CN110571409A - preparation method of negative electrode material, negative electrode material and lithium battery - Google Patents
preparation method of negative electrode material, negative electrode material and lithium battery Download PDFInfo
- Publication number
- CN110571409A CN110571409A CN201810567357.6A CN201810567357A CN110571409A CN 110571409 A CN110571409 A CN 110571409A CN 201810567357 A CN201810567357 A CN 201810567357A CN 110571409 A CN110571409 A CN 110571409A
- Authority
- CN
- China
- Prior art keywords
- producing
- anode material
- material according
- negative electrode
- capacity active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a preparation method of a negative electrode material, which comprises the steps of forming a precursor of a high-capacity active material doubly coated by a high-molecular compound and polyacrylonitrile by high-capacity active slurry, the high-molecular compound and a polyacrylonitrile solution through a coagulating bath; and carrying out pre-oxidation and carbonization treatment on the obtained precursor to obtain the cathode material. The negative electrode material forms a space structure in the preparation process, and the space structure provides a certain buffer space for the volume expansion of the negative electrode material in the charging and discharging processes, so that the capacity, the cycle performance and the first efficiency of the obtained lithium battery are obviously improved.
Description
Technical Field
the invention relates to a preparation method of a negative electrode material, the negative electrode material and a lithium battery.
Background
With the rapid development of portable electronic devices, power cars, and the like, there is an increasing demand for lithium ion batteries having high energy density and longer cycle life.
silicon material has ultrahigh theoretical specific capacity (3579mAh/g Li)15Si4) Low intercalation potential (less than 0.5V Li/Li)+) The lithium ion battery has attracted much attention due to environmental friendliness, abundant raw materials and the like, and is considered to be a next-generation high-performance lithium ion battery cathode material. However with intercalation of lithiumSi forms Li in the process22Si4Alloy phase, with a large volume expansion (400%), mechanical stress generated during this process causes material collapse, electrode structure instability and thus electrochemical performance degradation, and in addition, since silicon is a semiconductor, lower conductivity also affects battery performance. Therefore, in order to improve the cycle performance of the silicon-based negative electrode and improve the structural stability of the material in the cycle process, the silicon material is generally subjected to nano-crystallization and composite treatment. At present, in a silicon/carbon composite material, because a carbon material has higher electronic conductivity and ionic conductivity, the rate capability of a silicon-based material can be improved, and the volume effect of silicon in a circulating process is inhibited. In addition, the carbon material can prevent the silicon from directly contacting with the electrolyte, and the irreversible capacity is reduced. But the defects are that the interface contact between the silicon material and the carbon material is poor, and the difficulty of completely and uniformly coating the silicon material with carbon is high. Therefore, high-energy, high-safety silicon-based materials have not been widely used in commercial production.
disclosure of Invention
the invention provides a preparation method of a negative electrode material, which comprises the following steps:
1) Mixing the high-capacity active material slurry and a high-molecular compound to obtain a mixture A;
2) Mixing the mixture A and a polyacrylonitrile solution to obtain a suspension;
3) Adding the suspension into a coagulating bath to form a precursor of a high-capacity active material doubly coated by high polymer and polyacrylonitrile;
4) Carrying out pre-oxidation and carbonization treatment on the precursor obtained in the step 3) to obtain the cathode material.
According to the invention, a high molecular compound is uniformly dispersed on the surface of high-capacity active material particles, and then is mixed with a polyacrylonitrile solution, a precursor of the high-capacity active material which is doubly coated by the high molecular compound and the polyacrylonitrile is formed through a coagulation bath, after the precursor is pre-oxidized and carbonized, the high molecular compound is decomposed, a space structure is formed between the obtained high-capacity active material and a hard carbon layer coated on the surface of the high-capacity active material, and the formed space structure provides a certain buffer space for the volume expansion of the negative electrode material in the charging and discharging processes, so that the capacity, the cycle performance and the primary efficiency of the obtained lithium battery are remarkably improved.
In one embodiment, the negative electrode material includes a high capacity active material and a hard carbon layer coated on the surface of the high capacity active material, wherein the hard carbon layer has a thickness of 200nm to 800 nm; the average particle size of the negative electrode material is 5-35 μm.
In one embodiment, the hard carbon layer has a thickness of 300nm to 600 nm; the average particle size of the negative electrode material is 10-30 μm.
as an embodiment, a mass ratio of the high capacity active material to the anode material is 3: 20-12: 20.
As an embodiment, a mass ratio of the high capacity active material to the anode material is 1: 5-1: 2.
In one embodiment, the high capacity active material slurry according to step 1) is obtained by mixing and grinding a high capacity active material, a dispersant and a low boiling point organic solvent to obtain a mixture a, and then mixing and distilling the mixture a and the high boiling point organic solvent.
According to the invention, the particle size of the high-capacity active material is reduced by sanding, the high-capacity active material slurry is prepared by a solvent replacement method, and the high-capacity active material slurry and the high molecular compound are mixed and reacted, so that the agglomeration of the high-capacity active material is prevented, and the agglomeration of the high-capacity active material and the high molecular compound is also prevented.
the invention avoids the process of solvent separation-redispersion in the high-capacity active material through the process of solvent replacement, namely in the process of solvent separation, the traditional method is that the solvent in the sanding process is removed and separated firstly, the slurry obtained by sanding is changed into powder, the solvent is added into the powder to obtain new slurry, and in the process, the high-capacity active material can be agglomerated and lose the original highly dispersed state. The solvent replacement process of the present invention is to change the solvent in a dispersed state without liquid and solid transformation, so that the process is simplified and the high-capacity active material can be uniformly dispersed in the process of preparing the precursor.
The high-capacity active material and the high molecular compound can be uniformly dispersed in the high-boiling-point organic solvent better. In a low boiling point solvent, the high capacity active material is prone to agglomeration and cannot be uniformly dispersed during the precursor preparation process.
In one embodiment, the high capacity active material is selected from at least one of silicon, germanium, aluminum, tin oxide, and silicon monoxide.
As an embodiment, the high capacity active material is selected from nano-silicon and/or silicon monoxide.
In one embodiment, the dispersant is at least one selected from stearic acids, nickel acetate, polyvinyl alcohol, and polyethylene glycol.
As an embodiment, the mass ratio of the dispersant to the high capacity active material is 1: 100-5: 100.
as an embodiment, the mass ratio of the dispersant to the high capacity active material is 2: 100-4: 100.
In one embodiment, the low-boiling organic solvent is at least one selected from the group consisting of absolute ethanol, propanol, and butanol. In one embodiment, the high boiling point organic solvent is at least one selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, and N-methylpyrrolidone.
In one embodiment, the high boiling point organic solvent is at least one selected from the group consisting of dimethylformamide, dimethylsulfoxide, and dimethylacetamide.
As an embodiment, the mass ratio of the high capacity active material to the low boiling point organic solvent is 1: 13-8: 13.
As an embodiment, the mass ratio of the high capacity active material to the low boiling point organic solvent is 3: 13-7: 13.
As an embodiment, the mass ratio of the high capacity active material to the high boiling point organic solvent is 1: 10-1: 2.
as an embodiment, the mass ratio of the high capacity active material to the high boiling point organic solvent is 3: 13-1: 2.
As an embodiment, the sanding time is 2-25 h; the sanding speed is 1500-3000 n/min.
As an embodiment, the sanding time is 2-20 h; the sanding speed is 1800-2800 n/min.
in one embodiment, the distillation time is 0.5 to 4 hours; the distillation temperature is 30-70 ℃, and the distillation pressure is 0.01-0.2 Mpa.
In one embodiment, the distillation time is 0.5-2 h; the distillation temperature is 40-60 ℃, and the distillation pressure is 0.01-0.1 Mpa.
In one embodiment, the polymer compound in step 1) is at least one selected from the group consisting of polyacrylic acid (PAA), polyvinyl alcohol (PVA), Polymethylmethacrylate (PMMA), polystyrene sulfonic acid (PSS), and Polyacrylamide (PAM).
in one embodiment, the polymer compound in step 1) is at least one selected from the group consisting of polyacrylic acid (PAA), Polymethylmethacrylate (PMMA), and polystyrene sulfonic acid (PSS).
In one embodiment, the high capacity active material in the high capacity active material slurry has an average particle diameter of 30nm to 2 μm; the average particle size of the high-capacity active material in the high-capacity active material slurry is 30-500 nm.
As an embodiment, the mass ratio of the polymer compound to the high capacity active material in step 1) is 1: 120-1: 6.
As an embodiment, the mass ratio of the polymer compound to the high capacity active material in step 1) is 1: 120-1: 12.
in the invention, if the mass ratio of the high molecular compound to the high-capacity active material is too large, namely the mass of the high molecular compound is too high, the volume of a formed space structure is too large, the strength is poor in the charge and discharge processes of the lithium battery, the lithium battery is easy to collapse, and the cycle performance of the lithium battery is influenced. If the mass ratio of the high molecular compound to the high-capacity active material is too small, that is, the mass of the high-capacity active material is too high, the excessive high-capacity active material may agglomerate during the preparation process, thereby reducing the capacity and the first charge and discharge of the lithium battery.
As an embodiment, the temperature for mixing in the step 1) is 5-50 ℃; the mixing time in the step 1) is 0.5-5 h.
As an embodiment, the temperature for mixing in the step 1) is 10-40 ℃; the mixing time in the step 1) is 1-3 h.
In one embodiment, the high capacity active material in the step 1) is 15 to 50% of the high capacity active material slurry.
In one embodiment, the high capacity active material in the step 1) is 15 to 40% of the high capacity active material slurry.
In one embodiment, the mass concentration of the polyacrylonitrile in the step 2) is 5-25%.
as an implementation mode, the mass concentration of the polyacrylonitrile in the step 2) is 10-20%.
In one embodiment, the polyacrylonitrile in the step 2) has a number average molecular weight of 50000 to 200000.
as an embodiment, the polyacrylonitrile in the step 2) has a number average molecular weight of 60000-15000
As an embodiment, the mass ratio of the polyacrylonitrile to the polymer compound in the step 2) is 240: 1-12: 1.
as an embodiment, the mass ratio of polyacrylonitrile to the polymer compound in the step 2) is 240: 1-24: 1.
In the invention, if the mass ratio of the polyacrylonitrile to the high-molecular compound is too large, namely the mass of the polyacrylonitrile is too large, the carbon coating layer coated on the surface of the high-capacity active material is too thick, the migration of lithium ions in the charging and discharging process of the obtained lithium battery is difficult, and the first charging and discharging efficiency of the lithium battery is reduced. If the mass ratio of the polyacrylonitrile to the high molecular compound is too small, namely the high molecular compound has too high mass, the formed space structure has larger volume, the strength is poor in the charging and discharging processes of the lithium battery, the collapse is easy to happen, and the cycle performance of the lithium battery is influenced.
As an embodiment, the mixing time of the step 2) is 1-8 h; the mixing temperature is 15-60 ℃.
as an embodiment, the mixing time of the step 2) is 2-6 h; the mixing temperature is 20-50 ℃.
As an embodiment, the component of the coagulation bath in step 3) is deionized water.
As an embodiment, the components of the coagulation bath of step 3) further comprise a high boiling point organic solvent.
As an embodiment, the mass ratio of the high boiling point organic solvent to the deionized water in the components of the coagulation bath is 3: 2. as an embodiment, the mass ratio of the high boiling point organic solvent to the deionized water in the components of the coagulation bath is 1: 1.
in one embodiment, the coagulation time of the coagulation bath in step 3) is 10 to 60 min.
In one embodiment, the coagulation time of the coagulation bath in step 3) is 40 to 60 min.
in one embodiment, the temperature of the coagulation bath in step 3) is 10 to 80 ℃.
In one embodiment, the temperature of the coagulation bath in step 3) is 20 to 50 ℃.
in one embodiment, the pre-oxidation temperature in step 4) is 200-400 ℃.
In one embodiment, the pre-oxidation temperature in step 4) is 250-350 ℃.
As an embodiment, the pre-oxidation time in the step 4) is 1.5 to 5 hours.
in one embodiment, the carbonization process in step 4) is a low-temperature carbonization process followed by a high-temperature carbonization process.
In one embodiment, the temperature of the low-temperature carbonization is 200 to 500 ℃; the low-temperature carbonization time is 0.5-10 h; the temperature of the high-temperature carbonization is 600-1400 ℃; the high-temperature carbonization time is 0.5-10 h.
As an embodiment, the carbonization in step 4) is performed in an inert atmosphere; the inert atmosphere is nitrogen or argon.
In one embodiment, the method further includes mixing the negative electrode material with an organic carbon source, and performing secondary carbonization to obtain a negative electrode material coated with a soft carbon layer.
In one embodiment, the method further includes mixing the negative electrode material, the organic carbon source, and the high boiling point organic solvent to obtain a mixed solution B, and then performing spray drying and secondary carbonization to obtain the negative electrode material coated with the soft carbon layer.
In one embodiment, the solvent is at least one selected from the group consisting of deionized water, ethanol, acetone, dimethylformamide, and tetrahydrofuran.
in one embodiment, the soft carbon layer has a thickness of 20 to 100 nm.
in one embodiment, the soft carbon layer has a thickness of 50 to 100 nm.
in one embodiment, the average particle size of the anode material coated with the soft carbon layer is 10 to 50 μm.
In one embodiment, the average particle size of the anode material coated with the soft carbon layer is 15 to 35 μm.
In one embodiment, the mass ratio of the high capacity active material to the anode material coated with the soft carbon layer is 2: 20-11: 20.
In one embodiment, the mass ratio of the high capacity active material to the anode material coated with the soft carbon layer is 3: 20-12: 25.
As an embodiment, the mass ratio of the organic carbon source to the anode material is 1: 2-1: 5.
In one embodiment, the mass ratio of the organic carbon source to the anode material is 1: 2.5-1: 4.
in one embodiment, the mixing time is 2 to 4 hours.
In one embodiment, the temperature of the secondary carbonization is 600-1500 ℃; the temperature rise speed of the secondary carbonization is 1-5 ℃/min; the time of the secondary carbonization is 0.5-10 h.
In one embodiment, the atmosphere of the secondary carbonization is nitrogen or argon; the air flow of the secondary carbonization is 0.2-20L/min.
In one embodiment, the organic carbon source is at least one selected from the group consisting of polyvinyl chloride, polyvinyl butyral, sucrose, glucose, maltose, citric acid, asphalt, furfural resin, epoxy resin, and phenol resin.
in one embodiment, the temperature of the spray drying is 150 to 250 ℃; the time of spray drying is 0.5-2 h.
in one embodiment, the temperature of the spray drying is 180 to 220 ℃; the time of spray drying is 0.5-1.5 h.
The invention also provides a negative electrode material prepared by the preparation method.
A lithium battery comprising the negative electrode material as described above.
drawings
FIG. 1: SEM image of cross section of the negative electrode material described in example 1 of the present invention.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
The structure of the negative electrode material prepared by the invention (namely, the negative electrode material comprises a high-capacity active material and a hard carbon layer coated on the outer surface of the high-capacity active material) can be verified by a scanning electron microscope (Hitachi, model: SU8010) which is enlarged by 70.0K at normal temperature. The preparation method of the negative electrode material profile analysis sample comprises the following steps: mixing the negative electrode material powder and the conductive adhesive together, airing, centering through an optical microscope after airing, and placing the centering into an ion grinder for ion cutting to obtain a sample.
Example 1:
1) Mixing 240 g of silicon monoxide slurry with the particle size of 500nm, the mass fraction of which is 25%, with 10 g of polyacrylic acid, wherein the solvent is dimethylformamide, and stirring and mixing for 5 hours at the temperature of 5 ℃ to obtain a mixture A;
2) Mixing the mixture A with 2400 g of polyacrylonitrile solution with the mass concentration of 5%, wherein the molecular weight of polyacrylonitrile is 200000, and stirring and mixing for 1 hour at 60 ℃ to obtain a suspension;
3) adding the suspension into a coagulating bath, adding a coagulating agent deionized water, wherein the coagulating temperature is 10 ℃, and the coagulating time is 60min, so as to form a precursor of the high-capacity active material doubly coated by polyacrylic acid and polyacrylonitrile;
4) pre-oxidizing the precursor obtained in the step 3) for 1.5 hours at 400 ℃, then carbonizing the precursor for 0.5 hour at 500 ℃ in a nitrogen atmosphere, and obtaining the cathode material after high-temperature carbonization treatment at 1400 ℃ for 0.5 hour, wherein the diagram is shown in figure 1.
The prepared negative electrode material comprises silicon monoxide and a hard carbon layer coated on the outer surface of the silicon monoxide, wherein the thickness of the hard carbon layer is 200nm, the average particle size of the negative electrode material is 5 microns, and the mass ratio of the silicon monoxide to the negative electrode material is 12: 20.
As can be seen from fig. 1: the cathode material prepared by the invention has a buffer space.
Preparing a battery:
Mixing a negative electrode material, a conductive agent and a binder (sodium carboxymethyl cellulose (CMC) + Styrene Butadiene Rubber (SBR)) according to a mass ratio of 87: 5: 8, uniformly mixing, adding a proper amount of deionized water, stirring for 15min, and uniformly coating on a copper foil by using an automatic film coating machine, wherein the areal density is about 2.5mg/cm2. After air blast drying, rolling on a roller press to prepare a pole piece with the diameter of 14mm, and putting the pole piece into a vacuum drying oven to dry for 12 hours at the temperature of 100 ℃. Assembling a battery in a glove box, taking a negative electrode material pole piece as a positive electrode, taking a metal lithium piece as a counter electrode, and taking 1mol/L LiPF6Ethylene Carbonate (EC) -diethyl carbonate (DEC) (volume ratio 3: 7) was used as the electrolyte.
and (3) testing the battery performance:
and (3) testing conditions are as follows: the current density is 0.15mA/cm2And the voltage is 0.01-1.5V, and the charge and the discharge are carried out in a constant current mode.
and (3) testing results: the first discharge capacity is 1010mAh/g, and the first efficiency can reach 75.5 percent.
Example 2:
1) Mixing 120 g of silicon monoxide slurry with the particle size of 100nm, the mass fraction of which is 50%, with 0.5 g of polystyrene sulfonic acid, wherein the solvent is dimethyl sulfoxide, and stirring and mixing for 0.5 hour at 50 ℃ to obtain a mixture A;
2) Mixing the mixture A with 480 g of 25% polyacrylonitrile solution, wherein the molecular weight of polyacrylonitrile is 50000, and stirring and mixing at 15 ℃ for 8 hours to obtain a suspension;
3) Adding the suspension into a coagulating bath, wherein a coagulating agent is a dimethyl sulfoxide water solution containing 60%, the coagulating temperature is 80 ℃, and the coagulating time is 10min, so as to form a precursor of the high-capacity active material doubly coated by the polystyrene sulfonic acid and the polyacrylonitrile;
4) pre-oxidizing the precursor obtained in the step 3) for 5 hours at 200 ℃, then carbonizing the precursor for 10 hours at 200 ℃ in a nitrogen atmosphere, and carbonizing the precursor for 10 hours at 600 ℃ to obtain the negative electrode material.
The prepared negative electrode material comprises silicon monoxide and a hard carbon layer coated on the outer surface of the silicon monoxide, wherein the thickness of the hard carbon layer is 400nm, the average particle size of the negative electrode material is 10 microns, and the mass ratio of the silicon monoxide to the negative electrode material is 8: 20.
lithium batteries (button cells) were prepared as in example 1.
battery performance testing
The test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 900mAh/g, and the first efficiency can reach 76.5%.
Example 3:
1) mixing 100 g of nano silicon slurry with the particle size of 30nm, the mass fraction of which is 15%, with 1 g of polymethyl methacrylate, wherein the solvent is N-methyl pyrrolidone, and stirring and mixing for 2 hours at the temperature of 30 ℃ to obtain a mixture A;
2) mixing the mixture A with 600 g of polyacrylonitrile solution with the mass concentration of 20%, wherein the molecular weight of polyacrylonitrile is 60000, and stirring and mixing for 5 hours at 20 ℃ to obtain suspension;
3) adding the suspension into a coagulating bath, wherein a coagulating agent is an aqueous solution containing 20% of N-methylpyrrolidone, the coagulating temperature is 20 ℃, and the coagulating time is 60min, so as to form a precursor of the high-capacity active material doubly coated by polymethyl methacrylate and polyacrylonitrile;
4) Pre-oxidizing the precursor obtained in the step 3) for 3 hours at 300 ℃, and then carbonizing the precursor for 5 hours at 300 ℃ and carbonizing the precursor for 5 hours at 900 ℃ in an argon atmosphere to obtain the negative electrode material.
The prepared negative electrode material comprises nano silicon and a hard carbon layer coated on the outer surface of the nano silicon, wherein the thickness of the hard carbon layer is 800nm, the average particle size of the negative electrode material is 35 mu m, and the mass ratio of the nano silicon to the negative electrode material is 3: 20.
Lithium batteries (button cells) were prepared as in example 1.
Battery performance testing
The test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 750mAh/g, and the first efficiency can reach 81.5%.
Example 4:
1) Mixing 600 g of silicon monoxide, 30 g of stearic acid and 975 g of ethanol, sanding to obtain a mixture A, wherein the sanding rotation speed is 3000 r/min, and the time is 8 hours, then mixing the mixture A and 1200 g of dimethylformamide organic solvent, and distilling at the temperature of 30 ℃, the negative pressure of 0.1Mpa and the time of 2 hours to obtain silicon monoxide slurry.
2) mixing 240 g of the silicon monoxide slurry with the granularity of 300 nanometers and the mass fraction of 25 percent with 2 g of polystyrene sulfonic acid high molecular compound, wherein the solvent is dimethylformamide, and stirring and mixing the mixture for 2 hours at the temperature of 30 ℃ to obtain a mixture A;
3) Mixing the mixture A with 800 g of 15% polyacrylonitrile solution with the molecular weight of 90000, and stirring and mixing at 40 ℃ for 4 hours to obtain a suspension;
4) Adding the suspension into a coagulating bath, wherein the components of the coagulating bath are deionized water, the coagulating temperature is 50 ℃, and the coagulating time is 50min, so as to form a precursor of the high-capacity active material doubly coated by the polystyrene sulfonic acid and the polyacrylonitrile;
5) Pre-oxidizing the precursor obtained in the step 4) for 1.5 hours at 300 ℃, carbonizing the precursor for 3 hours at 500 ℃ in an argon atmosphere, and carbonizing the precursor for 2 hours at 1100 ℃ to obtain the negative electrode material.
The prepared negative electrode material comprises silicon monoxide and a hard carbon layer coated on the outer surface of the silicon monoxide, wherein the thickness of the hard carbon layer is 300nm, the average particle size of the negative electrode material is 25 micrometers, and the mass ratio of the silicon monoxide to the negative electrode material is 11: 20.
Lithium batteries (button cells) were prepared as in example 1.
Battery performance testing
The test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 950mAh/g, and the first efficiency can reach 75.5 percent.
Example 5:
1) mixing 400 g of silicon, 4 g of nickel acetate and 5200 g of ethanol, sanding to obtain a mixture A, wherein the sanding rotation speed is 1500 rpm and the sanding time is 20 hours, then mixing the mixture A and 4000 g of ethylene carbonate organic solvent, and distilling at the temperature of 70 ℃, the negative pressure of 0.02Mpa and the time of 8 hours to obtain the nano silicon slurry. .
2) taking 75 g of the nano silicon slurry, mixing the nano silicon slurry with the particle size of 150 nm and the mass fraction of 20% and 1 g of polyacrylic acid, wherein the solvent is ethylene carbonate, and stirring and mixing the mixture for 3 hours at the temperature of 20 ℃ to obtain a mixture A;
3) Mixing the mixture A with 1200 g of polyacrylonitrile solution with the mass concentration of 10%, wherein the molecular weight of polyacrylonitrile is 80000, and stirring and mixing for 6 hours at 20 ℃ to obtain suspension;
4) adding the suspension into a coagulating bath, wherein a coagulating agent is a water solution containing 50% of dimethyl sulfoxide, the coagulating temperature is 40 ℃, and the coagulating time is 30min, so as to form a precursor of the high-capacity active material doubly coated by polyacrylic acid and polyacrylonitrile;
5) pre-oxidizing the precursor obtained in the step 4) at 280 ℃ for 2 hours, then carbonizing the precursor at 400 ℃ for 2 hours in an argon atmosphere, and carbonizing the precursor at 1000 ℃ for 5 hours to obtain the cathode material.
The prepared negative electrode material comprises nano silicon and a hard carbon layer coated on the outer surface of the nano silicon, wherein the thickness of the hard carbon layer is 600nm, the average particle size of the negative electrode material is 30 micrometers, and the mass ratio of the nano silicon to the negative electrode material is 3: 20.
Lithium batteries (button cells) were prepared as in example 1.
Battery performance testing
the test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 760mAh/g, and the first efficiency can reach 80.5 percent.
example 6:
1) mixing 600 g of silicon monoxide slurry with the particle size of 300 nanometers, the mass fraction of which is 20 percent, with 0.5 g of polyacrylic acid, wherein the solvent is dimethylformamide, and stirring and mixing the mixture for 3 hours at the temperature of 20 ℃ to obtain a mixture A;
2) Mixing the mixture A with 800 g of polyacrylonitrile solution with the mass concentration of 15%, wherein the molecular weight of polyacrylonitrile is 100000, and stirring and mixing for 4 hours at 40 ℃ to obtain suspension;
3) Adding the suspension into a coagulating bath, wherein a coagulating agent is deionized water, the coagulating temperature is 30 ℃, and the coagulating time is 40 minutes, so as to form a precursor of the polyacrylic acid and polyacrylonitrile double-coated high-capacity active material;
4) Pre-oxidizing the precursor obtained in the step 3) at 250 ℃ for 4 hours, then carbonizing the precursor at 500 ℃ for 3 hours in an argon atmosphere, and carbonizing the precursor at 900 ℃ for 4 hours to obtain a negative electrode material (the prepared negative electrode material comprises silicon monoxide and a hard carbon layer coated on the outer surface of the silicon monoxide, wherein the thickness of the hard carbon layer is 600nm, the average particle size of the negative electrode material is 25 microns, and the mass ratio of the silicon monoxide to the negative electrode material is 12: 20.
5) adding 100 g of the negative electrode material obtained in the step 4) into a solution containing 20 g of asphalt to form a mixed solution B, mixing for 2h, taking dimethyl formamide as a solvent, then performing spray drying at the drying temperature of 250 ℃ for 0.5 h, then performing secondary carbonization in an atmosphere furnace at the carbonization temperature of 1500 ℃, keeping the temperature for 0.5 h, taking argon as an inert protective atmosphere, setting the temperature rise rate of carbonization at 5 ℃/min, and setting the gas flow in the inert protective atmosphere at 100 ml/min to obtain the negative electrode material coated by the soft carbon layer. The average particle size of the anode material coated by the soft carbon layer is 10 μm, and the mass ratio of the nano silicon to the anode material coated by the soft carbon layer is 11: 20.
Lithium batteries (button cells) were prepared as in example 1.
and (5) testing the performance of the battery.
The test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 850mAh/g, and the first efficiency can reach 80.5%.
Example 7:
1) Mixing 300 g of silicon slurry with the particle size of 80 nanometers, the mass fraction of which is 10 percent, with 1 g of polystyrene sulfonic acid, wherein the solvent is dimethyl sulfoxide, and stirring and mixing for 2 hours at the temperature of 40 ℃ to obtain a mixture A;
2) mixing the mixture A with 1200 g of polyacrylonitrile solution with the mass concentration of 10 percent, wherein the molecular weight of polyacrylonitrile is 120000, and stirring and mixing for 4 hours at 50 ℃ to obtain suspension;
3) Adding the suspension into a coagulating bath, wherein a coagulating agent is deionized water, the coagulating temperature is 20 ℃, and the coagulating time is 60 minutes, so as to form a precursor of the high-capacity active material doubly coated by the polystyrene sulfonic acid and the polyacrylonitrile;
4) Pre-oxidizing the precursor obtained in the step 3) for 5 hours at 280 ℃, then carbonizing the precursor for 5 hours at 400 ℃ in a nitrogen atmosphere, and carbonizing the precursor for 2 hours at 1000 ℃ to obtain the negative electrode material. (the prepared cathode material comprises nano-silicon and a hard carbon layer coated on the outer surface of the nano-silicon, wherein the thickness of the hard carbon layer is 500nm, the average particle size of the cathode material is 35 μm, and the mass ratio of the nano-silicon to the cathode material is 3: 20.
5) Adding 100 g of the negative electrode material obtained in the step 4) into a solution containing 50 g of cane sugar to form a mixed solution B, mixing for 4h, taking deionized water as a solvent, then performing spray drying at the drying temperature of 150 ℃ for 2h, performing secondary carbonization in an atmosphere furnace at the carbonization temperature of 600 ℃, keeping the temperature for 10h, taking argon as an inert protective atmosphere, and obtaining the negative electrode material coated by the soft carbon layer, wherein the temperature rise rate of the carbonization treatment is 1 ℃/min, and the gas flow in the inert protective atmosphere is 500 ml/min.
The average particle size of the anode material coated by the soft carbon layer is 50 μm, and the mass ratio of the nano silicon to the anode material coated by the soft carbon layer is 2: 20.
lithium batteries (button cells) were prepared as in example 1.
Battery performance testing
The test conditions were the same as in example 1.
And (3) testing results: the first discharge capacity is 650mAh/g, and the first efficiency can reach 85.5%.
example 8:
1) Mixing 200 g of silicon monoxide slurry with the particle size of 500 nanometers, the mass fraction of which is 20 percent, and 0.5 g of polyacrylic acid, wherein the solvent is dimethylformamide, and stirring and mixing the mixture for 3 hours at the temperature of 20 ℃ to obtain a mixture A;
2) Mixing the mixture A with 800 g of polyacrylonitrile solution with the mass concentration of 15%, wherein the molecular weight of polyacrylonitrile is 100000, and stirring and mixing for 4 hours at 40 ℃ to obtain suspension;
3) adding the suspension into a coagulating bath, wherein a coagulating agent is deionized water, the coagulating temperature is 30 ℃, and the coagulating time is 40 minutes, so as to form a precursor of the high-capacity active material doubly coated by polyacrylic acid and polyacrylonitrile;
4) Pre-oxidizing the precursor obtained in the step 3) at 250 ℃ for 4 hours, then carbonizing the precursor at 500 ℃ for 3 hours in a nitrogen atmosphere, and carbonizing the precursor at 900 ℃ for 4 hours to obtain a negative electrode material (the prepared negative electrode material comprises nano silicon and a hard carbon layer coated on the outer surface of the nano silicon, wherein the thickness of the hard carbon layer is 500nm, the average particle size of the negative electrode material is 30 microns, and the mass ratio of the nano silicon to the negative electrode material is 5: 20.
5) Adding 100 g of the material obtained in the step 4) into 25 g of phenolic resin, mixing for 3h, performing secondary carbonization in an atmosphere furnace at 1000 ℃, keeping the temperature for 3h, wherein the inert protective atmosphere is argon, the temperature rise rate of carbonization is 2 ℃/min, and the gas flow in the inert protective atmosphere is 100 ml/min, so as to obtain the cathode material coated by the soft carbon layer. (wherein the average particle diameter of the anode material coated by the soft carbon layer is 35 μm, and the mass ratio of the nano silicon to the anode material coated by the soft carbon layer is 4: 20.
Lithium batteries (button cells) were prepared as in example 1.
Battery performance testing
the test conditions were the same as in example 1.
and (3) testing results: the first discharge capacity is 780mAh/g, and the first efficiency can reach 80.5 percent.
Claims (37)
1. a preparation method of the anode material comprises the following steps:
1) Mixing the high-capacity active material slurry and a high-molecular compound to obtain a mixture A;
2) Mixing the mixture A and a polyacrylonitrile solution to obtain a suspension;
3) Adding the suspension into a coagulating bath to form a precursor of a high-capacity active material doubly coated by a high-molecular compound and polyacrylonitrile;
4) And (3) carrying out pre-oxidation and carbonization treatment on the precursor in the step 3) to obtain the cathode material.
2. The method for producing the anode material according to claim 1, wherein: the negative electrode material comprises a high-capacity active material and a hard carbon layer coated on the surface of the high-capacity active material, wherein the thickness of the hard carbon layer is 200-800 nm; the average particle size of the negative electrode material is 5-35 μm.
3. The method for producing the anode material according to claim 1, wherein: the mass ratio of the high-capacity active material to the negative electrode material is 3: 20-12: 20.
4. The method for producing the anode material according to claim 1, wherein: the high-capacity active material slurry in the step 1) is obtained by mixing and grinding a high-capacity active material, a dispersant and a low-boiling-point organic solvent to obtain a mixture A, and then mixing and distilling the mixture A and the high-boiling-point organic solvent.
5. The method for producing an anode material according to claim 4, wherein: the high capacity active material is selected from at least one of silicon, germanium, aluminum, tin oxide, and silicon monoxide.
6. the method for producing an anode material according to claim 4, wherein: the dispersing agent is at least one selected from stearic acids, nickel acetate, polyvinyl alcohol and polyethylene glycol.
7. The method for producing an anode material according to claim 4, wherein: the mass ratio of the dispersant to the high-capacity active material is 1: 100-5: 100.
8. The method for producing an anode material according to claim 4, wherein: the low-boiling-point organic solvent is at least one selected from absolute ethyl alcohol, propyl alcohol and butyl alcohol.
9. the method for producing an anode material according to claim 4, wherein: the high boiling point organic solvent is at least one selected from dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone.
10. The method for producing an anode material according to claim 4, wherein: the mass ratio of the high-capacity active material to the low-boiling-point organic solvent is 1: 13-8: 13.
11. The method for producing an anode material according to claim 4, wherein: the mass ratio of the high-capacity active material to the high-boiling-point organic solvent is 1: 10-1: 2.
12. The method for producing the anode material according to claim 1, wherein: the polymer compound in the step 1) is at least one selected from polyacrylic acid (PAA), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polystyrene sulfonic acid (PSS) and Polyacrylamide (PAM).
13. The method for producing the anode material according to claim 1, wherein: the high-capacity active material in the high-capacity active material slurry has an average particle diameter of 30nm to 2 μm.
14. The method for producing the anode material according to claim 1, wherein: the mass ratio of the high molecular compound to the high-capacity active material in the step 1) is 1: 120-1: 6.
15. the method for producing the anode material according to claim 1, wherein: the high-capacity active material in the step 1) is 15-50% of the high-capacity active material slurry.
16. the method for producing the anode material according to claim 1, wherein: the number average molecular weight of the polyacrylonitrile in the step 2) is 50000-200000.
17. The method for producing the anode material according to claim 1, wherein: the mass ratio of the polyacrylonitrile to the high molecular compound in the step 2) is 240: 1-12: 1.
18. The method for producing the anode material according to claim 1, wherein: the mixing time of the step 2) is 1-8 h; the mixing temperature is 15-60 ℃.
19. the method for producing the anode material according to claim 1, wherein: the component of the coagulating bath in the step 3) is deionized water.
20. the method for producing an anode material according to claim 19, wherein: the components of the coagulating bath in step 3) also comprise a high-boiling point organic solvent.
21. The method for producing an anode material according to claim 20, wherein: the mass ratio of the high-boiling-point organic solvent to the deionized water in the components of the coagulating bath is less than or equal to 3: 2.
22. The method for producing the anode material according to claim 1, wherein: and 3) controlling the temperature of the coagulating bath to be 10-80 ℃.
23. the method for producing the anode material according to claim 1, wherein: step 4), the pre-oxidation temperature is 200-400 ℃; the pre-oxidation time is 1.5-5 h.
24. The method for producing the anode material according to claim 1, wherein: step 4), the carbonization process comprises low-temperature carbonization and high-temperature carbonization; the temperature of the low-temperature carbonization is 200-500 ℃; the low-temperature carbonization time is 0.5-10 h; the temperature of the high-temperature carbonization is 600-1400 ℃; the high-temperature carbonization time is 0.5-10 h.
25. The method for producing the anode material according to claim 1, wherein: step 4) the carbonization is carried out in an inert atmosphere; the inert atmosphere is nitrogen or argon.
26. the method for producing the anode material according to claim 1, wherein: the method also comprises the steps of mixing the negative electrode material as claimed in claim 1 with an organic carbon source, and performing secondary carbonization to obtain the negative electrode material coated by the soft carbon layer.
27. The method for producing an anode material according to claim 26, wherein: the method further comprises the steps of mixing the negative electrode material, an organic carbon source and a solvent according to claim 1 to obtain a mixed solution B, and then carrying out spray drying and secondary carbonization to obtain the negative electrode material coated with the soft carbon layer.
28. The method for producing an anode material according to claim 27, wherein: the solvent is at least one selected from deionized water, ethanol, acetone, dimethylformamide and tetrahydrofuran.
29. the method for producing an anode material according to claim 26 or 27, wherein: the average particle size of the negative electrode material coated by the soft carbon layer is 10-50 mu m.
30. the method for producing an anode material according to claim 26 or 27, wherein: the mass ratio of the high-capacity active material to the anode material coated by the soft carbon layer is 2: 20-11: 20.
31. The method for producing an anode material according to claim 26 or 27, wherein: the mass ratio of the organic carbon source to the anode material is 1: 2-1: 5.
32. The method for producing an anode material according to claim 26 or 27, wherein: the temperature of the secondary carbonization is 600-1500 ℃; the temperature rise speed of the secondary carbonization is 1-5 ℃/min; the time of the secondary carbonization is 0.5-10 h.
33. The method for producing an anode material according to claim 26 or 27, wherein: the atmosphere of the secondary carbonization is nitrogen or argon; the air flow of the secondary carbonization is 0.2-20L/min.
34. the method for producing an anode material according to claim 26 or 27, wherein: the organic carbon source is selected from at least one of polyvinyl chloride, polyvinyl butyral, sucrose, glucose, maltose, citric acid, asphalt, furfural resin, epoxy resin and phenolic resin.
35. The method for producing an anode material according to claim 27, wherein: the temperature of the spray drying is 150-250 ℃; the time of spray drying is 0.5-2 h.
36. a negative electrode material produced by the production method according to claim 1.
37. a lithium battery comprising the negative electrode material as claimed in claim 36.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810567357.6A CN110571409B (en) | 2018-06-05 | 2018-06-05 | Preparation method of anode material, anode material and lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810567357.6A CN110571409B (en) | 2018-06-05 | 2018-06-05 | Preparation method of anode material, anode material and lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110571409A true CN110571409A (en) | 2019-12-13 |
| CN110571409B CN110571409B (en) | 2023-08-08 |
Family
ID=68772555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810567357.6A Active CN110571409B (en) | 2018-06-05 | 2018-06-05 | Preparation method of anode material, anode material and lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110571409B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276684A (en) * | 2020-02-17 | 2020-06-12 | 东南大学 | Preparation method and application of carbon-coated composite material |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003317802A (en) * | 2002-04-24 | 2003-11-07 | Teijin Ltd | Lithium ion secondary cell |
| CN101894939A (en) * | 2010-07-02 | 2010-11-24 | 重庆大学 | Nano-Si or nano-Sn containing composite cathode material for lithium ion battery and preparation method thereof |
| KR101341951B1 (en) * | 2012-07-23 | 2013-12-16 | 동국대학교 산학협력단 | Silicon-carbon composite for negative electrode of lithium secondary battery |
| WO2014030853A1 (en) * | 2012-08-22 | 2014-02-27 | 동국대학교 산학협력단 | Method for preparing silicon oxide/carbon composite for anode active material of lithium secondary battery |
| WO2014042485A1 (en) * | 2012-09-17 | 2014-03-20 | 동국대학교 산학협력단 | Lithium secondary battery having improved electrochemical properties, and method for manufacturing same |
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| WO2015114692A1 (en) * | 2014-01-31 | 2015-08-06 | 株式会社豊田自動織機 | Negative electrode for nonaqueous secondary batteries; nonaqueous secondary battery; negative electrode active material; method for producing negative electrode active material; composite body comprising nano-silicon, carbon layer and cationic polymer layer; and method for producing composite body composed of nano-silicon and carbon layer |
| WO2016009938A1 (en) * | 2014-07-15 | 2016-01-21 | 東レ株式会社 | Electrode material and a lithium-ion battery or lithium ion capacitor using same |
| CN106025211A (en) * | 2016-06-06 | 2016-10-12 | 田东 | Preparation method of high-capacity silicon-based negative electrode material of lithium-ion battery |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力***（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN108075110A (en) * | 2016-11-14 | 2018-05-25 | 微宏动力***（湖州）有限公司 | Negative electrode for lithium ion battery composite material and lithium ion battery |
-
2018
- 2018-06-05 CN CN201810567357.6A patent/CN110571409B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003317802A (en) * | 2002-04-24 | 2003-11-07 | Teijin Ltd | Lithium ion secondary cell |
| CN101894939A (en) * | 2010-07-02 | 2010-11-24 | 重庆大学 | Nano-Si or nano-Sn containing composite cathode material for lithium ion battery and preparation method thereof |
| KR101341951B1 (en) * | 2012-07-23 | 2013-12-16 | 동국대학교 산학협력단 | Silicon-carbon composite for negative electrode of lithium secondary battery |
| WO2014030853A1 (en) * | 2012-08-22 | 2014-02-27 | 동국대학교 산학협력단 | Method for preparing silicon oxide/carbon composite for anode active material of lithium secondary battery |
| WO2014042485A1 (en) * | 2012-09-17 | 2014-03-20 | 동국대학교 산학협력단 | Lithium secondary battery having improved electrochemical properties, and method for manufacturing same |
| WO2015114692A1 (en) * | 2014-01-31 | 2015-08-06 | 株式会社豊田自動織機 | Negative electrode for nonaqueous secondary batteries; nonaqueous secondary battery; negative electrode active material; method for producing negative electrode active material; composite body comprising nano-silicon, carbon layer and cationic polymer layer; and method for producing composite body composed of nano-silicon and carbon layer |
| WO2016009938A1 (en) * | 2014-07-15 | 2016-01-21 | 東レ株式会社 | Electrode material and a lithium-ion battery or lithium ion capacitor using same |
| CN104362311A (en) * | 2014-09-23 | 2015-02-18 | 清华大学深圳研究生院 | Silicon-carbon composite microsphere anode material and preparation method thereof |
| CN106025211A (en) * | 2016-06-06 | 2016-10-12 | 田东 | Preparation method of high-capacity silicon-based negative electrode material of lithium-ion battery |
| CN107681125A (en) * | 2016-08-02 | 2018-02-09 | 微宏动力***（湖州）有限公司 | A kind of cathode material of lithium ion battery, its preparation method and lithium rechargeable battery |
| CN108075110A (en) * | 2016-11-14 | 2018-05-25 | 微宏动力***（湖州）有限公司 | Negative electrode for lithium ion battery composite material and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| SUNG-WOO PARK，ET AL.: "Uniform Si nanoparticle-embedded nitrogen-doped carbon nanofiber electrodes for lithium ion batteries", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 728 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111276684A (en) * | 2020-02-17 | 2020-06-12 | 东南大学 | Preparation method and application of carbon-coated composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110571409B (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101687288B1 (en) | Silicon based Composite Anode Material for Lithium Ion Battery and its Preparation Method and Battery | |
| US10847789B2 (en) | Negative electrode material for secondary battery, method for preparing the same, and battery containing the same | |
| CN110048101B (en) | Silicon-oxygen-carbon microsphere composite negative electrode material and preparation method and application thereof | |
| WO2017008494A1 (en) | Method for fabricating graphite silicon-based composite negative-electrode material | |
| CN108232141B (en) | High-compaction lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof | |
| CN107026262B (en) | High-capacity spherical hard carbon negative electrode material coated with graphene on surface | |
| CN108682820B (en) | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery | |
| CN106784741B (en) | Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material | |
| CN108448080A (en) | A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof | |
| WO2017008606A1 (en) | Method for fabricating graphite tin-based composite negative-electrode material | |
| KR20220104684A (en) | Silicon-carbon negative electrode material for lithium ion battery and manufacturing method thereof | |
| CN113113572B (en) | High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof | |
| CN109360962B (en) | High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof | |
| CN111689500A (en) | Preparation method of low-expansibility SiO/graphite composite electrode material | |
| CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
| CN108682830B (en) | Silicon-carbon composite negative electrode material of lithium ion battery and preparation method thereof | |
| WO2017008624A1 (en) | Method for fabricating lithium titanate silicon-based composite negative-electrode material | |
| CN110931727A (en) | Preparation method of conductive polymer-coated silicon-based negative electrode material | |
| CN108258230B (en) | Hollow-structure silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| CN112421049A (en) | Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material | |
| CN110571409B (en) | Preparation method of anode material, anode material and lithium battery | |
| CN112768644A (en) | Modification method for coating silicon-carbon composite negative electrode material interface by using modified asphalt | |
| CN108288705B (en) | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof | |
| US20230261183A1 (en) | Negative electrode material, preparation method thereof, and lithium ion battery | |
| CN111725507B (en) | High-compaction silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230517 Address after: 1080 Greenwood Avenue, Lake Mary, Florida, USA Applicant after: Weihong Advanced Materials Co. Address before: 313000 No. 2198 Hongfeng Road, Huzhou Economic and Technological Development Zone, Zhejiang Province Applicant before: MICROVAST POWER SYSTEMS Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |