CN110571409B - Preparation method of anode material, anode material and lithium battery - Google Patents
Preparation method of anode material, anode material and lithium battery Download PDFInfo
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- CN110571409B CN110571409B CN201810567357.6A CN201810567357A CN110571409B CN 110571409 B CN110571409 B CN 110571409B CN 201810567357 A CN201810567357 A CN 201810567357A CN 110571409 B CN110571409 B CN 110571409B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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 coated by a high-molecular compound and polyacrylonitrile in a double manner by using high-capacity active slurry, the high-molecular compound and a polyacrylonitrile solution through a coagulating bath; and (3) pre-oxidizing and carbonizing the obtained precursor to obtain the anode 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 charge and discharge process, 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 automobiles, and the like, lithium ion batteries having high energy density and longer cycle life are increasingly demanded.
The silicon material has very high theoretical specific capacity (3579 mAh/g Li 15 Si 4 ) Low lithium intercalation potential (less than 0.5VLi/Li + ) The negative electrode material is environmentally friendly, has rich raw materials and the like, and is considered as a negative electrode material of a next-generation high-performance lithium ion battery. However, si forms Li during lithium intercalation 22 Si 4 The alloy phase is accompanied by a large volume expansion (400%), mechanical stress generated in the process causes material collapse, an electrode structure is unstable, and electrochemical performance is reduced, and in addition, the lower conductivity also affects battery performance because silicon is a semiconductor. Therefore, in order to improve the cycle performance of the silicon-based anode and to improve the structural stability of the material during the cycle, the silicon material is usually nanocrystallized and composited. Currently, silicon/carbon typeIn the composite material, the carbon material has higher electron conductivity and ion conductivity, so that the multiplying power performance of the silicon-based material can be improved, and the volume effect of silicon in the circulation process can be inhibited. In addition, the carbon material can prevent silicon from directly contacting with electrolyte, so that irreversible capacity is reduced. However, the disadvantage is 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 applied in large quantities to commercial production.
Disclosure of Invention
The invention provides a preparation method of a negative electrode material, which comprises the following steps:
1) Mixing high-capacity active material slurry and a high-molecular compound to obtain a mixture A;
2) Mixing the mixture A with a polyacrylonitrile solution to obtain a suspension;
3) Adding the suspension into a coagulation bath to form a precursor of a high-capacity active material with double coating of high polymer and polyacrylonitrile;
4) And 3) pre-oxidizing and carbonizing the precursor obtained in the step 3) to obtain the anode material.
According to the invention, the high-molecular compound is uniformly dispersed on the surface of the high-capacity active material particles, then the high-molecular compound is mixed with the polyacrylonitrile solution, and a precursor of the high-capacity active material double-coated by the high-molecular compound and the polyacrylonitrile is formed through a coagulating bath, the precursor is subjected to pre-oxidation and carbonization, 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 volume expansion of the negative electrode material in the charge-discharge process, so that the capacity, the cycle performance and the first efficiency of the obtained lithium battery are remarkably improved.
As one embodiment, 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 nm-800 nm; the average particle diameter of the negative electrode material is 5-35 mu m.
As one embodiment, the hard carbon layer has a thickness of 300nm to 600nm; the average particle diameter of the negative electrode material is 10-30 mu m.
As an embodiment, the mass ratio of the high-capacity active material to the negative electrode material is 3: 20-12: 20.
as one embodiment, the mass ratio of the high-capacity active material to the negative electrode material is 1:5 to 1:2.
in one embodiment, the high-capacity active material slurry of 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.
The invention firstly reduces the particle size of the high-capacity active material by sanding, prepares the high-capacity active material slurry by a solvent replacement method, uses the high-capacity active material slurry to react with the high-molecular compound in a mixing way, prevents the high-capacity active material from agglomerating, and simultaneously prevents the high-capacity active material and the high-molecular compound from agglomerating.
The invention uses the solvent replacement process of the high-capacity active material, avoids the process of solvent separation and redispersion in the high-capacity active material, namely, in the process of solvent separation, the traditional method is to remove and separate the solvent in the sanding process, change the slurry obtained by sanding into powder, add the solvent into the obtained 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 invention is to change the solvent in a dispersed state without liquid and solid state change, so that the process is simplified, and the high-capacity active material can be uniformly dispersed in the precursor preparation process.
The high-capacity active material and the high-molecular compound can be better and uniformly dispersed in the high-boiling point organic solvent. In low boiling point solvents, high capacity active materials are prone to agglomeration and cannot be uniformly dispersed during precursor preparation.
As an 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 dispersing agent is at least one selected from stearic acid, 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.
as an embodiment, the low boiling point organic solvent is at least one selected from the group consisting of absolute ethanol, propanol and butanol. As an embodiment, the high boiling point organic solvent is at least one selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate and N-methylpyrrolidone.
As an embodiment, the high boiling point organic solvent is at least one selected from dimethylformamide, dimethyl sulfoxide and dimethylacetamide.
As one embodiment, the mass ratio of the high capacity active material to the low boiling point organic solvent is 1:13 to 8:13.
as an embodiment, the mass ratio of the high capacity active material to the low boiling point organic solvent is 3:13 to 7:13.
as one embodiment, the mass ratio of the high capacity active material to the high boiling point organic solvent is 1:10 to 1:2.
as an embodiment, the mass ratio of the high capacity active material to the high boiling point organic solvent is 3:13 to 1:2.
as one embodiment, the sanding time is 2 to 25 hours; the sanding speed is 1500-3000 n/min.
As one embodiment, the sanding time is 2 to 20 hours; the sanding speed is 1800-2800 n/min.
As 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.
As one embodiment, the distillation time is 0.5 to 2 hours; 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), polymethyl methacrylate (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), polymethyl methacrylate (PMMA) and polystyrene sulfonic acid (PSS).
As 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 diameter 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 the formed space structure is too large, the strength is poor in the charging and discharging process 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, namely the mass of the high-capacity active material is too high, the excessive high-capacity active material can be agglomerated in the preparation process, so that the capacity and the primary charge and discharge of the lithium battery are reduced.
As an embodiment, the temperature of the mixing in step 1) is 5 to 50 ℃; the mixing time in the step 1) is 0.5-5 h.
As an embodiment, the temperature of the mixing in step 1) is 10 to 40 ℃; the mixing time in the step 1) is 1-3 h.
As one embodiment, the high capacity active material of step 1) is 15 to 50% of the high capacity active material slurry.
As one embodiment, the high capacity active material of step 1) is 15 to 40% of the high capacity active material slurry.
As one embodiment, the mass concentration of the polyacrylonitrile in the step 2) is 5 to 25%.
As one embodiment, the mass concentration of the polyacrylonitrile in the step 2) is 10-20%.
In one embodiment, the polyacrylonitrile in step 2) has a number average molecular weight of 50000 to 200000.
As one embodiment, the polyacrylonitrile of the step 2) has a number average molecular weight of 60000 to 15000
As an embodiment, the mass ratio of the polyacrylonitrile to the polymer compound in the step 2) is 240:1 to 12:1.
as an embodiment, the mass ratio of the polyacrylonitrile to the polymer compound of step 2) is 240:1 to 24:1.
in the invention, if the mass ratio of the polyacrylonitrile to the high polymer 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 charge and discharge process of the obtained lithium battery is not easy, and the first charge and discharge efficiency of the lithium ion battery is reduced. If the mass ratio of the polyacrylonitrile to the high polymer compound is too small, namely the mass of the high polymer compound is too high, the formed space structure is large in volume, the strength is poor in the charging and discharging process of the lithium battery, the lithium battery is easy to collapse, and the cycle performance of the lithium battery is influenced.
As an embodiment, the mixing time of step 2) is 1 to 8 hours; the temperature of the mixing is 15-60 ℃.
As an embodiment, the mixing time of step 2) is 2 to 6 hours; the temperature of the mixing is 20-50 ℃.
As one embodiment, the component of the coagulation bath of 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 deionized water in the components of the coagulation bath is 3 or less: 2. as one embodiment, the mass ratio of the high boiling point organic solvent to deionized water in the components of the coagulation bath is 1 or less: 1.
in one embodiment, the coagulation time of the coagulation bath in step 3) is 10 to 60 minutes.
In one embodiment, the coagulation time of the coagulation bath in step 3) is 40 to 60 minutes.
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 ℃.
As an embodiment, the pre-oxidation in step 4) is performed at a temperature of 200 to 400 ℃.
As an embodiment, the pre-oxidation in step 4) is performed at a temperature of 250 to 350 ℃.
As one embodiment, the pre-oxidation in step 4) takes 1.5 to 5 hours.
In one embodiment, the carbonization in step 4) is performed by first performing low-temperature carbonization and then performing high-temperature carbonization.
As one embodiment, the low-temperature carbonization temperature is 200-500 ℃; the low-temperature carbonization time is 0.5-10 h; the high-temperature carbonization temperature is 600-1400 ℃; the high-temperature carbonization time is 0.5-10 h.
As an embodiment, the carbonization of step 4) is performed in an inert atmosphere; the inert atmosphere is nitrogen or argon.
As an embodiment, the method further comprises mixing the negative electrode material with an organic carbon source, and performing secondary carbonization to obtain the negative electrode material coated with the soft carbon layer.
As an embodiment, the method further comprises mixing the anode 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 anode material coated with the soft carbon layer.
As an embodiment, the solvent is at least one selected from deionized water, ethanol, acetone, dimethylformamide and tetrahydrofuran.
As one embodiment, the soft carbon layer has a thickness of 20 to 100nm.
As one embodiment, the soft carbon layer has a thickness of 50 to 100nm.
As one embodiment, the average particle diameter of the soft carbon layer-coated negative electrode material is 10 to 50 μm.
In one embodiment, the soft carbon layer-coated negative electrode material has an average particle diameter of 15 to 35 μm.
As an embodiment, the mass ratio of the high-capacity active material to the soft carbon layer-coated anode material is 2: 20-11: 20.
as an embodiment, the mass ratio of the high-capacity active material to the soft carbon layer-coated anode material is 3: 20-12: 25.
as one embodiment, the mass ratio of the organic carbon source to the anode material is 1: 2-1: 5.
as an embodiment, the mass ratio of the organic carbon source to the anode material is 1:2.5 to 1:4.
in one embodiment, the mixing time is 2 to 4 hours.
As one embodiment, the temperature of the secondary carbonization is 600-1500 ℃; the temperature rising speed of the secondary carbonization is 1-5 ℃/min; the secondary carbonization time is 0.5-10 h.
As one embodiment, the atmosphere of the secondary carbonization is nitrogen or argon; the air flow rate of the secondary carbonization is 0.2-20L/min.
As one embodiment, the organic carbon source is at least one selected from polyvinyl chloride, polyvinyl butyral, sucrose, glucose, maltose, citric acid, asphalt, furfural resin, epoxy resin, and phenolic resin.
As one embodiment, the spray drying temperature is 150 to 250 ℃; the spray drying time is 0.5-2 h.
As one embodiment, the spray drying temperature is 180 to 220 ℃; the spray drying time is 0.5-1.5 h.
The invention also provides a cathode material prepared by the preparation method.
A lithium battery comprising a negative electrode material as described above.
Drawings
Fig. 1: SEM image of the cross section of the negative electrode material according to example 1 of the present invention.
Detailed Description
The following specific examples are provided to illustrate the present invention in detail, but the present invention is not limited to the following examples.
The structure of the anode material (namely, the anode 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: SU 8010), and the anode material is amplified by 70.0K at normal temperature). The preparation method of the negative electrode material profile analysis sample comprises the following steps: and mixing the negative electrode material powder with the conductive adhesive, airing, centering by an optical microscope, and then placing 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 and 10 g of polyacrylic acid with the mass fraction of 25%, and stirring and mixing the mixture at the temperature of 5 ℃ for 5 hours to obtain a mixture A;
2) Mixture A was mixed with 2400 g of a 5% strength by mass polyacrylonitrile solution, the molecular weight of the polyacrylonitrile being
200000, stirring and mixing for 1 hour at 60 ℃ to obtain a suspension;
3) Adding the suspension into a coagulation bath, and adding a coagulant deionized water, wherein the coagulation temperature is 10 ℃, and the coagulation time is 60 minutes, so as to form a precursor of the high-capacity active material double-coated by polyacrylic acid and polyacrylonitrile;
4) Pre-oxidizing the precursor obtained in the step 3) for 1.5 hours at 400 ℃, carbonizing at a low temperature of 500 ℃ for 0.5 hour in nitrogen atmosphere, and carbonizing at a high temperature of 1400 ℃ for 0.5 hour to obtain the anode material, as shown in figure 1.
The prepared anode 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 anode material is 5 mu m, and the mass ratio of the silicon monoxide to the anode material is 12:20.
as can be seen from fig. 1: the negative electrode material prepared by the invention has a buffer space.
Preparation of a battery:
the negative electrode material, the conductive agent and the binder (sodium carboxymethylcellulose (CMC, carboxymethylcellulose sodium) +styrene-butadiene rubber (SBR, styrene Butadiene Rubber)) are mixed according to a mass ratio of 87:5:8, adding a proper amount of deionized water, stirring for 15min, uniformly coating on the copper foil by using an automatic film coater, wherein the surface density is about 2.5mg/cm 2 . After air blast drying, rolling on a roll squeezer to prepare a pole piece with the diameter of 14mm, and putting the pole piece into a vacuum drying oven to be dried for 12 hours at the temperature of 100 ℃. The battery is assembled in a glove box, a negative electrode material pole piece is taken as a positive electrode, a metal lithium piece is taken as a counter electrode, and 1mol/L LiPF is adopted 6 Ethylene Carbonate (EC) -diethyl carbonate (DEC) (volume ratio 3:7) was used as electrolyte.
Cell performance test:
test conditions: current density 0.15mA/cm 2 The voltage is 0.01-1.5V, and the constant current charge and discharge are carried out.
Test results: the first discharge capacity is 1010mAh/g, and the first efficiency can reach 75.5%.
Example 2:
1) Mixing 120 g of silicon monoxide slurry with the particle size of 100nm with the mass fraction of 50% and 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 polyacrylonitrile solution with the mass concentration of 25%, wherein the molecular weight of polyacrylonitrile is 50000, and stirring and mixing for 8 hours at 15 ℃ to obtain a suspension;
3) Adding the suspension into a coagulating bath, wherein a coagulating agent is a dimethyl sulfoxide aqueous solution containing 60%, the coagulating temperature is 80 ℃, and the coagulating time is 10min, so that a precursor of the polystyrene sulfonic acid and polyacrylonitrile double-coated high-capacity active material is formed;
4) Pre-oxidizing the precursor obtained in the step 3) for 5 hours at 200 ℃, carbonizing at a low temperature of 200 ℃ for 10 hours in a nitrogen atmosphere, and carbonizing at a high temperature of 600 ℃ for 10 hours to obtain the anode material.
The prepared anode 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 anode material is 10 mu m, and the mass ratio of the silicon monoxide to the anode material is 8:20.
preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test 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 with the mass fraction of 15% and 1 g of polymethyl methacrylate, wherein the solvent is N-methylpyrrolidone, 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 a 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 ℃, the coagulating time is 60 minutes, and a precursor of the polymethyl methacrylate and polyacrylonitrile double-coated high-capacity active material is formed;
4) Pre-oxidizing the precursor obtained in the step 3) for 3 hours at 300 ℃, carbonizing at a low temperature of 300 ℃ for 5 hours in an argon atmosphere, and carbonizing at a high temperature of 900 ℃ for 5 hours to obtain the anode 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 grain diameter 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.
preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 750mAh/g, and the first efficiency can reach 81.5%.
Example 4:
1) 600 g of silicon monoxide, 30 g of stearic acid and 975 g of ethanol are mixed and sanded to obtain a mixture a, the sanding speed is 3000 revolutions per minute for 8 hours, then the mixture a and 1200 g of dimethylformamide organic solvent are mixed and distilled, the temperature is 30 ℃, the negative pressure is 0.1Mpa, and the time is 2 hours, so that the silicon monoxide slurry is obtained.
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 for 2 hours at the temperature of 30 ℃ to obtain a mixture A;
3) Mixing the mixture A with 800 g of polyacrylonitrile solution with the mass concentration of 15%, wherein the molecular weight of polyacrylonitrile is 90000, and stirring and mixing for 4 hours at 40 ℃ to obtain a suspension;
4) Adding the suspension into a coagulating bath, wherein the coagulating bath comprises deionized water, the coagulating temperature is 50 ℃, the coagulating time is 50min, and precursors of polystyrene sulfonic acid and polyacrylonitrile double-coated high-capacity active materials are formed;
5) Pre-oxidizing the precursor obtained in the step 4) for 1.5 hours at 300 ℃, carbonizing at a low temperature of 500 ℃ for 3 hours in an argon atmosphere, and carbonizing at a high temperature of 1100 ℃ for 2 hours to obtain the anode material.
The prepared anode 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 anode material is 25 mu m, and the mass ratio of the silicon monoxide to the anode material is 11:20.
preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 950mAh/g, and the first efficiency can reach 75.5%.
Example 5:
1) Mixing 400 g of silicon, 4 g of nickel acetate and 5200 g of ethanol, and sanding to obtain a mixture a, wherein the sanding speed is 1500 revolutions per minute for 20 hours, then mixing the mixture a with 4000 g of ethylene carbonate organic solvent, and then distilling, wherein the temperature is 70 ℃, the negative pressure is 0.02Mpa, and the time is 8 hours, so as to obtain nano silicon slurry;
2) Taking 75 g of the nano silicon slurry, with the particle size of 150 nanometers, the mass fraction of 20 percent, and 1 g of polyacrylic acid, mixing the mixture, wherein the solvent is ethylene carbonate, and stirring and mixing the mixture for 3 hours at 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 a suspension;
4) Adding the suspension into a coagulating bath, wherein the coagulating agent is an aqueous solution containing 50% dimethyl sulfoxide, the coagulating temperature is 40 ℃, and the coagulating time is 30min, so that a precursor of the high-capacity active material with double coating of polyacrylic acid and polyacrylonitrile is formed;
5) Pre-oxidizing the precursor obtained in the step 4) for 2 hours at 280 ℃, carbonizing at a low temperature of 400 ℃ for 2 hours in an argon atmosphere, and carbonizing at a high temperature of 1000 ℃ for 5 hours to obtain the anode 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 grain diameter of the negative electrode material is 30 mu m, and the mass ratio of the nano silicon to the negative electrode material is 3:20.
preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 760mAh/g, and the first efficiency can reach 80.5%.
Example 6:
1) 600 g of silicon monoxide slurry with the particle size of 300 nanometers is mixed with 0.5 g of polyacrylic acid by mass percent, and the solvent is dimethylformamide, and stirred and mixed 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 the polyacrylonitrile is 100000, and stirring and mixing for 4 hours at 40 ℃ to obtain a suspension;
3) Adding the suspension into a coagulation bath, wherein a coagulant is deionized water, the coagulation temperature is 30 ℃, and the coagulation time is 40 minutes, so that a precursor of the polyacrylic acid and polyacrylonitrile double-coated high-capacity active material is formed;
4) Pre-oxidizing the precursor obtained in the step 3) for 4 hours at 250 ℃, carbonizing at a low temperature of 500 ℃ for 3 hours in an argon atmosphere, and carbonizing at a high temperature of 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 mu m, and the mass ratio of the silicon monoxide to the negative electrode material is 12:20.
5) And (3) adding 100 g of the anode material obtained in the step (4) into a solution containing 20 g of asphalt to form a mixed solution B, wherein the mixing time is 2h, the solvent is dimethylformamide, then performing spray drying, the drying temperature is 250 ℃, the time is 0.5 h, then performing secondary carbonization in an atmosphere furnace, the carbonization temperature is 1500 ℃, the heat preservation time is 0.5 h, the inert protective atmosphere is argon, the heating rate of carbonization treatment is 5 ℃/min, and the gas flow rate in the inert protective atmosphere is 100 ml/min, so as to obtain the anode material coated with the soft carbon layer. Wherein the average grain diameter of the soft carbon layer coated anode material is 10 μm, and the mass ratio of the nano silicon to the soft carbon layer coated anode material is 11:20.
preparation of lithium battery (button cell battery) was the same as in example 1.
And (5) testing the performance of the battery.
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 850mAh/g, and the first efficiency can reach 80.5%.
Example 7:
1) 300 g of silicon slurry with the particle size of 80 nanometers is mixed with 1 g of polystyrene sulfonic acid with the mass fraction of 10 percent, and the solvent is dimethyl sulfoxide, and the mixture is stirred and mixed 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%, wherein the molecular weight of the polyacrylonitrile is 120000, and stirring and mixing for 4 hours at 50 ℃ to obtain a suspension;
3) Adding the suspension into a coagulation bath, wherein a coagulant is deionized water, the coagulation temperature is 20 ℃, the coagulation time is 60 minutes, and a precursor of the high-capacity active material double-coated by polystyrene sulfonic acid and polyacrylonitrile is formed;
4) Pre-oxidizing the precursor obtained in the step 3) for 5 hours at 280 ℃, carbonizing at a low temperature of 400 ℃ for 5 hours in a nitrogen atmosphere, and carbonizing at a high temperature of 1000 ℃ for 2 hours to obtain the anode material. (the prepared anode 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 anode material is 35 mu m, and the mass ratio of the nano silicon to the anode material is 3:20.
5) Adding 100 g of the anode material obtained in the step 4) into a solution containing 50 g of sucrose to form a mixed solution B, wherein the mixing time is 4h, the solvent is deionized water, then performing spray drying, the drying temperature is 150 ℃ for 2h, then performing secondary carbonization in an atmosphere furnace, the carbonization temperature is 600 ℃, the heat preservation time is 10h, the inert protective atmosphere is argon, the heating rate of carbonization treatment is 1 ℃/min, and the gas flow rate in the inert protective atmosphere is 500 ml/min, so as to obtain the anode material coated by the soft carbon layer.
Wherein the average grain diameter of the soft carbon layer coated anode material is 50 μm, and the mass ratio of the nano silicon to the soft carbon layer coated anode material is 2:20.
preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 650mAh/g, and the first efficiency can reach 85.5%.
Example 8:
1) 200 g of silicon monoxide slurry with the particle size of 500 nanometers is mixed with 0.5 g of polyacrylic acid by mass percent, and the solvent is dimethylformamide, and stirred and mixed 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 the polyacrylonitrile is 100000, and stirring and mixing for 4 hours at 40 ℃ to obtain a suspension;
3) Adding the suspension into a coagulation bath, wherein a coagulant is deionized water, the coagulation temperature is 30 ℃, and the coagulation time is 40 minutes, so that a precursor of the high-capacity active material double-coated by polyacrylic acid and polyacrylonitrile is formed;
4) Pre-oxidizing the precursor obtained in the step 3) for 4 hours at 250 ℃, carbonizing at a low temperature of 500 ℃ for 3 hours in nitrogen atmosphere, and carbonizing at a high temperature of 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 mu m, 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 3 hours, performing secondary carbonization by an atmosphere furnace, wherein the carbonization temperature is 1000 ℃, the heat preservation time is 3 hours, the inert protective atmosphere is argon, the heating rate of carbonization treatment is 2 ℃/min, and the gas flow rate in the inert protective atmosphere is 100 ml/min, so as to obtain the soft carbon layer coated anode material. (wherein the average particle diameter of the soft carbon layer coated anode material is 35 μm, and the mass ratio of the nano silicon to the soft carbon layer coated anode material is 4:20.
Preparation of lithium battery (button cell battery) was the same as in example 1.
Battery performance test
The test conditions were the same as in example 1.
Test results: the first discharge capacity is 780mAh/g, and the first efficiency can reach 80.5%.
Claims (34)
1. A preparation method of a negative electrode material comprises the following steps:
1) Mixing high-capacity active material slurry and a high-molecular compound to obtain a mixture A;
2) Mixing the mixture A with a polyacrylonitrile solution to obtain a suspension;
3) Adding the suspension into a coagulation bath to form a precursor of a high-capacity active material double-coated by a high-molecular compound and polyacrylonitrile;
4) Pre-oxidizing and carbonizing the precursor in the step 3) to obtain a cathode material;
the high molecular 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); the mass ratio of the polyacrylonitrile to the high molecular compound in the step 2) is 240:1 to 12:1, a step of;
the high-capacity active material slurry in the step 1) is obtained by mixing and grinding a high-capacity active material, a dispersing agent 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.
2. The method for producing a negative electrode material according to claim 1, characterized in that: 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 diameter of the negative electrode material is 5-35 mu m.
3. The method for producing a negative electrode material according to claim 1, characterized in that: the mass ratio of the high-capacity active material to the negative electrode material is 3: 20-12: 20.
4. the method for producing a negative electrode material according to claim 1, characterized in that: the high capacity active material is selected from at least one of silicon, germanium, aluminum, tin oxide and silicon monoxide.
5. The method for producing a negative electrode material according to claim 1, characterized in that: the dispersing agent is at least one selected from stearic acid, nickel acetate, polyvinyl alcohol and polyethylene glycol.
6. The method for producing a negative electrode material according to claim 1, characterized in that: the mass ratio of the dispersing agent to the high-capacity active material is 1: 100-5: 100.
7. the method for producing a negative electrode material according to claim 1, characterized in that: the low-boiling point organic solvent is at least one selected from absolute ethyl alcohol, propanol and butanol.
8. The method for producing a negative electrode material according to claim 1, characterized in that: the high boiling point organic solvent is at least one selected from dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone.
9. The method for producing a negative electrode material according to claim 1, characterized in that: the mass ratio of the high-capacity active material to the low-boiling point organic solvent is 1:13 to 8:13.
10. the method for producing a negative electrode material according to claim 1, characterized in that: the mass ratio of the high-capacity active material to the high-boiling point organic solvent is 1:10 to 1:2.
11. the method for producing a negative electrode material according to claim 1, characterized in that: the high-capacity active material in the high-capacity active material slurry has an average particle diameter of 30nm to 2 μm.
12. The method for producing a negative electrode material according to claim 1, characterized in that: the mass ratio of the high molecular compound to the high capacity active material in the step 1) is 1: 120-1: 6.
13. the method for producing a negative electrode material according to claim 1, characterized in that: the high-capacity active material in the step 1) accounts for 15-50% of the high-capacity active material slurry.
14. The method for producing a negative electrode material according to claim 1, characterized in that: the number average molecular weight of the polyacrylonitrile in the step 2) is 50000-200000.
15. The method for producing a negative electrode material according to claim 1, characterized in that: the mixing time of the step 2) is 1-8 h; the temperature of the mixing is 15-60 ℃.
16. The method for producing a negative electrode material according to claim 1, characterized in that: the component of the coagulating bath in the step 3) is deionized water.
17. The method for producing a negative electrode material according to claim 16, characterized in that: the components of the coagulation bath of step 3) further comprise a high boiling point organic solvent.
18. The method for producing a negative electrode material according to claim 17, characterized in that: 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.
19. the method for producing a negative electrode material according to claim 1, characterized in that: the temperature of the coagulating bath in the step 3) is 10-80 ℃.
20. The method for producing a negative electrode material according to claim 1, characterized in that: step 4) the pre-oxidation temperature is 200-400 ℃; the pre-oxidation time is 1.5-5 h.
21. The method for producing a negative electrode material according to claim 1, characterized in that: step 4), the carbonization process is to carry out low-temperature carbonization firstly and then high-temperature carbonization; the low-temperature carbonization temperature is 200-500 ℃; the low-temperature carbonization time is 0.5-10 h; the high-temperature carbonization temperature is 600-1400 ℃; the high-temperature carbonization time is 0.5-10 h.
22. The method for producing a negative electrode material according to claim 1, characterized in that: step 4) the carbonization is performed in an inert atmosphere; the inert atmosphere is nitrogen or argon.
23. The method for producing a negative electrode material according to claim 1, characterized in that: the method further comprises the step of mixing the negative electrode material according to claim 1 with an organic carbon source, and performing secondary carbonization to obtain the soft carbon layer-coated negative electrode material.
24. The method for producing a negative electrode material according to claim 1, characterized in that: the method further comprises the steps of mixing the negative electrode material, the organic carbon source and the solvent to obtain a mixed solution B, and then performing spray drying and secondary carbonization to obtain the soft carbon layer coated negative electrode material.
25. The method for producing a negative electrode material according to claim 24, characterized in that: the solvent is at least one selected from deionized water, ethanol, acetone, dimethylformamide and tetrahydrofuran.
26. The method for producing a negative electrode material according to claim 23 or 24, characterized in that: the average grain diameter of the negative electrode material coated by the soft carbon layer is 10-50 mu m.
27. The method for producing a negative electrode material according to claim 23 or 24, characterized in that: the mass ratio of the high-capacity active material to the soft carbon layer coated anode material is 2: 20-11: 20.
28. the method for producing a negative electrode material according to claim 23 or 24, characterized in that: the mass ratio of the organic carbon source to the anode material is 1: 2-1: 5.
29. the method for producing a negative electrode material according to claim 23 or 24, characterized in that: the temperature of the secondary carbonization is 600-1500 ℃; the temperature rising speed of the secondary carbonization is 1-5 ℃/min; the secondary carbonization time is 0.5-10 h.
30. The method for producing a negative electrode material according to claim 23 or 24, characterized in that: the secondary carbonization atmosphere is nitrogen or argon; the air flow rate of the secondary carbonization is 0.2-20L/min.
31. The method for producing a negative electrode material according to claim 23 or 24, characterized in that: the organic carbon source is at least one selected from polyvinyl chloride, polyvinyl butyral, sucrose, glucose, maltose, citric acid, asphalt, furfural resin, epoxy resin and phenolic resin.
32. The method for producing a negative electrode material according to claim 24, characterized in that: the temperature of the spray drying is 150-250 ℃; the spray drying time is 0.5-2 h.
33. A negative electrode material prepared by the preparation method of claim 1.
34. A lithium battery comprising the negative electrode material of claim 33.
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