CN112751007A - Porous silicon/carbon lithium ion battery cathode material and preparation method thereof - Google Patents

Porous silicon/carbon lithium ion battery cathode material and preparation method thereof Download PDF

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CN112751007A
CN112751007A CN202110072040.7A CN202110072040A CN112751007A CN 112751007 A CN112751007 A CN 112751007A CN 202110072040 A CN202110072040 A CN 202110072040A CN 112751007 A CN112751007 A CN 112751007A
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porous silicon
lithium ion
ion battery
hours
carbon lithium
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郭兴忠
刘威
王军长
王金田
杨辉
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a porous silicon/carbon lithium ion battery cathode material, which comprises the following steps: preparing porous silicon dioxide by using a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, 1,3, 5-trimethylbenzene, methyl orthosilicate and the like; carrying out heat treatment on the porous silicon dioxide and magnesium powder to obtain porous silicon; and adding the porous silicon and dopamine hydrochloride DA-HCl into a Tris-HCl solution, magnetically stirring, centrifuging, and thermally treating the precipitate to obtain the porous silicon/carbon lithium ion battery cathode material. The porous silicon/carbon composite negative electrode material has excellent pore characteristics and a co-continuous framework, and can better relieve the volume expansion of silicon in the lithium intercalation process.

Description

Porous silicon/carbon lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a preparation method of a hierarchical porous silicon/carbon lithium ion battery cathode material.
Background
When environmental protection is regarded as important and the artificial intelligence era comes, energy storage and transportation play an important role. Lithium ion batteries are becoming the mainstream of the market due to their advantages of large capacity, long cycle life, high safety, etc. The lithium ion battery mainly comprises three parts: a negative electrode, an electrolyte and a positive electrode. The performance of the negative electrode has a great influence on the application of the full battery. The carbon electrode is the anode material which is put into use at first, the cycling stability and the safety are both good, but the capacity is only 372mAh/g, and the demand of people cannot be met gradually. Therefore, it is an urgent need to find a negative electrode material with high capacity. The silicon material can be used as the negative electrode of a lithium ion battery, and the theoretical specific capacity of the silicon material is up to 4200mAh/g, which is the currently known negative electrode material with the highest capacity.
However, silicon as a negative electrode material of a lithium ion battery has a serious problem: theoretically, the volume expansion can reach 400% in the circulation process, which brings other problems, such as: the problems of pulverization of the electrode material, separation of the electrode material from the current collector resulting in capacity fading, continuous generation of a solid electrolyte interface layer (SEI layer), etc., result in poor cycle stability and low coulombic efficiency of a battery using silicon as a negative electrode material.
At present, the following approaches are mainly used for solving the adverse effect caused by the volume expansion of silicon:
1) the characteristics of preparing nano-scale silicon materials such as silicon nanospheres and silicon nanowires, and high yield strength and breaking strength of the nano materials can relieve the stress effect of the silicon materials in the circulation process, and avoid pulverization of active materials or separation of the active materials from a current collector;
2) designing special structures, such as a porous structure, a core-shell structure, a hollow structure and the like, namely designing a gap to accommodate the volume expansion of silicon, and essentially releasing stress generated by the volume expansion of the silicon in the circulation process;
3) the compound with carbon and other materials is used for improving the conductivity of an electrode material, reducing the generation of an SEI layer and improving the cycle stability of a battery. The porous material generally has the characteristic of excellent porosity or specific surface area, and reports that when the porosity reaches 68%, the volume of the silicon material basically does not change too much, and is beneficial to the diffusion of ions; the abundance of specific surface area can provide sufficient active sites, and because of these advantages, porous materials are often preferred as ideal electrode materials.
Disclosure of Invention
The invention aims to provide a preparation method of a porous silicon/carbon composite lithium ion battery cathode material.
In order to solve the technical problem, the invention provides a preparation method of a porous silicon/carbon lithium ion battery cathode material, which comprises the following steps:
1) and preparing porous silicon dioxide:
dissolving 10g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) in 50 +/-5 mL of hydrochloric acid solution with the concentration of 0.1M, then adding 5 +/-0.5 mL of 1,3, 5-trimethylbenzene, then adding 10-20 mL of methyl orthosilicate, magnetically stirring for 10 +/-1 h, then adding 10 +/-1 mL of propylene oxide serving as a gel accelerator, magnetically stirring for 5 +/-1 min, and standing until gel is formed;
the obtained gel is aged for 24 plus or minus 2 hours at the temperature of 60 plus or minus 10 ℃, replaced by ethanol and dried for 24 plus or minus 2 hours at the temperature of 60 plus or minus 10 ℃ to obtain porous silicon dioxide;
2) and preparing porous silicon:
mixing the porous silicon dioxide prepared in the step 1) with magnesium powder (200 meshes) according to a mass ratio of 1:1, and carrying out heat treatment for 4.5 +/-0.5 hours at 700-800 ℃ in an inert gas (such as argon) atmosphere;
washing the obtained heat treatment product with hydrochloric acid, centrifuging, and drying at 60 +/-10 ℃ for 12 +/-1 hours to obtain porous silicon;
3) preparation of porous silicon/carbon lithium ion battery cathode material
Adding the porous silicon prepared in the step 2) and dopamine DA-HCl hydrochloride in a mass ratio of 1:2 into a Tris-HCl solution (pH 8.5 and 10mM), magnetically stirring for 12 +/-1 hours, and centrifuging to obtain a precipitate;
the precipitate is vacuum dried at 60 +/-10 deg.c for 12 +/-1 hr and then heat treated at 800 +/-50 deg.c in inert gas atmosphere for 2 +/-0.5 hr to obtain porous negative material for Si/C lithium ion battery.
The improvement of the preparation method of the porous silicon/carbon lithium ion battery cathode material of the invention is as follows: in the step 3), 50-150 mL of Tris-HCl solution is used for every 1g of the porous silicon obtained in the step 2).
The preparation method of the porous silicon/carbon lithium ion battery cathode material is further improved as follows: the ethanol is replaced for 3 times in the step 1), and the treatment time is 12 hours each time.
The preparation method of the porous silicon/carbon lithium ion battery cathode material is further improved as follows: the rest time in step 1) is at least 1 hour.
The invention also provides the porous silicon/carbon lithium ion battery cathode material prepared by any one of the methods.
The porous silicon dioxide is prepared by a sol-gel method, and has a good co-continuous framework structure and porous characteristics. The invention takes porous silicon dioxide as a template and prepares porous silicon by magnesiothermic reduction; the porous silicon can better keep the co-continuous framework structure and the porous characteristic of the porous silicon dioxide. According to the invention, porous silicon and dopamine hydrochloride are compounded in situ to obtain the porous silicon/carbon lithium ion battery cathode material, and the material has a relatively complete co-continuous framework and relatively abundant pores, and is beneficial to relieving the volume expansion of silicon in the lithium intercalation process.
The invention has the following technical advantages:
1) the porous silicon dioxide prepared by the sol-gel method has a unique framework structure and higher porosity.
2) The method prepares the porous silicon with the co-continuous framework and rich pores by one-step magnesiothermic reduction, has simple steps, and can better reserve the structure of the porous silicon dioxide.
3) According to the invention, porous silicon and dopamine are compounded in situ, so that the coating effect is ideal, the co-continuous framework and rich pores of the porous silicon can be completely reserved, and the volume expansion of the silicon in the lithium intercalation process can be favorably relieved.
In conclusion, the process is simple, and the prepared porous silicon/carbon composite negative electrode material has excellent pore characteristics and a co-continuous framework, and can better relieve the volume expansion of silicon in the lithium intercalation process.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an SEM photograph of porous silica prepared in step 1) of example 1;
FIG. 2 is an SEM photograph of porous silicon prepared in step 2) of example 1;
FIG. 3 is an SEM photograph of the silicon/carbon composite lithium ion battery anode material finally prepared in example 1;
fig. 4 is an SEM photograph of the silicon/carbon composite lithium ion battery anode material prepared in example 2;
fig. 5 is an SEM photograph of the silicon/carbon composite lithium ion battery anode material prepared in example 3.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in the following case, the stirring speed was 100. + -.10 rpm.
Embodiment 1, a method for preparing a porous silicon/carbon composite lithium ion battery anode material, comprising the following steps:
1) and preparing porous silicon dioxide:
dissolving 10g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 in 50mL of hydrochloric acid solution with the concentration of 0.1M, adding 5mL of 1,3, 5-trimethylbenzene, then adding 15mL of methyl orthosilicate, magnetically stirring for 10 hours, then adding 10mL of propylene oxide serving as a gel accelerator, magnetically stirring for 5 minutes, standing for 1 hour, and forming gel;
the resulting gel was aged at 60 ℃ for 24 hours, and after 3 times of ethanol substitution treatment (12 hours each), it was dried in an oven at 60 ℃ for 24 hours to obtain a porous silica.
The SEM photograph of the porous silica is shown in fig. 1.
2) And preparing porous silicon:
mixing the porous silicon dioxide prepared in the step 1) with 200-mesh magnesium powder according to the mass ratio of 1:1, and carrying out heat treatment for 4.5 hours at 700-800 ℃ in an argon atmosphere;
and washing the obtained heat treatment product with hydrochloric acid, centrifuging, and drying in an oven at 60 ℃ for 12 hours to obtain the porous silicon.
The SEM photograph of the porous silicon is shown in fig. 2.
3) Preparation of porous silicon/carbon lithium ion battery cathode material
Adding 1g of the porous silicon obtained in the step 2) and 2g of dopamine hydrochloride DA-HCl into 100mL of Tris-HCl solution (with the pH value of 8.5 and the concentration of 10mM), magnetically stirring for 12 hours, and centrifuging to obtain a precipitate;
and drying the precipitate in a vacuum oven at 60 ℃ for 12 hours, and then carrying out heat treatment at 800 ℃ for 2 hours under the argon atmosphere to obtain the porous silicon/carbon lithium ion battery cathode material.
The SEM photograph of the porous silicon/carbon lithium ion battery cathode material is shown in figure 3; has a relatively complete co-continuous framework and relatively abundant pores.
Embodiment 2, a method for preparing a porous silicon/carbon composite lithium ion battery anode material:
compared with the example 1, the method is identical with the example 1 except that the dosage of the methyl orthosilicate in the step 1) is changed to 10 mL.
The SEM photograph of the porous silicon/carbon lithium ion battery cathode material is shown in FIG. 4; the silicon/carbon lithium ion battery cathode material still has a relatively complete co-continuous framework and relatively abundant pores, but the pore size is relatively large, which indicates that the framework strength is not high.
Embodiment 3, a method for preparing a porous silicon/carbon composite lithium ion battery anode material:
compared with the example 1, the method is identical with the example 1 except that the dosage of the methyl orthosilicate in the step 1) is changed to 20 mL.
The SEM photograph of the porous silicon/carbon lithium ion battery cathode material is shown in FIG. 5; the silicon/carbon lithium ion battery cathode material still has a relatively complete co-continuous framework and relatively abundant pores, but the pore size is relatively small, the number of pores is reduced, and the framework is too compact.
Comparative examples 1,
In step 1) of example 1, the use of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 with 1,3, 5-trimethylbenzene was eliminated, and the remainder was identical to step 1) of example 1.
The prepared silica is not porous, is glassy silica, is dried to form silica lithium particles, and is not suitable for subsequent reduction and carbon compounding.
Comparative examples 2,
The use of 1,3, 5-trimethylbenzene in step 1) of example 1 is eliminated and the remainder is identical to step 1) of example 1.
The prepared silicon dioxide has obviously reduced pore structure, collapse occurs in the drying process, and the silicon dioxide is not suitable for subsequent reduction.
Therefore, in the present invention, the best scheme is to add 10g of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 and 5mL of 1,3, 5-trimethylbenzene simultaneously, and then the obtained silica framework structure and pore structure are the best and are most suitable for the subsequent reduction.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (5)

1. The preparation method of the porous silicon/carbon lithium ion battery cathode material is characterized by comprising the following steps:
1) and preparing porous silicon dioxide:
dissolving 10g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in 50 +/-5 mL of hydrochloric acid solution with the concentration of 0.1M, adding 5 +/-0.5 mL of 1,3, 5-trimethylbenzene, then adding 10-20 mL of methyl orthosilicate, magnetically stirring for 10 +/-1 hour, then adding 10 +/-1 mL of propylene oxide serving as a gel accelerator, magnetically stirring for 5 +/-1 minute, and standing until gel is formed;
the obtained gel is aged for 24 plus or minus 2 hours at the temperature of 60 plus or minus 10 ℃, replaced by ethanol and dried for 24 plus or minus 2 hours at the temperature of 60 plus or minus 10 ℃ to obtain porous silicon dioxide;
2) and preparing porous silicon:
mixing the porous silicon dioxide prepared in the step 1) with magnesium powder according to the mass ratio of 1:1, and carrying out heat treatment for 4.5 +/-0.5 hours at 700-800 ℃ in an inert gas atmosphere;
washing the obtained heat treatment product with hydrochloric acid, centrifuging, and drying at 60 +/-10 ℃ for 12 +/-1 hours to obtain porous silicon;
3) preparation of porous silicon/carbon lithium ion battery cathode material
Adding the porous silicon prepared in the step 2) and dopamine hydrochloride DA-HCl into a Tris-HCl solution according to the mass ratio of 1:2, magnetically stirring for 12 +/-1 hours, and centrifuging to obtain a precipitate;
the precipitate is vacuum dried at 60 +/-10 ℃ for 12 +/-1 hours, and then is thermally treated at 800 +/-50 ℃ for 2 +/-0.5 hours under the inert gas atmosphere to obtain the porous silicon/carbon lithium ion battery negative electrode material.
2. The method for preparing the negative electrode material of the porous silicon/carbon lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step 3), 50-150 mL of Tris-HCl solution is used for every 1g of the porous silicon obtained in the step 2).
3. The method for preparing the negative electrode material of the porous silicon/carbon lithium ion battery according to claim 2, wherein the method comprises the following steps: the ethanol is replaced for 3 times in the step 1), and the treatment time is 12 hours each time.
4. The preparation method of the porous silicon/carbon lithium ion battery negative electrode material according to any one of claims 1 to 3, characterized by comprising the following steps: the rest time in step 1) is at least 1 hour.
5. The porous silicon/carbon lithium ion battery cathode material prepared by the method of any one of claims 1 to 4.
CN202110072040.7A 2021-01-20 2021-01-20 Porous silicon/carbon lithium ion battery cathode material and preparation method thereof Pending CN112751007A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113964297A (en) * 2021-10-21 2022-01-21 中国石油天然气股份有限公司 Porous silicon negative electrode material of lithium ion battery and preparation method and application thereof
CN117038913A (en) * 2023-08-29 2023-11-10 中化学华陆新材料有限公司 Preparation method of silicon-carbon negative electrode material porous Si@C for lithium ion battery
CN117038913B (en) * 2023-08-29 2024-11-19 中化学华陆新材料有限公司 Preparation method of silicon-carbon negative electrode material porous Si@C for lithium ion battery

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CN101514001A (en) * 2009-03-10 2009-08-26 中国科学院上海硅酸盐研究所 Bar-shaped ordered mesopore silicon dioxide nano material and preparation method thereof
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CN110828809A (en) * 2019-11-20 2020-02-21 厦门大学 Silicon-carbon composite material in form of bubble coral and preparation method and application thereof

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CN103979547A (en) * 2014-05-06 2014-08-13 浙江大学 Preparation method for hierarchical porous silicon oxide
CN107661748A (en) * 2017-10-30 2018-02-06 淮北师范大学 Organic amino-functionalization large aperture capacity silicon oxide CO2Adsorbent and preparation method thereof
CN110828809A (en) * 2019-11-20 2020-02-21 厦门大学 Silicon-carbon composite material in form of bubble coral and preparation method and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113964297A (en) * 2021-10-21 2022-01-21 中国石油天然气股份有限公司 Porous silicon negative electrode material of lithium ion battery and preparation method and application thereof
CN113964297B (en) * 2021-10-21 2024-04-09 中国石油天然气股份有限公司 Porous silicon anode material of lithium ion battery and preparation method and application thereof
CN117038913A (en) * 2023-08-29 2023-11-10 中化学华陆新材料有限公司 Preparation method of silicon-carbon negative electrode material porous Si@C for lithium ion battery
CN117038913B (en) * 2023-08-29 2024-11-19 中化学华陆新材料有限公司 Preparation method of silicon-carbon negative electrode material porous Si@C for lithium ion battery

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Application publication date: 20210504