CN114709386A - Porous silicon-carbon composite material and preparation method and application thereof - Google Patents
Porous silicon-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN114709386A CN114709386A CN202210294341.9A CN202210294341A CN114709386A CN 114709386 A CN114709386 A CN 114709386A CN 202210294341 A CN202210294341 A CN 202210294341A CN 114709386 A CN114709386 A CN 114709386A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000498 ball milling Methods 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 11
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- 239000008103 glucose Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
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- 235000019698 starch Nutrition 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 239000004964 aerogel Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- -1 silicon dioxide-glucose compound Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- NPXMWPNJQNAVDU-BTVCFUMJSA-N O=[Si]=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound O=[Si]=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O NPXMWPNJQNAVDU-BTVCFUMJSA-N 0.000 description 3
- 239000004965 Silica aerogel Substances 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
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Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a porous silicon-carbon composite material and a preparation method and application thereof. The preparation method of the porous silicon-carbon composite material comprises the following steps: 1) adding water into silicon dioxide and a carbon source to prepare a suspension, and freeze-drying to obtain a porous silicon dioxide-carbon source compound; 2) and calcining the porous silicon dioxide-carbon source compound, and then carrying out ball milling to obtain the porous silicon-carbon composite material. The porous silicon-carbon composite material has the advantages of excellent electrochemical performance, excellent conductivity, simple preparation method, environmental friendliness and low production cost, is suitable for being used as a lithium ion battery cathode material, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a porous silicon-carbon composite material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, high output voltage and the like, is one of battery systems with the most excellent performance, and has a very wide application range. The theoretical energy density of the lithium ion battery is determined by the energy densities of the anode material and the cathode material, and under the condition that the energy density of the anode material is not changed, the improvement of the energy density of the cathode material is beneficial to the improvement of the whole energy density of the lithium ion battery.
Graphite is a common negative electrode material and is widely applied, but the theoretical specific capacity of the graphite is only 372mAh/g, so that the demand of people for high-capacity batteries cannot be met. The theoretical specific capacity of the silicon is up to 4200mAh/g, and the silicon has good application prospect, but the silicon has obvious defects, and the specific expression is as follows: 1) the volume expansion of silicon after lithium intercalation is close to 400%, which can cause the crushing of negative electrode powder particles, lead an unstable SEI film to be generated repeatedly, further consume lithium ions in the electrolyte and even fall off from a current collector; 2) the semiconductor property of silicon itself causes its conductivity to be very limited, and it needs to be combined with conductive phase to meet the practical application requirement.
Therefore, the development of a silicon-based material with excellent electrochemical performance, excellent conductivity and simple preparation process is of great significance.
Disclosure of Invention
The invention aims to provide a porous silicon-carbon composite material and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of the porous silicon-carbon composite material comprises the following steps:
1) adding water into silicon dioxide and a carbon source to prepare a suspension, and then carrying out freeze drying to obtain a porous silicon dioxide-carbon source compound;
2) and calcining the porous silicon dioxide-carbon source compound, and then carrying out ball milling to obtain the porous silicon-carbon composite material.
Preferably, the mass ratio of the silicon dioxide to the carbon source in the step 1) is 1: 0.1-10.
Preferably, the silica in step 1) is selected from at least one of silica aerogel, nano silica, white carbon black, silica sol and silica molecular sieve. The silicon dioxide aerogel, the nano silicon dioxide, the white carbon black, the silica sol and the silicon dioxide molecular sieve are all amorphous silicon dioxide, and compared with crystalline quartz silica, the amorphous silicon dioxide has lower reduction reaction activation energy and better activity.
Preferably, the carbon source in step 1) is at least one selected from glucose, sucrose, soluble starch and resin.
Preferably, the mass percentage concentration of the suspension in the step 1) is 50-75%.
Preferably, the freeze drying in the step 1) is carried out under the conditions that the vacuum degree is 10Pa to 50Pa and the temperature is-50 ℃ to-20 ℃, and the drying time is 48h to 96 h.
Preferably, the calcination in step 2) is specifically performed by: heating to 800-1300 ℃ at the heating rate of 5-10 ℃/min, and then preserving the heat for 1-24 h.
Preferably, the ball milling in the step 2) is carried out under the condition that the rotation speed of the ball mill is 50 rpm-2000 rpm, and the ball milling time is 10 min-48 h.
Preferably, the ball milling tank used in the ball milling in the step 2) is selected from one of a polyurethane ball milling tank, a corundum ball milling tank, a zirconia ball milling tank, an agate ball milling tank and a stainless steel ball milling tank.
Preferably, the ball milling beads used in the ball milling in step 2) are selected from at least one of polyurethane ball milling beads, corundum ball milling beads, zirconia ball milling beads, agate ball milling beads and stainless steel ball milling beads.
A porous silicon-carbon composite material is prepared by the preparation method.
Preferably, the porous silicon-carbon composite material exhibits a coral-like stacked pore structure composed of nanoparticles having a particle diameter of 100nm to 800 nm.
The composition of the negative electrode of the lithium ion battery comprises the porous silicon-carbon composite material.
The invention has the beneficial effects that: the porous silicon-carbon composite material has the advantages of excellent electrochemical performance, excellent conductivity, simple preparation method, environmental friendliness and low production cost, is suitable for being used as a lithium ion battery cathode material, and has wide application prospect.
Specifically, the method comprises the following steps:
1) the porous silicon-carbon composite material is prepared from a silicon dioxide-carbon source suspension by processes of freeze drying, high-temperature reduction, ball milling and the like, nano mesopores can be formed by water sublimation pore-forming in the freeze drying process, partial reduction of silicon dioxide and compounding with carbon can be completed by high-temperature reduction in one step, reduction of the silicon dioxide is not required to be performed by adopting reducing metal, the preparation process is simple, environment-friendly, low in cost and the like;
2) the invention carries out partial reduction of silicon dioxide, and keeps the porous structure of the material, so that the porous silicon-carbon composite material can play the characteristic of high specific capacity of the silicon cathode while keeping the stability.
Drawings
Fig. 1 is an SEM image of the porous silicon-carbon composite of example 1.
Fig. 2 is an XRD pattern of the porous silicon-carbon composite of example 1.
Fig. 3 is an XPS plot of the porous silicon-carbon composite of example 1.
Fig. 4 is a pore distribution diagram of the porous silicon-carbon composite of example 1.
FIG. 5 is a graph of the cycling performance test results of the coin cell of example 1 at a current density of 100 mAh/g.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing nano silicon dioxide, glucose and water according to a mass ratio of 1:1:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-45 ℃ to obtain a porous silicon dioxide-glucose compound;
2) heating the porous silicon dioxide-glucose composite to 900 ℃ at the heating rate of 5 ℃/min, then preserving heat for 2h, adding the calcined product into a polyurethane ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 10:1, adjusting the rotating speed of the ball mill to 450rpm, and carrying out ball milling for 6h to obtain the porous silicon-carbon composite material.
Assembling the button cell:
dispersing a porous silicon-carbon composite material, acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 in N-methylpyrrolidone (NMP) to prepare slurry, coating the slurry on a copper foil current collector, drying and cutting the copper foil current collector into a negative plate, taking metal lithium as a counter electrode, taking a polypropylene microporous membrane as a diaphragm, and taking LiPF with the concentration of 1mol/L6The solution (the solvent is composed of ethylene carbonate and dimethyl carbonate according to the volume ratio of 1: 1) is used as electrolyte, and the button cell is assembled in an argon-filled gas glove box.
Example 2:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing nano silicon dioxide, glucose and water according to a mass ratio of 1:2:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-30 ℃ to obtain a porous silicon dioxide-glucose compound;
2) heating the porous silicon dioxide-glucose composite to 1000 ℃ at the heating rate of 5 ℃/min, then preserving heat for 2h, adding the calcined product into a polyurethane ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 15:1, adjusting the rotating speed of the ball mill to 500rpm, and carrying out ball milling for 6h to obtain the porous silicon-carbon composite material.
The button cell was assembled as in example 1.
Example 3:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing silicon dioxide aerogel, soluble starch and water according to a mass ratio of 1:2:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 10Pa and the temperature is-45 ℃ to obtain a porous silicon dioxide-soluble starch compound;
2) heating the porous silicon dioxide-soluble starch compound to 1100 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 4h, adding the calcined product into a zirconia ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 10:1, adjusting the rotating speed of the ball mill to 600rpm, and carrying out ball milling for 12h to obtain the porous silicon-carbon composite material.
The button cell was assembled as in example 1.
Example 4:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing white carbon black, sucrose and water according to a mass ratio of 1:3:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-30 ℃ to obtain a porous silicon dioxide-sucrose compound;
2) heating the porous silicon dioxide-sucrose composite to 1100 ℃ at the heating rate of 5 ℃/min, then preserving heat for 8 hours, adding the calcined product into a zirconia ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 5:1, adjusting the rotating speed of the ball mill to 400rpm, and carrying out ball milling for 12 hours to obtain the porous silicon-carbon composite material.
The button cell was assembled as in example 1.
Example 5:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing silica aerogel, glucose and water according to a mass ratio of 2:1:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-45 ℃ to obtain a porous silica-glucose compound;
2) heating the porous silicon dioxide-glucose composite to 900 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 4h, adding the calcined product into a zirconia ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 20:1, adjusting the rotating speed of the ball mill to 300rpm, and carrying out ball milling for 20h to obtain the porous silicon-carbon composite material.
The button cell was assembled as in example 1.
Example 6:
a porous silicon-carbon composite material is prepared by the following steps:
1) mixing silica aerogel, sucrose and water according to a mass ratio of 1:2:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-30 ℃ to obtain a porous silica-sucrose compound;
2) heating the porous silicon dioxide-sucrose composite to 1000 ℃ at the heating rate of 5 ℃/min, then preserving heat for 2h, adding the calcined product into a zirconia ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 20:1, adjusting the rotating speed of the ball mill to 500rpm, and carrying out ball milling for 12h to obtain the porous silicon-carbon composite material.
The button cell was assembled as in example 1.
Comparative example:
a silicon-carbon composite material is prepared by the following steps:
1) mixing quartz sand, glucose and water according to a mass ratio of 1:1:2 to prepare a suspension, and drying for 92 hours under the conditions that the vacuum degree is 30Pa and the temperature is-45 ℃ to obtain a silicon dioxide-glucose compound;
2) heating the silicon dioxide-glucose compound to 1000 ℃ at the heating rate of 5 ℃/min, then preserving heat for 2h, adding the calcined product into a polyurethane ball milling tank, adding zirconia balls, wherein the mass ratio of the zirconia balls to the calcined product is 10:1, adjusting the rotating speed of the ball mill to 450rpm, and carrying out ball milling for 6h to obtain the silicon-carbon composite material.
The button cell was assembled as in example 1.
And (3) performance testing:
1) a Scanning Electron Microscope (SEM) image of the porous silicon-carbon composite of example 1 is shown in fig. 1.
As can be seen from fig. 1: the porous silicon-carbon composite material has a coral-like stacked pore structure composed of nanoparticles having a particle diameter of 100nm to 800 nm.
2) An X-ray diffraction (XRD) pattern of the porous silicon-carbon composite of example 1 is shown in fig. 2, and an X-ray photoelectron spectroscopy (XPS) pattern is shown in fig. 3.
As can be seen from fig. 2: the porous silicon-carbon composite material is amorphous and does not contain any crystallization peak.
As can be seen from fig. 3: only characteristic peaks of silicon, oxygen and carbon are observed, which indicates that the porous silicon-carbon composite material only contains three elements of silicon, oxygen and carbon.
3) The pore distribution pattern of the porous silicon-carbon composite material of example 1 tested by the nitrogen adsorption-desorption method is shown in fig. 4.
As can be seen from fig. 4: the pore size of the porous silicon-carbon composite material is concentrated around 5nm and 40 nm.
4) The result of the cycle performance test of the button cell of example 1 at a current density of 100mAh/g is shown in FIG. 5.
As can be seen from fig. 5: the specific capacity of the button battery in example 1 is still 630mAh/g after the button battery is cycled for 300 circles under the current density of 100mAh/g, which shows that the porous silicon-carbon composite material in example 1 has excellent performance.
5) The button cells of examples 1 to 6 and comparative example were subjected to charge-discharge cycle testing, the current density was 60mA/g, the charge-discharge voltage interval was 0.01V to 2.5V, and the test results are shown in the following table:
TABLE 1 Charge-discharge cycling test results for coin cells of examples 1-6 and comparative examples
As can be seen from Table 1: the first charge-discharge specific capacity of the button cells of examples 1-6 is improved by 1-4 times compared with that of the button cells of comparative example, and the button cells of examples 1-6 also have good cycling stability, which indicates that the performance of the porous silicon-carbon composite material of examples 1-6 is significantly better than that of the silicon-carbon composite material of comparative example.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a porous silicon-carbon composite material is characterized by comprising the following steps:
1) adding water into silicon dioxide and a carbon source to prepare a suspension, and freeze-drying to obtain a porous silicon dioxide-carbon source compound;
2) and calcining the porous silicon dioxide-carbon source compound, and then carrying out ball milling to obtain the porous silicon-carbon composite material.
2. The method for preparing a porous silicon-carbon composite material according to claim 1, characterized in that: the mass ratio of the silicon dioxide to the carbon source in the step 1) is 1: 0.1-10.
3. The method for preparing a porous silicon-carbon composite material according to claim 1 or 2, characterized in that: the silicon dioxide in the step 1) is selected from at least one of silicon dioxide aerogel, nano silicon dioxide, white carbon black, silica sol and silicon dioxide molecular sieves.
4. The method for preparing a porous silicon-carbon composite material according to claim 1 or 2, characterized in that: the carbon source in the step 1) is at least one selected from glucose, sucrose, soluble starch and resin.
5. The method for preparing a porous silicon-carbon composite material according to claim 1 or 2, characterized in that: the mass percentage concentration of the suspension in the step 1) is 50-75%.
6. The method for preparing a porous silicon-carbon composite material according to claim 1 or 2, characterized in that: the freeze drying in the step 1) is carried out under the conditions that the vacuum degree is 10 Pa-50 Pa and the temperature is-50 ℃ to-20 ℃, and the drying time is 48h to 96 h.
7. The method for preparing a porous silicon-carbon composite material according to claim 1, characterized in that: the calcination in the step 2) is specifically carried out as follows: heating to 800-1300 ℃ at the heating rate of 5-10 ℃/min, and then preserving the heat for 1-24 h.
8. The method for preparing a porous silicon-carbon composite material according to claim 1 or 7, characterized in that: the ball milling in the step 2) is carried out under the condition that the rotating speed of the ball mill is 50 rpm-2000 rpm, and the ball milling time is 10 min-48 h.
9. A porous silicon-carbon composite material produced by the production method according to any one of claims 1 to 8.
10. A lithium ion battery, characterized in that the composition of the negative electrode comprises the porous silicon-carbon composite of claim 9.
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