CN112397693A - High-rate rapid charging negative electrode material and preparation method thereof, negative electrode plate and battery - Google Patents
High-rate rapid charging negative electrode material and preparation method thereof, negative electrode plate and battery Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-rate rapid-charging cathode material which comprises a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene. The mesocarbon microbeads are highly isotropic, so that internal lithium ion transmission is facilitated, the graphene can promote electron conduction, the hard carbon coating layer is beneficial to embedding and releasing of lithium ions, and the large-rate charge-discharge performance and the cycle performance of the negative electrode material can be remarkably improved under the combined action of the mesocarbon microbeads, the hard carbon coating layer and the hard carbon coating layer.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a high-rate quick-charging negative electrode material, a preparation method thereof, a negative electrode sheet and a battery.
Background
For many years, lithium ion batteries have been widely used in electronic products, particularly in the fields of 3C digital products, unmanned aerial vehicles, small electric tools, electric vehicles, and the like, due to the advantages of stable working voltage platform, high energy density, long cycle life, environmental friendliness, and the like.
At present, the requirement of having higher energy density and larger current quick-charging performance becomes one of the important technical challenges in the development of the current lithium ion batteries. The negative electrode material of the lithium ion battery is a key factor for determining the high-rate charging performance of the lithium ion battery, and graphite is widely applied to the negative electrode material of the lithium ion battery due to high conductivity, mature process, wide source and low price.
However, the graphite negative electrode with the conventional structure has slow lithium ion insertion and extraction rate, and lithium dendrite is easily precipitated on the surface of the negative electrode under the condition of high-rate charge and discharge, which severely limits the quick charge capacity of the lithium ion battery, so that the design of a high-performance negative electrode material of the lithium ion battery to realize the quick charge performance and the consideration of high energy density are key problems to be solved urgently in the field of the lithium ion battery.
In view of the above, it is necessary to provide a technical solution to solve the above technical problems.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the cathode material with high multiplying power and rapid charging is provided, and high energy density can be considered while the rapid charging performance is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the negative electrode material comprises a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene.
As an improvement of the high-rate rapid charging cathode material, the number of graphene layers is 2-10, the thickness of the graphene is less than 5nm, and the maximum diameter of a graphene sheet layer is less than 15 microns.
As an improvement of the high-rate fast-charging negative electrode material of the present invention, the hard carbon includes a thermoplastic polymer or a meltable biomass molecule, the thermoplastic polymer includes a thermoplastic resin or pitch, and the meltable biomass molecule includes at least one of sucrose, glucose and fructose.
The second purpose of the invention is: the preparation method of the negative electrode material with high-rate quick charge comprises the following steps:
step 1), adding graphene into a carbon source solution for dispersion, and obtaining a first precursor after hydrothermal reaction;
step 2), dispersing the first precursor in a thermal stabilizing medium, and heating the first precursor to obtain a second precursor;
and 3) melting and coating a hard carbon source on the surface of the second precursor, and carbonizing to obtain the high-rate quick-charging negative electrode material.
The hydrothermal reaction can prepare a carbon source solution into carbon source crystal grains which are complete in development, small in particle size, uniform in distribution and light in particle aggregation, and after the carbon source crystal grains are fully contacted with graphene, small-molecule carbon source crystals are tightly attached to the surface of the graphene to form a first precursor. The first precursor further undergoes dehydrogenation polycondensation, dealkylation, aromatization, cyclization and other reactions to form macromolecules with mesophase properties, and the macromolecules further undergo polymerization reaction along with the rise of temperature to form a spherical second precursor with small particle size, uniform distribution and smooth surface.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 1), the temperature of the hydrothermal reaction is 130-250 ℃, the vapor pressure of water in the hydrothermal reaction is 0.3-4 MPa, and the time of the hydrothermal reaction is 4-8 h.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 1), the number of graphene layers is 2-10, the thickness of the graphene is less than 5nm, and the maximum diameter of each graphene layer is less than 15 microns.
As an improvement of the preparation method of the high-rate fast-charging negative electrode material, in the step 1), the carbon source solution includes at least one of a sucrose solution, a glucose solution, a fructose solution, a cellulose solution, a phenolic resin alcohol solution, an asphalt solution, and a sodium hydroxymethyl cellulose solution.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 1), the concentration of the carbon source solution is 5-20%, and the mass ratio of the graphene to the carbon source solution is 1: (20 to 50).
As an improvement of the preparation method of the high-rate fast-charging negative electrode material, in the step 1), after the hydrothermal reaction, washing and drying treatment are further included.
As an improvement of the preparation method of the high-rate fast-charging negative electrode material, in the step 2), before dispersing the first precursor in a thermal stabilizing medium, the method further comprises ball-milling and drying the first precursor.
As an improvement of the preparation method of the negative electrode material with high rate rapid charging of the present invention, in the step 2), the thermal stabilizing medium includes at least one of silicone oil, dimethyl silicone oil, and benzyl silicone oil.
As an improvement of the preparation method of the negative electrode material with high rate of rapid charging, in step 2), the mass ratio of the thermal stabilizing medium to the first precursor is 100: (0.5 to 10).
As an improvement of the method for preparing the high-rate fast-charging anode material according to the present invention, in step 2), the first precursor is heated under an inert gas atmosphere, and the inert gas includes at least one of nitrogen, argon, and helium.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 2), the heating temperature is 350-400 ℃, the heating temperature rise rate is 5-10 ℃/min, and the heating time is 3-8 h.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 2), after the first precursor is heated, the steps of cooling, organic solvent extraction, suction filtration, drying, ball milling and screening are further included to obtain a second precursor.
As an improvement of the method for preparing the high-rate fast-charging negative electrode material, in step 3), the hard carbon includes a thermoplastic polymer or a meltable biomass molecule, the thermoplastic polymer includes a thermoplastic resin or pitch, the meltable biomass molecule includes at least one of sucrose, glucose and fructose, and the mass ratio of the second precursor to the hard carbon is (3-8): 1.
as an improvement of the preparation method of the high-rate quick-charging cathode material, in the step 3), the temperature of the melting coating is 100-300 ℃, the temperature of the carbonization treatment is 500-1200 ℃, the time of the carbonization treatment is 2-6 h, and the temperature rise rate of the carbonization treatment is 0.5-20 ℃/min.
As an improvement of the preparation method of the high-rate rapid charging negative electrode material, in the step 3), after the carbonization treatment, ball milling, sieving and demagnetizing treatment are further performed, so that the high-rate rapid charging negative electrode material is obtained.
As an improvement of the preparation method of the high-rate fast-charging negative electrode material, in the step 3), the carbonization treatment includes a low-temperature carbonization treatment of the second precursor coated with the hard carbon, and a high-temperature carbonization treatment after depolymerization. The low-temperature treatment makes the hard carbon precursor softened regularly and coated uniformly, and the high-temperature carbonization improves the purity and reduces defects.
The third purpose of the invention is that: provided is a high-rate rapid-charge negative electrode sheet comprising the negative electrode material described in any one of the preceding specifications.
The fourth purpose of the invention is that: the lithium ion battery comprises a negative electrode sheet, wherein the negative electrode sheet is the negative electrode sheet in any one of the specifications.
Compared with the prior art, the invention at least has the following beneficial effects: the invention provides a composite precursor coated with hard carbon, which comprises graphene and mesocarbon microbeads attached to the surface of the graphene. The graphene structure is a planar hexagonal lattice, each carbon atom is hybridized by sp2, and contributes to electrons on the remaining p orbit to form a large pi bond, and pi electrons can move freely, so that the graphene structure is endowed with good electronic conductivity. The mesocarbon microbeads tend to spherical structures, and the arrangement of the internal layers tends to high isotropy, which is beneficial to the ion transmission of lithium ions in all directions in the mesocarbon microbeads. The graphene also has a large specific surface area, and is in surface contact with the mesocarbon microbeads, so that the electronic conduction is accelerated. The hard carbon has the characteristic of low graphitization degree, the defects such as internal gaps of molecules are obvious, and the interlamellar spacing is far larger than that of graphite, so that the resistance of lithium ion intercalation can be reduced, the high-rate charge polarization is reduced, and the lithium ion intercalation rate is obviously improved. In conclusion, the mesocarbon microbeads are highly isotropic, so that internal lithium ion transmission is facilitated, the graphene can promote electron conduction, the hard carbon coating layer is beneficial to insertion and extraction of lithium ions, and the high-rate charge-discharge performance and cycle performance of the negative electrode material can be remarkably improved under the combined action of the mesocarbon microbeads, the hard carbon coating layer and the hard carbon coating layer.
Drawings
Fig. 1 is a graph of the retention rate of the cycling capacity of 5# cell and 8# cell.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. High-rate fast-charging cathode material
The application provides a negative electrode material that high magnification is charged fast, including the compound precursor that the cladding has hard carbon, compound precursor includes graphite alkene and the mesocarbon microbeads that adhere to on graphite alkene surface.
In some embodiments, the number of graphene layers is 2-10, the thickness of the graphene is less than 5nm, and the maximum diameter of the graphene sheet layer is less than 15 μm. In some embodiments, the number of layers of graphene is 2, 3, 4, 5, 6, 7, 8, 9, 10. In some embodiments, the graphene has a thickness of 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5 nm. In some embodiments, the graphene has a maximum sheet diameter of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm.
In some embodiments, the hard carbon comprises a thermoplastic polymer comprising a thermoplastic resin or pitch or a meltable biomass molecule comprising at least one of sucrose, glucose, and fructose.
2. Preparation method of high-rate rapid-charging cathode material
A second aspect of the present application provides a method for preparing a high-rate fast-charging anode material, comprising the following steps:
step 1), adding graphene into a carbon source solution for dispersion, and obtaining a first precursor after hydrothermal reaction;
step 2), dispersing the first precursor in a thermal stabilizing medium, and heating the first precursor to obtain a second precursor;
and 3) melting and coating the hard carbon source on the surface of the second precursor, and carbonizing to obtain the high-rate fast-charging cathode material.
In some embodiments, the temperature of the hydrothermal reaction is 130 to 250 ℃, the vapor pressure of water in the hydrothermal reaction is 0.3 to 4MPa, and the time of the hydrothermal reaction is 4 to 8 hours. In some embodiments, the temperature of the hydrothermal reaction is 130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃. In some embodiments, the vapor pressure of water in the hydrothermal reaction is 0.3MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4 MPa. In some embodiments, the hydrothermal reaction time is 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8 h.
In some embodiments, the number of graphene layers is 2-10, the thickness of the graphene is less than 5nm, and the maximum diameter of the graphene sheet layer is less than 15 μm. In some embodiments, the graphene has a thickness of 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5 nm. In some embodiments, the graphene has a maximum sheet diameter of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm.
In some embodiments, the carbon source solution comprises at least one of a sucrose solution, a glucose solution, a fructose solution, a cellulose solution, a phenolic resin alcohol solution, an asphalt solution, a sodium carboxymethylcellulose solution.
In some embodiments, the concentration of the carbon source solution is 5-20%, and the mass ratio of the graphene to the carbon source solution is 1: (20 to 50). In some embodiments, the concentration of the carbon source solution is 5%, 8%, 12%, 15%, 18%, 20%. In some embodiments, the mass ratio of graphene to carbon source solution is 1: 20. 1: 25. 1: 30. 1: 35. 1: 40. 1: 45. 1: 50.
in some embodiments, after the hydrothermal reaction, washing and drying treatments are also included.
In some embodiments, prior to dispersing the first precursor in the thermally stable medium, further comprising ball milling and baking the first precursor.
In some embodiments, the thermally stable medium comprises at least one of silicone oil, dimethicone, and benzyl silicone oil.
In some embodiments, the mass ratio of the thermally stable medium to the first precursor is 100: (0.5 to 10). In some embodiments, the mass ratio of the thermally stable medium to the first precursor is 100: 0.5, 100: 1. 100, and (2) a step of: 2. 100, and (2) a step of: 3. 100, and (2) a step of: 4. 100, and (2) a step of: 5. 100, and (2) a step of: 6. 100, and (2) a step of: 7. 100, and (2) a step of: 8. 100, and (2) a step of: 9. 100, and (2) a step of: 10.
in some embodiments, the first precursor is heated under an inert gas atmosphere, the inert gas including at least one of nitrogen, argon, and helium.
In some embodiments, the heating temperature is 350-400 ℃, the heating temperature rise rate is 5-10 ℃/min, and the heating time is 3-8 h. In some embodiments, the temperature of heating is 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃. In some embodiments, the temperature increase rate of heating is 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min. In some embodiments, the heating time is 3h, 4h, 5h, 6h, 7h, 8 h.
In some embodiments, after heating the first precursor, cooling, organic solvent extraction, suction filtration, drying, ball milling, and sieving are further included to obtain a second precursor.
In some embodiments, the hard carbon comprises a thermoplastic polymer or a meltable biomass molecule, the thermoplastic polymer comprises a thermoplastic resin or pitch, the meltable biomass molecule comprises at least one of sucrose, glucose and fructose, and the mass ratio of the second precursor to the hard carbon is (3-8): 1. in some embodiments, the mass ratio of the second precursor to the hard carbon is 3: 1. 4: 1.5: 1. 6: 1. 7: 1. 8: 1.
in some embodiments, the temperature of the melt coating is 100-300 ℃, the temperature of the carbonization treatment is 500-1200 ℃, the time of the carbonization treatment is 2-6 h, and the temperature rise rate of the carbonization treatment is 0.5-20 ℃/min. In some embodiments, the temperature of the melt coating is 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃. In some embodiments, the temperature of the carbonization treatment is 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃. In some embodiments, the time for the carbonization treatment is 2h, 3h, 4h, 5h, 6 h. In some embodiments, the carbonization treatment is performed at a temperature increase rate of 0.5 deg.C/min, 1 deg.C/min, 5 deg.C/min, 10 deg.C/min, 15 deg.C/min, 20 deg.C/min.
In some embodiments, after the carbonization treatment, ball milling, sieving and demagnetizing treatment are further included, so that the high-rate fast-charging negative electrode material is obtained.
3. High-rate quick-charging negative plate
The third aspect of the invention provides a high-rate fast-charging negative plate, which comprises a negative plate main body, a negative tab, a negative active material layer and a protective coating, wherein the negative plate main body and the negative tab are made of copper foil, but not limited to, and the negative active material layer is selected from the negative active materials described in the application.
In some embodiments, the negative active material layer may include a binder that improves the binding of the negative active material particles to each other and to the current collector. Non-limiting examples of binders include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, nylon, and the like. In some embodiments, the negative electrode active material layer further includes a conductive material, thereby imparting conductivity to the electrode.
The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
4. Lithium ion battery
The fourth aspect of the invention provides a lithium ion battery, which comprises a negative plate, wherein the negative plate is the negative plate described in the application.
In some embodiments, the battery described herein comprises a positive electrode sheet, a negative electrode sheet, and a separator, wherein the negative electrode sheet is the negative electrode sheet described herein.
Positive electrode
In the battery according to this application, the positive plate includes positive pole piece main part, anodal utmost point ear, anodal active material layer and protective coating, and the material of positive pole piece main part and anodal utmost point ear includes but not limited to the aluminium foil, and the concrete kind on anodal active material layer does not receive specific restriction, can select according to the demand. In some embodiments, the positive active material includes a compound that reversibly intercalates and deintercalates lithium ions. In some embodiments, the positive active material may include a composite oxide containing lithium and at least one element selected from cobalt, manganese, and nickel. In still other embodiments, the positive active material is selected from lithium cobaltate (LiCoO)2) Lithium nickel manganese cobalt ternary material and lithium manganate (LiMn)2O4) Lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Lithium iron phosphate (LiFePO)4) One or more of them.
In some embodiments, the positive electrode active material layer further comprises a binder to improve the binding of the positive electrode active material particles to each other and also to improve the binding of the positive electrode active material to the main body of the pole piece. Non-limiting examples of binders include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy, nylon, and the like.
In some embodiments, the positive electrode active material layer further includes a conductive material, thereby imparting conductivity to the electrode. The conductive material may include any conductive material as long as it does not cause a chemical change. Non-limiting examples of the conductive material include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.
Diaphragm
In the battery according to the present application, a separator is provided between the positive electrode tab and the negative electrode tab to prevent short circuit. The material and shape of the separator used in the battery of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, or a polypropylene-polyethylene-polypropylene porous composite film can be used. At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer comprises inorganic particles and a binder, wherein the inorganic particles are selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is selected from one or a combination of more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene. The polymer layer comprises a polymer, and the material of the polymer is selected from at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride and poly (vinylidene fluoride-hexafluoropropylene).
Embodiments of the present application are illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the claims herein.
Example 1
The negative electrode material comprises a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene.
The preparation method of the high-rate quick-charging cathode material comprises the following steps:
step 1), adding graphene into a sucrose solution for uniform dispersion, carrying out constant-temperature hydrothermal reaction on the obtained slurry solution at 150 ℃ for 6 hours, washing and drying to obtain a first precursor; the number of layers of the graphene is 2, the thickness of the graphene is less than 5nm, the maximum diameter of a sheet layer of the graphene is less than 15 microns, the concentration of the sucrose solution is 20%, and the mass ratio of the graphene to the sucrose solution is 1: 40.
step 2), drying and ball-milling the first precursor, dispersing the ball-milled first precursor in benzyl silicone oil to form a suspension, placing the suspension in a reaction kettle, heating to 380 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of inert gas nitrogen, heating the first precursor at a constant temperature, reacting for 6 hours, cooling, extracting the obtained product with organic solvent ethanol, filtering, drying, ball-milling, and screening to obtain a second precursor; wherein the mass ratio of the benzyl silicone oil to the first precursor is 100: 10.
step 3), mixing the second precursor material and sucrose according to the ratio of 100: and (3) putting the mixture into a mixer according to the mass ratio of 20, mixing for 30min, discharging, transferring into a coating kettle, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and treating for 4h to ensure that the sucrose is molten and coated on the surfaces of the second precursor particles. And (3) putting the obtained surface sucrose coating product into a well type furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 1.5h, cooling to room temperature, depolymerizing for 30min in a mixer, then putting into an atmosphere furnace, heating to 1100 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 4h, cooling to room temperature, discharging, performing ball milling, screening and demagnetizing to obtain the high-rate quick-charging negative electrode material.
Example 2
The negative electrode material comprises a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene.
The preparation method of the high-rate quick-charging cathode material comprises the following steps:
step 1), adding graphene into a sucrose solution for uniform dispersion, carrying out constant-temperature hydrothermal reaction on the obtained slurry solution at 150 ℃ for 6 hours, washing and drying to obtain a first precursor; the number of layers of the graphene is 5, the thickness of the graphene is less than 5nm, the maximum diameter of a sheet layer of the graphene is less than 15 microns, the concentration of the sucrose solution is 8%, and the mass ratio of the graphene to the sucrose solution is 1: 40.
step 2), drying and ball-milling the first precursor, dispersing the ball-milled first precursor in benzyl silicone oil to form a suspension, placing the suspension in a reaction kettle, heating to 380 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of inert gas nitrogen, heating the first precursor at a constant temperature, reacting for 6 hours, cooling, extracting the obtained product with organic solvent ethanol, filtering, drying, ball-milling, and screening to obtain a second precursor; wherein the mass ratio of the benzyl silicone oil to the first precursor is 100: 20.
step 3), mixing the second precursor material and sucrose according to the ratio of 100: and (3) putting the mixture into a mixer according to the mass ratio of 20, mixing for 30min, discharging, transferring into a coating kettle, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and treating for 4h to ensure that the sucrose is molten and coated on the surfaces of the second precursor particles. And (3) putting the obtained surface sucrose coating product into a well type furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 1.5h, cooling to room temperature, depolymerizing for 30min in a mixer, then putting into an atmosphere furnace, heating to 1100 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 4h, cooling to room temperature, discharging, performing ball milling, screening and demagnetizing to obtain the high-rate quick-charging negative electrode material.
Example 3
The negative electrode material comprises a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene.
The preparation method of the high-rate quick-charging cathode material comprises the following steps:
step 1), adding graphene into a sucrose solution for uniform dispersion, carrying out constant-temperature hydrothermal reaction on the obtained slurry solution at 150 ℃ for 6 hours, washing and drying to obtain a first precursor; the number of layers of the graphene is 8, the thickness of the graphene is less than 5nm, the maximum diameter of a sheet layer of the graphene is less than 15 microns, the concentration of the sucrose solution is 5%, and the mass ratio of the graphene to the sucrose solution is 1: 40.
step 2), drying and ball-milling the first precursor, dispersing the ball-milled first precursor in benzyl silicone oil to form a suspension, placing the suspension in a reaction kettle, heating to 380 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of inert gas nitrogen, heating the first precursor at a constant temperature, reacting for 6 hours, cooling, extracting the obtained product with organic solvent ethanol, filtering, drying, ball-milling, and screening to obtain a second precursor; wherein the mass ratio of the benzyl silicone oil to the first precursor is 100: 20.
step 3), mixing the second precursor material and sucrose according to the ratio of 100: and (3) putting the mixture into a mixer according to the mass ratio of 20, mixing for 30min, discharging, transferring into a coating kettle, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and treating for 4h to ensure that the sucrose is molten and coated on the surfaces of the second precursor particles. And (3) putting the obtained surface sucrose coating product into a well type furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 1.5h, cooling to room temperature, depolymerizing for 30min in a mixer, then putting into an atmosphere furnace, heating to 1100 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 4h, cooling to room temperature, discharging, performing ball milling, screening and demagnetizing to obtain the high-rate quick-charging negative electrode material.
Comparative example 1
The comparative example provides an anode material, and the preparation method thereof includes the steps of:
step 1), adding graphite into a sucrose solution for uniform dispersion, carrying out constant-temperature hydrothermal reaction on the obtained slurry solution at 150 ℃ for 6 hours, washing and drying to obtain a first precursor; the concentration of the sucrose solution is 5%, and the mass ratio of the graphite to the sucrose solution is 1: 40.
step 2), drying and ball-milling the first precursor, dispersing the ball-milled first precursor in benzyl silicone oil to form a suspension, placing the suspension in a reaction kettle, heating to 380 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of inert gas nitrogen, heating the first precursor at a constant temperature, reacting for 6 hours, cooling, extracting the obtained product with organic solvent ethanol, filtering, drying, ball-milling, and screening to obtain a second precursor; wherein the mass ratio of the benzyl silicone oil to the first precursor is 100: 20.
step 3), mixing the second precursor material and sucrose according to the ratio of 100: and (3) putting the mixture into a mixer according to the mass ratio of 20, mixing for 30min, discharging, transferring into a coating kettle, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and treating for 4h to ensure that the sucrose is molten and coated on the surfaces of the second precursor particles. And (3) putting the obtained surface sucrose coating product into a well type furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 1.5h, cooling to room temperature, depolymerizing for 30min in a mixer, then putting into an atmosphere furnace, heating to 1100 ℃ at a speed of 2 ℃/min under the protection of nitrogen, carbonizing for 4h, cooling to room temperature, discharging, performing ball milling, screening and demagnetizing to obtain the negative electrode material.
The negative electrode materials obtained in the above examples 1 to 3 and comparative example 1, conductive carbon, a dispersant (sodium carboxymethyl cellulose), and a binder (styrene butadiene rubber) were uniformly mixed in deionized water according to a mass ratio of 95:1.5:2.0:1.5 to prepare a negative electrode slurry, and then the negative electrode slurry was coated on a copper foil and dried, and then cold-pressed, striped, and cut to prepare 1#, 2#, 3#, and 4# negative electrode sheets.
Respectively stacking the 1#, 2#, 3#, 4# negative pole pieces, the diaphragm and the lithium cobaltate positive pole piece in sequence, so that the diaphragm is positioned between the positive pole piece and the negative pole piece, and winding the bare cell in a full-automatic manner; and packaging the top side of the bare cell by using an aluminum plastic film outer package with a certain size, injecting a certain amount of electrolyte into the dried semi-packaged cell, and completing packaging. And continuously carrying out the working procedures of standing, formation, shaping, capacity grading and the like to finish the preparation of the 5#, 6#, 7#, 8# lithium ion soft package batteries.
Performance testing
The negative pole pieces 1#, 2#, 3#, and 4# are subjected to granularity test, true density test and tap density test, and the test results are shown in table 1; the electrical performance tests were performed on the 5#, 6#, 7#, and 8# lithium ion soft package batteries, and the test results are shown in table 2.
TABLE 1
| Group of | Particle size (. mu.m) | True density (g/cm)3) | Tap density (g/cm)3) |
| 1# | 9.8 | 2.23 | 0.93 |
| 2# | 10.3 | 2.21 | 0.91 |
| 3# | 11.4 | 2.21 | 0.94 |
| 4# | 12.2 | 2.23 | 0.99 |
TABLE 2
As can be seen from tables 1 and 2, the true densities and tap densities of the 1#, 2#, 3#, and 4# negative electrode sheets are substantially close to each other, and the first discharge capacities and first efficiencies of the 5#, 6#, 7#, and 8# lithium ion batteries are also substantially close to each other. This shows that the energy density of the anode material of the present invention is not reduced compared to the conventional graphite anode material.
However, the charging time of 80% SOC of 5#, 6#, and 7# lithium ion batteries is improved by more than 5min compared with that of 8# lithium ion batteries. This shows that the rate charging performance of the negative electrode material is obviously improved.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (20)
1. The negative electrode material is characterized by comprising a composite precursor coated with hard carbon, wherein the composite precursor comprises graphene and mesocarbon microbeads attached to the surface of the graphene.
2. The negative electrode material for high-rate rapid charging according to claim 1, wherein the number of graphene layers is 2-10, the thickness of graphene is less than 5nm, and the maximum diameter of graphene sheet layers is less than 15 μm.
3. The high-rate fast-charge negative-electrode material of claim 1, wherein said hard carbon comprises a thermoplastic polymer comprising a thermoplastic resin or pitch or meltable biomass molecules comprising at least one of sucrose, glucose, and fructose.
4. A preparation method of a negative electrode material with high-rate quick charge is characterized by comprising the following steps:
step 1), adding graphene into a carbon source solution for dispersion, and obtaining a first precursor after hydrothermal reaction;
step 2), dispersing the first precursor in a thermal stabilizing medium, and heating the first precursor to obtain a second precursor;
and 3) melting and coating a hard carbon source on the surface of the second precursor, and carbonizing to obtain the high-rate quick-charging negative electrode material.
5. The method for preparing the negative electrode material for high-rate rapid charging according to claim 4, wherein in the step 1), the temperature of the hydrothermal reaction is 130 to 250 ℃, and the vapor pressure of water in the hydrothermal reaction is 0.3 to 4 MPa.
6. The preparation method of the negative electrode material for high-rate rapid charging according to claim 4, wherein in the step 1), the number of graphene layers is 2-10, the thickness of the graphene is less than 5nm, and the maximum diameter of each graphene layer is less than 15 μm.
7. The method for preparing the negative electrode material for high-rate rapid charge according to claim 4, wherein in the step 1), the carbon source solution comprises at least one of a sucrose solution, a glucose solution, a fructose solution, a cellulose solution, a phenolic resin alcohol solution, an asphalt solution and a sodium hydroxymethyl cellulose solution.
8. The preparation method of the negative electrode material with high-rate and rapid charging according to claim 4, wherein in the step 1), the concentration of the carbon source solution is 5-20%, and the mass ratio of the graphene to the carbon source solution is 1: (20 to 50).
9. The method for preparing the negative electrode material for high-rate rapid charge according to claim 4, wherein in the step 1), after the hydrothermal reaction, the method further comprises washing and drying treatment.
10. The method for preparing the negative electrode material with high-rate and rapid charging according to claim 4, wherein in the step 2), before dispersing the first precursor in the thermal stabilizing medium, the method further comprises ball milling and drying the first precursor.
11. The method for preparing a negative electrode material for high-rate rapid charge according to claim 4, wherein in the step 2), the thermal stabilization medium comprises at least one of silicone oil, dimethyl silicone oil and benzyl silicone oil.
12. The method for preparing the negative electrode material for high-rate rapid charging according to claim 4, wherein in the step 2), the mass ratio of the thermal stabilizing medium to the first precursor is 100: (0.5 to 10).
13. The method for preparing a high-rate fast-charging anode material according to claim 4, wherein in the step 2), the first precursor is heated under an inert gas atmosphere, and the inert gas comprises at least one of nitrogen, argon and helium.
14. The preparation method of the negative electrode material for high-rate rapid charging according to claim 4, wherein in the step 2), the heating temperature is 350-400 ℃, the heating temperature rise rate is 5-10 ℃/min, and the heating time is 3-8 h.
15. The method for preparing the negative electrode material with high-rate and rapid charging according to claim 4, wherein in the step 2), after the first precursor is heated, the steps of cooling, organic solvent extraction, suction filtration, drying, ball milling and screening are further included to obtain a second precursor.
16. The method for preparing the negative electrode material for high-rate rapid charge according to claim 4, wherein in step 3), the hard carbon comprises a thermoplastic polymer or a meltable biomass molecule, the thermoplastic polymer comprises a thermoplastic resin or asphalt, and the meltable biomass molecule comprises at least one of sucrose, glucose and fructose.
17. The method for preparing the negative electrode material for high-rate rapid charge according to claim 4, wherein in the step 3), the temperature of the melt coating is 100-300 ℃, the temperature of the carbonization treatment is 500-1200 ℃, the time of the carbonization treatment is 2-6 h, and the temperature rise rate of the carbonization treatment is 0.5-20 ℃/min.
18. The method for preparing the negative electrode material for high-rate rapid charge according to claim 4, wherein in the step 3), the carbonization treatment is followed by ball milling, sieving and demagnetizing treatment to obtain the negative electrode material for high-rate rapid charge.
19. A high-rate rapid-charging negative electrode sheet, characterized by comprising the negative electrode material according to any one of claims 1 to 3.
20. A lithium ion battery comprising a negative electrode sheet according to claim 19.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307962A (en) * | 2022-01-04 | 2022-04-12 | 西安热工研究院有限公司 | Rock asphalt-based demercuration adsorbent and preparation method thereof |
| CN115536000A (en) * | 2022-10-14 | 2022-12-30 | 中国科学院合肥物质科学研究院 | Preparation method of hard carbon material with graphite coating layer on surface and application of hard carbon material in sodium-ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
| CN108075110A (en) * | 2016-11-14 | 2018-05-25 | 微宏动力系统（湖州）有限公司 | Negative electrode for lithium ion battery composite material and lithium ion battery |
| CN109638212A (en) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | A kind of high magnification fast charge lithium ion battery |
| KR20190058271A (en) * | 2017-11-20 | 2019-05-29 | 한국생산기술연구원 | Cathode comprising nano cathode active material particle and flexible secondary battery laminate comprising the same |
| CN109888200A (en) * | 2018-12-29 | 2019-06-14 | 深圳市卓能新能源股份有限公司 | Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery |
| US20190379039A1 (en) * | 2018-06-06 | 2019-12-12 | Nanotek Instruments, Inc. | Multi-level graphene-protected anode active material particles for fast-charging lithium-ion batteries |
| CN111244401A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Hard carbon coated graphite negative electrode material, lithium ion battery and preparation method and application thereof |
| CN111342031A (en) * | 2020-03-28 | 2020-06-26 | 兰溪致德新能源材料有限公司 | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof |
-
2020
- 2020-10-10 CN CN202011077974.1A patent/CN112397693B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
| CN108075110A (en) * | 2016-11-14 | 2018-05-25 | 微宏动力系统（湖州）有限公司 | Negative electrode for lithium ion battery composite material and lithium ion battery |
| KR20190058271A (en) * | 2017-11-20 | 2019-05-29 | 한국생산기술연구원 | Cathode comprising nano cathode active material particle and flexible secondary battery laminate comprising the same |
| US20190379039A1 (en) * | 2018-06-06 | 2019-12-12 | Nanotek Instruments, Inc. | Multi-level graphene-protected anode active material particles for fast-charging lithium-ion batteries |
| CN109638212A (en) * | 2018-11-20 | 2019-04-16 | 东莞锂威能源科技有限公司 | A kind of high magnification fast charge lithium ion battery |
| CN111244401A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Hard carbon coated graphite negative electrode material, lithium ion battery and preparation method and application thereof |
| CN109888200A (en) * | 2018-12-29 | 2019-06-14 | 深圳市卓能新能源股份有限公司 | Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery |
| CN111342031A (en) * | 2020-03-28 | 2020-06-26 | 兰溪致德新能源材料有限公司 | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIN ZHANG等: "Composite of mesocarbon microbeads/hard carbon as anode material for lithium ion capacitor with high electrochemical performance", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307962A (en) * | 2022-01-04 | 2022-04-12 | 西安热工研究院有限公司 | Rock asphalt-based demercuration adsorbent and preparation method thereof |
| CN115536000A (en) * | 2022-10-14 | 2022-12-30 | 中国科学院合肥物质科学研究院 | Preparation method of hard carbon material with graphite coating layer on surface and application of hard carbon material in sodium-ion battery |
| CN115536000B (en) * | 2022-10-14 | 2024-03-15 | 中国科学院合肥物质科学研究院 | Preparation method of hard carbon material with graphite coating layer on surface and application of hard carbon material in sodium ion battery |
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