CN110212170B - Silicon-based negative electrode material prepared by solid-phase hot pressing and preparation method thereof - Google Patents
Silicon-based negative electrode material prepared by solid-phase hot pressing and preparation method thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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Abstract
The invention discloses a method for preparing a carbon-silicon negative electrode material by a solid phase method, which is mainly characterized in that a silicon-based raw material is subjected to pre-coating treatment to construct a pre-new interface, then a silicon-based precursor with the new interface is subjected to solid phase uniform mixing with asphalt, then compression molding is carried out at a certain temperature, and then pre-oxidation and carbonization are carried out to obtain the carbon-coated silicon-based composite negative electrode material. The method has the characteristics of environmental protection, no pollution, good uniformity, excellent electrochemical performance, low cost, simple process, high efficiency, easy large-scale production and the like, and has good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery electrode materials, in particular to a preparation method of a silicon-based negative electrode material.
Background
Compared with the traditional graphite negative electrode material, the silicon has ultrahigh theoretical specific capacity (4200mAh/g) and lower lithium removal potential (less than 0.5V), and the voltage platform of the silicon is slightly higher than that of the graphite, so that the surface lithium precipitation behavior is not easy to occur during charging, and the safety performance is better, thereby becoming a new research direction of the negative electrode material of the battery.
However, the lithium ion is inserted and removed in the charging and discharging process, so that the silicon volume expands and contracts by more than 300%, the powder material structure gradually collapses, and finally, the electrode active material is separated from the current collector, so that the battery cycle performance is greatly reduced. The carbon coating is widely applied to a main research method for improving the volume expansion and the conductivity of a silicon-based material, the asphalt is widely applied to a carbon source precursor due to low cost and good conductivity after carbonization, but the compatibility of the asphalt and the surface of the silicon-based material is poor, so that the later electrochemical performance is greatly influenced, and the improvement of the compatibility of the carbon source precursor and the silicon surface is very important.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a silicon-based negative electrode material by solid-phase hot pressing, which mainly solves the problem of interface compatibility through two ways, and firstly, a layer of long-chain titanate coupling agent is pre-coated on the surface of a silicon-based powder material to improve the lipophilicity of the surface of the silicon-based material; and the other is that the asphalt precursor is uniformly coated on the surface of the silicon-based material by adopting a hot-pressing composite process. The method has the advantages of simple process, low cost, no pollution, low requirement on equipment and easy realization of industrial application.
The technical scheme of the invention is as follows: a method for preparing a silicon-based anode material by solid-phase hot pressing comprises the following specific steps:
adding a silicon-based raw material into an aqueous solution containing a pretreating agent of isopropyl titanium triisostearate, uniformly stirring and mixing, then evaporating to remove water, and drying to obtain a pre-coated silicon-based powder material;
step two, uniformly mixing the pre-coated silicon-based powder material prepared in the step one with asphalt powder in a solid phase manner;
step three, putting the mixed material prepared in the step two into a grinding tool, and uniformly coating the pitch precursor on the surface of the silicon-based powder material by adopting a hot-pressing composite process;
step four, crushing the silicon-based powder material coated with the pitch precursor on the surface in the step three;
step five, pre-oxidation and carbonization;
step six, crushing;
and step seven, screening to obtain the silicon-based negative electrode material powder.
Further, in the step one, the size of the silicon-based raw material particles is 0.05-15 mu m, and the specific surface area is 5-100m2The mass of the pretreating agent isopropyl titanium triisostearate is 0.1-1% of the total mass.
Further, in the first step, the volume concentration of the pretreating agent isopropyl titanium triisostearate in water is 2-25%.
Further, in the first step, the stirring and mixing speed is 300-.
Further, in the second step, the mass ratio of the silicon-based powder material to the asphalt powder is 10: 1-1: 1.
Furthermore, in the second step, the particle size of the asphalt powder is 1-30 μm.
Furthermore, in the third step, the pressure range adopted in the hot-pressing composite process is 5-15 t, the temperature range is 100-300 ℃, and the time is 0.2-4 h.
Further, in the fifth step, the pre-oxidation and carbonization are specifically calcination under an inert atmosphere, the temperature is 500-1200 ℃, and the calcination time is 3-20 h.
The invention also provides a silicon-based negative electrode material prepared by the method for preparing the silicon-based negative electrode material by solid-phase hot pressing.
The invention also provides an electrode prepared by the silicon-based negative electrode material.
The invention has the beneficial effects that: the method for preparing the silicon-based negative electrode material by solid-phase hot pressing is provided, and the problem of interface compatibility is solved mainly through two ways, namely, a layer of long-chain titanate coupling agent is coated on the surface of a silicon-based powder material in advance, so that the lipophilicity of the surface of the silicon-based material is improved (when the method is not adopted, the hydrophilic-lipophilic value (HLB) of the surface of the silicon-based material is larger than 10), and the hydrophilic-lipophilic value (HLB) of the surface of the silicon-based material is improved by less than 10 after the method is adopted to coat a layer of long-; and the other is that the asphalt precursor is uniformly coated on the surface of the silicon-based material by adopting a hot-pressing composite process. The method has the advantages of simple process, low cost, no pollution, low requirement on equipment and easy realization of industrial application.
Drawings
FIG. 1 is a diagram showing the distribution of the particle size of nano-silicon;
FIG. 2 is the cycle data after the nano-silicon coating in example 1;
FIG. 3 is a graph of SiO particle size distribution;
FIG. 4 is the cycle data after SiO coating in example 2;
FIG. 5 shows the cycle data after SiO coating in example 3.
Detailed Description
The present invention is described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention, and all similar methods and similar variations thereof using the present invention are intended to be encompassed by the present invention.
Example 1
60g of silicon powder (particle size 50nm, specific surface area 45 m) is taken2The distribution diagram of the particle size of the nano silicon is shown in figure 1) is added into 90ml of deionized water containing 8.4g of isopropyl titanium triisostearate, and after stirring at a high speed of 600r/min for 5h, the water is removed by evaporation, and the mixture is dried to obtain a pre-coated silicon-based powder material; and then carrying out solid phase mixing on the prepared pre-coated silicon-based powder material and 12g of asphalt powder through low-speed ball milling for 4 hours. Transferring into a grinding tool, and maintaining at 150 deg.C under 10 ton pressure for 4 hr by hot pressing. And finally, placing the pressed material in a tubular furnace, and sintering for 5 hours at 850 ℃ under an inert atmosphere. And crushing, and screening by adopting a 150-mesh screen to obtain silicon-based negative electrode material powder, which is named as an S-1 sample. As shown in fig. 2, the cycle data after the nano silicon coating is shown, the method adopts a hot-pressing composite process, and innovatively provides a silicon-carbon coating method which has a good coating effect and stable cycle performance.
The obtained silicon-based negative electrode material powder is prepared into an electrode according to the following formula: according to the following steps of 8: 1:1, respectively weighing an S-1 sample, a carbon black conductive agent and a polyimide binder. Firstly, dissolving a polyimide binder with the quality required in proportion in N-methyl pyrrolidone, then uniformly dispersing carbon black in the mixture, adding an S-1 sample to form uniform slurry, finally, blade-coating the uniform slurry on a copper foil, drying at 80 ℃ to remove most of solvent, and drying at 120 ℃ in vacuum for 5 hours to remove residual solvent. And then curing for half an hour at 250 ℃ under an inert atmosphere, cooling to room temperature, rolling, punching, weighing, vacuum drying, transferring into a glove box for liquid injection and packaging, and performing electrochemical performance evaluation.
As can be seen from FIG. 2, the capacity of the nano-silicon treated by the method is still kept above 1000mAh/g after 50 cycles, which is greatly improved compared with the capacity reduced by 80% in 50 cycles of the common nano-silicon coating method. The cycling stability is improved.
Example 2
60g of silicon monoxide powder (particle size of 3-5um, specific surface area of 6.8 m)2G, particle size distribution of SiOAs shown in FIG. 3) was added to 90ml of deionized water containing 2.3g of isopropyl titanium triisostearate, and after stirring at a high speed of 800r/min for 5 hours, water was evaporated and dried to obtain a precoated silicon monoxide powder; then the prepared pre-coated silicon monoxide powder and 12g of asphalt powder are subjected to solid phase mixing by low-speed ball milling for 4 hours. Transferring into a grinding tool, and maintaining at 150 deg.C under 10 ton pressure for 2 hr by hot pressing. And finally, placing the pressed material in a tube furnace, and sintering for 5 hours at 850 ℃ under an inert atmosphere. And crushing, and screening by adopting a 600-mesh screen to obtain silicon monoxide negative electrode material powder, which is named as an S-2 sample.
The silicon-based negative electrode material is prepared by the following formula: according to the following steps of 8: 1:1, respectively weighing the S-2 sample, the carbon black conductive agent and the polyimide binder. Firstly, dissolving a polyimide binder with the quality required in proportion in N-methyl pyrrolidone, then uniformly dispersing carbon black in the mixture, adding an S-2 sample to form uniform slurry, finally, blade-coating the uniform slurry on a copper foil, drying at 80 ℃ to remove most of solvent, and drying at 120 ℃ in vacuum for 5 hours to remove residual solvent. And then curing for half an hour at 250 ℃ under an inert atmosphere, cooling to room temperature, rolling, punching, weighing, vacuum drying, transferring into a glove box for liquid injection and packaging, and performing electrochemical performance evaluation. FIG. 4 shows the cycle data after SiO coating, and the capacity remained over 1000mAh/g and was relatively stable after 80 cycles.
The implementation effect is as follows: and forming a half cell by taking the metal lithium as a counter electrode. The silicon negative electrode of the lithium ion battery adopting the silicon monoxide carbon composite material has the first discharge specific capacity of more than 1800mAh/g under the 1C discharge condition, the charge specific capacity of more than 1300mAh/g and the first efficiency of nearly 70 percent.
Example 3
80g of silicon monoxide powder (particle diameter of 3-5um, specific surface area of 6.8 m)2The particle size distribution diagram of silicon monoxide is shown in figure 3) is added into 120ml of deionized water containing 3.5g of isopropyl titanium triisostearate, stirred at a high speed of 1000r/min for 6h, evaporated to remove water and dried to obtain pre-coated silicon monoxide powder;then the prepared precoated silicon monoxide powder and 15g of asphalt powder are subjected to solid phase mixing by low-speed ball milling for 6 hours. Transferring into a grinding tool, and maintaining for 4h at 200 deg.C under 10 ton pressure by hot pressing composite process. And finally, placing the pressed material in a tube furnace, and sintering for 6 hours at 850 ℃ under an inert atmosphere. And crushing, and screening by using a 600-mesh screen to obtain silicon monoxide negative electrode material powder, which is named as an S-3 sample.
The silicon-based negative electrode material is prepared by the following formula: according to the following steps of 8: 1:1, respectively weighing the S-2 sample, the carbon black conductive agent and the polyimide binder. Firstly, dissolving a polyimide binder with the quality required in proportion in N-methyl pyrrolidone, then uniformly dispersing carbon black in the mixture, adding an S-3 sample to form uniform slurry, finally, blade-coating the uniform slurry on a copper foil, drying at 80 ℃ to remove most of solvent, and drying at 120 ℃ in vacuum for 5 hours to remove residual solvent. And then curing for half an hour at 250 ℃ under an inert atmosphere, cooling to room temperature, rolling, punching, weighing, vacuum drying, transferring into a glove box for liquid injection and packaging, and performing electrochemical performance evaluation. As shown in FIG. 5, the cycle data after SiO coating is shown, and it can be seen from the figure that the capacity is still maintained at 1000mAh/g or more after 100 cycles, and the cycle stability is good.
The implementation effect is as follows: and forming a half cell by taking the metal lithium as a counter electrode. The silicon negative electrode of the lithium ion battery adopting the silicon monoxide carbon composite material has the first discharge specific capacity of more than 1800mAh/g under the 1C discharge condition, the charge specific capacity of more than 1100mAh/g and the first efficiency of more than 70 percent.
The invention has the advantages of low cost, environmental protection, obvious effect, good cyclicity, good conductivity and better application prospect.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. A method for preparing a silicon-based negative electrode material by solid-phase hot pressing is characterized by comprising the following steps: the method comprises the following specific steps:
adding a silicon-based raw material into an aqueous solution containing a pretreating agent of isopropyl titanium triisostearate, uniformly stirring and mixing, then evaporating to remove water, and drying to obtain a pre-coated silicon-based powder material; wherein the silicon-based raw material has a particle size of 0.05-15 μm and a specific surface area of 5-100m2The mass of the pretreating agent isopropyl titanium triisostearate accounts for 0.1 to 1 percent of the total mass; the volume concentration of the pretreating agent isopropyl titanium triisostearate in water is 2-25 percent;
step two, uniformly mixing the pre-coated silicon-based powder material prepared in the step one with asphalt powder in a solid phase manner; the particle size of the asphalt powder is 1-30 μm;
step three, putting the mixed material prepared in the step two into a grinding tool, and uniformly coating the pitch precursor on the surface of the silicon-based powder material by adopting a hot-pressing composite process;
step four, crushing the silicon-based powder material coated with the pitch precursor on the surface in the step three;
step five, pre-oxidation and carbonization;
step six, crushing;
and step seven, screening to obtain the silicon-based negative electrode material powder.
2. The method for preparing the silicon-based anode material by the solid-phase hot pressing according to claim 1, wherein the method comprises the following steps: in the first step, the stirring and mixing speed is 300- & lt1000 & gt r/min, and the time is 1-5 h.
3. The method for preparing the silicon-based anode material by the solid-phase hot pressing according to claim 1, wherein the method comprises the following steps: in the second step, the mass ratio of the silicon-based powder material to the asphalt powder is 10: 1-1: 1.
4. The method for preparing the silicon-based anode material by the solid-phase hot pressing according to claim 1, wherein the method comprises the following steps: in the third step, the pressure range adopted in the hot-pressing composite process is 5-15 t, the temperature range is 100-300 ℃, and the time is 0.2-4 h.
5. The method for preparing the silicon-based anode material by the solid-phase hot pressing according to claim 1, wherein the method comprises the following steps: in the fifth step, the pre-oxidation and carbonization are specifically calcination under inert atmosphere, the temperature is 500-1200 ℃, and the calcination time is 3-20 h.
6. A silicon-based anode material prepared by the method for preparing the silicon-based anode material by the solid-phase hot pressing according to any one of claims 1 to 5.
7. An electrode prepared by using the silicon-based anode material of claim 6.
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