CN109860527B - Carbon-based composite material for preparing lithium battery cathode and preparation method thereof - Google Patents
Carbon-based composite material for preparing lithium battery cathode and preparation method thereof Download PDFInfo
- Publication number
- CN109860527B CN109860527B CN201811422226.5A CN201811422226A CN109860527B CN 109860527 B CN109860527 B CN 109860527B CN 201811422226 A CN201811422226 A CN 201811422226A CN 109860527 B CN109860527 B CN 109860527B
- Authority
- CN
- China
- Prior art keywords
- carbon
- lithium battery
- composite material
- based composite
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a carbon-based composite material for preparing a lithium battery cathode, which is characterized by comprising the following steps of: s1 preparation of hollow porous Cu-Mo-O, S2 surface modification of hollow porous Cu-Mo-O, S3 high-temperature carbonization and S4 loading. The invention also discloses the carbon-based composite material for preparing the lithium battery cathode, which is prepared by the preparation method. The preparation method of the carbon-based composite material for preparing the lithium battery cathode, disclosed by the invention, is simple and feasible, the equipment is simple, the process is controllable, and the prepared carbon-based composite material for preparing the lithium battery cathode has higher theoretical specific capacity and conductivity, better stability and better low-temperature performance.
Description
Technical Field
The invention belongs to the technical field of new energy new material, relates to a material for a lithium battery and a preparation method thereof, and particularly relates to a carbon-based composite material for preparing a lithium battery cathode and a preparation method thereof.
Background
With the rapid development of the fields of portable electronic devices, space technology, power grids, electric vehicles and the like, people have higher and higher requirements on batteries, and a novel lithium battery with high capacity, long cycle life, low cost and environmental friendliness is developed to become a popular research field. Lithium batteries have been widely used in various fields as green and environmentally friendly energy sources, but their use in special fields such as aviation, aerospace and military is limited due to their more or less poor low temperature performance, low gram capacity, first coulombic efficiency and compaction density. The main reason for this phenomenon is related to the negative electrode material of lithium battery, and the improvement of the negative electrode material of lithium battery is the key to improve the diffusion rate of lithium ions, solve the problem of low temperature performance, increase gram capacity, first coulombic efficiency and compaction density.
As a main body for storing lithium, a negative electrode material plays an important role in a lithium ion battery, the capacity of the negative electrode material is one of important factors influencing the capacity of the battery, and the performance of the negative electrode material directly influences the battery capacity and the cycle service life of the lithium ion battery. At present, the commercial lithium ion battery mainly adopts graphite or modified graphite as a negative electrode material. Such negative electrode materials have a low theoretical lithium intercalation capacity, a large first irreversible loss, and poor rate discharge performance, and also, when lithium ions are intercalated, a part of the solvent is intercalated, and the structure is easily broken. The modified graphite is mainly introduced with nonmetal, metal or surface treatment and the like. The modification methods can effectively improve the structural stability of lithium ions in the intercalation process, thereby improving the electrochemical stability, but the modification methods in the prior art are harsh on the synthesis conditions of materials, and the synthesized materials are easy to shrink and expand in volume, thereby causing the damage of electrode structures.
In recent years, nanometer transition metal oxides used as negative electrode materials of lithium batteries attract extensive attention of researchers due to high theoretical specific capacity and high capacity retention rate, but the transition metal oxide materials have large volume expansion and shrinkage changes in the process of lithium ion intercalation and deintercalation, so that electrode materials are pulverized, and further lose electrical contact with a current collector, and the cycle performance and the application of the materials are greatly influenced. Second, these materials have inferior electron conductivity compared to conventional graphite anode materials.
Therefore, the lithium battery cathode material which is stable, has higher theoretical specific capacity and conductivity and high capacity retention rate is developed, meets the market demand, and has wide market value and application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a carbon-based composite material for preparing a lithium battery cathode and a preparation method thereof.
The invention can be realized by the following technical scheme:
the preparation method of the carbon-based composite material for preparing the negative electrode of the lithium battery is characterized by comprising the following steps of:
step S1 preparation of hollow porous Cu-Mo-O: adding glucose, copper salt and molybdenum salt into deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20-25 hours at the temperature of 180 ℃ plus 220 ℃, centrifuging after the reaction is finished, placing the mixture into a vacuum drying box at the temperature of 100 ℃ plus 110 ℃ for drying for 18-24 hours, heating the mixture in air at the temperature rise rate of 5-10 ℃/min to the temperature of 600 ℃ plus 700 ℃, calcining at the temperature for 6-8 hours, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing the hollow porous Cu-Mo-O prepared in the step S1 in an organic solvent, adding ferric acrylate, 2,4, 6-trivinyl boroxine, tri (2-methoxyethoxy) vinyl silane, 1,2, 2-trifluoroethyl triphenylsilane and an initiator into the organic solvent, stirring the mixture at normal temperature for 3 to 5 hours, centrifuging the mixture, placing the mixture in an atmosphere of nitrogen or inert gas, and irradiating the mixture for 20 to 30 minutes by using ultraviolet light with the wavelength of 200-250 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 700-1000 ℃ at a heating rate of 2-5 ℃/min in an air atmosphere for carbonization for 1-3 hours to obtain an intermediate;
step S4 load: and (4) uniformly mixing the intermediate prepared in the step S3 and the carbon-based material to obtain the carbon-based composite material for preparing the lithium battery negative electrode.
Preferably, the mass ratio of the glucose, the copper salt, the molybdenum salt and the deionized water in the step S1 is (3-5):1:1 (20-40).
Preferably, the copper salt is selected from one or more of copper chloride, copper nitrate and copper carbonate.
Preferably, the molybdenum salt is selected from one or more of molybdenum chloride, molybdenum sulfate and molybdenum nitrate.
Preferably, the mass ratio of the hollow porous Cu-Mo-O, the organic solvent, the ferric acrylate, the 2,4, 6-trivinyl boroxine, the tri (2-methoxyethoxy) vinylsilane, the 1,2, 2-trifluorovinyl triphenylsilane and the initiator in the step S2 is 1 (5-10) to 0.02 to 0.01 to 0.03 to 0.02 to 0.01.
Preferably, the organic solvent is selected from one or more of ethanol, ethylene glycol and tetrahydrofuran; the initiator is selected from one or more of benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenyl acetone, benzoin isopropyl ether and benzoin butyl ether.
Preferably, the inert gas is selected from one of helium, neon and argon.
Preferably, the mass ratio of the intermediate to the carbon-based material in the step S4 is 1 (5-8).
Preferably, the carbon-based material is selected from one or more of carbon nano tube, fullerene and expandable graphite.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the carbon-based composite material for preparing the lithium battery cathode, disclosed by the invention, is simple and feasible, small in equipment dependence, controllable in process, high in efficiency, low in production cost, green and pollution-free, and suitable for large-scale production.
(2) The carbon-based composite material for preparing the lithium battery cathode disclosed by the invention avoids the technical defects that the traditional lithium battery cathode material is low in low-temperature performance, gram capacity, low first coulombic efficiency and harsh in synthesis conditions, and the synthesized material is easy to shrink and expand in volume so as to damage an electrode structure, and has the advantages of higher theoretical specific capacity and conductivity, better stability and better low-temperature performance.
(3) The carbon-based composite material for preparing the negative electrode of the lithium battery, disclosed by the invention, is compounded with the advantages of transition metal oxides, alloy materials and carbon-based materials, and active ingredients such as iron, silicon, fluorine, boron and the like are introduced through modification, so that the electrochemical performance of the negative electrode material is favorably improved.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.
The raw materials involved in the examples of the present invention were purchased from Aladdin reagent Inc.
Example 1
A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding 30g of glucose, 10g of copper chloride and 10g of molybdenum chloride into 200g of deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20 hours at 180 ℃, centrifuging after the reaction is finished, placing the mixture into a 100 ℃ vacuum drying oven for drying for 18 hours, heating the mixture to 600 ℃ in air at a heating rate of 5 ℃/min, calcining for 6 hours at the temperature, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing 10g of the hollow porous Cu-Mo-O prepared in the step S1 in 50g of ethanol, adding 0.2g of ferric acrylate, 0.1g of 2,4, 6-trivinyl boroxine, 0.3g of tris (2-methoxyethoxy) vinylsilane, 0.2g of 1,2, 2-trifluorovinyl triphenylsilane and 0.1g of benzoin ethyl ether into the ethanol, stirring the mixture at normal temperature for 3 hours, centrifuging the mixture, placing the mixture in a nitrogen atmosphere, and irradiating the mixture for 20 minutes by using ultraviolet light with the wavelength of 200 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 700 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and carbonizing for 1 hour to obtain an intermediate;
step S4 load: and (4) uniformly mixing 10g of the intermediate prepared in the step S3 and 50g of the carbon nano tube to obtain the carbon-based composite material for preparing the lithium battery cathode.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Uniformly mixing the prepared carbon-based composite material for preparing the lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methyl pyrrolidone solution (NMP) into the carbon-based composite material, uniformly stirring the mixture into viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in vacuum at 100 ℃ for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the copper foil to room temperature, taking the copper foil out, preparing the copper foil into a wafer with the diameter of 14cm by using a slicing machine, and compacting the wafer to be used as a negative electrode piece. Then, a 2016 button cell is assembled in a glove box filled with argon. And (3) charging and discharging the assembled battery on a LAND battery test system for 100 circles at a multiplying power of 0.1C, and measuring the specific discharge capacity to be 940 mAh/g.
Example 2
A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding 35g of glucose, 10g of copper nitrate and 10g of molybdenum sulfate into 250g of deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 21 hours at 190 ℃, centrifuging after the reaction is finished, placing the mixed solution into a vacuum drying oven at 102 ℃, drying for 19 hours, heating to 620 ℃ in air at a heating rate of 6 ℃/min, calcining for 6.5 hours at the temperature, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing 10g of the hollow porous Cu-Mo-O prepared in the step S1 in 65g of ethylene glycol, adding 0.2g of ferric acrylate, 0.1g of 2,4, 6-trivinyl boroxine, 0.3g of tris (2-methoxyethoxy) vinylsilane, 0.2g of 1,2, 2-trifluorovinyl triphenylsilane and 0.1g of 2-hydroxy-2-methyl-1-phenyl acetone into the mixture, stirring the mixture at normal temperature for 3.5 hours, centrifuging the mixture, placing the mixture in a helium gas atmosphere, and irradiating the mixture for 22 minutes by using ultraviolet light with the wavelength of 210 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 800 ℃ at a heating rate of 3 ℃/min in an air atmosphere, and carbonizing for 1.5 hours to obtain an intermediate;
step S4 load: and (4) uniformly mixing 10g of the intermediate prepared in the step S3 with 60g of fullerene to obtain the carbon-based composite material for preparing the lithium battery cathode.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Uniformly mixing the prepared carbon-based composite material for preparing the lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methyl pyrrolidone solution (NMP) into the carbon-based composite material, uniformly stirring the mixture into viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in vacuum at 100 ℃ for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the copper foil to room temperature, taking the copper foil out, preparing the copper foil into a wafer with the diameter of 14cm by using a slicing machine, and compacting the wafer to be used as a negative electrode piece. Then, a 2016 button cell is assembled in a glove box filled with argon. The assembled battery is charged and discharged for 100 circles on a LAND battery test system at a multiplying power of 0.1C, and the specific discharge capacity is measured to be about 942 mAh/g.
Example 3
A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding 40g of glucose, 10g of copper carbonate and 10g of molybdenum nitrate into 300g of deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 23 hours at 200 ℃, centrifuging after the reaction is finished, placing the mixed solution into a 105 ℃ vacuum drying oven for drying for 22 hours, heating the mixed solution to 660 ℃ in air at a heating rate of 8 ℃/min, calcining for 7 hours at the temperature, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing 10g of the hollow porous Cu-Mo-O prepared in the step S1 in 80g of tetrahydrofuran, adding 0.2g of ferric acrylate, 0.1g of 2,4, 6-trivinyl boroxine, 0.3g of tris (2-methoxyethoxy) vinylsilane, 0.2g of 1,2, 2-trifluorovinyl triphenylsilane and 0.1g of benzoin isopropyl ether into the mixture, stirring the mixture at normal temperature for 4 hours, centrifuging the mixture, placing the mixture in a neon atmosphere, and irradiating the mixture for 25 minutes by using ultraviolet light with the wavelength of 230 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 900 ℃ at a heating rate of 3 ℃/min in an air atmosphere for 2 hours to obtain an intermediate;
step S4 load: and (4) uniformly mixing 10g of the intermediate prepared in the step S3 and 70g of expandable graphite to obtain the carbon-based composite material for preparing the negative electrode of the lithium battery.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Uniformly mixing the prepared carbon-based composite material for preparing the lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methyl pyrrolidone solution (NMP) into the carbon-based composite material, uniformly stirring the mixture into viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in vacuum at 100 ℃ for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the copper foil to room temperature, taking the copper foil out, preparing the copper foil into a wafer with the diameter of 14cm by using a slicing machine, and compacting the wafer to be used as a negative electrode piece. Then, a 2016 button cell is assembled in a glove box filled with argon. And (3) charging and discharging the assembled battery on an LAND battery test system for 100 circles at a multiplying power of 0.1C, and measuring the specific discharge capacity to be about 945 mAh/g.
Example 4
A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding 45g of glucose, 10g of copper salt and 10g of molybdenum salt into 350g of deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at 210 ℃, centrifuging after the reaction is finished, placing the mixture in a vacuum drying oven at 108 ℃, drying for 23 hours, heating to 680 ℃ in air at a heating rate of 9 ℃/min, calcining for 7.5 hours at the temperature, and removing carbon nuclei to obtain hollow porous Cu-Mo-O; the copper salt is a mixture formed by mixing copper chloride, copper nitrate and copper carbonate according to the mass ratio of 1:2: 1; the molybdenum salt is a mixture formed by mixing molybdenum chloride, molybdenum sulfate and molybdenum nitrate according to the mass ratio of 2:3: 1;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing 10g of the hollow porous Cu-Mo-O prepared in the step S1 in 95g of an organic solvent, adding 0.2g of ferric acrylate, 0.1g of 2,4, 6-trivinyl boroxine, 0.3g of tris (2-methoxyethoxy) vinylsilane, 0.2g of 1,2, 2-trifluorovinyl triphenylsilane and 0.1g of an initiator into the organic solvent, stirring the mixture at normal temperature for 4.5 hours, centrifuging the mixture, placing the mixture in an argon atmosphere, and irradiating the mixture for 28 minutes by using ultraviolet light with the wavelength of 240 nm; obtaining surface modified hollow porous Cu-Mo-O; the organic solvent is a mixture formed by mixing ethanol, ethylene glycol and tetrahydrofuran according to a mass ratio of 1:3: 2; the initiator is a mixture formed by mixing benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenyl acetone, benzoin isopropyl ether and benzoin butyl ether according to the mass ratio of 1:1:3: 2;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 950 ℃ at a heating rate of 4 ℃/min in an air atmosphere, and carbonizing for 2.5 hours to obtain an intermediate;
step S4 load: uniformly mixing 10g of the intermediate prepared in the step S3 with 78g of the carbon-based material to obtain a carbon-based composite material for preparing the negative electrode of the lithium battery; the carbon-based material is a mixture formed by mixing carbon nano tubes, fullerene and expandable graphite according to the mass ratio of 3:2: 5.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Uniformly mixing the prepared carbon-based composite material for preparing the lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methyl pyrrolidone solution (NMP) into the carbon-based composite material, uniformly stirring the mixture into viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in vacuum at 100 ℃ for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the copper foil to room temperature, taking the copper foil out, preparing the copper foil into a wafer with the diameter of 14cm by using a slicing machine, and compacting the wafer to be used as a negative electrode piece. Then, a 2016 button cell is assembled in a glove box filled with argon. The assembled battery is charged and discharged for 100 circles on a LAND battery test system at a multiplying power of 0.1C, and the discharge specific capacity is measured to be about 947 mAh/g.
Example 5
A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding 50g of glucose, 10g of copper carbonate and 10g of molybdenum chloride into 400g of deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 25 hours at 220 ℃, centrifuging after the reaction is finished, placing the mixed solution into a vacuum drying oven at 110 ℃, drying for 24 hours, heating to 700 ℃ in air at a heating rate of 10 ℃/min, calcining for 8 hours at the temperature, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing 10g of the hollow porous Cu-Mo-O prepared in the step S1 in 100g of tetrahydrofuran, adding 0.2g of ferric acrylate, 0.1g of 2,4, 6-trivinyl boroxine, 0.3g of tris (2-methoxyethoxy) vinylsilane, 0.2g of 1,2, 2-trifluorovinyl triphenylsilane and 0.1g of benzoin butyl ether into the tetrahydrofuran, stirring the mixture at normal temperature for 5 hours, centrifuging the mixture, placing the mixture in a nitrogen atmosphere, and irradiating the mixture for 30 minutes by using ultraviolet light with the wavelength of 250 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 1000 ℃ at a heating rate of 5 ℃/min in an air atmosphere, and carbonizing for 3 hours to obtain an intermediate;
step S4 load: and (4) uniformly mixing 10g of the intermediate prepared in the step S3 and 80g of fullerene to obtain the carbon-based composite material for preparing the lithium battery cathode.
A carbon-based composite material for preparing a lithium battery cathode material is prepared by the preparation method of the carbon-based composite material for preparing the lithium battery cathode material.
Uniformly mixing the prepared carbon-based composite material for preparing the lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methyl pyrrolidone solution (NMP) into the carbon-based composite material, uniformly stirring the mixture into viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in vacuum at 100 ℃ for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the copper foil to room temperature, taking the copper foil out, preparing the copper foil into a wafer with the diameter of 14cm by using a slicing machine, and compacting the wafer to be used as a negative electrode piece. Then, a 2016 button cell is assembled in a glove box filled with argon. The assembled battery is charged and discharged for 100 circles on a LAND battery test system at a multiplying power of 0.1C, and the discharge specific capacity is measured to be about 948 mAh/g.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon-based composite material for preparing a negative electrode of a lithium battery is characterized by comprising the following steps:
step S1 preparation of hollow porous Cu-Mo-O: adding glucose, copper salt and molybdenum salt into deionized water, uniformly mixing to obtain a mixed solution, adding the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 20-25 hours at the temperature of 180 ℃ plus 220 ℃, centrifuging after the reaction is finished, placing the mixture into a vacuum drying box at the temperature of 100 ℃ plus 110 ℃ for drying for 18-24 hours, heating the mixture in air at the temperature rise rate of 5-10 ℃/min to the temperature of 600 ℃ plus 700 ℃, calcining at the temperature for 6-8 hours, and removing carbon nuclei to obtain hollow porous Cu-Mo-O;
step S2 surface modification of hollow porous Cu-Mo-O: dispersing the hollow porous Cu-Mo-O prepared in the step S1 in an organic solvent, adding ferric acrylate, 2,4, 6-trivinyl boroxine, tri (2-methoxyethoxy) vinyl silane, 1,2, 2-trifluoroethyl triphenylsilane and an initiator into the organic solvent, stirring the mixture at normal temperature for 3 to 5 hours, centrifuging the mixture, placing the mixture in an atmosphere of nitrogen or inert gas, and irradiating the mixture for 20 to 30 minutes by using ultraviolet light with the wavelength of 200-250 nm; obtaining surface modified hollow porous Cu-Mo-O;
step S3 high-temperature carbonization: heating the surface modified hollow porous Cu-Mo-O obtained in the step S2 to 700-1000 ℃ at a heating rate of 2-5 ℃/min in an air atmosphere for carbonization for 1-3 hours to obtain an intermediate;
step S4 load: and (4) uniformly mixing the intermediate prepared in the step S3 and the carbon-based material to obtain the carbon-based composite material for preparing the lithium battery negative electrode.
2. The method of claim 1, wherein the mass ratio of the glucose, the copper salt, the molybdenum salt and the deionized water in step S1 is (3-5):1:1 (20-40).
3. The method as claimed in claim 1, wherein the copper salt is selected from one or more of copper chloride, copper nitrate and copper carbonate.
4. The method of claim 1, wherein the molybdenum salt is selected from one or more of molybdenum chloride, molybdenum sulfate, and molybdenum nitrate.
5. The method of claim 1, wherein the mass ratio of the hollow porous Cu-Mo-O, the organic solvent, the iron acrylate, the 2,4, 6-trivinylboroxine, the tris (2-methoxyethoxy) vinylsilane, the 1,2, 2-trifluorovinyltriphenylsilane, and the initiator is 1 (5-10):0.02:0.01:0.03:0.02:0.01 in step S2.
6. The method for preparing the carbon-based composite material for the negative electrode of the lithium battery as claimed in claim 1, wherein the organic solvent is one or more selected from ethanol, ethylene glycol and tetrahydrofuran; the initiator is selected from one or more of benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenyl acetone, benzoin isopropyl ether and benzoin butyl ether.
7. The method of claim 1, wherein the inert gas is selected from helium, neon, and argon.
8. The method of claim 1, wherein the intermediate and the carbon-based material are present in the step S4 in a mass ratio of 1 (5-8).
9. The method as claimed in claim 1, wherein the carbon-based material is selected from one or more of carbon nanotube, fullerene, and expandable graphite.
10. The carbon-based composite material for preparing a negative electrode material for a lithium battery, prepared by the method for preparing a carbon-based composite material for a negative electrode for a lithium battery according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811422226.5A CN109860527B (en) | 2018-11-27 | 2018-11-27 | Carbon-based composite material for preparing lithium battery cathode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811422226.5A CN109860527B (en) | 2018-11-27 | 2018-11-27 | Carbon-based composite material for preparing lithium battery cathode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109860527A CN109860527A (en) | 2019-06-07 |
| CN109860527B true CN109860527B (en) | 2022-01-28 |
Family
ID=66890319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811422226.5A Active CN109860527B (en) | 2018-11-27 | 2018-11-27 | Carbon-based composite material for preparing lithium battery cathode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109860527B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111453773A (en) * | 2020-04-10 | 2020-07-28 | 陶健君 | Lithium battery negative electrode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835961A (en) * | 2015-05-27 | 2015-08-12 | 厦门大学 | Transition metal sulfide coated with carbon, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA200800196A1 (en) * | 2005-07-01 | 2008-06-30 | Синвеншен Аг | METHOD OF MAKING A POROUS COMPOSITION MATERIAL |
| CN104716335B (en) * | 2013-12-15 | 2017-03-01 | 中国科学院大连化学物理研究所 | A kind of flow battery electrode and preparation and application |
| CN110140241A (en) * | 2016-10-07 | 2019-08-16 | 克雷多斯公司 | Graphite and IVA race composite particles and production method |
| CN106410221A (en) * | 2016-12-08 | 2017-02-15 | 天津工业大学 | Method for preparing nanowire sheet intercalated structure supported type direct alcohol fuel cell catalyst |
| CN108807862A (en) * | 2017-05-03 | 2018-11-13 | 溧阳天目先导电池材料科技有限公司 | A kind of silicon based composite material and preparation method thereof, negative material and lithium battery |
-
2018
- 2018-11-27 CN CN201811422226.5A patent/CN109860527B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104835961A (en) * | 2015-05-27 | 2015-08-12 | 厦门大学 | Transition metal sulfide coated with carbon, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109860527A (en) | 2019-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109148847B (en) | Boron-doped modified hard carbon-coated negative electrode material with high rate performance and liquid-phase preparation method thereof | |
| CN108448080B (en) | Graphene-coated silicon/metal composite negative electrode material and preparation method thereof | |
| CN112133896B (en) | High-capacity graphite-silicon oxide composite material and preparation method and application thereof | |
| CN107611411B (en) | Preparation method and application of three-dimensional hierarchical porous nitrogen-doped carbon-coated silicon composite material | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN109616654B (en) | C/Si/SiOxMaterial, preparation method and application thereof | |
| CN107623109A (en) | A kind of preparation method of high power capacity long circulating stability lithium ion battery negative material | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN105304866B (en) | A kind of lithium-sulphur cell positive electrode containing metal magnesium powder and preparation method thereof | |
| CN105047894A (en) | Preparation method of halogen-doped carbon and silicon nano-material and application thereof | |
| CN110797516B (en) | C-coated SiO-SnSiO4-Si super-particle material and preparation method and application thereof | |
| CN109860527B (en) | Carbon-based composite material for preparing lithium battery cathode and preparation method thereof | |
| CN112421049A (en) | Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material | |
| CN112209366A (en) | Preparation method of lithium-sulfur battery electrode material | |
| CN103035895A (en) | Method for preparing carbon coated lead powder composite material for lead carbon battery | |
| CN115566167A (en) | Silicon-based composite material prepared by gaseous atomization method and preparation method | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN115207304A (en) | Graphite cathode composite material, preparation method thereof and lithium ion battery | |
| CN115148946A (en) | Preparation method of positive pole piece of lithium-sulfur battery and lithium-sulfur battery | |
| CN108039490B (en) | High-performance sodium-ion battery negative electrode material and preparation method thereof | |
| CN112397701A (en) | Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof | |
| CN111293297A (en) | Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof | |
| CN105845905B (en) | Bismuth fluoride and copper fluoride composite lithium battery positive electrode material with gradient coating layer and preparation method thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN103208613B (en) | Production method of anode plate in lithium ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |