CN108807903B - Preparation method of composite modified lithium battery negative electrode material for lithium battery - Google Patents
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Abstract
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a preparation method of a composite modified lithium battery anode material for a lithium battery, which comprises the following steps: mixing the following components in a mass ratio of (1-2): 1, putting graphene and carbon nano tubes into a solvent, performing ultrasonic primary crushing treatment, mixing and stirring at normal temperature for 4-6 minutes, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, then preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution.
Description
The technical field is as follows:
the invention relates to the technical field of lithium ion battery electrode materials, in particular to a preparation method of a composite modified lithium battery anode material for a lithium battery.
Background art:
the lithium battery is a primary battery using lithium metal or lithium alloy as a negative electrode material and using a non-aqueous electrolyte solution, unlike a lithium ion battery, which is a rechargeable battery, and a lithium ion polymer battery. The inventor of lithium batteries was edison. Because the chemical characteristics of lithium metal are very active, the requirements on the environment for processing, storing and using the lithium metal are very high. Therefore, lithium batteries have not been used for a long time. With the development of microelectronic technology at the end of the twentieth century, miniaturized devices are increasing, and high requirements are made on power supplies. The lithium battery has then entered a large-scale practical stage. Lithium iron phosphate system anode reaction: lithium ions are intercalated and deintercalated during discharge and charge. During charging: LiFePO4 → Li1-xFePO4+ xLi + + xe-when discharging: li1-xFePO4+ xLi + + xe- → LiFePO4 negative electrode, negative electrode material: graphite is mostly used. New studies found that titanate may be a better material. And (3) cathode reaction: lithium ions are deintercalated during discharge and are intercalated during charge. During charging: when xLi + + xe- +6C → LixC6 discharges: LixC6 → xLi + + xe- + 6C.
The cathode material is one of the key materials of the lithium ion battery, and the lithium ion battery cathode material which is commercially used at present is mainly a carbon cathode material. The lithium ion battery has the advantages of high specific capacity (200-400 mAh/g), low electrode potential (less than 1.0Vvs Li +/Li), high cycle efficiency (more than 95%), long cycle life and the like. The carbon negative electrode material comprises mesocarbon microbeads (MCMB), graphite and amorphous carbon, wherein the graphite has good conductivity and high crystallinity and has a good layered structure, the reversible specific capacity can reach more than 300mah/g, Chen and other people have invented a superfine graphite negative electrode material, auxiliary materials after high-end graphite production are adopted as main raw materials of the product, the granularity is reduced to 5um by fine crushing, the reference is the standard, surface treatment is carried out, 3000-degree graphitization sintering is carried out after 1200-degree carbonization, corresponding products are obtained by coarse crushing and sieving, and the product has good conductive effect, low resistance, good processing performance in the production process of lithium ion batteries, stable performance and high cost performance, and is the optimal negative electrode material of a multiplying power lithium battery. But the disadvantages are that the graphite material has poor structural stability and poor compatibility with electrolyte, and the diffusion speed of Li ions in the ordered layered structure is slow, so that the material cannot be charged and discharged at a large multiplying power. The soft carbon has low crystallinity, small crystal grain size, large crystal face spacing and good compatibility with electrolyte, but has good charge-discharge irreversible capacity for the first time and small application range, and the artificial graphite has certain structural defects of the lithium ion battery cathode material itself, and needs to be subjected to further surface modification and modification in order to obtain the cathode material with high electrochemical performance.
The invention content is as follows:
the invention overcomes the defects of the prior art, provides the lithium battery with high first charge-discharge efficiency and high specific capacity, and solves the problems of large irreversible capacity loss and low specific capacity of carbon in the prior art when the carbon is applied to actually prepare the negative electrode of the lithium battery.
The technical problem to be solved by the invention is realized by adopting the following technical scheme: a preparation method of a composite modified lithium battery negative electrode material for a lithium battery comprises the following steps:
(1) mixing the following components in a mass ratio of (1-2): 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution;
(2) the method comprises the following steps of (1) adopting petroleum asphalt as a base material, crushing and ball-milling the base material until the particle size is 120-140 um, and then putting the treated particles into a reaction kettle for modification treatment, wherein the method comprises the following steps:
(2.1) introducing nitrogen at the air speed of 80-120 per hour, heating to 300-420 ℃, keeping the temperature at 40-60 ℃/h, and keeping the temperature for 2-6 h;
(2.2) taking part of the asphalt in the step (2.1) to be crushed until the particle size is below 20 mu m, measuring the softening point, and preserving the heat for 4-6 h at the temperature until the measured softening point is 180-380 ℃ of the asphalt base material;
(2.3) naturally cooling the asphalt base material in the step (2.2) to room temperature, and then crushing the plum light base material to obtain a modified asphalt base material with the particle size of 18-20 um;
(3) dissolving the asphalt screen base material obtained in the step (2) in tetrahydrofuran to obtain a tetrahydrofuran solution of asphalt, pouring the prepared tetrahydrofuran solution of asphalt into the mixed solution, stirring for 20-40 min to obtain mixed slurry, and then adding a solvent to adjust the solid mass percentage content of the mixed slurry to 10-20%;
(4) drying the mixed slurry obtained in the step (3) through a closed circulation spray dryer, wherein the inlet temperature and the outlet temperature of the closed circulation spray dryer are respectively 120-140 ℃ and 70-60 ℃, and the rotating speed of an atomizer of the closed circulation spray dryer is 24000-26000 r/min, so as to form a precursor;
(5) putting the precursor in the step (4) into an atomizer, and adopting the following precursors: the volume ratio of the solvent is 1: 30-35 of the precursor, forming a spray, heating to 500-700 ℃ under the protection of protective gas for annealing, loading 24-26% of a gaseous carbon source into the protective gas, keeping the gas flow rate at 50-1000 ml/min, starting an atomizer, carrying fine components atomized in the atomizer into a high-temperature furnace by the protective gas, preserving the temperature for 1-12 hours, cracking the gaseous carbon source on the surface of the precursor to form amorphous carbon, and coating the amorphous carbon on the surface of the precursor to form a uniform coating layer to obtain the lithium battery cathode material.
The solvent is at least one of distilled water, methanol, ethanol, ethylene glycol, diethyl ether and acetone.
In the step (1), the graphene is multilayer graphene, the interior of the multilayer graphene is of a three-dimensional conductive network structure, the carbon nano tubes are inserted into the three-dimensional conductive network, and the particle diameter of particles formed by the multilayer graphene and the carbon nano tubes after the action is 700 nm-22 um.
In the step (1), the ratio of the parts by weight of the graphene and the carbon nano tube to the parts by weight of the solvent is 1: 1-1: 5.
in the application, the petroleum asphalt is modified, the oxidation reaction system of the existing asphalt is optimized, namely volatile light components are firstly removed by using inert atmosphere at high temperature, then low-temperature oxidation reaction is carried out, and the oxidation reaction of the asphalt is exothermic reaction at high temperature, so that the oxidation polymerization of the asphalt is favorable at relatively low temperature in theory, and the energy consumption can be reduced. The heat release effect is not considered in the existing asphalt softening point improving method, only the asphalt is heated at high temperature for a long time to separate light components while performing polymerization reaction, the modified asphalt has the advantage of high softening point, so that the asphalt, graphene and carbon nanotubes can perform carbonization reaction quickly, the structure between the graphene and the carbon nanotubes can be ensured, and meanwhile, amorphous carbon is coated on the periphery, so that the structural stability is improved, the carbon nanotubes and the graphene structure are protected, and the reaction time is shortened.
Compared with the prior art, the preparation method comprises the steps of firstly modifying a carbon nano-tube and graphene, utilizing the high conductivity of the graphene and the carbon nano-tube, wherein the graphene is multilayer graphene, the interior of the multilayer graphene is of a three-dimensional conductive network structure, further improving the migration speed of lithium electrons in a coating layer, inserting the carbon nano-tube into the three-dimensional conductive network, the particle diameter of particles formed after the multilayer graphene and the carbon nano-tube are acted is 700 nm-22 um, mixing and stirring for 4-6 minutes at normal temperature, then heating to 40-60 ℃ at the speed of 2-4 ℃/min under the environment protected by inert gas, then preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution, so that micro bubbles between the multilayer graphene and the carbon nano-tube can be further removed, a stable binding layer is formed, and the conductive properties of the graphene and the carbon nano-tube can be better exerted, then preparing a precursor by using a closed cycle spray drying mode, uniformly dispersing modified asphalt on the surface of graphene, forming a layer of amorphous carbon after high-temperature heat treatment and carbonizing the asphalt to tightly wrap the surface of the graphene to form a composite material with a core-shell structure, wherein the existence of a coating layer not only reduces the specific surface area of the material and prevents an organic solvent from entering so as to achieve the purpose of obtaining a uniform and compact SEI film, but also can fix a graphite flake by using a surface carbon material and prevent the surface layer of the graphite from falling off so that the first efficiency, specific capacity and cycle stability of the material are improved to a certain extent, and finally heating to 500-700 ℃ under the protection of protective gas is adopted for annealing treatment, so that the stability between a carbon nanotube and the graphene can be further improved by the annealing treatment, and the prepared negative electrode material has strong stability, and then loading 24-26% of a gaseous carbon source by protective gas, wherein the gas flow rate is 50-1000 ml/min, simultaneously starting an atomizer, carrying atomized fine components in the atomizer into a high-temperature furnace by the protective gas, preserving heat for 1-12 hours, so that the gaseous carbon source is cracked on the surface of a precursor to form amorphous carbon, the amorphous carbon is coated on the surface of the precursor to form a uniform coating layer, and the lithium battery cathode material is obtained.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1:
a preparation method of a composite modified lithium battery negative electrode material for a lithium battery comprises the following steps:
(1) mixing the following components in a mass ratio of 1: 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution;
(2) the method comprises the following steps of (1) adopting petroleum asphalt as a base material, crushing and ball-milling the base material until the particle size is 120-140 um, and then putting the treated particles into a reaction kettle for modification treatment, wherein the method comprises the following steps:
(2.1) introducing nitrogen at the air speed of 80-120 per hour, heating to 300-420 ℃, keeping the temperature at 40-60 ℃/h, and keeping the temperature for 2-6 h;
(2.2) taking part of the asphalt in the step (2.1) to be crushed until the particle size is below 20 mu m, measuring the softening point, and preserving the heat for 4-6 h at the temperature until the measured softening point is 180-380 ℃ of the asphalt base material;
(2.3) naturally cooling the asphalt base material in the step (2.2) to room temperature, and then crushing the plum light base material to obtain a modified asphalt base material with the particle size of 18-20 um;
(3) dissolving the asphalt screen base material obtained in the step (2) in tetrahydrofuran to obtain a tetrahydrofuran solution of asphalt, pouring the prepared tetrahydrofuran solution of asphalt into the mixed solution, stirring for 20-40 min to obtain mixed slurry, and then adding a solvent to adjust the solid mass percentage content of the mixed slurry to 10-20%;
(4) drying the mixed slurry obtained in the step (3) through a closed circulation spray dryer, wherein the inlet temperature and the outlet temperature of the closed circulation spray dryer are respectively 120-140 ℃ and 70-60 ℃, and the rotating speed of an atomizer of the closed circulation spray dryer is 24000-26000 r/min, so as to form a precursor;
(5) putting the precursor in the step (4) into an atomizer, and adopting the following precursors: the volume ratio of the solvent is 1: 30-35 of the precursor, forming a spray, heating to 500-700 ℃ under the protection of protective gas for annealing, loading 25% of gaseous carbon source into the protective gas, keeping the gas flow rate at 50-1000 ml/min, starting an atomizer, carrying the atomized fine components in the atomizer into a high-temperature furnace by the protective gas, preserving the temperature for 1-12 hours, cracking the gaseous carbon source on the surface of the precursor to form amorphous carbon, and coating the amorphous carbon on the surface of the precursor to form a uniform coating layer to obtain the lithium battery cathode material.
The solvent is acetone.
In the step (1), the graphene is multilayer graphene, the interior of the multilayer graphene is of a three-dimensional conductive network structure, the carbon nano tubes are inserted into the three-dimensional conductive network, and the particle diameter of particles formed by the multilayer graphene and the carbon nano tubes after the action is 700 nm-22 um.
In the step (1), the ratio of the parts by weight of the graphene and the carbon nano tube to the parts by weight of the solvent is 1: 1-1: 5.
example 2:
the content of the present embodiment is substantially the same as that of embodiment 1, and the same points are not repeated, except that: in the step (1), the mass ratio of 1.5: 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution.
Example 3:
the content of the present embodiment is substantially the same as that of embodiment 1, and the same points are not repeated, except that: the step (1) comprises the following steps of: 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution.
Example 4:
the content of the present embodiment is substantially the same as that of embodiment 2, and the same points are not repeated, except that: and (5) putting the precursor in the step (4) into an atomizer, wherein the precursor is as follows: the volume ratio of the solvent is 1: 30-35 of the precursor, forming a spray, heating to 500-700 ℃ under the protection of protective gas for annealing, loading 24% of gaseous carbon source into the protective gas, keeping the gas flow rate at 50-1000 ml/min, starting an atomizer, carrying the atomized fine components in the atomizer into a high-temperature furnace by the protective gas, and carrying out heat preservation for 1-12 hours to crack the gaseous carbon source on the surface of the precursor to form amorphous carbon, wherein the amorphous carbon is coated on the surface of the precursor to form a uniform coating layer, so that the lithium battery anode material is obtained.
Example 5:
the content of the present embodiment is substantially the same as that of embodiment 2, and the same points are not repeated, except that: and (5) putting the precursor in the step (4) into an atomizer, wherein the precursor is as follows: the volume ratio of the solvent is 1: 30-35, heating to 500-700 ℃ under the protection of protective gas for annealing treatment, loading 26% of gaseous carbon source into the protective gas, enabling the gas flow rate to be 50-1000 ml/min, simultaneously starting an atomizer, enabling the protective gas to bring atomized fine components in the atomizer into a high-temperature furnace, preserving the temperature for 1-12 hours, enabling the gaseous carbon source to be cracked on the surface of a precursor to form amorphous carbon, and enabling the amorphous carbon to be coated on the surface of the precursor to form a uniform coating layer, thereby obtaining the lithium battery cathode material.
Comparative example 1:
the content of the comparative example is basically the same as that of the example 2, and the same parts are not repeated, except that the step (1) is carried out by mixing the components in a mass ratio of 0.5: 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution.
Comparative example 2:
the content of the comparative example is basically the same as that of the example 2, and the same parts are not repeated, except that the step (1) is implemented by mixing the components in a mass ratio of 3: 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution.
Comparative example 3:
this comparative example is substantially the same as example 2, and the same points are not repeated, except that the precursor in the step (4) is put into an atomizer in the step (5), and the precursor: the volume ratio of the solvent is 1: 30-35 of the precursor, forming a spray, heating to 500-700 ℃ under the protection of protective gas for annealing, loading 22% of gaseous carbon source into the protective gas, starting the atomizer at the gas flow rate of 50-1000 ml/min, carrying the atomized fine components in the atomizer into a high-temperature furnace by the protective gas, preserving the temperature for 1-12 hours, cracking the gaseous carbon source on the surface of the precursor to form amorphous carbon, and coating the amorphous carbon on the surface of the precursor to form a uniform coating layer to obtain the lithium battery anode material.
Comparative example 4:
this comparative example is substantially the same as example 2, and the same points are not repeated, except that the precursor in the step (4) is put into an atomizer in the step (5), and the precursor: the volume ratio of the solvent is 1: 30-35 of the precursor, forming a spray, heating to 500-700 ℃ under the protection of protective gas for annealing, loading 28% of gaseous carbon source into the protective gas, keeping the gas flow rate at 50-1000 ml/min, starting an atomizer, carrying the atomized fine components in the atomizer into a high-temperature furnace by the protective gas, and carrying out heat preservation for 1-12 hours to crack the gaseous carbon source on the surface of the precursor to form amorphous carbon, wherein the amorphous carbon is coated on the surface of the precursor to form a uniform coating layer, so that the lithium battery anode material is obtained.
Comparative example 5:
in the comparative example, a graphene-doped hollow porous carbon/silicon nanofiber lithium battery anode material disclosed in CN201510545414.7 is selected to prepare the lithium battery anode.
Preparing the negative electrode materials obtained in the examples 1-5 and the comparative examples 1-5, styrene butadiene rubber and a water-based adhesive into a paste adhesive, uniformly coating the paste adhesive on two sides of a copper foil, rolling and cutting to obtain a negative electrode sheet; the lithium ion battery is used for lithium battery assembly, and 10C charge-discharge capacity retention rate, first discharge capacity and first coulombic efficiency of the lithium ion battery are tested. The data obtained are shown in table 1.
TABLE 1
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A preparation method of a composite modified lithium battery negative electrode material for a lithium battery is characterized by comprising the following steps:
(1) mixing the following components in a mass ratio of (1-2): 1, putting graphene and a carbon nano tube into a solvent, carrying out ultrasonic primary crushing treatment, mixing and stirring for 4-6 minutes at normal temperature, heating to 40-60 ℃ at a speed of 2-4 ℃/min in an inert gas protection environment, preserving heat for 4-6 hours, and naturally cooling to room temperature to obtain a mixed solution;
(2) the method comprises the following steps of (1) taking petroleum asphalt as a base material, crushing and ball-milling the base material until the particle size is 120-140 mu m, and then putting the treated particles into a reaction kettle for modification treatment, wherein the method comprises the following steps:
(2.1) introducing nitrogen at the air speed of 80-120 per hour, heating to 300-420 ℃, keeping the temperature at 40-60 ℃/h, and keeping the temperature for 2-6 h;
(2.2) taking part of the asphalt in the step (2.1) to be crushed to the particle size of below 20 mu m, measuring the softening point, and preserving the heat for 4-6 h at the temperature until the measured softening point is the asphalt base stock at 180-380 ℃;
(2.3) naturally cooling the asphalt base material in the step (2.2) to room temperature, and then crushing the asphalt base material to obtain the modified asphalt base material with the particle size of 18-20 microns;
(3) dissolving the asphalt base material obtained in the step (2) in tetrahydrofuran to obtain a tetrahydrofuran solution of asphalt, pouring the prepared tetrahydrofuran solution of asphalt into the mixed solution, stirring for 20-40 min to obtain mixed slurry, and then adding a solvent to adjust the solid mass percentage content of the mixed slurry to 10-20%;
(4) drying the mixed slurry obtained in the step (3) through a closed circulation spray dryer, wherein the inlet temperature and the outlet temperature of the closed circulation spray dryer are respectively 120-140 ℃ and 70-60 ℃, and the rotating speed of an atomizer of the closed circulation spray dryer is 24000-26000 r/min, so as to form a precursor;
(5) putting the precursor in the step (4) into an atomizer, and adopting the following precursors: the volume ratio of the solvent is 1: 30-35, heating to 500-700 ℃ under the protection of protective gas for annealing treatment, loading 24-26% of gaseous carbon source into the protective gas, keeping the gas flow rate at 50-1000 ml/min, starting an atomizer, carrying the atomized fine components in the atomizer into a high-temperature furnace by the protective gas, preserving the temperature for 1-12 hours, cracking the gaseous carbon source on the surface of a precursor to form amorphous carbon, and coating the amorphous carbon on the surface of the precursor to form a uniform coating layer to obtain the lithium battery cathode material.
2. The method for preparing the composite modified lithium battery negative electrode material for the lithium battery as claimed in claim 1, wherein the solvent is at least one of distilled water, methanol, ethanol, ethylene glycol, diethyl ether and acetone.
3. The method for preparing the negative electrode material of the composite modified lithium battery for the lithium battery as claimed in claim 1, wherein the graphene in the step (1) is multi-layer graphene, the multi-layer graphene has a three-dimensional conductive network structure, the carbon nanotubes are embedded in the three-dimensional conductive network, and the particle diameter of particles formed by the multi-layer graphene and the carbon nanotubes after the action is 700nm to 22 μm.
4. The method for preparing the negative electrode material of the composite modified lithium battery for the lithium battery as claimed in claim 1, wherein the ratio of the parts by weight of the graphene and the carbon nanotubes to the parts by weight of the solvent in the step (1) is 1: 1-1: 5.
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| CN104091934B (en) * | 2014-07-17 | 2017-06-06 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of multi-component composite anode material, its preparation method and the lithium ion battery comprising it |
| CA2990347A1 (en) * | 2015-10-21 | 2017-04-27 | Imerys Graphite & Carbon Switzerland Ltd. | Carbonaceous composite materials with snowball-like morphology |
| JP2017084759A (en) * | 2015-10-30 | 2017-05-18 | 大阪瓦斯株式会社 | Electrode active material-carbon nanotube composite and manufacturing method thereof |
| CN106067547A (en) * | 2016-08-10 | 2016-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite |
| CN106876709B (en) * | 2017-02-22 | 2019-11-12 | 江西紫宸科技有限公司 | A kind of preparation method of high magnification carbon negative pole material |
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