CN110854368B - High-capacity silicon-carbon negative electrode precursor material and preparation method thereof - Google Patents
High-capacity silicon-carbon negative electrode precursor material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-capacity silicon-carbon cathode precursor material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, carrying out wet grinding on the silicon source to prepare a pre-oxidized silicon source; wherein the pre-oxidized silicon source contains 5-35% of oxygen, and the thickness of the oxide layer is 5-20 nm; s2, dispersing the pre-oxidized silicon source, the carbon source and the dispersing agent in a solvent, and uniformly stirring to obtain a suspension; wherein, the dispersant is a copolymer containing acid groups, and the acid groups are one or two of sulfonic acid groups and carboxylic acid groups; s3, granulating the prepared suspension by spray drying; and S4, calcining the spray-dried sample at the temperature of 600-1100 ℃ to obtain the high-capacity silicon-carbon cathode precursor material. The invention pre-oxidizes the nano silicon and realizes good dispersion and compounding with the carbon source under the auxiliary action of the dispersing agent, simplifies the preparation method and reduces the production cost under the conditions of high capacity and circulating stability.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a high-capacity silicon-carbon negative electrode precursor material and a preparation method thereof.
Background
In recent years, the increasing use demand of 3C electronic products and electric vehicles for long endurance and light weight has made higher demands on the performance of lithium ion batteries, particularly electrode materials. The silicon material has the advantages of the ultrahigh theoretical specific capacity (Li22Si5) of 4200mAh/g, wide source, low cost and the like, and is the focus and hot spot of current electrode material research and development. However, the silicon material is accompanied with huge volume expansion (up to 300%) in the charging and discharging processes, so that silicon particles are easy to crack or pulverize, the electric contact fails, and the battery performance is rapidly degraded, which seriously restricts the industrialization way of the silicon cathode material.
In order to inhibit and relieve the volume expansion of the silicon cathode, the silicon-carbon composite material which is mainly formed by nano-crystallization of silicon, loose and porous structure and good particle dispersion is improved. In the silicon-carbon composite material, the carbon material can inhibit the agglomeration of nano silicon and buffer the volume expansion of the silicon; meanwhile, the good conductivity of the carbon material can effectively improve the electric contact of the silicon after volume expansion, thereby effectively improving the electrochemical performance of the material. In the high-capacity silicon-carbon material (>700mAh/g), along with the increase of the silicon content, how to effectively realize the good dispersion of the nano silicon particles and reduce the absolute value of volume expansion becomes important to improve the cycle performance of the high-specific-capacity silicon-carbon material.
At the present stage, in order to realize good dispersion of the carbon material and the nano silicon, surface functional groups of the carbon material and the nano silicon are often required to be modified, and the technical means have the problems of complex process, high cost, low productivity and the like, so that effective industrial amplification is difficult to realize, and the industrialization process of the silicon-carbon cathode material is hindered. For example, patent CN 105226253A reports a method for preparing nano-silicon particle-graphite flake-carbon nanotube composite material, which involves amino modification of nano-silicon and acid treatment of graphite flake and carbon nanotube, and requires a long reflow time and a low yield.
Disclosure of Invention
The invention provides a high-capacity silicon-carbon negative electrode precursor material and a preparation method thereof, aiming at the problems of complex dispersion and compounding processes of a carbon material and nano-silicon, high cost, low productivity and the like in the preparation process of the high-capacity silicon-carbon negative electrode precursor material.
The invention is realized by the following technical scheme:
a preparation method of a high-capacity silicon-carbon negative electrode precursor material comprises the following steps:
s1, carrying out wet grinding on the silicon source to prepare a pre-oxidized silicon source; wherein the pre-oxidized silicon source contains 5-35% of oxygen, and the thickness of the oxide layer is 5-20 nm;
s2, dispersing the pre-oxidized silicon source, the carbon source and the dispersing agent in a solvent, and uniformly stirring to obtain a suspension; wherein, the dispersant is a copolymer containing acid groups, and the acid groups are one or two of sulfonic acid groups and carboxylic acid groups;
s3, granulating the prepared suspension by spray drying;
and S4, calcining the spray-dried sample at the temperature of 600-1100 ℃ to obtain the high-capacity silicon-carbon cathode precursor material.
Preferably, in step S1, the silicon source is one or more of elemental silicon, a silicon alloy and silicon monoxide.
Preferably, in step S1, the solvent used for wet grinding is one or more of ethylene glycol, water, methanol, propanol and ethanol; the diameter of the grinding medium zirconia ball is 0.1-1.0 mm, the grinding speed is 2000-4000 rpm, and the grinding time is 5-25 h.
Preferably, in step S2, the pre-oxidized silicon source has a particle size of 50 to 500 nm. The mass ratio of the pre-oxidized silicon source to the dispersing agent is 100: (1-20).
Preferably, in step S2, the carbon source is one or a combination of a simple substance and a carbon-containing compound, and the simple substance is one or a combination of graphite, mesocarbon microbeads, soft carbon, hard carbon, graphene, carbon nanotubes, carbon fibers and conductive carbon black; the carbon-containing compound is one or the combination of asphalt, resin, polyvinyl alcohol, rosin, polyvinylpyrrolidone, polyvinyl butyral, starch, dextrin, cellulose, polyaniline, polyimide, glucose, citric acid and sucrose.
Preferably, in step S2, the stirring speed is 500-3000rpm, and the stirring time is 0.2-3.0 h.
Preferably, in step S3, the spray drying is performed by using a centrifugal or two-fluid spray drying apparatus, wherein the spray inlet temperature is 150 to 190 ℃ and the outlet temperature is 75 to 100 ℃.
Preferably, in step S4, the content of silicon in the high-capacity silicon-carbon negative electrode precursor material is 30 wt.% to 90 wt.%.
Preferably, in the step S4, the calcination time is 4.0-8.0 h; the calcining atmosphere comprises inert gas and second gas, the inert gas is one or two of nitrogen and argon, the second gas is one or combination of air, oxygen and acetylene, and the volume of the inert gas in the total gas accounts for 50-100%.
The high-capacity silicon-carbon cathode precursor material is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
1) the nano silicon prepared by wet grinding has a flat plate shape, and is easier to effectively compound with a sheet carbon source; the prepared nano silicon has more abundant dislocation and crystal boundary, can provide more channels for lithium ion diffusion, and is beneficial to improving the stability and rate capability of a lithium-embedded structure;
2) in the wet grinding process, the in-situ oxide layer coating of the nano silicon can be realized and different coating thicknesses can be obtained by selecting a proper solvent composition (one or more of ethylene glycol, water, methanol, propanol and ethanol), the size (0.1-1.0 mm) of a grinding medium and the grinding time (5-25h), and the bond energy of a Si-O bond is twice that of a Si-Si bond, so that the volume change of the nano silicon material can be better inhibited in the charging and discharging process, meanwhile, the oxide coating layer on the surface can strengthen the interaction between silicon and carbon, stabilize the silicon-carbon interface, and realize the preparation of the Si @ SiOx/C composite material with different Si and C composition ratios, high capacity and high cycle stability;
3) the polymer containing acid groups can effectively disperse the nanoscale silicon source and the carbon source through the effects of steric hindrance, electrostatic repulsion and the like by serving as a dispersing agent, and meanwhile, rich functional groups can form a bonding effect with oxygen-containing groups on the surfaces of the silicon source and the carbon source, so that the silicon source and the carbon source are tightly combined with each other, and the carbon source is uniformly and tightly coated on the surfaces of silicon particles.
The invention pre-oxidizes the nano silicon and realizes good dispersion and compounding with the carbon source under the auxiliary action of the dispersing agent, simplifies the preparation method and reduces the production cost under the conditions of high capacity and circulating stability.
Drawings
FIG. 1 is an enlarged view of a cross-section of a high-capacity silicon carbon precursor material in example 1;
FIG. 2 is an infrared spectrum before and after pre-oxidation of the silicon source in example 1;
FIG. 3 is a first charge-discharge curve of a high-capacity Si-C precursor material in example 1;
FIG. 4 is a graph of the cycle performance of high capacity silicon carbon precursor materials in example 1 and comparative example;
fig. 5 is a scanning electron microscope image of the high-capacity silicon carbon precursor material in example 2.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the high-capacity silicon-carbon cathode precursor material provided by the invention has the advantages that the pre-oxidized silicon source and the carbon source are well dispersed and compounded under the assistance of the dispersing agent, and the preparation method specifically comprises the following steps:
s1, carrying out wet grinding on the silicon source, wherein the wet grinding adopts one or more solvents of ethylene glycol, water, methanol, propanol and ethanol, the diameter of a zirconia ball is 0.1-1.0 mm, the grinding speed is 2000-4000 rpm, and the grinding time is 5-25h to prepare the pre-oxidized silicon source;
s2, dispersing the pre-oxidized silicon source, the carbon source and the dispersing agent in a solvent, and uniformly stirring to obtain a suspension, wherein the stirring speed is 500-3000rpm, and the stirring time is 0.2-3.0 h, preferably 0.5-1 h;
s3, granulating the prepared suspension by using centrifugal or two-fluid spray drying equipment, wherein the temperature of a spray inlet is 150-190 ℃, and the temperature of an outlet is 75-100 ℃.
S4, calcining the spray-dried sample in an inert atmosphere at the temperature of 600-1100 ℃ for 4.0-8.0 h to obtain a high-capacity silicon-carbon cathode precursor material;
in step S4, the content of silicon in the high-capacity silicon-carbon negative electrode precursor material is 30 wt.% to 90 wt.%, preferably 45 wt.% to 65 wt.%.
In the step S1, the silicon source is one or a combination of simple substance silicon, silicon alloy and silicon monoxide; the particle size of the pre-oxidized silicon source is 50-500 nm, the oxygen content is 5% -35%, and the thickness of the oxidation layer is 5-20 nm.
In step S2, the mass ratio of the silicon source to the dispersant is 100: (1-20); the dispersing agent is a copolymer containing acid groups, the acid groups are one or two of sulfonic acid groups and carboxylic acid groups, such as methacrylic acid homopolymer, olefine acid-sulfonic acid copolymer, maleic anhydride/styrene sulfonic acid copolymer or carboxyl-terminated long-chain terpolymer; the solvent is one or the combination of ethanol, polyethylene glycol, isopropanol and propylene glycol; the carbon source can be one or a combination of a simple substance carbon and a carbon-containing compound, and the simple substance carbon can be one or a combination of graphite, mesocarbon microbeads, soft carbon, hard carbon, graphene, carbon nanotubes, carbon fibers and conductive carbon black; the carbon-containing compound can be one or a combination of asphalt, resin, polyvinyl alcohol, rosin, polyvinylpyrrolidone, polyvinyl butyral, starch, dextrin, cellulose, polyaniline, polyimide, glucose, citric acid and sucrose.
In step S4, the calcining atmosphere includes an inert gas and a second gas, the inert gas is one or two of nitrogen and argon, the second gas is one or a combination of air, oxygen and acetylene, wherein the volume of the inert gas in the total gas is 50% to 100%.
The precursor material obtained in step S4 can be used for a commercial lithium ion battery after being subjected to a subsequent process.
Example 1
S1, grinding the micron silicon in a mixed solution of methanol and water, wherein the diameter of a zirconia ball is 0.1mm, the grinding speed is 4000rpm, and the grinding time is 5 hours, so that a pre-oxidized silicon source is prepared, the particle size is 200nm, the oxygen content is 5%, and the thickness of an oxide layer is 5 nm. The scanning electron microscope photograph of fig. 1 shows that the micro silicon is wet-ground to form flat nano silicon with a particle size of about 200 nm; the infrared spectrum of FIG. 2 shows that the absorption peaks of Si-O-Si and Si-OH groups are significantly enhanced, i.e., the material has been successfully pre-oxidized;
s2, mixing the components in a mass ratio of 100: 20: 50: 20, dispersing the pre-oxidized nano silicon, citric acid, asphalt and methacrylic acid homopolymer in ethanol, and uniformly stirring to prepare a suspension, wherein the stirring speed is 500rpm, and the stirring time is 3.0 h;
s3, granulating the prepared suspension by using centrifugal spray drying equipment, wherein the temperature of a spray inlet is 150 ℃, and the temperature of an outlet is 85 ℃;
s4, mixing the sample after spray drying in a volume ratio of 9: 1, calcining at 1100 ℃ for 4.0h in a mixed atmosphere of nitrogen and air to obtain a high-capacity silicon-carbon anode precursor material; the thermogravimetric test results showed that the silicon content in the material was 65 wt.%.
And (3) electrochemical performance characterization:
preparing a silicon-carbon negative electrode precursor material, a carbon nano tube, conductive carbon black Super Pli and CMC: and violently stirring the SBR in deionized water according to a mass ratio of 90:2:2:4 to prepare uniformly mixed slurry, uniformly coating the slurry on a copper foil current collector, drying the copper foil current collector in an oven at 80 ℃ for 10 hours, and cutting the copper foil current collector into a circular pole piece with the diameter of 10 mm. A button cell is assembled by taking a metal lithium sheet as a positive electrode, a PP/PE/PP microporous membrane (Celgard 2400) as a diaphragm and 1.15mol/L LiPF6 (a solvent is a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1: 1: 1) as an electrolyte in an argon-protected glove box, and a charging and discharging test is carried out. As shown in fig. 3, the first charge specific capacity of the high-capacity silicon-carbon anode precursor material can reach 1880.1mAh/g, and the first effect can reach 85.3%; meanwhile, the material shows excellent cycle performance (figure 4), the stable specific capacity can reach 1191.2mAh/g by 1C multiplying power charging and discharging, the capacity can still reach 982.1mAh/g after 160 times of charging and discharging, and the capacity retention rate is 82.5%.
Example 2
S1: and (2) carrying out wet grinding on the ferrosilicon alloy material in a mixed solvent of propanol and ethanol, wherein the diameter of a zirconia ball is 0.5mm, the grinding speed is 2000rpm, the grinding time is 10h, and the prepared pre-oxidized ferrosilicon has the particle size of 150nm, the oxygen content of 12% and the thickness of an oxide layer of 15 nm.
S2: and (2) mixing the following components in percentage by mass as 100: 40: 30: 10, dispersing the pre-oxidized silicon-iron alloy, graphite, resin and acrylic acid-sulfonic acid copolymer in a mixed solvent of propylene glycol and ethanol, and uniformly stirring to obtain a suspension, wherein the stirring speed is 3000rpm, and the stirring time is 0.2 h;
s3, granulating the prepared suspension by using two-fluid spray drying equipment, wherein the temperature of a spray inlet is 170 ℃, and the temperature of an outlet is 100 ℃;
s4, mixing the sample after spray drying in a volume ratio of 5: 1, calcining at 850 ℃ for 6.0h in a mixed atmosphere of nitrogen and acetylene to obtain the high-capacity silicon-carbon cathode precursor material, wherein the content of silicon in the material is 30 wt% according to thermogravimetry and ICP test data, and a scanning electron microscope (figure 5) shows that the material has a loose and porous structure and graphite, pyrolytic carbon and the like in the material are uniformly dispersed.
By adopting the electrochemical test method which is the same as that of the embodiment 1, the reversible specific capacity of the high-capacity silicon-carbon anode precursor material can reach 1002.6mAh/g, and the capacity retention rate is 87.2% after 100 charge-discharge cycles.
Example 3
S1: carrying out wet grinding on the silicon oxide in ethanol, wherein the diameter of a zirconia ball is 1.0mm, the grinding speed is 3000rpm, and the grinding time is 6h, so as to prepare a pre-oxidized silicon source; the particle size of the pre-oxidized silicon source is 500nm, the oxygen content is 35%, and the thickness of the oxide layer is 5 nm.
S2: and (2) mixing the following components in percentage by mass as 100: 2: 10: 20: 1, dispersing the silicon oxide, the carbon nano tube, the polyvinylpyrrolidone, the resin and the maleic anhydride/styrene sulfonic acid copolymer in ethanol, and uniformly stirring to prepare a suspension, wherein the stirring speed is 1500rpm, and the stirring time is 1.5 h;
s3, granulating the prepared suspension by using centrifugal spray drying equipment, wherein the temperature of a spray inlet is 190 ℃ and the temperature of an outlet is 75 ℃;
s4, mixing the sample after spray drying in a volume ratio of 4: 1: 1 nitrogen gas: argon gas: calcining under acetylene at 600 ℃ for 8.0h to obtain the high-capacity silicon-carbon cathode precursor material, and combining thermogravimetry and ICP test data to obtain that the content of silicon in the material is 58 wt.%.
By adopting the electrochemical test method which is the same as that of the embodiment 1, the first discharge specific capacity of the high-capacity silicon-carbon anode precursor material can reach 2105.2mAh/g, the first effect is 80.1%, and the capacity retention rate is 96.6% after 200 charge-discharge cycles.
Example 4
And S1, carrying out wet grinding on the micron silicon in ethylene glycol, wherein the diameter of a zirconia ball is 0.3mm, the grinding speed is 3000rpm, the grinding time is 25h, and the pre-oxidized silicon source with the particle size of 130nm, the oxygen content of 18% and the oxide layer thickness of 20nm is prepared.
S2, mixing the components in a mass ratio of 100: 20: 10: 20, dispersing the pre-oxidized nano silicon, citric acid, asphalt and the carboxyl-terminated long-chain terpolymer dispersing agent in ethanol, and uniformly stirring to obtain a suspension, wherein the stirring speed is 1800rpm, and the stirring time is 1.0 h;
s3, granulating the prepared suspension by using centrifugal spray drying equipment, wherein the temperature of a spray inlet is 170 ℃, and the temperature of an outlet is 80 ℃;
s4, calcining the spray-dried sample in a nitrogen atmosphere at 1000 ℃ for 6.0h to obtain the high-capacity silicon-carbon cathode precursor material; the thermogravimetric test results showed that the silicon content in the material was 90 wt.%.
By adopting the electrochemical test method which is the same as that of the embodiment 1, the reversible specific capacity of the high-capacity silicon-carbon anode precursor material can reach 1997.6mAh/g, the first effect is 76.1%, and the capacity retention rate is 78.2% after 50 cycles. Compared with example 1, the reason why the cycle performance of the material is not ideal is probably that the dispersion difficulty is greatly increased due to the excessively high silicon source proportion, the material is pulverized in the repeated charging and discharging process, a local failure mechanism and interface side reactions frequently occur, and the capacity is rapidly attenuated.
Comparative example
S1, mixing the components in a mass ratio of 100: 20: dispersing 50 purchased nano silicon (the granularity is 100nm), citric acid and asphalt in ethanol, uniformly stirring to prepare a suspension, wherein the stirring speed is 500rpm, and the stirring time is 3.0 h;
s2, granulating the prepared suspension by using centrifugal spray drying equipment, wherein the temperature of a spray inlet is 150 ℃, and the temperature of an outlet is 85 ℃;
s3, mixing the sample after spray drying in a volume ratio of 9: 1, calcining at 1100 ℃ for 4.0h in a mixed atmosphere of nitrogen and air to obtain a high-capacity silicon-carbon anode precursor material; wherein the silicon content is 65 wt.%.
By adopting the electrochemical test method which is the same as that of the embodiment 1, the reversible specific capacity of the high-capacity silicon-carbon anode precursor material under the multiplying power of 1C can reach 1460.7mAh/g, the capacity is attenuated to 895.1mAh/g after 100 cycles, and the retention rate is 61.3% (see figure 4). Compared with the embodiment 1, the pre-oxidation treatment and the dispersing agent of the silicon source are not introduced in the preparation process of the high-capacity silicon-carbon cathode precursor material, so that the electrochemical performance is not ideal. Therefore, the preoxidation treatment of the silicon source and the dispersing agent have the advantages of improving the good dispersion and effective compounding of the high-proportion silicon source and the carbon source; meanwhile, the method is simple and easy to implement, and the precursor material is subjected to subsequent process treatment, so that large-scale production of the high-capacity silicon-carbon anode material can be realized, and the practical process of the high-capacity silicon-carbon anode material is promoted.
Claims (8)
1. A preparation method of a high-capacity silicon-carbon negative electrode precursor material is characterized by comprising the following steps:
s1, carrying out wet grinding on the silicon source to prepare a pre-oxidized silicon source; wherein the pre-oxidized silicon source contains 5-35% of oxygen, and the thickness of the oxide layer is 5-20 nm;
s2, dispersing the pre-oxidized silicon source, the carbon source and the dispersing agent in a solvent, and uniformly stirring to obtain a suspension; wherein, the dispersant is a copolymer containing acid groups, and the acid groups are one or two of sulfonic acid groups and carboxylic acid groups; the dispersant is methacrylic acid homopolymer, olefine acid-sulfonic acid copolymer, maleic anhydride/styrene sulfonic acid copolymer or carboxyl-terminated long-chain terpolymer;
s3, granulating the prepared suspension by spray drying;
s4, calcining the spray-dried sample at 600-1100 ℃ to obtain a high-capacity silicon-carbon negative electrode precursor material;
in step S1, the solvent used for wet grinding is one or more of ethylene glycol, water, methanol, propanol, and ethanol; the diameter of the grinding medium zirconia ball is 0.1-1.0 mm, the grinding speed is 2000-4000 rpm, and the grinding time is 5-25 h;
in step S2, the carbon source is a carbon-containing compound or a combination of a simple substance and a carbon-containing compound, and the simple substance is one or a combination of graphite, mesocarbon microbeads, soft carbon, hard carbon, graphene, carbon nanotubes, carbon fibers and conductive carbon black; the carbon-containing compound is one or the combination of asphalt, resin, polyvinyl alcohol, rosin, polyvinylpyrrolidone, polyvinyl butyral, starch, dextrin, cellulose, polyaniline, polyimide, glucose, citric acid and sucrose.
2. The method for preparing a high-capacity silicon-carbon anode precursor material according to claim 1, wherein in step S1, the silicon source is one or more of elemental silicon, a silicon alloy and silicon monoxide.
3. The method for preparing the high-capacity silicon-carbon negative electrode precursor material according to claim 1, wherein in step S2, the particle size of the pre-oxidized silicon source is 50-500 nm, and the mass ratio of the pre-oxidized silicon source to the dispersing agent is 100: (1-20).
4. The method as claimed in claim 1, wherein in step S2, the stirring speed is 500-3000rpm, and the stirring time is 0.2-3.0 h.
5. The method for preparing the high-capacity silicon-carbon anode precursor material according to claim 1, wherein in the step S3, spray drying is performed by using a centrifugal or two-fluid spray drying device, wherein the spray inlet temperature is 150-190 ℃ and the spray outlet temperature is 75-100 ℃.
6. The method for preparing the high-capacity silicon-carbon negative electrode precursor material according to claim 1, wherein in the step S4, the content of silicon in the high-capacity silicon-carbon negative electrode precursor material is 30 wt.% to 90 wt.%.
7. The method for preparing the high-capacity silicon-carbon anode precursor material according to claim 1, wherein in the step S4, the calcination time is 4.0-8.0 h; the calcining atmosphere comprises inert gas and second gas, the inert gas is one or two of nitrogen and argon, the second gas is one or combination of air, oxygen and acetylene, and the volume of the inert gas in the total gas accounts for 50-100%.
8. The high-capacity silicon-carbon negative electrode precursor material obtained by the preparation method of any one of claims 1 to 7.
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