CN110335993B - Spherical nano porous silicon/silicon oxide/carbon composite material for lithium ion battery and preparation method thereof - Google Patents
Spherical nano porous silicon/silicon oxide/carbon composite material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a spherical nano porous silicon/silicon oxide/carbon composite material for a lithium ion battery and a preparation method thereof, wherein the spherical nano porous silicon/silicon oxide/carbon composite material for the lithium ion battery comprises the following raw materials: the composite material comprises spherical nano porous silicon/silicon oxide/carbon, a conductive agent and a binder in a mass ratio of 6-8:1-3: 1-3; the specific surface area of the spherical nano porous silicon/silicon oxide/carbon is 5-60m2(ii) in terms of/g. According to the invention, the micron-sized spherical nano porous silicon/silicon oxide/carbon composite cathode active material with the multilayer core-shell structure is successfully prepared, the silicon oxide and the carbon layer are coated on the nano porous structure, so that the strength of the nano porous silicon structure can be enhanced, the volume expansion effect of silicon can be effectively buffered, meanwhile, the carbon material can improve the conductivity of the composite material, and the composite material can be successfully applied to a lithium ion battery, so that the composite cathode active material shows better cycle performance.
Description
Technical Field
The invention relates to a composite material and a preparation method thereof, in particular to a spherical nano porous silicon/silicon oxide/carbon composite material for a lithium ion battery and a preparation method thereof.
Background
In order to further meet the requirements of the fields of new energy automobiles and the like on high-energy density batteries, novel and practical high-capacity lithium ion battery cathode materials must be developed. The silicon material has high theoretical lithium storage capacity (about 4200mAh/g) which is far higher than that of the graphite negative electrode material (about 376mAh/g) used commercially at present, and has low de-intercalated lithium potential and rich resource content, but the silicon material has large volume expansion (about 300%) in the charging and discharging process, has poor structural stability and is easy to cause the crushing of the electrode material and the serious attenuation of the capacity. On the other hand, silicon is an intrinsic semiconductor, and has poor conductivity, and the electrical performance of the silicon is also seriously influenced, so that the defects limit the rapid promotion of the commercialization progress of the silicon-based cathode material. In order to overcome the defects, domestic and foreign scholars propose a plurality of solutions, and currently, silicon-carbon composite materials, nanocrystallization and porosification are widely considered as potential materials for developing high-energy-density lithium ion batteries in the future.
CN103474667A discloses a silicon-carbon composite material and a preparation method thereof, wherein nano silicon particles and a graphite material are uniformly mixed by ball milling, then a carbon layer is firstly deposited on the composite particles by a CVD method, and then a liquid phase method is used for coating the carbon layer by organic cracking. The silicon-carbon composite material prepared by the series of methods has excellent cycle performance and rate capability. However, the method has a long operation flow, uses a CVD method, has high cost and is not suitable for industrial production in a short time. CN104332621A discloses a method for preparing hollow nano silicon spheres by using metallothermic reduction, which is to reduce silicon dioxide nanospheres by using active metal, reduce only the surface of the silicon dioxide spheres by controlling reaction time and metal content, remove metal oxide and silicon dioxide of the inner core by using hydrochloric acid and hydrofluoric acid, and finally obtain the hollow nano silicon spheres. The method can effectively reduce the volume expansion of silicon, but the preparation method is also complex and not easy for industrial production, and the electrical properties need to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a spherical nano porous silicon/silicon oxide/carbon multilayer core-shell structure composite material which has excellent cycle performance, simple preparation method and lower cost and is suitable for industrial popularization and a preparation method thereof. The technical means adopted by the invention are as follows:
a spherical nano porous silicon/silicon oxide/carbon composite material for a lithium ion battery comprises the following raw materials:
spherical nanoporous silicon/silicon oxide/carbon, a conductive agent and a binder.
The mass ratio of the spherical nano porous silicon/silicon oxide/carbon to the conductive agent to the binder is 6-8:1-3: 1-3.
The specific surface area of the spherical nano porous silicon/silicon oxide/carbon is 5-60m2/g。
The conductive agent is graphite powder or conductive carbon black.
The binder is one of sodium carboxymethylcellulose, polyvinylidene fluoride or sodium alginate.
The invention also discloses a preparation method of the spherical nano porous silicon/silicon oxide/carbon composite material for the lithium ion battery, which comprises the following steps:
preparing spherical nano porous silicon/silicon oxide/carbon:
s1, mixing the silicon/metal alloy powder with an inorganic acid solution, and magnetically stirring for reaction;
s2, quantitatively filtering the reacted mixture for multiple times by using deionized water and absolute ethyl alcohol solution to obtain a spherical nano porous silicon precipitate;
s3, pre-oxidizing the spherical nano porous silicon precipitate to coat a silicon oxide layer on the surface of the spherical nano porous silicon for improving the strength and structural stability of the nano porous silicon structure;
s4, mixing the spherical nano porous silicon subjected to pre-oxidation treatment and an organic carbon source polymer in a liquid phase medium by magnetic stirring, and then quantitatively filtering for many times by deionized water and an absolute ethyl alcohol solution to obtain a uniform mixture of porous silicon/silicon oxide/polymer;
s5, sintering the obtained uniform mixture of porous silicon/silicon oxide/polymer at high temperature in a protective gas atmosphere to obtain spherical nano porous silicon/silicon oxide/carbon;
preparing a spherical nano porous silicon/silicon oxide/carbon composite material:
s6, grinding the spherical nano porous silicon/silicon oxide/carbon;
s7, mixing the ground spherical nano porous silicon/silicon oxide/carbon with a conductive agent and a binder according to the mass ratio of 6-8:1-3:1-3, and pouring the mixture into a solvent for grinding to obtain uniformly mixed slurry;
and S8, coating the slurry on a metal copper collector, and drying to obtain the spherical nano porous silicon/silicon oxide/carbon composite material.
In the step S1:
the grain size of the silicon/metal alloy powder is 0.1-50 mu m, wherein the metal alloy powder is one or a combination of Al powder, Fe powder, Mg powder, Zn powder or Ca powder;
the inorganic acid solution has a mass concentration of 1-20%, and is HCl or HNO3、H2SO4Or one or more combinations of HF;
the reaction temperature is 25-100 ℃, and the reaction time is 1-20 h.
In the step S2:
the times of quantitative suction filtration are 3-6 times;
in the step S3:
the device for pre-oxidation treatment is a tubular furnace;
in the pre-oxidation treatment process, an air pump provides oxygen flow, the pre-oxidation treatment temperature is 80-300 ℃, and the pre-oxidation treatment time is 1-15 h;
the thickness of the silicon oxide layer is 2-20 nm;
in the step S4:
the mass ratio of the spherical nano porous silicon subjected to pre-oxidation treatment to the organic carbon source polymer is 1-6: 1-6, magnetically stirring and mixing in a liquid phase medium for 1-6 hours;
the times of quantitative suction filtration are 3-6 times;
the organic carbon source polymer is one or a combination of more of petroleum asphalt powder, phenolic resin, Polyacrylonitrile (PAN) or polyvinylpyrrolidone (PVP);
in the step S5:
the high-temperature sintering temperature is 500-1000 ℃, and the heat preservation time is 1-8h at the high-temperature sintering temperature;
the protective gas is one or more of nitrogen, argon, helium, hydrogen or carbon monoxide.
In the step S6:
the grinding time is 0.2-1h, and the specific surface area of the ground spherical nano porous silicon/silicon oxide/carbon is 5-60m2/g；
In the step S7:
the grinding time is 0.5-1 h;
the solvent is deionized water or N-methyl pyrrolidone;
the conductive agent is graphite powder or conductive carbon black;
the binder is one of sodium carboxymethylcellulose, polyvinylidene fluoride or sodium alginate;
in the step S8:
the thickness of the slurry coating coated on the metal copper collector is 50-200 μm;
the drying device is a vacuum drying oven, the drying temperature is 60-120 ℃, and the drying time is 5-15 h.
The invention has the following advantages:
1. according to the invention, the micron-sized spherical nano porous silicon/silicon oxide/carbon composite cathode active material with the multilayer core-shell structure is successfully prepared, the silicon oxide and the carbon layer are coated on the nano porous structure, so that the strength of the nano porous silicon structure can be enhanced, the volume expansion effect of silicon can be effectively buffered, meanwhile, the carbon material can improve the conductivity of the composite material, and the composite material can be successfully applied to a lithium ion battery and shows better cycle performance;
2. the raw materials involved in the invention have low cost and simple process flow, and are easy for large-scale industrial production.
Based on the reasons, the invention can be widely popularized in the fields of materials, preparation methods thereof and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of the silicon/metal alloy powder of example 1.
FIG. 2 is an SEM image of spherical nanoporous silicon/silicon oxide in example 1.
FIG. 3 is an XRD pattern of the silicon/metal alloy powder of example 1.
Fig. 4 is an XRD pattern of spherical nanoporous silicon/silicon oxide/carbon in example 2.
Fig. 5 is a graph of the spherical nanoporous silicon/silica/carbon cycle performance in examples 1 and 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Silicon/aluminum alloy powder is used as a raw material, and the particle size of D50 is 20 mu m; reacting silicon/aluminum alloy powder with 7% of HCl solution by mass concentration, stirring for 10h under mild magnetic force at 50 ℃, and quantitatively filtering for 4 times by using deionized water and absolute ethyl alcohol solution to obtain spherical nano porous silicon precipitate; and placing the spherical nano porous silicon precipitate in a tubular furnace for pre-oxidation treatment, wherein the heating temperature is 120 ℃, and the pre-oxidation reaction time is 5 hours, so that the surface of the spherical nano porous silicon is coated with a silicon oxide layer for improving the strength and the structural stability of the nano porous silicon structure. The spherical nano porous silicon and polyacrylonitrile after pre-oxidation treatment are mixed according to the mass ratio of 1: 1, magnetically stirring for 3 hours; and (3) sintering the obtained uniform mixture of porous silicon/silicon oxide/polymer at high temperature under the argon atmosphere, keeping the reaction temperature at 800 ℃, and preserving the temperature for 3 hours to finally obtain the spherical nano porous silicon/silicon oxide/carbon. Grinding spherical nano porous silicon/silicon oxide/carbon for 0.5h to obtainThe specific surface area of the spherical nanoporous silicon/silica/carbon is 13.1m2Mixing and grinding the ground spherical nano porous silicon/silicon oxide/carbon, conductive carbon black and sodium carboxymethyl cellulose according to the mass ratio of 7:2:1 to obtain uniformly mixed slurry; and coating the slurry on a metal copper collector, wherein the thickness of the coating is 100 mu m, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12h to obtain the spherical nano porous silicon/silicon oxide/carbon composite material. The battery test result shows; the first discharge capacity reaches 1814.1mAh/g, the first charge capacity is 909.6mAh/g, the coulombic efficiency reaches more than 50%, the discharge specific capacity reaches 907.4mAh/g after 100-time circulation under the current density of 100mA/g, the charge capacity is 887.3mAh/g, and the good stability is displayed. It can be seen from FIG. 1 that the silicon/metal alloy powder is spherical in shape, has a uniform particle distribution, and has an average particle size of about 21 μm. From fig. 2, it can be seen that the shape of the nanoporous silicon/silicon oxide material is a sphere, and the morphology mainly comprises blocky primary crystal silicon and nanocluster eutectic silicon. It can be seen from FIG. 3 that the phase structure of the silicon/metal alloy powder is Al3.21Si0.47。
Example 2
Silicon/aluminum alloy powder is used as a raw material, and the particle size of D50 is 20 mu m; reacting silicon/aluminum alloy powder with 7% of HCl solution by mass concentration, stirring for 10h under mild magnetic force at 50 ℃, and quantitatively filtering for 4 times by using deionized water and absolute ethyl alcohol solution to obtain spherical nano porous silicon precipitate; and placing the spherical nano porous silicon precipitate in a tubular furnace for pre-oxidation treatment, wherein the heating temperature is 360 ℃, and the pre-oxidation reaction time is 5 hours, so that the surface of the spherical nano porous silicon is coated with a silicon oxide layer for improving the strength and the structural stability of the nano porous silicon structure. The spherical nano porous silicon and polyacrylonitrile after pre-oxidation treatment are mixed according to the mass ratio of 1: 1, magnetically stirring for 3 hours; and (3) sintering the obtained uniform mixture of porous silicon/silicon oxide/polymer at high temperature under the argon atmosphere, keeping the reaction temperature at 800 ℃, and preserving the temperature for 3 hours to finally obtain the spherical nano porous silicon/silicon oxide/carbon. Grinding the spherical nano porous silicon/silicon oxide/carbon for 0.5h, mixing and grinding the spherical nano porous silicon/silicon oxide/carbon with conductive carbon black and sodium carboxymethylcellulose according to the mass ratio of 7:2:1 to obtain uniformly mixed slurry; and coating the slurry on a metal copper collector, wherein the thickness of the coating is 100 mu m, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12h to obtain the spherical nano porous silicon/silicon oxide/carbon composite material. The battery test result shows; the first discharge capacity reaches 1786.5mAh/g, and the discharge specific capacity reaches 798.1mAh/g after 100-time circulation under the current density of 100 mA/g. Fig. 4 shows that the intensity of the Al peak is reduced, and the main peaks are mainly the silicon peak and the carbon peak.
Fig. 5 shows that the specific capacity of the spherical nanoporous silicon/silicon oxide/carbon is attenuated along with the increase of the cycle number, wherein the cycle performance of the example 1 is the best, the first discharge capacity reaches 1814.1mAh/g, the first charge capacity is 909.6mAh/g, the coulombic efficiency reaches 50.2%, the discharge specific capacity reaches 907.4mAh/g after 100 cycles under the current density of 100mA/g, and the charge capacity is 887.3 mAh/g.
Example 3
Silicon/aluminum alloy powder is used as a raw material, and the particle size of D50 is 20 mu m; carrying out chemical reaction on silicon/aluminum alloy powder and an HCl solution with the mass concentration of 7%, carrying out magnetic mild stirring for 10 hours, wherein the reaction temperature is 50 ℃, and carrying out quantitative suction filtration for 4 times by using deionized water and an absolute ethyl alcohol solution to obtain a spherical nano porous silicon precipitate; and placing the spherical nano porous silicon precipitate in a tubular furnace for pre-oxidation treatment, wherein the heating temperature is 480 ℃, and the pre-oxidation reaction time is 5 hours, so that the surface of the spherical nano porous silicon is coated with a silicon oxide layer for improving the strength and the structural stability of the nano porous silicon structure. Mixing the porous silicon material subjected to pre-oxidation treatment and polyacrylonitrile according to the mass ratio of 1: 1, magnetically stirring for 3 hours; and (3) sintering the obtained uniform mixture of porous silicon/silicon oxide/polymer at high temperature under the argon atmosphere, keeping the reaction temperature at 800 ℃, and preserving the temperature for 3 hours to finally obtain the spherical nano porous silicon/silicon oxide/carbon. Grinding the spherical nano porous silicon/silicon oxide/carbon for 0.5h, mixing and grinding the spherical nano porous silicon/silicon oxide/carbon with conductive carbon black and sodium carboxymethylcellulose according to the mass ratio of 7:2:1 to obtain uniformly mixed slurry; and coating the slurry on a metal copper collector, wherein the thickness of the coating is 100 mu m, and placing the coating in a vacuum drying oven at 80 ℃ for drying for 12h to obtain the spherical nano porous silicon/silicon oxide/carbon composite material. The battery test result shows; the first discharge capacity reaches 1397.3mAh/g, and the discharge specific capacity reaches 592.1mAh/g after 100-time circulation under the current density of 100 mA/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A preparation method of a spherical nano porous silicon/silicon oxide/carbon multilayer core-shell structure composite material for a lithium ion battery is characterized by comprising the following steps:
preparing spherical nano porous silicon/silicon oxide/carbon:
s1, mixing the silicon/metal alloy powder with an inorganic acid solution, and magnetically stirring for reaction; the reaction temperature is 50 ℃;
s2, quantitatively filtering the reacted mixture for multiple times by using deionized water and absolute ethyl alcohol solution to obtain a spherical nano porous silicon precipitate;
s3, pre-oxidizing the spherical nano porous silicon precipitate to coat a silicon oxide layer on the surface of the spherical nano porous silicon; the heating temperature is 120 ℃, and the pre-oxidation reaction time is 5 hours;
s4, mixing the spherical nano porous silicon subjected to pre-oxidation treatment and an organic carbon source polymer in a liquid phase medium by magnetic stirring, and then quantitatively filtering for many times by deionized water and an absolute ethyl alcohol solution to obtain a uniform mixture of porous silicon/silicon oxide/polymer; stirring for 3 hours by magnetic force;
s5, sintering the obtained uniform mixture of porous silicon/silicon oxide/polymer at high temperature in a protective gas atmosphere to obtain spherical nano porous silicon/silicon oxide/carbon; the specific surface area of the obtained spherical nanoporous silicon/silicon oxide/carbon is 13.1m2/g；
Preparing a spherical nano porous silicon/silicon oxide/carbon multilayer core-shell structure composite material:
s6, grinding the spherical nano porous silicon/silicon oxide/carbon;
s7, mixing the ground spherical nano porous silicon/silicon oxide/carbon with a conductive agent and a binder according to the mass ratio of 7:2:1, and pouring the mixture into a solvent for grinding to obtain uniformly mixed slurry;
s8, coating the slurry on a metal copper collector, and drying to obtain the spherical nano porous silicon/silicon oxide/carbon multilayer core-shell structure composite material;
the first discharge capacity reaches 1814.1mAh/g, the first charge capacity is 909.6mAh/g, the coulombic efficiency reaches 50.2%, the discharge specific capacity reaches 907.4mAh/g after 100-time circulation under the current density of 100mA/g, and the charge capacity is 887.3 mAh/g.
2. The method of claim 1, wherein: in the step S1:
the grain size of the silicon/metal alloy powder is 0.1-50 mu m, wherein the metal alloy powder is one or a combination of Al powder, Fe powder, Mg powder, Zn powder or Ca powder;
the inorganic acid solution has a mass concentration of 1-20%, and is HCl or HNO3、H2SO4Or one or more combinations of HF;
the reaction time is 1-20 h.
3. The method of claim 1, wherein: in the step S2:
the times of quantitative suction filtration are 3-6 times;
in the step S3:
the device for pre-oxidation treatment is a tubular furnace;
in the pre-oxidation treatment process, an air pump provides oxygen flow;
the thickness of the silicon oxide layer is 2-20 nm;
in the step S4:
the mass ratio of the spherical nano porous silicon subjected to pre-oxidation treatment to the organic carbon source polymer is 1-6: 1-6, magnetically stirring and mixing in a liquid phase medium;
the times of quantitative suction filtration are 3-6 times;
the organic carbon source polymer is one or a combination of more of petroleum asphalt powder, phenolic resin, polyacrylonitrile or polyvinylpyrrolidone;
in the step S5:
the high-temperature sintering temperature is 500-1000 ℃, and the heat preservation time is 1-8h at the high-temperature sintering temperature;
the protective gas is one or more of nitrogen, argon, helium, hydrogen or carbon monoxide.
4. The method of claim 1, wherein: in the step S6:
the grinding time is 0.2-1h, and the specific surface area of the ground spherical nano porous silicon/silicon oxide/carbon is 5-60m2/g；
In the step S7:
the grinding time is 0.5-1 h;
the solvent is deionized water or N-methyl pyrrolidone;
the conductive agent is graphite powder or conductive carbon black;
the binder is one of sodium carboxymethylcellulose, polyvinylidene fluoride or sodium alginate.
5. The method of claim 1, wherein: in the step S8:
the thickness of the slurry coating coated on the metal copper collector is 50-200 μm;
the drying device is a vacuum drying oven, the drying temperature is 60-120 ℃, and the drying time is 5-15 h.
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| CN111584859B (en) * | 2020-05-22 | 2022-05-27 | 合肥国轩高科动力能源有限公司 | Hollow silicon microsphere-nitrogen-doped carbon nanowire silicon negative electrode material and preparation method and application thereof |
| CN112054178A (en) * | 2020-09-14 | 2020-12-08 | 大连理工大学 | Porous silicon @ silicon oxide @ Al-MOF negative electrode material for lithium ion battery and preparation method and application thereof |
| KR20240011827A (en) * | 2021-05-27 | 2024-01-26 | 시노 어플라이드 테크놀로지 타이완 씨오., 엘티디. | Cathode active material, manufacturing method thereof, and lithium secondary battery manufactured based thereon |
| CN113809296B (en) * | 2021-09-08 | 2022-08-30 | 生态环境部华南环境科学研究所 | Porous silicon-carbon composite material and preparation thereof |
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