CN111129440A - Silicon dioxide-carbon composite material, preparation method thereof and application thereof in lithium ion battery cathode material - Google Patents
Silicon dioxide-carbon composite material, preparation method thereof and application thereof in lithium ion battery cathode material Download PDFInfo
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Abstract
The invention discloses a silicon dioxide-carbon composite material and a preparation method thereof and application thereof in a lithium ion battery cathode material. Compared with the prior art, the invention adoptsThe self-assembly method has mild conditions, simple steps, no need of complex and expensive equipment, and is beneficial to large-scale popularization, and the prepared silicon dioxide/carbon composite material has a specific discharge capacity of 600 mAh.g after 300 charge-discharge cycles‑1The electrochemical performance is obviously improved.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery cathode materials, and particularly relates to a silicon dioxide/carbon cathode material of a lithium ion battery and a preparation method thereof.
Background
In the face of global energy crisis and such severe environmental pollution, the use of new energy is inevitable, and mobile electronic products and new energy automobiles are rapidly developed by means of continuous progress of scientific technology, and the demand for high-energy-density energy storage batteries is increasing, so that lithium ion batteries with the advantages of high energy density, high output voltage, long cycle life, no memory effect, low self-discharge, no environmental pollution and the like become the object of continuous research of people. The most widely commercialized negative electrode material at present is graphite carbon material, and the carbon material as the negative electrode material has the advantages of abundant source, low cost, high cycle stability, good conductivity and the like, but the actual specific capacity of the graphite carbon negative electrode material is close to 372mAh g-1The theoretical value of (2) is difficult to have a space for improving, the low storage capacity of the graphite can not meet the requirements of mobile electronic products and electric automobiles, on the other hand, the lithium-embedded potential platform of the graphite is close to the deposition potential of metallic lithium, the phenomenon of 'lithium precipitation' is easy to occur in the process of quick charging or low-temperature charging, reduced lithium ions form dendritic crystals on the negative electrode of the graphite, and the graphite is likely to pierce through a diaphragm to reach the positive electrode and generate short circuit, so that potential safety hazards are caused. Therefore, a negative electrode material with high specific capacity and good safety performance needs to be found to replace a carbon material urgently.
Researchers have found that oxides of silicon, such as silicon dioxide, have a relatively high lithium storage capacity. The theoretical capacity of the silica was 1965mAh g-1Although the theoretical capacity of silicon dioxide is less than half of the theoretical capacity of silicon, the cost of silicon dioxide is much less than that of silicon materials, and the volume change is not as serious as that of silicon materials. According to the research of silicon materials, researchers also find that the nano silicon dioxide has better electrochemical activity, but the agglomeration is serious, the conductivity is poor, and the researchers research the defects of the silicon dioxide material to find that the silicon dioxide/carbon composite material is preparedThe material is an effective method for solving the above problems. At present, the preparation methods of the silicon dioxide/carbon composite material mainly comprise a CVD method, a mechanical mixing method and the like, but the preparation methods are complicated in preparation process and expensive in equipment, and the industrial production of the silicon dioxide/carbon composite material is seriously hindered.
Disclosure of Invention
The invention aims to provide a silicon dioxide-carbon composite material, a preparation method thereof and application thereof in a lithium ion battery cathode material, and the silicon dioxide-carbon composite material with good electrochemical performance is prepared and the industrial production thereof is promoted.
The technical purpose of the invention is realized by the following technical scheme.
The silicon dioxide-carbon composite material and the preparation method thereof are carried out according to the following steps:
step 1, treating a carbon skeleton by using mixed acid to enable the surface of the carbon skeleton to have oxygen-containing functional groups
In step 1, the oxygen-containing functional group is a hydroxyl group, a carboxyl group, or a carbonyl group.
In step 1, the carbon skeleton is mesocarbon microbeads, carbon black BP2000, carbon nanotubes and graphite nodules.
In the step 1, the mixed acid is a mixed acid of concentrated sulfuric acid and concentrated nitric acid, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, the mass percent of the concentrated sulfuric acid is 95-98 wt%, and the mass percent of the concentrated nitric acid is 60-65 wt%.
In step 1, the carbon skeleton is oxidized by using mixed acid treatment, and the mixture is stirred uniformly at a stirring speed of 100 to 500 revolutions per minute at a temperature of 60 to 80 ℃ for 0.5 to 20 hours, preferably 6 to 15 hours.
Ammonia water is adopted: deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-3): (3-8) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (5-18): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral; or 3-aminopropyl-trimethylsilane: ammonia water according to the volume ratio (1-6): (1-5) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-10): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral;
in step 2, ammonia water (30-35% by mass of ammonia): deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-2): (3-6); the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (6-14): (0-1); the reaction is carried out at a temperature of from 40 to 50 ℃ for from 10 to 15 hours, preferably from 10 to 12 hours, with stirring at a rate of from 100 to 500 revolutions per minute.
In step 2, 3-aminopropyl-trimethylsilane: ammonia water (the mass percentage of ammonia is 30-35%) according to the volume ratio (1-6): (1-2) preparing to form a mixed solution; the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-8): (0-1); the reaction is carried out at a temperature of from 40 to 50 ℃ for from 10 to 15 hours, preferably from 10 to 12 hours, with stirring at a rate of from 100 to 500 revolutions per minute.
In step 2, a silicon dioxide film is coated on the surface of the carbon skeleton to form a silica-carbon material (deposited silica is connected with the carbon skeleton through hydrogen bonds), and the content of the silica is between 5 and 60 percent (the content of the silica is the mass percent of the silica which is the sum of the mass of the silica and the mass of the carbon skeleton).
Step 3, compounding the silicon dioxide-carbon material prepared in the step 2 with a carbon-containing compound
Stirring to uniformly mix the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2 in a mixed solvent of ethanol and water, evaporating the solvent to dryness at 60-100 ℃ to obtain a composite material of the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2, pyrolyzing the composite material in an inert protective gas atmosphere to pyrolyze the carbon-containing compound into amorphous carbon, heating to 700-800 ℃ from the room temperature of 20-25 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 1-5 hours, and cooling to the room temperature of 20-25 ℃ along with a furnace.
In step 3, the inert protective gas atmosphere is nitrogen, argon or helium.
In step 3, the carbon-containing compound is sucrose, phenolic resin, glucose, polyethylene glycol.
In step 3, the stirring speed is 100-500 revolutions per minute.
In step 3, the volume ratio of ethanol to water is 1: (3-5).
In step 3, the mass ratio of the silica-carbon material prepared in step 2 to the carbon-containing compound is 5: (1-5), preferably 5: (2-4).
In step 3, the temperature is kept for 2 to 3 hours at 700 to 800 ℃.
Compared with the existing method for preparing the silicon dioxide/carbon composite material, the self-assembly method adopted by the invention has the advantages of mild conditions, simple steps, no need of complex and expensive equipment and contribution to large-scale popularization. And the prepared silicon dioxide/carbon composite material can reach a specific discharge capacity of 600 mAh.g after being subjected to charge-discharge cycle for 300 times-1Compared with the silicon dioxide/carbon composite material prepared by simple mixing (the specific discharge capacity can reach 400 mAh.g after 100 times of charge-discharge circulation)-1) The electrochemical performance of the catalyst is obviously improved.
Drawings
FIG. 1 is a scanning electron micrograph of a silica-coated mesocarbon microbead composite material according to the present invention.
FIG. 2 is a scanning electron micrograph of the silica/carbon composite of the present invention.
FIG. 3 is an X-ray diffraction pattern of the silica/carbon composite of the present invention.
FIG. 4 is a thermogravimetric plot of a silica/carbon composite of the present invention.
FIG. 5 is a graph of the cycle life and coulombic efficiency curves for the silica/carbon composite of the present invention.
Fig. 6 is an infrared sum xps spectrum of a silica/carbon composite (green) according to the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples. The mass percent of the ammonia water is 35 percent, the mass percent of the concentrated sulfuric acid is 98 percent, and the mass percent of the concentrated nitric acid is 63w percent, mechanical or magnetic stirring is adopted, and the stirring speed is 300 revolutions per minute.
Example 1
(1) Adding 2g of the intermediate-phase carbon microspheres of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 2
(1) Adding 2g of the intermediate-phase carbon microspheres with the diameter of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 0.5h at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 3
(1) Adding 2g of the intermediate-phase carbon microspheres with the diameter of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 20h at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 4
(1) Adding 2g of the intermediate-phase carbon microspheres of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 4ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 5
(1) Adding 2g of the intermediate-phase carbon microspheres of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 24ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 6
(1) Adding 2g of the intermediate-phase carbon microspheres of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' of MCMB, adding 0.4g of diethyl orthosilicate (TEOS), finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 80mg of phenolic resin into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 7
(1) Adding 2g of graphite nodules of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 5 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized meso-carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' of MCMB, adding 0.4g of diethyl orthosilicate (TEOS), finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 80mg of phenolic resin into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 8
(1) Adding 2g of 8-10um carbon nano-tube into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 5h at the temperature of 70 ℃, washing with deionized water to be neutral, and drying to obtain the oxidized meso-carbon microsphere (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' of MCMB, adding 0.4g of diethyl orthosilicate (TEOS), finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 80mg of phenolic resin into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 9
(1) Adding 2g of 8-10um carbon black BP200 into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 5h at the temperature of 70 ℃, washing with deionized water to be neutral, and drying to obtain the oxidized meso-carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' of MCMB, adding 0.4g of diethyl orthosilicate (TEOS), finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 80mg of phenolic resin into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 10
(1) Adding 2g of the intermediate-phase carbon microspheres of 8-10um into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized intermediate-phase carbon microspheres (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of ammonia water and 4ml of water into a three-neck flask, then adding 0.4g O' MCMB, adding 0.4g of polydiallyldimethylammonium chloride (PDDA), finally dropwise adding 6ml of diethyl orthosilicate (TEOS), mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
Example 11
(1) Adding 2g of the mesocarbon microbeads with the diameter of 8-10 μm into 90ml of mixed solution of concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1, magnetically stirring and reacting for 10 hours at the temperature of 70 ℃, washing the mixture to be neutral by deionized water, and drying the mixture to obtain the oxidized mesocarbon microbeads (O' MCMB).
(2) Adding 200ml of ethanol, 8ml of citric acid and 4ml of water into a three-neck flask, then adding 0.4g O' of MCMB, adding 0.4g of polydiallyldimethylammonium chloride (PDDA), finally dropwise adding 6ml of 3-aminopropyl-trimethylsilane, mechanically stirring and reacting for 12 hours at the temperature of 40 ℃, washing to be neutral by deionized centrifugal water, and drying to obtain the silicon dioxide coated mesocarbon microbeads.
(3) Adding 200mg of sucrose into 10ml of water for dissolving, adding 40ml of ethanol, uniformly stirring, finally adding 200mg of silicon dioxide coated mesocarbon microbeads, ultrasonically dispersing for 30 minutes, stirring in a water bath at 100 ℃, and evaporating the solvent to dryness. And putting the dried sample into an argon tube type furnace, and calcining for 2 hours at 700 ℃ to obtain a final product.
As shown in fig. 1, the surface of the mesocarbon microbeads is uniformly coated with silica. As is clear from figure 2, there is a coating of amorphous carbon on the surface of the silica. From fig. 3 it can be determined that silica and graphite are present in the composite, wherein the silica is amorphous, has no sharp peaks, and has a steamed bread peak around 23 °. FIG. 4 is a thermogravimetric plot of a silica/carbon composite material, determining a composite material having a silicon content of about 15-16% and a carbon content of about 84-85%.
And (3) testing conditions are as follows: mixing the obtained final material with conductive carbon black and polyvinylidene fluoride (mass ratio is 8:1:1), stirring, mixing and grinding under the condition of using N-methyl pyrrolidone as solvent, coating on copper foil of 10um, vacuum drying, tabletting as negative electrode, using lithium sheet as positive electrode, making into button cell, and using blue light test system at voltage of 100 mA-g-1The cycle test was carried out at room temperature. Fig. 5 is a graph of cycle life and coulombic efficiency for a silica/carbon composite. The first charge capacity of the material is 459.5 mAh.g-1After 300 cycles, the reversible capacity of the material climbs to 600mAh g-1. In addition, after the composite material is circulated for 20 times, the coulombic efficiency can reach more than 99%.
| Specific first charge capacity (mAh. g)-1) | Specific charging capacity (mAh. g) after 300 cycles-1) | |
| Example 1 | 470 | 610 |
| Example 2 | 409 | 510 |
| Example 3 | 434 | 560 |
| Example 4 | 411 | 541 |
| Example 5 | 453.6 | 592 |
| Example 6 | 406 | 580 |
| Example 7 | 403 | 439 |
| Example 8 | 412 | 553 |
| Example 9 | 423 | 466 |
| Example 10 | 440 | 473 |
| Example 11 | 420 | 489 |
Fig. 6 is an infrared sum xps spectrum of a silica/carbon composite (green). In the infrared spectrum (a), compared with the silica-coated mesocarbon microbead composite material (red) and the mesocarbon microbead (black), the peak of the silica/carbon composite material (green) is weakened and widened at a hydroxyl group, and the peak of a carbon-oxygen single bond shifts to a low frequency region, so that the existence of a hydrogen bond is proved. Meanwhile, in the map (b) of xps, compared with the oxidized mesocarbon microbeads, the carbon-oxygen single bond, the carbon-oxygen double bond and the carbon-oxygen double bond plus the single bond of the silicon dioxide/carbon composite material (above) all shift to high electronic energy regions to different degrees, which proves that the hydroxyl on the surface of the silicon dioxide and the oxygen-containing functional group on the surface of the mesocarbon microbeads have bonding action to form hydrogen bonds.
The preparation of the silica-carbon composite material can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A silica-carbon composite material, characterized by the following steps:
step 1, treating a carbon skeleton by using mixed acid to enable the surface of the carbon skeleton to have oxygen-containing functional groups; the mixed acid is the mixed acid of concentrated sulfuric acid and concentrated nitric acid, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, the mass percent of the concentrated sulfuric acid is 95-98 wt%, and the mass percent of the concentrated nitric acid is 60-65 wt%
Step 2, in-situ generated silicon dioxide is deposited on the surface of the carbon skeleton, a silicon dioxide film is formed to cover the surface of the carbon skeleton, and a silicon dioxide-carbon material is formed
Ammonia water is adopted: deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-3): (3-8) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (5-18): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral; or 3-aminopropyl-trimethylsilane: ammonia water according to the volume ratio (1-6): (1-5) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-10): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral;
step 3, compounding the silicon dioxide-carbon material prepared in the step 2 with a carbon-containing compound
Stirring to uniformly mix the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2 in a mixed solvent of ethanol and water, evaporating the solvent to dryness at 60-100 ℃ to obtain a composite material of the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2, pyrolyzing the composite material in an inert protective gas atmosphere to pyrolyze the carbon-containing compound into amorphous carbon, heating to 700-800 ℃ from the room temperature of 20-25 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 1-5 hours, and cooling to the room temperature of 20-25 ℃ along with a furnace.
2. The silica-carbon composite according to claim 1, wherein in step 1, the oxygen-containing functional group is a hydroxyl group, a carboxyl group, a carbonyl group; the carbon skeleton is mesocarbon microbeads, carbon black BP2000, carbon nanotubes and graphite spheres; the carbon skeleton is oxidized by mixed acid treatment and stirred uniformly at a speed of 100-500 rpm at 60-80 ℃ for 0.5-20 hours, preferably 6-15 hours.
3. A silica-carbon composite according to claim 1 wherein in step 2, a silica film is coated on the surface of the carbon skeleton to form a silica-carbon material (the deposited silica is bonded to the carbon skeleton by hydrogen bonding) with a silica content of between 5% and 60%; in step 2, ammonia water (30-35% by mass of ammonia): deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-2): (3-6); the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (6-14): (0-1); the reaction is carried out at a temperature of 40-50 ℃ for 10-15 hours, preferably 10-12 hours, with stirring at a rate of 100-500 revolutions per minute; 3-aminopropyl-trimethylsilane: ammonia water (the mass percentage of ammonia is 30-35%) according to the volume ratio (1-6): (1-2) preparing to form a mixed solution; the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-8): (0-1); the reaction is carried out at a temperature of from 40 to 50 ℃ for from 10 to 15 hours, preferably from 10 to 12 hours, with stirring at a rate of from 100 to 500 revolutions per minute.
4. A silica-carbon composite material according to claim 1, wherein in step 3, the inert protective gas atmosphere is nitrogen, argon or helium; the carbon-containing compound is sucrose, phenolic resin, glucose, polyethylene glycol; the stirring speed is 100-500 revolutions per minute.
5. The silica-carbon composite material according to claim 1, wherein in step 3, the volume ratio of ethanol to water is 1: (3-5); the mass ratio of the silicon dioxide-carbon material prepared in the step 2 to the carbon-containing compound is 5: (1-5), preferably 5: (2-4); keeping the temperature for 2-3 hours at 700-800 ℃.
6. The preparation method of the silicon dioxide-carbon composite material is characterized by comprising the following steps of:
step 1, treating a carbon skeleton by using mixed acid to enable the surface of the carbon skeleton to have oxygen-containing functional groups; the mixed acid is the mixed acid of concentrated sulfuric acid and concentrated nitric acid, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1, the mass percent of the concentrated sulfuric acid is 95-98 wt%, and the mass percent of the concentrated nitric acid is 60-65 wt%
Step 2, in-situ generated silicon dioxide is deposited on the surface of the carbon skeleton, a silicon dioxide film is formed to cover the surface of the carbon skeleton, and a silicon dioxide-carbon material is formed
Ammonia water is adopted: deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-3): (3-8) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (5-18): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral; or 3-aminopropyl-trimethylsilane: ammonia water according to the volume ratio (1-6): (1-5) preparing to form a mixed solution, adding poly (diallyldimethylammonium chloride) (PDDA), wherein the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-10): (0-1), adding the carbon skeleton treated in the step 1 into the mixed solution with the volume unit of ml and the mass unit of the poly (diallyldimethylammonium chloride) of mg, reacting at the temperature of 40-60 ℃ under the stirring condition, and performing centrifugal water washing on the obtained product to be neutral;
step 3, compounding the silicon dioxide-carbon material prepared in the step 2 with a carbon-containing compound
Stirring to uniformly mix the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2 in a mixed solvent of ethanol and water, evaporating the solvent to dryness at 60-100 ℃ to obtain a composite material of the silicon dioxide-carbon material and the carbon-containing compound prepared in the step 2, pyrolyzing the composite material in an inert protective gas atmosphere to pyrolyze the carbon-containing compound into amorphous carbon, heating to 700-800 ℃ from the room temperature of 20-25 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 1-5 hours, and cooling to the room temperature of 20-25 ℃ along with a furnace.
7. The method of claim 6, wherein in step 1, the oxygen-containing functional group is a hydroxyl group, a carboxyl group, a carbonyl group; the carbon skeleton is mesocarbon microbeads, carbon black BP2000, carbon nanotubes and graphite spheres; the carbon skeleton is oxidized by mixed acid treatment and stirred uniformly at a speed of 100-500 rpm at 60-80 ℃ for 0.5-20 hours, preferably 6-15 hours.
8. The method of claim 6, wherein in step 2, the silica film is coated on the surface of the carbon skeleton to form a silica-carbon material (the deposited silica is bonded to the carbon skeleton via hydrogen bonds), and the silica content is 5-60%; in step 2, ammonia water (30-35% by mass of ammonia): deionized water: tetraethyl orthosilicate according to the volume ratio of (1-6): (1-2): (3-6); the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (6-14): (0-1); the reaction is carried out at a temperature of 40-50 ℃ for 10-15 hours, preferably 10-12 hours, with stirring at a rate of 100-500 revolutions per minute; 3-aminopropyl-trimethylsilane: ammonia water (the mass percentage of ammonia is 30-35%) according to the volume ratio (1-6): (1-2) preparing to form a mixed solution; the volume mass ratio of the mixed solution to the poly (diallyldimethylammonium chloride) is (2-8): (0-1); the reaction is carried out at a temperature of from 40 to 50 ℃ for from 10 to 15 hours, preferably from 10 to 12 hours, with stirring at a rate of from 100 to 500 revolutions per minute.
9. The method for preparing a silica-carbon composite material according to claim 6, wherein in the step 3, the inert protective gas atmosphere is nitrogen, argon or helium; the carbon-containing compound is sucrose, phenolic resin, glucose, polyethylene glycol; the stirring speed is 100-500 revolutions per minute; the volume ratio of the ethanol to the water is 1: (3-5); the mass ratio of the silicon dioxide-carbon material prepared in the step 2 to the carbon-containing compound is 5: (1-5), preferably 5: (2-4); keeping the temperature for 2-3 hours at 700-800 ℃.
10. Use of a silica-carbon composite according to any one of claims 1 to 5 in the negative electrode material of a lithium ion battery.
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