CN113003559A - Preparation method of carbon negative electrode material for lithium ion battery - Google Patents
Preparation method of carbon negative electrode material for lithium ion battery Download PDFInfo
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- CN113003559A CN113003559A CN202110174042.7A CN202110174042A CN113003559A CN 113003559 A CN113003559 A CN 113003559A CN 202110174042 A CN202110174042 A CN 202110174042A CN 113003559 A CN113003559 A CN 113003559A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
A method for preparing a carbon negative electrode material for a lithium ion battery, comprising the steps of: (1) carbonizing the raw materials; (2) first mechanical shaping; (3) acid washing and purifying; (4) high-temperature carbonization; (5) second mechanical shaping; (6) coating the surface; (7) and (3) performing third mechanical shaping. The preparation method of the carbon cathode material for the lithium ion battery provided by the invention can obviously improve the rate performance and low-temperature performance of the battery, has excellent cycle performance, is cheap in raw materials, mature in preparation process and equipment, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a carbon negative electrode material for a lithium ion battery.
Background
The lithium ion battery has the advantages of good stability, high energy density, no memory effect and the like, and is widely applied to the field of 3C consumer batteries, power batteries and energy storage batteries, the current commercial lithium ion battery negative electrode material mainly comprises a graphite negative electrode, but the theoretical specific capacity of the graphite negative electrode is lower and is only 372mAh/g, and the high-rate continuous charging and discharging capacity and the low-temperature performance are difficult to effectively improve, so that the development of a novel lithium ion battery negative electrode material which is high in specific capacity, excellent in rate performance and good in low-temperature performance is an important direction of current research.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a carbon anode material for a lithium ion battery, the method comprising the steps of:
carbonizing the carbonized raw material in a carbonization furnace filled with inert atmosphere to obtain a first carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 300-500 ℃, and the carbonization time is 4-10 h;
crushing the first carbonized material to 5-10 microns in particle size D50, screening by using a 325-mesh screen, controlling the particle size D10 of the received material to be more than or equal to 1 micron, and obtaining a first mechanical shaping material;
washing the first mechanical shaping material in an acid solution, washing with pure water until the pH value of the solution is 6-8, and drying to obtain purified powder;
carrying out high-temperature carbonization on the purified powder in a carbonization furnace filled with a preset atmosphere to obtain a second carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 1000-1500 ℃, and the carbonization time is 4-10 h;
crushing the second carbonized material to 5-10 microns of granularity D50, screening by using a 325-mesh screen, controlling the received material granularity D10 to be more than or equal to 1 micron, and obtaining a second mechanical shaping material;
covering amorphous carbon formed by thermal decomposition of a carbon source material on the surface of the second mechanical shaping material to obtain a wrapping material;
scattering the coating material until the particle size D50 is 5-10 μm, screening by using a 325-mesh screen, and then demagnetizing to obtain the carbon negative electrode material; wherein the total amount of magnetic substances is less than or equal to 1 ppm.
Preferably, the charring raw material is one or more of a high molecular material or a saccharide.
Preferably, the polymer material is one or more of polyvinyl chloride resin, acrylic resin, phenolic resin, epoxy resin, polyester resin, polyamide resin, bismaleimide, polypropylene polycarbonate, polyether ether ketone or polystyrene.
Preferably, the saccharide is one or more of fructose, mannose, sucrose, glucose, galactose, galactan, amino sugar, ribose, deoxyribose, starch, cellulose, polysaccharide, pectin, pentose, mannose, mannan, chitin, maltose, gum arabic, glycogen or inulin.
Preferably, the acid solution is one or more of carbonic acid, hydrofluoric acid, formic acid, acetic acid, stearic acid, hydrosulfuric acid, hypochlorous acid, oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, perchloric acid, hydroiodic acid, sulfuric acid, hydrobromic acid, hydrochloric acid, or nitric acid.
Preferably, the content of iron element in the purified powder is less than or equal to 10 ppm.
Preferably, the preset atmosphere is one of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, carbon dioxide, a chlorine atmosphere, a hydrogen sulfide atmosphere, a nitrogen dioxide atmosphere, a hydrogen chloride atmosphere, a sulfur dioxide atmosphere, a bromine atmosphere, or a hydrogen bromide atmosphere.
Preferably, the carbon source material is one or more of methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butene, pentane, hexane, citric acid, triose, tetrose, pentose, hexose, glucose, sucrose, asphalt, epoxy resin, phenol resin, furfural resin, acrylic resin, polyvinyl chloride resin, polyether polyester resin, polyamide resin, polyimide resin, formaldehyde resin, polyoxymethylene, polyamide, polysulfone, polyethylene glycol, bismaleimide, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polypropylene, polyacrylonitrile, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, carboxymethyl cellulose, sodium carboxymethyl cellulose, or ammonium carboxymethyl cellulose.
Preferably, the thermal decomposition temperature of the carbon source material is 600 ℃ to 1200 ℃.
Preferably, the amorphous carbon has an average thickness of 10nm to 1000 nm.
The preparation method of the carbon negative electrode material for the lithium ion battery has the following advantages:
(1) the carbon negative electrode material prepared by the invention has high delithiation capacity, in a charge-discharge curve obtained by button cell test, the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 0.8V is more than 320mAh/g, the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 1.1V is more than 400mAh/g, and the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 1.5V is more than 500 mAh/g;
(2) in the carbon negative electrode material prepared by the invention, the carbon coating can reduce the side reaction of the carbon negative electrode material and the electrolyte, reduce the irreversible lithium ion loss, contribute to providing the stability of SEM and simultaneously improve the cycle performance;
(3) in the carbon cathode material prepared by the invention, the carbonized raw material is preferably a substance with higher purity, and the pickling purification process is combined, so that the content of metal impurities and ash in the carbon cathode material is reduced, and the electrochemical performance is favorably improved;
(4) the carbon cathode material prepared by the invention has the advantages of low price of raw materials, mature preparation process and equipment, and suitability for large-scale production;
(5) when the carbon cathode material prepared by the invention is used as a cathode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate of the battery after 2000 cycles under the 2C/1C multiplying power is about 92%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of a carbon negative electrode material prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the carbon negative electrode material prepared in example 1 of the present invention;
fig. 3 is a first charge-discharge curve of a button cell made of carbon negative electrode material according to example 1 of the present invention;
fig. 4 is a cycle curve of the carbon anode material prepared in example 1 of the present invention at a 1C/1C rate in a pouch cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
In an embodiment of the present application, the present invention provides a method for preparing a carbon anode material for a lithium ion battery, the method including the steps of:
carbonizing the carbonized raw material in a carbonization furnace filled with inert atmosphere to obtain a first carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 300-500 ℃, and the carbonization time is 4-10 h;
crushing the first carbonized material to 5-10 microns in particle size D50, screening by using a 325-mesh screen, controlling the particle size D10 of the received material to be more than or equal to 1 micron, and obtaining a first mechanical shaping material;
washing the first mechanical shaping material in an acid solution, washing with pure water until the pH value of the solution is 6-8, and drying to obtain purified powder;
carrying out high-temperature carbonization on the purified powder in a carbonization furnace filled with a preset atmosphere to obtain a second carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 1000-1500 ℃, and the carbonization time is 4-10 h;
crushing the second carbonized material to 5-10 microns of granularity D50, screening by using a 325-mesh screen, controlling the received material granularity D10 to be more than or equal to 1 micron, and obtaining a second mechanical shaping material;
covering amorphous carbon formed by thermal decomposition of a carbon source material on the surface of the second mechanical shaping material to obtain a wrapping material;
scattering the coating material until the particle size D50 is 5-10 μm, screening by using a 325-mesh screen, and then demagnetizing to obtain the carbon negative electrode material; wherein the total amount of magnetic substances is less than or equal to 1 ppm.
In the embodiment of the present application, the carbonized raw material is one or more of a polymer material or a saccharide.
In the embodiment of the present application, the polymer material is one or more of polyvinyl chloride resin, acrylic resin, phenolic resin, epoxy resin, polyester resin, polyamide resin, bismaleimide, polypropylene polycarbonate, polyether ether ketone, or polystyrene.
In the examples herein, the saccharide is one or more of fructose, mannose, sucrose, glucose, galactose, galactan, amino sugar, ribose, deoxyribose, starch, cellulose, polysaccharide, pectin, pentose, mannose, mannan, chitin, maltose, gum arabic, glycogen or inulin.
In embodiments of the present application, the acid solution is one or more of carbonic acid, hydrofluoric acid, formic acid, acetic acid, stearic acid, hydrosulfuric acid, hypochlorous acid, oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, perchloric acid, hydroiodic acid, sulfuric acid, hydrobromic acid, hydrochloric acid, or nitric acid.
In the examples of the present application, the content of elemental iron in the purified powder was 10ppm or less.
In the embodiment of the present application, the predetermined atmosphere is one of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, carbon dioxide, a chlorine atmosphere, a hydrogen sulfide atmosphere, a nitrogen dioxide atmosphere, a hydrogen chloride atmosphere, a sulfur dioxide atmosphere, a bromine atmosphere, or a hydrogen bromide atmosphere.
In the embodiment of the present application, the carbon source material is one or more of methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butene, pentane, hexane, citric acid, triose, tetrose, pentose, hexose, glucose, sucrose, pitch, epoxy resin, phenol resin, furfural resin, acrylic resin, polyvinyl chloride resin, polyether polyester resin, polyamide resin, polyimide resin, formaldehyde resin, polyoxymethylene, polyamide, polysulfone, polyethylene glycol, bismaleimide, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polypropylene, polyacrylonitrile, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, carboxymethyl cellulose, sodium carboxymethyl cellulose, or ammonium carboxymethyl cellulose.
In the embodiment of the application, the thermal decomposition temperature of the carbon source material is 600-1200 ℃.
In the examples of the present application, the amorphous carbon has an average thickness of 10nm to 1000 nm.
In the embodiment of the application, the specific surface area of the carbon negative electrode material is 1m2/g-10m2/g, and the median particle diameter D50 of the carbon negative electrode material is 3 μm-15 μm.
Further, in the embodiment of the present application, the specific surface area of the carbon anode material is further preferably 1m2/g to 7m2/g, and the median particle diameter D50 of the carbon anode material is 5 μm to 10 μm.
In the embodiment of the present application, the inert atmosphere is one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.
In the embodiment of the application, the carbon negative electrode material is not graphitized and has a partially disordered microcrystalline structure, in a charge-discharge curve obtained by a button cell test, the delithiation capacity of the carbon negative electrode material at a 0.8V cut-off voltage is more than 320mAh/g, the delithiation capacity of the carbon negative electrode material at a 1.1V cut-off voltage is more than 400mAh/g, and the delithiation capacity of the carbon negative electrode material at a 1.5V cut-off voltage is more than 500 mAh/g.
Example 1
In an embodiment of the present application, a method for preparing a carbon negative electrode material for a lithium ion battery includes the following steps:
(1) carbonizing starch in nitrogen atmosphere, controlling the initial oxygen content in a carbonization furnace to be less than or equal to 100ppm, the carbonization temperature to be 500 ℃, and the carbonization time to be 4 hours;
(2) crushing and crushing the carbonized material obtained in the step (1), wherein the particle size D50 of the material is 6.1 mu m; sieving with 325 mesh sieve to remove large particles and foreign matters; finally, fine micro powder with the volume content of at least 1 percent is removed through classification, and the material receiving granularity D10 is 1.4 mu m;
(3) placing the material mechanically shaped in the step (2) in a dilute hydrochloric acid solution, repeatedly washing to remove impurities, washing with pure water to obtain a solution with a pH value of 7.4, and drying to obtain purified powder;
(4) carbonizing the raw material at high temperature in nitrogen atmosphere, controlling the initial oxygen content in a carbonization furnace to be less than or equal to 100ppm, the carbonization temperature to be 1100 ℃, and the carbonization time to be 9 h;
(5) crushing and crushing the carbonized material obtained in the step (4), wherein the particle size D50 of the material is 6.6 mu m; sieving with 325 mesh sieve to remove large particles and foreign matters; finally, fine micro powder with the volume content of at least 1 percent is removed through classification, and the material receiving granularity D10 is 1.7 mu m;
(6) and (5) placing the material subjected to the mechanical shaping in the step two in a vapor deposition furnace, introducing nitrogen for protection, heating to 700 ℃ at the heating rate of 3 ℃/min, introducing methane for vapor deposition, and depositing for 4 hours to form the amorphous carbon coating.
(7) Scattering the coating material obtained in the step (6), wherein the material receiving granularity D50 is 6.6 mu m; sieving with 325 mesh sieve to remove large particles and foreign matters; finally, the total amount of magnetic substances of the obtained material is 0.23ppm by demagnetization.
Example 2
The difference from example 1 is that the carbonized material in step (1) is a phenol resin, and a carbon negative electrode material was obtained in the same manner as in example 1.
Example 3
The difference from the embodiment 1 is that after the carbonized material is crushed and smashed in the step (2), the grain size of the received material D50 is 9.5 μm; sieving with 325 mesh sieve to remove large particles and foreign matters; finally, fine micro powder with the volume content of at least 1 percent is removed through classification, and the D10 of the material receiving granularity is 2.3 mu m. The rest was the same as example 1 to obtain a carbon negative electrode material.
Example 4
The difference from the example 1 is that the step (4) high temperature carbonization: performing high-temperature carbonization on the material subjected to acid cleaning and purification in the step (3) in an argon atmosphere, controlling the initial oxygen content in a carbonization furnace to be less than or equal to 100ppm, controlling the carbonization temperature to be 1400 ℃, and controlling the carbonization time to be 5 hours; the rest was the same as example 1 to obtain a carbon negative electrode material.
Example 5
The difference from example 1 is that in the surface coating process in step (6), the thermal decomposition carbon source used is asphalt, the thermal decomposition temperature is 1000 ℃, and the thermal decomposition atmosphere is nitrogen atmosphere. The rest was the same as example 1 to obtain a carbon negative electrode material.
Comparative example 1
The difference from example 1 is that in step (1), the raw material is carbonized in an air atmosphere, and the rest is the same as example 1, and the description is omitted.
Comparative example 2
The difference from example 1 is that in step (2), the carbonized material obtained in step (1) is crushed and pulverized, the received material particle size D50 is 3.2 μm, and fine micro powder is not removed by classification, which is the same as example 1 and is not repeated here.
Comparative example 3
The difference from example 1 is that in step (2), the carbonized material obtained in step (1) is crushed and pulverized, the received material particle size D50 is 14.5 μm, and fine micro powder is not removed by classification, which is the same as example 1 and is not repeated here.
Example 4
The difference from example 1 is that step (3) is not carried out, i.e. the material from step (2) is not purified by acid washing. The rest was the same as example 1 to obtain a carbon negative electrode material.
Example 5
The difference from example 1 is that the carbonization temperature in step (4) was 800 ℃. The rest was the same as example 1 to obtain a carbon negative electrode material.
Example 6
The difference from example 1 is that the carbonization temperature in step (4) was 1700 ℃. The rest was the same as example 1 to obtain a carbon negative electrode material.
Example 7
The difference from example 1 is that step (6) was not performed, i.e., the surface of the material was not coated with amorphous carbon. The rest was the same as example 1 to obtain a carbon negative electrode material.
Example 8
The difference from example 1 is that demagnetization is not performed in step (7). The rest was the same as example 1 to obtain a carbon negative electrode material.
The carbon negative electrode materials in examples 1 to 5 and comparative examples 1 to 5 were tested by the following methods:
the material particle size range was tested using a malvern laser particle sizer Mastersizer 3000.
The material was subjected to morphological analysis using a JSM-7160 scanning electron microscope from Japan Electron corporation.
The material was subjected to phase analysis using an XRD diffractometer (X' Pert3 Powder) to determine the grain size of the material.
The material was tested for specific surface area using the american conta NOVA 4000 e.
The carbon negative electrode material obtained in the embodiments 1 to 5 and the comparative examples 1 to 5 is mixed in pure water according to the mass ratio of 92:3:5 of the carbon material, the conductive carbon black and the binder, homogenized, the solid content is controlled to be 45%, the mixture is coated on a copper foil current collector, vacuum baking is carried out for 12 hours at the temperature of 110-120 ℃, and the negative electrode pole piece is prepared through punching after compression molding. The button cells were assembled in an argon-filled glove box, the counter electrode was a metallic lithium plate, the separator used was Celgard2400 and the electrolyte was 1mol/L EC/DMC from LiPF6 (Vol 1: 1). And (3) performing charge and discharge tests on the button cell, wherein the voltage interval is 0.005V-1.5V, and the current density is 80 mA/g. The first reversible capacity and efficiency of the carbon anode materials in examples and comparative examples were measured.
The carbon negative electrode material in example 1 was evaluated using a pouch full cell, wherein the positive electrode was a mature ternary positive electrode sheet, 1mol/L LiPF6/EC + DMC + EMC (v/v ═ 1:1:1) electrolyte, and a Celgard2400 separator. On a LanD battery test system of Wuhanjinnuo electronics Limited company, the electrochemical performance of the prepared soft package battery is tested, and the test conditions are as follows: and (3) charging and discharging at a constant current of 1.0 ℃ at normal temperature, wherein the charging and discharging voltage is limited to 2.75V-4.2V.
The testing equipment of the button cell and the soft package battery is a LAND battery testing system of Wuhanjinnuo electronic Co.
Results of performance test of the carbon anode materials of examples 1 to 5 and comparative examples 1 to 8:
table 1 electrochemical performance test data of the carbon anode materials in examples 1 to 5 and comparative examples 1 to 8:
as can be seen from table 1, the carbon negative electrode material prepared by the method of the present application can exert high lithium removal capacity at a high potential of 1.5V, and also has high lithium removal capacity at low potentials of 1.1V and 0.8V, so as to meet the performance requirements of the battery in practical use conditions.
In examples 1 to 5, the electrochemical performance of the carbon negative electrode material was greatly affected by changing the type of the carbon material, the particle size, the calcination temperature, the coating method, and the like. The carbon cathode material prepared by different raw materials has different internal structures and pores, and different electrochemical performances. The particle size greatly influences the migration rate of lithium ions, and when the particle size is higher than the upper limit, the cycle performance is slightly reduced. The calcination atmosphere also causes a slight difference in performance, possibly due to adsorption of atmospheric atoms on the particle surface, which causes a difference in electrochemical performance. The coated amorphous carbon has a large influence on the electrochemical performance, and the capacity exertion and the cycle performance of the carbon negative electrode material are reduced to a certain extent after the carbon negative electrode material is replaced by the asphalt solid phase coating.
In comparative example 1, the initial raw material carbonization was performed in an air atmosphere, which resulted in severe material oxidation, greatly reduced delithiation capacity, and significant cycle performance reduction.
In comparative examples 2 to 3, the particle size of the crushed and pulverized carbonized material was outside the range of the claims, and the fine powder was not removed by classification, and the lithium removal capacity of the obtained carbon negative electrode material was significantly low, because the particle size was too small or too large, which would be detrimental to the electrochemical performance, and the non-classified fine powder resulted in increased side reactions during charging and discharging, and increased irreversible lithium ion loss.
In comparative example 4, the electrochemical performance of the composite negative electrode material is obviously affected by the magnetic foreign matters with higher inevitable content in the material without acid cleaning and purification, and the capacity retention rate of the soft package battery after 2C/1C circulation for 2000 weeks is only 77.8%.
In comparative examples 5 to 6, the carbonization temperatures were 800 ℃ and 1700 ℃, respectively, and the carbonization temperatures exceeded the ranges of the claims, the lithium removal capacity of the obtained carbon negative electrode material was significantly deteriorated, and the cycle performance was also somewhat lowered. The carbonization process is crucial to capacity exertion, and the electrochemical performance of the carbon cathode material can be greatly and obviously influenced no matter the temperature is too low or too high.
In comparative example 7, the surface of the material is not coated with amorphous carbon, the cycle performance of the obtained carbon negative electrode material is obviously reduced, and the capacity retention rate of the soft-package battery for 2C/1C cycle of 2000 weeks is 62.7%.
In comparative example 8, demagnetization was not performed, the magnetic foreign matter of the obtained carbon negative electrode material was high, and local micro short circuit was easily formed during charge and discharge, which resulted in deterioration of cycle performance and acceleration of battery failure.
The preparation method of the carbon negative electrode material for the lithium ion battery has the following advantages:
(1) the carbon negative electrode material prepared by the invention has high delithiation capacity, in a charge-discharge curve obtained by button cell test, the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 0.8V is more than 320mAh/g, the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 1.1V is more than 400mAh/g, and the delithiation capacity of the carbon negative electrode material at a cut-off voltage of 1.5V is more than 500 mAh/g;
(2) in the carbon negative electrode material prepared by the invention, the carbon coating can reduce the side reaction of the carbon negative electrode material and the electrolyte, reduce the irreversible lithium ion loss, contribute to providing the stability of SEM and simultaneously improve the cycle performance;
(3) in the carbon cathode material prepared by the invention, the carbonized raw material is preferably a substance with higher purity, and the pickling purification process is combined, so that the content of metal impurities and ash in the carbon cathode material is reduced, and the electrochemical performance is favorably improved;
(4) the carbon cathode material prepared by the invention has the advantages of low price of raw materials, mature preparation process and equipment, and suitability for large-scale production;
(5) when the carbon cathode material prepared by the invention is used as a cathode active material of a lithium ion battery, the cycle performance of the battery can be obviously improved, and the capacity retention rate of the battery after 2000 cycles under the 2C/1C multiplying power is about 92%.
The preparation method of the carbon cathode material for the lithium ion battery provided by the invention can obviously improve the rate performance and low-temperature performance of the battery, has excellent cycle performance, is cheap in raw materials, mature in preparation process and equipment, and is suitable for large-scale production.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A method for preparing a carbon negative electrode material for a lithium ion battery, comprising the steps of:
carbonizing the carbonized raw material in a carbonization furnace filled with inert atmosphere to obtain a first carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 300-500 ℃, and the carbonization time is 4-10 h;
crushing the first carbonized material to 5-10 microns in particle size D50, screening by using a 325-mesh screen, controlling the particle size D10 of the received material to be more than or equal to 1 micron, and obtaining a first mechanical shaping material;
washing the first mechanical shaping material in an acid solution, washing with pure water until the pH value of the solution is 6-8, and drying to obtain purified powder;
carrying out high-temperature carbonization on the purified powder in a carbonization furnace filled with a preset atmosphere to obtain a second carbonized material; wherein the initial oxygen content in the carbonization furnace is less than or equal to 100ppm, the carbonization temperature is 1000-1500 ℃, and the carbonization time is 4-10 h;
crushing the second carbonized material to 5-10 microns of granularity D50, screening by using a 325-mesh screen, controlling the received material granularity D10 to be more than or equal to 1 micron, and obtaining a second mechanical shaping material;
covering amorphous carbon formed by thermal decomposition of a carbon source material on the surface of the second mechanical shaping material to obtain a wrapping material;
scattering the coating material until the particle size D50 is 5-10 μm, screening by using a 325-mesh screen, and then demagnetizing to obtain the carbon negative electrode material; wherein the total amount of magnetic substances is less than or equal to 1 ppm.
2. The method for producing a carbon negative electrode material for a lithium ion battery according to claim 1, wherein the carbonized material is one or more of a polymer material and a saccharide.
3. The method for preparing a carbon negative electrode material for a lithium ion battery according to claim 2, wherein the polymer material is one or more of polyvinyl chloride resin, acrylic resin, phenol resin, epoxy resin, polyester resin, polyamide resin, bismaleimide, polypropylene polycarbonate, polyether ether ketone, or polystyrene.
4. The method for producing a carbon negative electrode material for a lithium ion battery according to claim 2, wherein the saccharide is one or more of fructose, mannose, sucrose, glucose, galactose, galactan, an amino sugar, ribose, deoxyribose, starch, cellulose, polysaccharide, pectin, pentose, mannose, mannan, chitin, maltose, gum arabic, a glycogen, and inulin.
5. The method of claim 1, wherein the acid solution is one or more of carbonic acid, hydrofluoric acid, formic acid, acetic acid, stearic acid, hydrosulfuric acid, hypochlorous acid, oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, perchloric acid, hydroiodic acid, sulfuric acid, hydrobromic acid, hydrochloric acid, or nitric acid.
6. The method for producing a carbon negative electrode material for a lithium ion battery according to claim 1, wherein the content of iron element in the purified powder is 10ppm or less.
7. The method according to claim 1, wherein the predetermined atmosphere is one of a nitrogen atmosphere, an argon atmosphere, a helium atmosphere, carbon dioxide, a chlorine atmosphere, a hydrogen sulfide atmosphere, a nitrogen dioxide atmosphere, a hydrogen chloride atmosphere, a sulfur dioxide atmosphere, a bromine gas atmosphere, or a hydrogen bromide atmosphere.
8. The method for producing a carbon negative electrode material for a lithium ion battery according to claim 1, wherein the carbon source material is one or more of methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butene, pentane, hexane, citric acid, triose, tetrose, pentose, hexose, glucose, sucrose, asphalt, epoxy resin, phenol resin, furfural resin, acrylic resin, polyvinyl chloride resin, polyether polyester resin, polyamide resin, polyimide resin, formaldehyde resin, polyoxymethylene, polyamide, polysulfone, polyethylene glycol, bismaleimide, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polypropylene, polyacrylonitrile, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, carboxymethylcellulose, sodium carboxymethylcellulose, or ammonium carboxymethylcellulose.
9. The method for preparing a carbon negative electrode material for a lithium ion battery according to claim 1, wherein the thermal decomposition temperature of the carbon source material is 600 ℃ to 1200 ℃.
10. The method of preparing a carbon negative electrode material for a lithium ion battery according to claim 1, wherein the amorphous carbon has an average thickness of 10nm to 1000 nm.
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