CN117577783B - Silicon-based negative electrode, preparation method thereof and solid-state battery - Google Patents

Silicon-based negative electrode, preparation method thereof and solid-state battery Download PDF

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CN117577783B
CN117577783B CN202410051263.9A CN202410051263A CN117577783B CN 117577783 B CN117577783 B CN 117577783B CN 202410051263 A CN202410051263 A CN 202410051263A CN 117577783 B CN117577783 B CN 117577783B
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silicon
particles
sns
based anode
parts
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CN117577783A (en
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郝雪纯
别晓非
翟喜民
赵孟迪
高欣宇
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FAW Group Corp
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FAW Group Corp
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/36—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
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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
    • 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
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    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of batteries, in particular to a silicon-based negative electrode, a preparation method thereof and a solid-state battery. The silicon-based negative electrode provided by the invention comprises the following components in parts by mass: 60-70 parts of silicon particles, 10-15 parts of SnS 2 particles, 10-15 parts of carbon nanotubes and 5-10 parts of Li 4SnS4 particles. In the silicon-based anode of the present invention, silicon is used as a main component, and a higher capacity can be provided; the introduction of SnS 2 improves the conductivity of the silicon-based anode while providing capacity; the carbon nano tube is used as a framework to play a supporting role, and a good conductive network is constructed between the silicon particles and the SnS 2 particles; the addition of the sulfide solid electrolyte Li 4SnS4 improves the ion conductivity of the silicon-based negative electrode; the problems of high volume expansion rate and poor conductivity of the silicon-based negative electrode are solved, so that the cycling stability and the multiplying power performance of the battery are improved.

Description

Silicon-based negative electrode, preparation method thereof and solid-state battery
Technical Field
The invention relates to the technical field of batteries, in particular to a silicon-based negative electrode, a preparation method thereof and a solid-state battery.
Background
With the further popularization of electric vehicles, the market has created a higher demand for the performance of power batteries, wherein the development of key electrode materials is critical to improving battery performance. Silicon anodes have received extensive attention from the scientific and industrial community due to their high specific capacity.
However, silicon is accompanied by a large volume change (about 300%) during lithiation or delithiation, which can lead to cracking and pulverization of large silicon particles, limiting the practical application of silicon cathodes, and in addition, the poor conductivity of silicon limits the performance of the electrodes. For the volume expansion effect of a silicon-based electrode in the charge and discharge process, a silicon-carbon composite method is proposed in recent years, and the prepared silicon-carbon negative electrode material can provide a buffer space for the volume change of silicon in the lithium intercalation/deintercalation process so as to counteract partial internal stress. However, the cycle stability and the conductivity of the silicon-carbon anode material still need to be further improved.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a silicon-based anode, which solves the problems of high volume expansion rate and poor conductivity of the silicon-based anode in the prior art in whole or in part.
The second aim of the invention is to provide a preparation method of the silicon-based negative electrode, which has simple steps and is suitable for large-scale industrial production.
A third object of the present invention is to provide a solid-state battery having excellent cycle stability and rate performance.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a silicon-based negative electrode which comprises the following components in parts by mass:
60-70 parts of silicon particles, 10-15 parts of SnS 2 particles, 10-15 parts of carbon nanotubes and 5-10 parts of Li 4SnS4 particles.
Further, the surface of the SnS 2 particles is attached with the Li 4SnS4 particles.
Further, the particle size of the silicon particles is 50-200 nm.
Further, the particle size of the SnS 2 particles is 3-5 μm.
Further, the particle size of the Li 4SnS4 particles is 500 nm-2 μm.
Further, the thickness of the silicon-based negative electrode is 1-5 mu m.
The invention also provides a preparation method of the silicon-based anode, which comprises the following steps:
s1, grinding a silicon source, elemental tin and a lithium source to obtain a mixed material;
s2, mixing the mixed material with the carbon nanotube suspension, and carrying out solid-liquid separation to obtain a membrane material;
And S3, sintering the film material in CS 2 atmosphere to obtain the silicon-based negative electrode.
Further, in step S1, the silicon source includes elemental Si and/or SiO x;
and/or, the lithium source comprises Li 2CO3.
Further, in step S1, the mass ratio of the silicon source to the elemental tin is 10: (1-5).
Further, in step S1, the mass ratio of the elemental tin to the lithium source is 10: (1-3).
Further, in step S1, the grinding includes wet grinding.
Further, in step S1, the grinding temperature is-30-10 ℃.
Further, in step S2, the mass ratio of the silicon source to the carbon nanotubes in the carbon nanotube suspension is 10: (1-5).
Further, in step S2, the solid-liquid separation includes: vacuum filtering is carried out for 4-16 h.
Further, in step S3, the temperature of the sintering treatment is 300-800 ℃.
The invention also provides a solid-state battery comprising the silicon-based anode.
Compared with the prior art, the invention has the beneficial effects that:
1. the silicon-based negative electrode comprises carbon nanotubes, nano silicon particles, snS 2 particles and Li 4SnS4 particles which are uniformly dispersed in the carbon nanotubes; wherein, silicon can provide higher capacity as the main component, and the addition of SnS 2 particles improves the conductivity of the electrode while providing capacity; the carbon nano tube is used as a framework to play a supporting role, a good conductive network is constructed between the nano silicon particles and the SnS 2 particles, the electron transport capacity is improved, and meanwhile, the volume expansion of the silicon particles and the SnS 2 particles in the charge and discharge process is effectively relieved; li 4SnS4 particles and SnS 2 particles are tightly combined and uniformly dispersed in the silicon-based negative electrode, so that the ion conductivity of the silicon-based negative electrode is effectively improved, the interface resistance is reduced, and the capacity and the cycle performance of the battery are improved.
2. The silicon-based negative electrode does not additionally use a binder, so that capacity loss caused by the use of the binder is avoided.
3. In the preparation method of the silicon-based negative electrode, firstly, a silicon source, elemental tin and a lithium source are ground at low temperature to convert white tin into gray tin, so that the dispersion of tin is facilitated; then adding carbon nano tubes for solid-liquid separation to obtain a membrane material; then sintering is carried out in CS 2 atmosphere, snS 2 is generated by reaction in the sintering process, sulfide electrolyte Li 4SnS4 is generated in situ, the ion conductivity of the silicon-based negative electrode is further improved, and the silicon-based negative electrode with excellent performance is obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of a silicon-based anode of the invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In some embodiments of the invention, a silicon-based anode is provided, which comprises the following components in parts by mass:
60-70 parts of silicon particles, 10-15 parts of SnS 2 particles, 10-15 parts of carbon nanotubes and 5-10 parts of Li 4SnS4 particles.
The silicon-based negative electrode comprises silicon particles, snS 2 particles, carbon nanotubes and Li 4SnS4 particles which are uniformly distributed; wherein silicon is used as a main component, and can provide higher capacity; the introduction of SnS 2 improves the conductivity of the silicon-based anode while providing capacity; the carbon nano tube is used as a framework to support the silicon particles and the SnS 2 particles to form a self-supporting flexible film, and a good conductive network is constructed between the silicon particles and the SnS 2 particles by the carbon nano tube; the addition of the sulfide solid electrolyte Li 4SnS4 improves the ion conductivity of the silicon-based negative electrode, constructs a good ion conductive network and reduces the interface impedance between the negative electrode and the electrolyte.
The silicon-based negative electrode does not use an adhesive additionally, and avoids capacity loss caused by using the adhesive.
In some embodiments of the invention, typical but non-limiting, for example, the parts by mass of silicon particles may be 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, or a range of values consisting of any two thereof; the mass part of the SnS 2 particles can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts or a range value formed by any two of the above parts; the mass parts of the carbon nano tube can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts or a range value formed by any two of the above parts; the mass fraction of Li 4SnS4 particles may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts or a range of values consisting of any two of these.
In the silicon-based anode, each component in the range is beneficial to improving the structural stability of the silicon-based anode, so that the cycle performance of the battery is beneficial to improvement.
In some embodiments of the invention, the surface of the SnS 2 particles has Li 4SnS4 particles attached to it.
Li 4SnS4 is tightly combined with SnS 2 and uniformly distributed in the silicon-based negative electrode, so that the ion conductivity of the silicon-based negative electrode can be effectively improved, the interface resistance is reduced, and the capacity and the cycle performance of the battery are improved.
In the silicon-based negative electrode of the invention, one part of Li 4SnS4 particles are attached to the surface of SnS 2 particles, and the other part of Li 4SnS4 particles are dispersed in the gaps of the carbon nano tubes.
As a potential negative electrode material with high theoretical capacity (about 1288 mAh/g), low cost and environmental friendliness, snS 2 has received a great deal of attention in terms of lithium storage mechanism and practical application, and similar to silicon, snS 2 also has problems of volume expansion and low conductivity.
In some embodiments of the present invention, in the silicon-based anode, the nano silicon particles and the SnS 2 particles are dot-shaped materials, the carbon nanotubes are linear materials, and the SnS 2 particles and the nano silicon particles are uniformly distributed between the carbon nanotubes.
In the silicon-based negative electrode, the carbon nano tube builds a good conductive network between the silicon particles and the SnS 2 particles, improves the electron transport capacity, and effectively relieves the volume expansion of the silicon particles and the SnS 2 particles in the charge and discharge process.
In some embodiments of the invention, the silicon particles have a particle size of 50-200 nm; typically, but not by way of limitation, the particle size of the silicon particles may be, for example, 50nm, 70nm, 100nm, 130nm, 150nm, 180nm, 200nm or a range of values consisting of any two of these.
In some embodiments of the invention, the SnS 2 particles have a particle size of 3-5 μm; typical, but non-limiting, for example, the particle size of the SnS 2 particles may be 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, or a range of values consisting of any two of them.
In some embodiments of the invention, the particle size of the Li 4SnS4 particles is 500nm to 2 μm; typical, but non-limiting, particle sizes of Li 4SnS4 particles may be, for example, 500nm, 800nm, 1 μm, 1.2 μm, 1.5 μm, 1.7 μm,2 μm, or a range of values of any two of these.
In some embodiments of the invention, the silicon-based negative electrode further comprises amorphous carbon; preferably, the amorphous carbon content in the silicon-based anode is 0.5wt% to 1wt%.
Amorphous carbon in a silicon-based anode acts to improve the electron conductivity of the silicon-based anode.
In some embodiments of the invention, the silicon-based negative electrode has a thickness of 1-5 μm; typical, but non-limiting, for example, silicon-based cathodes may have a thickness of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or a range of values consisting of any two of these.
Referring to fig. 1, in some embodiments of the present invention, there is further provided a method for preparing the silicon-based anode, including the steps of:
s1, grinding a silicon source, elemental tin and a lithium source to obtain a mixed material;
s2, uniformly mixing the mixed material and the carbon nanotube suspension, and carrying out solid-liquid separation to obtain a membrane material;
And S3, sintering the film material in CS 2 atmosphere to obtain the silicon-based negative electrode.
The silicon-based negative electrode is prepared by a solid-liquid separation film forming and high-temperature vulcanization method, the base material in the prepared silicon-based negative electrode is a carbon nano tube, the carbon nano tube forms a self-supporting flexible film, and silicon particles, snS 2 particles and in-situ generated sulfide solid electrolyte Li 4SnS4 are uniformly dispersed therein.
In the preparation method of the silicon-based negative electrode, a silicon source, elemental tin and a lithium source are firstly ground and mixed, then carbon nano tubes are added, and solid-liquid separation is carried out after uniform dispersion, so as to obtain a film material; and then sintering the film material in CS 2 atmosphere, taking Li 2CO3 as an example, and reacting ：2Li2CO3+Sn+2CS2=Li4SnS4+C+3CO2,Sn+CS2=SnS2+C; as follows in the process to generate SnS 2 and sulfide electrolyte Li 4SnS4 in the process, so as to further improve the ion conductivity and obtain the silicon-based negative electrode.
In the sintering treatment process under CS 2 atmosphere, the generated C is attached to the surfaces of Li 4SnS4 particles and SnS 2 particles in the form of amorphous carbon, which is beneficial to improving the electron conductivity of the silicon-based negative electrode.
In some embodiments of the invention, in step S1, the silicon source comprises elemental Si and/or SiO x.
In some embodiments of the present invention, in step S1, the lithium source includes, but is not limited to, li 2CO3.
In some embodiments of the invention, in step S1, the mass ratio of the silicon source to elemental tin is 10: (1-5); typical, but not limiting, for example, the mass ratio of silicon source to elemental tin may be 10: 1. 10: 2. 10: 3. 10: 4. 10:5 or any two of them.
In some embodiments of the invention, in step S1, the mass ratio of the silicon source to elemental tin is 10: (2-3).
In some embodiments of the invention, in step S1, the mass ratio of elemental tin to lithium source is 10: (1-3); typical, but not limiting, for example, the mass ratio of elemental tin to lithium source may be 10: 1. 10: 2. 10:3 or any two thereof.
In some embodiments of the invention, in step S1, the mass ratio of elemental tin to Li 2CO3 is 10: (2-2.5).
In some embodiments of the invention, in step S1, milling comprises wet milling; preferably, milling comprises ball milling.
According to the invention, a silicon source, elemental tin and a lithium source are crushed and mixed through grinding, so that a uniformly mixed material is obtained.
The wet ball milling process is one kind of grinding and crushing process with water or solvent added into material, and the material is crushed into fine grains through the interaction between the grinding ball and the material inside the ball mill.
In some embodiments of the present invention, in step S1, the temperature of grinding is-30 to 10 ℃; typically, but not by way of limitation, for example, the temperature of the milling may be-30 ℃, -20 ℃, -10 ℃, 0 ℃,10 ℃ or a range of values consisting of any two thereof; preferably, the grinding temperature is-20 to-10 ℃.
In some embodiments of the present invention, in step S1, the grinding time is 8 to 15 hours; typically, but not by way of limitation, the time of grinding may be, for example, 8h, 10h, 12h, 14h, 15h, or a range of values consisting of any two of these.
In some embodiments of the present invention, in step S1, the grinding time is 10 to 15 hours. The milling time can be in the above range to uniformly disperse the components.
In the mixing stage of the silicon source, the elemental tin and the lithium source, the invention adopts a low-temperature wet grinding method, and utilizes the principle that the tin is converted from white tin to gray tin at low temperature, so that the soft and high-ductility white tin is converted into gray tin with a relatively brittle texture, and the phenomenon of tin metal adhesion is avoided, thereby being beneficial to the uniform dispersion of metal tin, silicon particles and the lithium source.
The grinding temperature has an influence on the performance of the silicon-based negative electrode, because white tin cannot be completely converted into gray tin under the condition of higher temperature, and the dispersing effect of silicon and tin is affected.
In some embodiments of the invention, in step S2, the mass ratio of the silicon source to the carbon nanotubes in the carbon nanotube suspension is 10: (1-5); typically, but not by way of limitation, the mass ratio of the silicon source to the carbon nanotubes in the carbon nanotube suspension may be 10: 1. 10: 2. 10: 3. 10: 4. 10:5 or any two of them.
In some embodiments of the invention, in step S2, the mass ratio of the silicon source to the carbon nanotubes in the carbon nanotube suspension is 10: (2-3).
In some embodiments of the present invention, in step S2, the carbon nanotube suspension includes carbon nanotubes and an organic solvent; preferably, the organic solvent comprises absolute ethanol.
In some embodiments of the present invention, in step S2, the mixing includes: stirring for 2-8 h.
In some embodiments of the present invention, in step S2, the solid-liquid separation includes: vacuum filtering for 4-16 h; typical, but non-limiting, times for vacuum filtration may be, for example, 4h, 6h, 8h, 10h, 12h, 14h, 16h, or a range of values consisting of any two of these.
In some embodiments of the present invention, in step S2, the time of vacuum filtration is 8-10 hours.
The vacuum filtration method is a simple and efficient method for preparing the carbon nanotube film. In the method, a solution containing carbon nano tubes is poured into a vacuum filtration device provided with a microporous filter membrane, the solvent permeates the microporous filter membrane, and the carbon nano tubes are trapped on the surface of the microporous filter membrane to form a film.
The invention adopts a vacuum filtration method to directly form a film, fully utilizes the self-supporting function of the carbon nano tube, and simultaneously has good conductivity with the SnS 2, thereby avoiding the capacity loss without additionally introducing adhesive and other conductive agents.
The vacuum filtration time has great influence on the film forming effect, and the too short filtration time can lead to low strength of the pole piece, easy breakage and incapability of being applied; the excessively long suction filtration time can lead to too tight combination of the pole piece and the filter paper, and the pole piece and the filter paper cannot be separated and applied.
In some embodiments of the invention, the membrane material and filter paper are manually separated after the vacuum filtration is completed.
In some embodiments of the present invention, in step S3, the temperature of the sintering process is 300 to 800 ℃; typically, but not by way of limitation, the temperature of the sintering process may be, for example, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, or a range of values consisting of any two of these.
In some embodiments of the present invention, in step S3, the sintering process is performed at a temperature of 400 to 600 ℃.
In some embodiments of the present invention, in step S3, the sintering time is 4 to 8 hours; typically, but not by way of limitation, the time of the sintering process may be, for example, 4h, 5h, 6h, 7h, 8h, or a range of values consisting of any two of these.
In the preparation method of the silicon-based negative electrode, the sulfide solid electrolyte Li 4SnS4 is generated in situ in the self-supporting film structure by adopting a one-step thermal reduction method through sintering treatment, and the sulfide solid electrolyte Li 4SnS4 is tightly combined with the SnS 2 component in the electrode and is uniformly distributed in the silicon-based negative electrode, so that the ion conductivity of the silicon-based negative electrode is effectively improved, the interface resistance is reduced, and the capacity and the cycle performance of a battery are improved.
The sintering treatment temperature and time of the invention are in the above range, which is beneficial to improving the utilization rate of raw materials and improving the oxidation-reduction reaction rate.
In some embodiments of the present invention, a solid-state battery is also provided, including the silicon-based anode described above.
In some embodiments of the invention, the solid state battery comprises an all-solid state lithium ion battery.
The silicon-based anode is used in an all-solid-state lithium ion battery, solves the problems of poor cycling stability and rate capability of the all-solid-state lithium ion battery caused by high volume expansion rate and poor conductivity of the anode material in the prior art, and is beneficial to improving the performance of the battery.
Example 1
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 2
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.05g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 12 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 3
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.2g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 4
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of 10 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixture, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, vacuum filtering for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 5
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.05g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 6
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.25g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 7
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 4 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based negative electrode.
Example 8
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixture, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, vacuum filtering for 12 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the silicon-based anode.
Example 9
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment for 5 hours at 300 ℃, and naturally cooling to obtain the silicon-based negative electrode.
Example 10
The preparation method of the silicon-based anode provided by the embodiment comprises the following steps:
S1, 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 are placed in a ball milling tank, 100mL of absolute ethyl alcohol is added, and vacuum ball milling is carried out for 10 hours at the temperature of minus 20 ℃ at the rotating speed of 400r/min, so as to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 800 ℃ for 5 hours, and naturally cooling to obtain the silicon-based anode.
Comparative example 1
The preparation method of the composite anode provided by the comparative example comprises the following steps:
S1, placing 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling at the temperature of-20 ℃ for 10 hours at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the composite anode.
Comparative example 2
The preparation method of the composite anode provided by the comparative example comprises the following steps:
s1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm) and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of minus 20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the composite anode.
Comparative example 3
The preparation method of the composite anode provided by the comparative example comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm) and 0.2g of tin powder into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, and then carrying out vacuum filtration for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the composite anode.
Comparative example 4
The preparation method of the composite anode provided by the comparative example comprises the following steps:
S1, placing 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 into a ball milling tank, adding 100mL of absolute ethyl alcohol, and carrying out vacuum ball milling for 10 hours at the temperature of-20 ℃ at the rotating speed of 400r/min to obtain a mixed material.
S2, mixing the mixed material with absolute ethyl alcohol, magnetically stirring for 4 hours, vacuum filtering for 8 hours, and manually separating from filter paper to obtain the membrane material.
S3, placing the membrane material in a vacuum tube furnace, introducing CS 2 gas, carrying out heat preservation treatment at 500 ℃ for 5 hours, and naturally cooling to obtain the composite anode.
Comparative example 5
The preparation method of the composite anode provided by the comparative example comprises the following steps:
S1, 0.5g of silicon powder (simple substance silicon, granularity is 200 nm), 0.1g of tin powder and 0.02g of Li 2CO3 are placed in a ball milling tank, 100mL of absolute ethyl alcohol is added, and vacuum ball milling is carried out for 10 hours at the temperature of minus 20 ℃ at the rotating speed of 400r/min, so as to obtain a mixed material.
S2, mixing the mixed material, 0.1g of carbon nano tube and absolute ethyl alcohol, magnetically stirring for 4 hours, vacuum filtering for 8 hours, and manually separating from filter paper to obtain the composite negative electrode.
Test example 1
The silicon-based negative electrodes of examples 1 to 10 and the composite negative electrodes of comparative examples 1 to 5 were assembled into all-solid-state mold batteries, respectively, and the counter electrode was a Li-In alloy, and the results are shown In table 1.
The electrochemical performance test conditions were as follows: and carrying out constant current charge and discharge test on the assembled battery by adopting LANDCT A tester (Wuhan city blue electric power electronic Co., ltd.) at a test temperature of 25 ℃ and a test voltage range of 0.01-1.5V, wherein the test current density is 1/3C, and the nominal specific capacity is set to 2000mAh/g.
TABLE 1
The silicon-based anode provided by the invention has higher gram capacity and better cycle performance. Comparing example 1 with comparative example 1, the silicon-based negative electrode of the present invention has higher gram capacity (from 565mAh/g to 1932 mAh/g) and better cycle performance (from 15.8% to 82.7%) than the composite negative electrode without silicon addition; as can be seen from comparing example 1 and comparative example 2, the silicon-based anode of the present invention exhibited better cycle performance (from 52.6% to 82.7%) compared to the composite anode without Sn addition; as can be seen from comparison of example 1 and comparative example 3, the silicon-based anode of the present invention has a higher gram capacity (from 1845mAh/g to 1932 mAh/g) and better cycle performance (from 44.5% to 82.7%) than the anode without Li 4SnS4. As can be seen from comparative examples, comparative example 4 and comparative example 5, the silicon-based anode of the present invention has a higher gram capacity and better cycle performance than an anode that does not contain carbon nanotubes or is not subjected to high temperature vulcanization.
The technical proposal of the invention is only used for illustration and not limitation; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (15)

1. The silicon-based anode is characterized by comprising the following components in parts by weight:
60-70 parts of silicon particles, 10-15 parts of SnS 2 particles, 10-15 parts of carbon nanotubes and 5-10 parts of Li 4SnS4 particles;
The surface of the SnS 2 particles is attached with the Li 4SnS4 particles.
2. The silicon-based anode according to claim 1, wherein the silicon particles have a particle diameter of 50 to 200nm.
3. The silicon-based anode according to claim 1, wherein the SnS 2 particles have a particle size of 3-5 μm.
4. The silicon-based anode according to claim 1, wherein the particle size of the Li 4SnS4 particles is 500nm to 2 μm.
5. The silicon-based anode according to claim 1, wherein the thickness of the silicon-based anode is 1-5 μm.
6. The method for preparing the silicon-based anode according to any one of claims 1 to 5, comprising the steps of:
s1, grinding a silicon source, elemental tin and a lithium source to obtain a mixed material;
S2, uniformly mixing the mixed material with the carbon nanotube suspension, and carrying out solid-liquid separation to obtain a membrane material;
And S3, sintering the film material in CS 2 atmosphere to obtain the silicon-based negative electrode.
7. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S1, the silicon source comprises elemental Si and/or SiO x;
and/or, the lithium source comprises Li 2CO3.
8. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S1, the mass ratio of the silicon source to the elemental tin is 10: (1-5).
9. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S1, the mass ratio of the elemental tin to the lithium source is 10: (1-3).
10. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S1, the grinding includes wet grinding.
11. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S1, the grinding temperature is-30 to 10 ℃.
12. The method according to claim 6, wherein in step S2, the mass ratio of the silicon source to the carbon nanotubes in the carbon nanotube suspension is 10: (1-5).
13. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S2, the solid-liquid separation includes: vacuum filtering is carried out for 4-16 h.
14. The method of manufacturing a silicon-based anode according to claim 6, wherein in step S3, the sintering treatment is performed at a temperature of 300 to 800 ℃.
15. A solid-state battery comprising the silicon-based anode of any one of claims 1 to 5.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN110651385A (en) * 2017-10-20 2020-01-03 株式会社Lg化学 Negative electrode active material and negative electrode for solid-state battery comprising same
JP2023180901A (en) * 2022-06-10 2023-12-21 Ｕｂｅ株式会社 Lithium titanate powder, negative electrode active material composition using the same, and all-solid-state secondary battery

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Publication number Priority date Publication date Assignee Title
EP3349289B1 (en) * 2016-01-12 2019-03-06 LG Chem, Ltd. All-solid-state battery with a sulfide-based solid electrolyte

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN110651385A (en) * 2017-10-20 2020-01-03 株式会社Lg化学 Negative electrode active material and negative electrode for solid-state battery comprising same
JP2023180901A (en) * 2022-06-10 2023-12-21 Ｕｂｅ株式会社 Lithium titanate powder, negative electrode active material composition using the same, and all-solid-state secondary battery

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