CN114242987B - Preparation method of three-dimensional porous silicon-carbon composite material - Google Patents
Preparation method of three-dimensional porous silicon-carbon composite material Download PDFInfo
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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Abstract
The invention discloses a preparation method of a three-dimensional porous silicon-carbon composite material, which comprises the following steps: firstly preparing silicon dioxide-polymer nanofiber, then soaking the nanofiber in a dispersion liquid of nano silicon, and obtaining the silicon-carbon composite material through hydrothermal reaction, freeze drying and carbonization. The composite material is characterized in that nano silicon is uniformly dispersed in meshes of a three-dimensional frame formed by silicon dioxide fibers, and the fibers are mutually staggered and penetrated to form pores, so that the expansion of a silicon-carbon material is reduced; meanwhile, the network structure formed by the coupling effect of the silane coupling agent between the nano-silicon is utilized to improve the conductivity and the structural stability of the material, and finally the silicon-carbon material with high porosity, large specific surface area and low expansion rate is obtained.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a preparation method of a three-dimensional porous silicon-carbon composite material.
Background
Along with the increase of the market demand for lithium ion batteries with high specific energy density, the lithium ion battery negative electrode material is required to have high specific capacity and low expansion, and most of lithium ion battery negative electrodes in the market at present adopt graphite as a raw material, however, the theoretical capacity of the graphite is only 372mAh/g, and the higher requirement of the market for the negative electrode is difficult to meet. Silicon materials are consistently valued by researchers for their advantages of theoretical capacity up to 4200mAh/g, lower delithiation potential, and rich storage capacity. However, silicon generates a great volume change during charge and discharge, and its low conductivity of material affects its rate capability and cycle performance. The measures for reducing the expansion of the silicon-carbon material mainly comprise the nanocrystallization, the porosification and the carbon coating of the silicon, but the primary efficiency of the material is low while the expansion of the material is reduced, the electronic conductivity is not improved, and meanwhile, the material stripping easily occurs between the silicon core and the carbon shell in the long-term circulation process, so that the circulation performance is influenced. On the one hand, the three-dimensional porous technology can better accommodate the multidirectional volume expansion of silicon in the cyclic process, and meanwhile, the multidimensional structure can increase the dimension of the volume expansion, so that the expansion of the silicon in the direction perpendicular to the electrode is reduced, and the electronic conductivity of the material is improved by utilizing the silicon and carbon composite technology.
Disclosure of Invention
In order to reduce the expansion of the silicon-carbon material and improve the cycle performance, nano silicon is dispersed between network layers formed by the silicon dioxide-polymer nano fiber by a hydrothermal method, and a network structure formed by the action of a coupling agent is utilized to obtain the silicon-carbon composite material, and the composite material has the characteristics of high porosity, large specific surface area, low expansion rate, high specific capacity and the like.
The invention provides a preparation method of a three-dimensional porous silicon-carbon composite material, which comprises the following steps:
(1) Preparation of silica-polymer nanofibers:
dissolving a polymer and a silicon source in an organic solvent to obtain a precursor solution, then carrying out electrostatic spinning, and drying under vacuum condition to obtain the silica-polymer nanofiber, wherein the mass ratio of each component is polymer to silicon source to organic solvent= (1-10) = (1-10): 100;
(2) Preparing a three-dimensional porous silicon-carbon composite material:
dispersing silicon dioxide-polymer nano fiber in an organic solvent of a silane coupling agent, adding nano silicon and carbon nano tube for dispersion, transferring into a high-pressure reaction kettle, reacting for 1-6 h at 100-200 ℃, then adopting 1wt% of dilute hydrochloric acid for cleaning, freeze-drying to obtain a silicon dioxide/nano silicon composite material B, transferring into a mixed solution of ammonium fluoride and water for soaking for 24-72 h, filtering, vacuum-drying, heating to 600-1000 ℃ at a heating rate of 1-10 ℃/min under an inert atmosphere, preserving heat for 1-24 h, naturally cooling to room temperature under the inert atmosphere, and then ball-milling and crushing to obtain the three-dimensional porous silicon-carbon composite material, wherein the mass ratio of each component is the silicon dioxide-polymer nano fiber, the silane coupling agent, the nano silicon and the carbon nano tube, the organic solvent= (10-20): (0.5-2): (1-5): (0.5-2): 500.
In a preferred embodiment of the invention, the polymer in step (1) is polyvinyl alcohol, polyvinylidene fluoride, polyethylene oxide, polyvinyl acetate, polyvinyl butyral or polyvinylpyrrolidone.
In a preferred embodiment of the present invention, the silicon source in step (1) is tetramethyl orthosilicate, tetraethyl orthosilicate, diethoxydimethylsilane, tetrapropyl orthosilicate, tetrabutyl orthosilicate or silicon tetrachloride.
In a preferred embodiment of the present invention, the organic solvent in step (1) and step (2) is ethanol, ethylene glycol, isopropanol, glycerol, N-dimethylformamide or N-methylpyrrolidone.
In a preferred embodiment of the present invention, the silane coupling agent in step (2) is gamma-aminopropyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane or gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
In a preferred embodiment of the present invention, in the step (2), the freeze-drying temperature is-50 to-20 ℃ and the time is 24 to 72 hours.
The beneficial effects are that:
according to the invention, the polymer is combined with various silicon sources through electrostatic spinning, so that the formed nano silicon dioxide fiber has high strength and proper pores, a proper space is provided for embedding nano silicon later, the expansion of silicon in the charge and discharge process is greatly relieved, and the cycle performance of the nano silicon dioxide fiber is improved. Meanwhile, nano silicon is filled between silicon dioxide fiber layers, so that the tap density and the contact area of the material are improved, the electronic impedance of the material is reduced, and the bonding force between the nano silicon and the silicon dioxide is improved by utilizing the bridge action of the coupling agent between the nano silicon and the silicon dioxide.
Drawings
The invention may be better understood by reference to the following description of an embodiment of the invention, taken in conjunction with the accompanying drawings in which:
fig. 1 is an SEM image of the three-dimensional porous silicon carbon composite material prepared in example 1.
Detailed Description
Example 1
1) Preparation of silica-polymer nanofibers:
dissolving 5g of polyvinyl alcohol and 5g of ethyl orthosilicate in 100ml of ethylene glycol organic solvent to obtain a precursor solution, carrying out electrostatic spinning, and drying for 48 hours at 50 ℃ under vacuum condition to obtain silica nanofiber;
2) Preparing a three-dimensional porous silicon-carbon composite material:
dispersing 15g of silica nanofiber in 500ml of ethylene glycol organic solvent with the concentration of 0.2wt% gamma-aminopropyl triethoxysilane, adding 3g of nano-silicon and 1g of carbon nano-tubes, transferring into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 150 ℃, cleaning for 3 times by adopting 1wt% dilute hydrochloric acid, and freeze-drying for 48 hours at the temperature of minus 30 ℃ to obtain a silica/nano-silicon composite material B; then transferring the mixture into a mixed solution of ammonium fluoride and water (volume ratio is 1:1) for soaking for 48 hours, filtering, drying in vacuum, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon inert atmosphere, preserving heat for 12 hours, naturally cooling to room temperature under the argon inert atmosphere, and performing ball milling and crushing to obtain the three-dimensional porous silicon-carbon composite material.
Example 2
1) Preparation of silica-polymer nanofibers:
1g of polyethylene oxide and 1g of tetrabutyl orthosilicate are dissolved in 100ml of isopropanol organic solvent to obtain precursor solution, and then electrostatic spinning is carried out, and drying is carried out for 48 hours under the vacuum condition of 50 ℃ to obtain silica nanofiber;
2) Preparing a three-dimensional porous silicon-carbon composite material:
dispersing 10g of silica nanofiber in 500ml of isopropanol organic solvent of 0.1wt% gamma- (methacryloyloxy) propyl trimethoxysilane, adding 1g of nano silicon and 0.5g of carbon nano tubes, transferring to a high-pressure reaction kettle, reacting at 100 ℃ for 6 hours, washing with 1wt% dilute hydrochloric acid for 3 times, and freeze-drying at-50 ℃ for 72 hours to obtain a silica/nano silicon composite material B; then transferring the mixture into a mixed solution of ammonium fluoride and water (volume ratio is 1:1) for soaking for 24 hours, filtering, drying in vacuum, heating to 600 ℃ at a heating rate of 1 ℃/min under an argon inert atmosphere, preserving heat for 24 hours, naturally cooling to room temperature under the argon inert atmosphere, and performing ball milling and crushing to obtain the three-dimensional porous silicon-carbon composite material.
Example 3
1) Preparation of silica-polymer nanofibers:
10g of polyvinyl acetate and 10g of silicon tetrachloride are dissolved in 100ml of N, N-dimethylformamide organic solvent to obtain precursor solution, and then electrostatic spinning is carried out, and drying is carried out for 48 hours under the vacuum condition at 50 ℃ to obtain silicon dioxide nano fibers;
2) Preparing a three-dimensional porous silicon-carbon composite material:
dispersing 20g of silica nanofiber in 500ml of N, N-dimethylformamide organic solvent of 0.4wt% gamma- (2, 3-glycidoxy) propyl trimethoxysilane, adding 5g of nano silicon and 2g of carbon nano tubes, transferring into a high-pressure reaction kettle, reacting for 1h at 200 ℃, cleaning for 3 times by adopting 1wt% dilute hydrochloric acid, and freeze-drying for 24h at-20 ℃ to obtain a silica/nano silicon composite material B; then transferring the mixture into a mixed solution of ammonium fluoride and water (volume ratio is 1:1) for soaking for 72 hours, filtering, drying in vacuum, heating to 1000 ℃ at a heating rate of 10 ℃/min under an argon inert atmosphere, preserving heat for 1 hour, naturally cooling to room temperature under the argon inert atmosphere, and performing ball milling and crushing to obtain the three-dimensional porous silicon-carbon composite material.
Comparative example
Adding 15g of silicon dioxide, 3g of nano silicon and 3g of polyvinyl alcohol into 100ml of ethylene glycol, uniformly mixing by ball milling, transferring into a tube furnace, heating to 700 ℃ in an argon inert atmosphere at a heating rate of 5 ℃/min, preserving heat for 12 hours, naturally cooling to room temperature in the argon inert atmosphere, ball milling and crushing to obtain the silicon-carbon composite material.
Test section
Test 1
SEM testing was performed on the three-dimensional porous silicon carbon composite material of example 1, and the test results are shown in fig. 1. As can be seen from FIG. 1, the particle size of the silicon-carbon composite material is 10-15 μm, and the size distribution is uniform and reasonable.
Test 2
The three-dimensional porous silicon-carbon composite materials of examples 1-3 and the silicon-carbon composite materials of comparative examples were tested for specific surface area, powder conductivity and porosity according to the method in the national standard GBT-245332009, lithium ion battery graphite negative electrode material, and the test results are shown in Table 1.
Table 1 comparison of physicochemical test results
As can be seen from table 1: the three-dimensional porous silicon-carbon composite material has larger porosity and specific surface area due to the pore structure left between the silicon dioxide fiber layers, and simultaneously, the synthesis method can fully and uniformly mix and fully contact the silicon dioxide and the nano silicon, and simultaneously, the carbon nano tube with high conductivity is added in the method, so that the conductivity of the material is improved.
Test 3
The three-dimensional porous silicon-carbon composite materials of examples 1 to 3 and the silicon-carbon composite material of comparative example are respectively used as active materials to prepare pole pieces, and the specific preparation method is as follows: adding 9g of active substances, 0.5g of conductive agent SP and 0.5g of binder LA136D into 220mL of deionized water, and uniformly stirring to obtain slurry; and coating the slurry on a copper foil current collector to obtain the copper foil current collector.
The sheet with the silicon carbon composite of example 1 and doped with 80% of artificial graphite as an active material is labeled a, the sheet with the silicon carbon composite of example 2 and doped with 80% of artificial graphite as an active material is labeled B, the sheet with the silicon carbon composite of example 3 and doped with 80% of artificial graphite as an active material is labeled C, and the sheet with the silicon carbon composite of comparative example and doped with 80% of artificial graphite as an active material is labeled D.
Then the prepared pole piece is used as a positive electrode and is combined with a lithium piece, electrolyte and a diaphragmThe button cell was assembled in a glove box with both oxygen and water contents below 0.1 ppm. Wherein the diaphragm is Celgard 2400, and the electrolyte is LiPF 6 LiPF, solution of LiPF) 6 The concentration of (C) is 1mol/L, and the solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DMC) (weight ratio is 1:1). The button cells are designated A-1, B-1, C-1, D-1, respectively. Then, the performance of the button cell is tested by adopting a blue electric tester, and the test conditions are as follows: the charge and discharge rate of 0.1C is 0.05-2V, and the cycle is stopped after 3 weeks. The test results are shown in Table 2.
TABLE 2 Performance test results
As can be seen from Table 2, the silicon-carbon composite material of the present invention has high first discharge capacity and first efficiency, on one hand, the high electron conductivity of the silicon-carbon material of the embodiment improves gram capacity of the material, and on the other hand, the method of the present invention can uniformly contact nano silicon with silicon dioxide and generate silicon monoxide and other materials in the subsequent sintering process to improve the first charge and discharge efficiency of the material, thereby improving the discharge capacity of the material.
Test 4
The pole pieces a to D were used as negative electrodes, and were made of a ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) The electrolyte and the separator are assembled into a soft package battery of 5 Ah. Wherein the diaphragm is Celgard 2400, and the electrolyte is LiPF 6 Solution (solvent is a mixed solution of EC and DEC in volume ratio of 1:1, liPF) 6 At a concentration of 1.3 mol/L). The prepared soft package batteries are respectively marked as A-2, B-2, C-2 and D-2.
The following performance tests were performed on the pouch cell:
(1) The thickness D1 of the negative pole piece of the soft package battery A-2~D-2 after constant volume is anatomically tested, then the soft package battery is fully charged after each soft package battery is circulated for 100 times (1C/1C@25+/-3 ℃ @2.8-4.2V), and then the thickness of the negative pole piece after the anatomically test circulation is carried out againD2, then the expansion ratio was calculated (expansion ratio is) The test results are shown in table 3. And the liquid absorption capacity of the pole piece is tested. Details are shown in Table 3.
TABLE 3 expansion ratio test results of negative electrode plate
As can be seen from table 3, the expansion rate of the negative electrode tab of the soft-pack lithium ion battery using the silicon-carbon composite material of the present invention is significantly lower than that of the comparative example. The reason is that the material of the invention contains a network structure formed by silicon dioxide fibers with high mechanical strength, and the carbon nano tube is buffered and expanded in the charge and discharge process, and has high specific surface area, so that the liquid absorption capacity of the pole piece is improved.
(2) And (3) carrying out cycle performance test on the soft package battery A-2~D-2, wherein the test conditions are as follows: the charge-discharge voltage range is 2.8-4.2V, the temperature is 25+/-3.0 ℃, and the charge-discharge multiplying power is 1.0C/1.0C. The test results are shown in Table 4.
TABLE 4 results of cycle performance test
As can be seen from Table 4, the soft-pack lithium ion battery prepared from the silicon-carbon composite material of the invention has better cycle performance at each stage of cycle than the comparative example, because the three-dimensional network structure in the silicon-carbon composite material of the invention reduces the volume expansion rate and improves the structural stability of the electrode, thereby improving the cycle performance.
Claims (5)
1. The preparation method of the three-dimensional porous silicon-carbon composite material is characterized by comprising the following steps of:
(1) Preparation of silica-polymer nanofibers:
dissolving a polymer and a silicon source in an organic solvent to obtain a precursor solution, then carrying out electrostatic spinning, and drying under vacuum condition to obtain the silica-polymer nanofiber, wherein the mass ratio of each component is polymer to silicon source to organic solvent= (1-10) = (1-10): 100;
(2) Preparing a three-dimensional porous silicon-carbon composite material:
dispersing the silicon dioxide-polymer nano fiber in an organic solvent of a silane coupling agent, adding nano silicon and carbon nano tubes for dispersion, transferring the dispersed silicon dioxide-polymer nano fiber into a high-pressure reaction kettle, reacting for 1-6 h at the temperature of 100-200 ℃, then adopting 1wt% of diluted hydrochloric acid for cleaning, freeze-drying for 72h at the temperature of 50 ℃ below zero to obtain a silicon dioxide/nano silicon composite material B, transferring the silicon dioxide/nano silicon composite material B into a mixed solution of ammonium fluoride and water for soaking for 24-72 h, filtering, vacuum drying, heating to 600-1000 ℃ at the heating rate of 1-10 ℃/min under an inert atmosphere, preserving heat for 1-24 h, naturally cooling to room temperature under the inert atmosphere, and then ball-milling and crushing to obtain the three-dimensional porous silicon-carbon composite material, wherein the mass ratio of each component is that the silicon dioxide-polymer nano fiber comprises the silicon nano silicon and the carbon nano tube comprises the organic solvent= (10-20) = (0.5-2): (1-5): (0.5-2): (500).
2. The method according to claim 1, wherein the polymer in the step (1) is polyvinyl alcohol, polyvinylidene fluoride, polyethylene oxide, polyvinyl acetate, polyvinyl butyral, or polyvinyl pyrrolidone.
3. The method according to claim 1, wherein the silicon source in the step (1) is tetramethyl orthosilicate, tetraethyl orthosilicate, diethoxydimethylsilane, tetrapropyl orthosilicate, tetrabutyl orthosilicate, or silicon tetrachloride.
4. The method according to claim 1, wherein the organic solvent in the step (1) and the step (2) is ethanol, ethylene glycol, isopropyl alcohol, glycerol, N-dimethylformamide or N-methylpyrrolidone.
5. The method according to claim 1, wherein the silane coupling agent in the step (2) is gamma-aminopropyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane or gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
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