24 h.
And 2) mixing the porous silicon and the natural graphite according to the mass ratio of 4: 6. The ball milling tank is a corundum tank, and the ball milling ball is a corundum ball. The rotating speed of the ball mill is 300rpm, and the ball milling time is 36 h.
The porous silicon/carbon composite was characterized as in example 1.
The positive electrode, negative electrode, electrolyte and battery assembly of the battery were the same as in example 1, and the battery test results of the obtained porous silicon/carbon composite material are shown in the table
Table 1.
It should be understood by those skilled in the art that the foregoing is only an embodiment of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention will be within the scope and disclosure of the present invention.
Claims (11)
1. A preparation method of a porous silicon/carbon composite material comprises the following steps:
1) converting the silicon dioxide template into porous silicon under the metallothermic reduction;
2) and (3) carrying out ball milling on the porous silicon and the carbon source in the step 1) to obtain the silicon-carbon composite material.
2. The method of claim 1, wherein: the silica template selected in the step 1) is one or a combination of more of quartz sand, diatomite, white carbon black and SBA-15.
3. The method according to claim 1 or 2, characterized in that: the metal selected in the step 1) is one or a combination of more of magnesium, aluminum, zinc and iron.
4. A method according to any one of claims 1-3, characterized in that: the mass ratio of the silicon dioxide template to the metal in the step 1) is (1-10): (1-10).
5. The method according to any one of claims 1-4, wherein: the temperature of the metal thermal reduction in the step 1) is 300-1800 ℃, and the temperature is kept for 1-48 h.
6. The method according to any one of claims 1-5, wherein: the carbon source selected in the step 2) is one or a combination of a plurality of natural graphite, artificial graphite, mesocarbon microbeads and porous carbon.
7. The method according to any one of claims 1-6, wherein: the material of the ball milling tank in the step 2) is one of polyurethane, corundum, zirconia and agate; the ball grinding ball is made of one or a combination of more of polyurethane, corundum, zirconia and agate.
8. The method according to any one of claims 1-7, wherein: and 2) the mass ratio of the porous silicon to the carbon source is (1-10): (1-30); the mass ratio of the materials to the ball grinding balls is (1-10): (1-20), preferably (1-8): (1-18).
9. The method according to any one of claims 1-8, wherein: the ball milling conditions in the step 2) are as follows: the rotating speed is 50-2000 rpm; the ball milling time is 10min-48 h.
10. A porous silicon/carbon composite obtainable by the process of any one of claims 1 to 9.
11. A lithium ion battery, wherein a negative electrode material of the lithium ion battery comprises the porous silicon/carbon composite material according to claim 10.
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| CN108682817A (en) * | 2018-05-21 | 2018-10-19 | 北京工业大学 | A kind of porous silicon-carbon cathode material preparation method for lithium ion battery |
| CN109659529A (en) * | 2018-12-17 | 2019-04-19 | 潍坊汇成新材料科技有限公司 | A kind of preparation process of silicon-carbon cathode material |
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|---|---|---|---|---|
| CN102208636A (en) * | 2011-05-12 | 2011-10-05 | 北京科技大学 | Method for preparing porous silicon/carbon composite material by using diatomite as raw material and application |
| CN104979540A (en) * | 2015-07-09 | 2015-10-14 | 东北师范大学 | Preparation method and application of bicontinuous-structural nanocomposite material |
| CN108682817A (en) * | 2018-05-21 | 2018-10-19 | 北京工业大学 | A kind of porous silicon-carbon cathode material preparation method for lithium ion battery |
| CN109659529A (en) * | 2018-12-17 | 2019-04-19 | 潍坊汇成新材料科技有限公司 | A kind of preparation process of silicon-carbon cathode material |
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