CN110828794B - Preparation method of multiple modified silicon-manganese alloy composite negative electrode material - Google Patents
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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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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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention relates to a preparation method of a multiple modified silicon-manganese alloy composite negative electrode material, which comprises the following steps: mixing silicon powder, manganese powder and a ball milling medium, and performing ball milling to obtain a silicon-manganese alloy; adding deionized water into the silicon-manganese alloy for dilution, drying and granulating to obtain silicon-manganese alloy powder; crystallizing the silicon-manganese alloy powder, introducing mixed gas of argon and oxygen, heating, preserving heat, and cooling to room temperature; and adding asphalt and a conductive agent into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain a precursor of the silicon-manganese alloy composite negative electrode material, and pyrolyzing the precursor in an argon atmosphere to obtain the multiple modified silicon-manganese alloy composite negative electrode material. The negative electrode material prepared by the method has excellent first discharge specific capacity, first charge-discharge efficiency and cycle stability, and the preparation method is simple, short in preparation period and low in raw material cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a multiple modified silicon-manganese alloy composite negative electrode material.
Background
The new energy automobile power battery field has higher requirements on the energy density and the service life of the lithium ion battery, the theoretical specific capacity of the traditional graphite cathode material is only 372mAh/g, and the ever-increasing use requirement on the energy density of the lithium ion battery can not be met. Silicon has higher theoretical capacity (4200mAh/g) and is regarded as a novel negative electrode material with the greatest development prospect, but the capacity of the silicon is rapidly attenuated due to the huge volume expansion effect generated in the charging and discharging processes, the service life of a battery is shortened, and the production application cannot be realized.
The existing silicon-based negative electrode material generally has the problems of low first charge-discharge efficiency, large volume expansion, slow early-stage efficiency improvement, rapid capacity attenuation and the like, most of the existing modification methods buffer volume change by forming a core-shell structure through carbon coating, but the effect is improved only through carbon coating, but the actual use requirement cannot be met, and the electrochemical performance needs to be further improved.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a multiple modified silicon-manganese alloy composite negative electrode material.
The invention aims to provide a preparation method of a multiple modified silicon-manganese alloy composite negative electrode material, which comprises the following steps:
(1) mixing silicon powder, manganese powder and a ball milling medium, and performing ball milling to obtain a silicon-manganese alloy;
(2) adding deionized water into the silicon-manganese alloy for dilution, drying and granulating to obtain silicon-manganese alloy powder;
(3) crystallizing the silicon-manganese alloy powder, introducing mixed gas of argon and oxygen, heating, preserving heat, and cooling to room temperature;
(4) and adding asphalt and a conductive agent into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain a precursor of the silicon-manganese alloy composite negative electrode material, and pyrolyzing the precursor in an argon atmosphere to obtain the multiple modified silicon-manganese alloy composite negative electrode material.
Further, in the step (1), the mass ratio of the silicon powder to the manganese powder is 3-5:1, and the volume mass ratio of the ball-milling medium to the total mass of the silicon powder and the manganese powder is 13-17ml:6-8 g. Further, the ball milling medium in the step (1) is absolute ethyl alcohol.
Furthermore, in the step (1), the average grain diameter of the silicon powder is 8-14 μm, and the average grain diameter of the manganese powder is 4-8 μm.
Furthermore, in the step (1), the average grain diameter of the silicon powder is 11 μm, and the average grain diameter of the manganese powder is 6 μm
Further, the drying in the step (2) is spray drying, the inlet temperature of the spray drying is 280-.
Further, the drying in the step (2) is spray drying, wherein the inlet temperature of the spray drying is 300 ℃, and the outlet temperature of the spray drying is 150 ℃.
Further, the mass ratio of argon to oxygen in the mixed gas of argon and oxygen in the step (3) is 17-21: 1.
Further, the temperature rise rate in the step (3) is 8-12 ℃/min, the temperature is raised to 600-900 ℃, and the temperature is maintained for 0.5-2 h.
Further, the conductive agent in the step (4) is graphene and/or carbon nanotubes.
Further, the mass ratio of the asphalt to the total mass of the silicon powder and the manganese powder in the step (4) is 2-4:7, and the mass ratio of the asphalt to the conductive agent is 15: 2-6.
Further, the pyrolysis temperature in the step (4) is 800-.
Compared with the prior art, the invention has the beneficial effects that:
(1) the negative electrode material prepared by the method has excellent first discharge specific capacity, first charge-discharge efficiency and cycle stability, and the preparation method is simple, short in preparation period and low in raw material cost, and is suitable for large-scale industrialized production;
(2) according to the preparation method of the multiple modified silicon-manganese alloy composite negative electrode material, the cycle stability of the silicon-manganese alloy material can be effectively improved through crystallization treatment, the first charge-discharge efficiency and the cycle stability of the silicon-manganese alloy negative electrode material are effectively improved through pyrolytic carbon coating, and the first discharge specific capacity can be obviously improved through adding a conductive agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material comprises the following steps:
(1) putting 56g of silicon powder with the average particle size of 11 microns and 14g of manganese powder with the average particle size of 6 microns into a high-energy ball mill, adding 150ml of absolute ethyl alcohol as a ball milling medium, wherein the ball-material ratio is 10:1, and carrying out ball milling at 2000r/min for 10 hours to obtain a silicon-manganese alloy;
(2) adding 1000ml of deionized water into the silicon-manganese alloy for dilution, and then drying and granulating by using a spray dryer, wherein the inlet temperature of spray drying is 300 ℃, and the outlet temperature of spray drying is 150 ℃, so as to obtain silicon-manganese alloy powder;
(3) putting the silicon-manganese alloy powder into a tubular furnace, introducing a mixed gas of argon and oxygen, wherein the mass fraction of the argon is 95%, the mass fraction of the oxygen is 5%, heating to 600 ℃ at a heating rate of 10 ℃/min, preserving heat for 0.5h, carrying out crystallization treatment, and cooling to room temperature;
(4) and adding 30g of asphalt and 4g of carbon nano tubes as conductive agents into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain precursor powder of the silicon-manganese alloy composite negative electrode material, putting the precursor powder into a tubular furnace, heating to 800 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, preserving heat for 3 hours, performing high-temperature pyrolysis, and cooling to obtain the multiple modified silicon-manganese alloy composite negative electrode material.
Examples 2-13 were compared with example 1, and only some of the conditions were changed, and the other preparation methods were the same as example 1, and the specific changed conditions are shown in table 1.
TABLE 1
Example 14
The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material comprises the following steps:
(1) putting 42g of silicon powder with the average particle size of 8 mu m and 14g of manganese powder with the average particle size of 4 mu m into a high-energy ball mill, adding 122ml of absolute ethyl alcohol as a ball milling medium, wherein the ball-to-material ratio is 10:1, and carrying out ball milling at 2000r/min for 10 hours to obtain a silicon-manganese alloy;
(2) adding 1000ml of deionized water into the silicon-manganese alloy for dilution, and then drying and granulating by using a spray dryer, wherein the inlet temperature of spray drying is 280 ℃, and the outlet temperature of spray drying is 130 ℃ to obtain silicon-manganese alloy powder;
(3) putting the silicon-manganese alloy powder into a tubular furnace, introducing mixed gas of argon and oxygen, wherein the mass fraction of the argon is 94.5 percent, the mass fraction of the oxygen is 5.5 percent, heating to 750 ℃ at the heating rate of 8 ℃/min, preserving heat for 1.25h, carrying out crystallization treatment, and cooling to room temperature;
(4) and adding 16g of asphalt and 2.13g of carbon nano tubes as conductive agents into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain precursor powder of the silicon-manganese alloy composite negative electrode material, putting the precursor powder into a tubular furnace, heating to 875 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, keeping the temperature for 2.5 hours, performing high-temperature pyrolysis, and cooling to obtain the multiple modified silicon-manganese alloy composite negative electrode material.
Example 15
The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material comprises the following steps:
(1) putting 70g of silicon powder with the average particle size of 14 microns and 14g of manganese powder with the average particle size of 8 microns into a high-energy ball mill, adding 178.5ml of absolute ethyl alcohol as a ball milling medium, wherein the ball-material ratio is 10:1, and carrying out ball milling at 2000r/min for 10 hours to obtain a silicon-manganese alloy;
(2) adding 1000ml of deionized water into the silicon-manganese alloy for dilution, and then drying and granulating by using a spray dryer, wherein the inlet temperature of spray drying is 320 ℃, and the outlet temperature of spray drying is 170 ℃ to obtain silicon-manganese alloy powder;
(3) putting the silicon-manganese alloy powder into a tubular furnace, introducing mixed gas of argon and oxygen, wherein the mass of the argon is 95.45%, the mass of the oxygen is 4.55%, heating to 900 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, carrying out crystallization treatment, and cooling to room temperature;
(4) and adding 48g of pitch and 19.2g of carbon nano tubes as conductive agents into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain precursor powder of the silicon-manganese alloy composite negative electrode material, putting the precursor powder into a tubular furnace, heating to 950 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, keeping the temperature for 3.5 hours, performing high-temperature pyrolysis, and cooling to obtain the multiple modified silicon-manganese alloy composite negative electrode material.
Comparative example 1
The preparation method of the multiple modified silicon manganese alloy composite negative electrode material of the comparative example is the same as that of example 1, except that steps (3) and (4) are eliminated.
Comparative example 2
The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material of the comparative example is the same as that of the example 1, except that the step (3) is omitted, and no conductive agent is added in the step (4).
Comparative example 3
The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material of the comparative example is the same as that of the example 1, except that the conductive agent is not added in the step (4).
Test example 1
The negative electrode materials prepared in examples 1 to 15 and comparative examples 1 to 3 were fabricated into button cells, respectively, and the results of the electrochemical performance tests are shown in table 2.
TABLE 2
As can be seen from Table 2, in comparative examples 1 and 3, the cycling stability of comparative example 3 is much higher than that of comparative example 1, because the crystallization treatment is performed in comparative example 3, the cycling stability of the silicon-manganese alloy composite material is greatly improved by the crystallization treatment, and under a high-temperature environment, a small amount of oxygen reacts with the surface of silicon-manganese alloy particles to form SiOxThe oxide layer effectively limits the volume expansion of the silicon-manganese alloy particles in the charging and discharging processes, and greatly improves the cycling stability of the material.
It can be known from comparative examples 1 and 2 that the pyrolytic carbon coating effectively improves the first charge-discharge efficiency and the cycle stability of the cathode material, the pyrolytic treatment greatly improves the first charge-discharge efficiency of the material, the amorphous carbon formed after asphalt pyrolysis effectively reduces the contact between the electrolyte and the silicon particles, increases the coulombic efficiency, and simultaneously the amorphous carbon coating buffers the volume change of the particles, thereby improving the cycle stability.
In example 4, it can be seen that the carbon nanotubes and the graphene which are added simultaneously as the conductive agent have a better synergistic effect on the negative electrode material, and the stability of the material is better. The addition of the conductive material has a remarkable improvement on the initial specific discharge capacity, and in addition, the addition of the conductive agent can be found to obviously improve the initial specific discharge capacity of the material from the example 1 and the comparative example 3.
From examples 5 to 7, it can be seen that the temperature of the crystallization treatment has a large influence on the electrical properties of the prepared negative electrode material, and as the temperature of the crystallization treatment increases, the initial specific discharge capacity decreases, and as the cycle stability increases, the heat preservation time of the crystallization treatment also has a large influence on the electrical properties of the negative electrode material, and from examples 8 to 10, as the heat preservation time increases, the initial specific discharge capacity decreases, but the capacity retention rate increases.
From examples 11 to 13, it can be seen that the high-temperature pyrolysis temperature has a large influence on the initial specific discharge capacity and the capacity retention rate, and when the pyrolysis temperature is 850 ℃, the initial specific discharge capacity of the prepared anode material is the best.
From this analysis, the electrochemical performance of the negative electrode material prepared by the method of the present invention is related to each factor, and the inventors have obtained the optimal conditions for each process through a large number of experiments to prepare the negative electrode material of the present invention, wherein the preparation method of example 11 is the optimal preparation conditions, and the initial discharge specific capacity, the first charge-discharge efficiency and the capacity retention rate of the negative electrode material prepared under the conditions of this example are the best.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material is characterized by comprising the following steps of:
(1) mixing silicon powder, manganese powder and a ball milling medium, and performing ball milling to obtain a silicon-manganese alloy;
(2) adding deionized water into the silicon-manganese alloy for dilution, drying and granulating to obtain silicon-manganese alloy powder;
(3) crystallizing the silicon-manganese alloy powder, introducing a mixed gas of argon and oxygen, wherein the mass ratio of argon to oxygen in the mixed gas of argon and oxygen is 17-21:1, heating, carrying out heat preservation treatment, and cooling to room temperature;
(4) and adding asphalt and a conductive agent into the cooled silicon-manganese alloy powder, fully and uniformly mixing to obtain a precursor of the silicon-manganese alloy composite negative electrode material, and pyrolyzing the precursor in an argon atmosphere to obtain the multiple modified silicon-manganese alloy composite negative electrode material.
2. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1, wherein the mass ratio of the silicon powder to the manganese powder in the step (1) is 3-5:1, and the volume mass ratio of the ball-milling medium to the total mass of the silicon powder and the manganese powder is 13-17ml:6-8 g.
3. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1 or 2, wherein the ball milling medium in the step (1) is absolute ethyl alcohol.
4. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1 or 2, wherein the average particle size of the silicon powder in the step (1) is 8-14 μm, and the average particle size of the manganese powder is 4-8 μm.
5. The method for preparing the multiple modified silicon-manganese alloy composite anode material as claimed in claim 1, wherein the drying in the step (2) is spray drying, the inlet temperature of the spray drying is 280-320 ℃, and the outlet temperature is 130-170 ℃.
6. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1, wherein the temperature rise rate in the step (3) is 8-12 ℃/min, the temperature rises to 600-900 ℃, and the temperature is maintained for 0.5-2 h.
7. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1, wherein the conductive agent in the step (4) is graphene and/or carbon nanotubes.
8. The preparation method of the multiple modified silicon-manganese alloy composite negative electrode material as claimed in claim 1, wherein the ratio of the mass of the asphalt to the total mass of the silicon powder and the manganese powder in the step (4) is 2-4:7, and the mass ratio of the asphalt to the conductive agent is 15: 2-6.
9. The preparation method of the multiple modified silicon-manganese alloy composite anode material as claimed in claim 1, wherein the pyrolysis temperature in the step (4) is 800-950 ℃, and the pyrolysis time is 2.5-3.5 h.
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