CN113130876A - Preparation method and application of acid-modified spherical natural graphite negative electrode material - Google Patents
Preparation method and application of acid-modified spherical natural graphite negative electrode material Download PDFInfo
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Abstract
The invention discloses a method for preparing an acid modified spherical natural graphite cathode material, which belongs to the field of cathode materials of lithium ion power batteries and is provided based on the problem of poor high-temperature performance of the conventional graphite cathode material. The invention uses spherical naturalGraphite as raw material, H2SO4Carrying out oxidation modification on the graphite, then carrying out coating modification on the graphite by using a precursor, and exploring the optimal coating conditions through the processes of pre-curing, carbonization, ball milling, sieving and the like to prepare the spherical natural graphite cathode material with improved high-temperature performance; the prepared oxidized modified spherical natural graphite negative electrode material is used as a raw material for preparing electrode slurry, the electrode slurry is coated on copper foil to prepare electrode slices, the electrode slices are assembled into a button cell, tests show that the prepared modified spherical natural graphite negative electrode material has the best high-temperature performance under the condition that the mass of a precursor is 9% of that of spherical natural graphite, the first charge-discharge efficiency of the prepared cell reaches 94%, and the charge-discharge efficiency after 5 times of circulation is 99.41%.
Description
Technical Field
The invention relates to the field of negative electrode materials of lithium ion power batteries, in particular to a preparation method and application of an acid modified spherical natural graphite negative electrode material.
Background
Graphite is the mainstream commercial lithium battery negative electrode material at present, but due to the restriction of the structural characteristics of graphite, the development of the graphite negative electrode material also meets the bottleneck, for example, the specific capacity reaches the limit, the continuous large-current discharge capacity required by a large-scale power battery cannot be met, the high-temperature performance is poor, and the like. The natural graphite can not be directly used as a lithium ion battery cathode material, and the most main reason is that in the charging process, the phenomenon that solvent molecules are co-inserted into a graphite sheet layer along with lithium ions to cause graphite layer peeling can occur, so that the structure is damaged to cause the rapid deterioration of the electrode cycle performance. Therefore, in order to prepare a graphite negative electrode material with good high-temperature performance, modification research needs to be carried out on the graphite negative electrode material.
Many studies are currently made on modification treatment of natural graphite, including mechanical grinding, oxidation treatment, surface coating, doping, and the like. Patent CN111960413A discloses a modification method of natural graphite negative electrode material, which is to purify natural crystalline flake graphite at high temperature under the protection of nitrogen; crushing the purified graphite, and performing spheroidization modification to obtain spherical graphite; soaking the spherical graphite in a mixed solution of ethylenediamine and ammonia water, stirring, washing and drying; mixing the dried graphite with asphalt, ball-milling, mixing and coating, and then carrying out carbonization treatment under the protection of inert gas to obtain the modified natural graphite cathode material. Patent CN108751187A discloses a preparation method of an acid-modified spherical natural graphite negative electrode material, in which natural graphite is dispersed in an acid solution to obtain a dispersion a; separating out solid in the dispersion liquid a, and drying to obtain solid material b; and (4) heating, carbonizing the solid material b, and crushing to obtain the acid modified spherical natural graphite negative electrode material.
Disclosure of Invention
The invention aims to solve the technical problem that the existing graphite cathode material is poor in high-temperature performance.
The invention solves the technical problems through the following technical means:
a method for preparing an acid modified spherical natural graphite negative electrode material comprises the following steps:
(1) placing spherical natural graphite in H2SO4In the water solution, the spherical natural graphite is fully dispersed in H by ultrasonic stirring for 2 to 12 hours2SO4In the aqueous solution, the prepared aqueous solution is placed at 0-120 ℃ and stirred for 2-12h, suction filtration is carried out, and a filter cake is taken and dried in a drying oven at 60-100 ℃ to obtain the acid modified spherical natural graphite cathode material;
(2) weighing a precursor, wherein the mass of the precursor is 1-20% of that of the spherical natural graphite, stirring and dissolving the precursor in absolute ethyl alcohol, stirring for 3-8h to completely dissolve the precursor, and performing suction filtration to obtain a filtrate;
(3) adding the acid-modified spherical natural graphite negative electrode material obtained in the step (1) into the filtrate obtained in the step (2), stirring for 3-12h, placing into a drying oven, and drying at 60-100 ℃;
(4) putting the dried sample into a tube furnace, and carbonizing at 600-1600 ℃ for 1-10h at a heating rate of 0.1-10 ℃/min under an argon atmosphere;
(5) and ball-milling the carbonized sample in a ball mill at 800r/min for 1-2h, and then sieving with a 200-600 mesh sieve to obtain the oxidation modified spherical natural graphite cathode material.
The invention takes spherical natural graphite as raw material and H2SO4The spherical natural graphite negative electrode material with improved high-temperature performance is prepared by carrying out oxidation modification on the spherical natural graphite negative electrode material, then carrying out coating modification on the spherical natural graphite negative electrode material by using a precursor, and exploring the optimal coating conditions through the processes of pre-curing, carbonization, ball milling, sieving and the like.
Preferably, H in said step (1)2SO4The molar mass of the aqueous solution is 1-5M.
Preferably, the mass of the acid solution in the step (1) is 5-50% of the mass of the spherical natural graphite.
Preferably, the prepared aqueous solution is stirred at 0 ℃ for 3-5h in the step (1).
Preferably, the precursor in step (2) comprises phenolic resin or coal pitch.
Preferably, the ball milling speed in the step (5) is 300-.
Preferably, the ball milling time in the step (5) is 1-1.5 h.
Preferably, the step (5) is carried out by a 400-mesh and 600-mesh sieve.
A lithium ion battery comprises electrode slurry and copper foil, wherein the electrode slurry comprises the oxidized modified spherical natural graphite negative electrode material.
Further, the preparation method of the lithium ion battery comprises the following steps:
(a) preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil;
(b) preparing 100mg/mL polyvinylidene fluoride solution by taking N-methyl pyrrolidone as a solvent, mixing an oxidized modified spherical natural graphite negative electrode material, carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry;
(c) uniformly coating the prepared electrode slurry on the copper foil treated in the step (a), and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice;
(d) and (c) vertically wrapping the electrode plate prepared in the step (c) by using the copper foil treated in the step (a), putting the electrode plate into a flat, rigid and clean die, performing compression molding under the pressure of 10Mpa, and then assembling the electrode plate into a battery in an argon-filled glove box.
The invention has the following beneficial effects:
1. the invention takes spherical natural graphite as raw material and H2SO4Subjecting it to oxygenAnd coating and modifying the modified graphite by using a precursor, and exploring the optimal coating conditions through the processes of pre-curing, carbonization, ball milling, sieving and the like to prepare the spherical natural graphite cathode material with improved high-temperature performance.
2. According to the invention, the prepared oxidized modified spherical natural graphite cathode material is used as a raw material for preparing electrode slurry, the electrode slurry is coated on copper foil to prepare electrode slices, and the electrode slices are assembled into the button cell, so that the high-temperature performance of the prepared modified spherical natural graphite cathode material is best under the condition that the mass of a precursor is 9% of that of spherical natural graphite, the first charge-discharge efficiency of the prepared cell reaches 94%, and the charge-discharge efficiency after 5 times of circulation is 99.41%.
Drawings
Fig. 1 is a charge and discharge performance test chart of button half cells prepared in examples 1 to 4 of the present invention and comparative example 1 at a rate of 0.2C.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings and the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A method for preparing an acid modified spherical natural graphite negative electrode material comprises the following steps:
(1) preparation of 2M H2SO4200mL of aqueous solution, and 20g of spherical natural graphite is weighed to prepare H2SO4Ultrasonically stirring the aqueous solution in distilled water for 2 hours to completely disperse the spherical natural graphite in H2SO4In the water solution, the prepared water solution is placed at 0 ℃ and stirred for 2H, the filtration is carried out, the filter cake is taken out and dried in a 60 ℃ oven, and H is obtained2SO4Modified spherical natural graphite negative electrode material;
(2) weighing 1g of phenolic resin, stirring and dissolving in 50mL of absolute ethyl alcohol, stirring for 5H to completely dissolve the phenolic resin, carrying out suction filtration, taking filtrate, and mixing with H2SO4Adding the oxidized and modified spherical natural graphite into a beaker containing the filtrate, stirring for 10 hours, putting into an oven, and drying at 80 ℃;
(3) putting the dried sample into a tubular furnace, and carbonizing at 900 ℃ for 3 hours at a heating rate of 5 ℃/min under the argon atmosphere;
(4) and ball-milling the carbonized sample in a ball mill at 400r/min for 1h, and then sieving the ball by a 400-mesh sieve. Obtaining the spherical natural graphite cathode material after oxidation coating modification.
Preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil; preparing 100mg/mL polyvinylidene fluoride solution by taking N-methylpyrrolidone as a solvent, mixing the oxidized modified spherical natural graphite negative electrode material prepared in the embodiment with carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry; uniformly coating the prepared electrode slurry on the treated copper foil, and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice; wrapping the electrode plate with the treated copper foil, placing in a flat, rigid and clean mold, press-molding under 10Mpa pressure, and assembling the button-type half cell in an argon-filled glove box.
Example 2
A method for preparing an acid modified spherical natural graphite negative electrode material comprises the following steps:
(1) preparation of 2M H2SO4200mL of the aqueous solution, and 20g of spherical natural stoneInk preparation H2SO4Ultrasonically stirring the aqueous solution in distilled water for 2 hours to completely disperse the spherical natural graphite in H2SO4In the water solution, the prepared water solution is placed at 0 ℃ and stirred for 2H, the filtration is carried out, the filter cake is taken out and dried in a 60 ℃ oven, and H is obtained2SO4Modified spherical natural graphite negative electrode material;
(2) weighing 1.8g of phenolic resin, stirring and dissolving in 50mL of absolute ethyl alcohol, stirring for 5H to completely dissolve the phenolic resin, carrying out suction filtration, taking filtrate, and mixing with H2SO4Adding the oxidized and modified spherical natural graphite into a beaker containing the filtrate, stirring for 10 hours, putting into an oven, and drying at 80 ℃;
(3) putting the dried sample into a tubular furnace, and carbonizing at 900 ℃ for 3 hours at a heating rate of 5 ℃/min under the argon atmosphere;
(4) and ball-milling the carbonized sample in a ball mill at 400r/min for 1h, and then sieving the ball by a 400-mesh sieve. Obtaining the spherical natural graphite cathode material after oxidation coating modification.
Preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil; preparing 100mg/mL polyvinylidene fluoride solution by taking N-methylpyrrolidone as a solvent, mixing the oxidized modified spherical natural graphite negative electrode material prepared in the embodiment with carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry; uniformly coating the prepared electrode slurry on the treated copper foil, and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice; wrapping the electrode plate with the treated copper foil, placing in a flat, rigid and clean mold, press-molding under 10Mpa pressure, and assembling the button-type half cell in an argon-filled glove box.
Example 3
A method for preparing an acid modified spherical natural graphite negative electrode material comprises the following steps:
(1) preparation of 2M H2SO4Dissolving in water200mL of the solution, 20g of spherical natural graphite is weighed to prepare H2SO4Ultrasonically stirring the aqueous solution in distilled water for 2 hours to completely disperse the spherical natural graphite in H2SO4In the water solution, the prepared water solution is placed at 0 ℃ and stirred for 2H, the filtration is carried out, the filter cake is taken out and dried in a 60 ℃ oven, and H is obtained2SO4Modified spherical natural graphite negative electrode material;
(2) weighing 2.6g of phenolic resin, stirring and dissolving in 50mL of absolute ethyl alcohol, stirring for 5H to completely dissolve the phenolic resin, carrying out suction filtration, taking filtrate, and mixing with H2SO4Adding the oxidized and modified spherical natural graphite into a beaker containing the filtrate, stirring for 10 hours, putting into an oven, and drying at 80 ℃;
(3) putting the dried sample into a tubular furnace, and carbonizing at 900 ℃ for 3 hours at a heating rate of 5 ℃/min under the argon atmosphere;
(4) and ball-milling the carbonized sample in a ball mill at 400r/min for 1h, and then sieving the ball by a 400-mesh sieve. Obtaining the spherical natural graphite cathode material after oxidation coating modification.
Preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil; preparing 100mg/mL polyvinylidene fluoride solution by taking N-methylpyrrolidone as a solvent, mixing the oxidized modified spherical natural graphite negative electrode material prepared in the embodiment with carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry; uniformly coating the prepared electrode slurry on the treated copper foil, and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice; wrapping the electrode plate with the treated copper foil, placing in a flat, rigid and clean mold, press-molding under 10Mpa pressure, and assembling the button-type half cell in an argon-filled glove box.
Example 4
A method for preparing an acid modified spherical natural graphite negative electrode material comprises the following steps:
(1) preparation 2H of M2SO4200mL of aqueous solution, and 20g of spherical natural graphite is weighed to prepare H2SO4Ultrasonically stirring the aqueous solution in distilled water for 2 hours to completely disperse the spherical natural graphite in H2SO4In the water solution, the prepared water solution is placed at 0 ℃ and stirred for 2H, the filtration is carried out, the filter cake is taken out and dried in a 60 ℃ oven, and H is obtained2SO4Modified spherical natural graphite negative electrode material;
(2) weighing 3.4g of phenolic resin, stirring and dissolving in 50mL of absolute ethyl alcohol, stirring for 5H to completely dissolve the phenolic resin, carrying out suction filtration, taking filtrate, and mixing with H2SO4Adding the oxidized and modified spherical natural graphite into a beaker containing the filtrate, stirring for 10 hours, putting into an oven, and drying at 80 ℃;
(3) putting the dried sample into a tubular furnace, and carbonizing at 900 ℃ for 3 hours at a heating rate of 5 ℃/min under the argon atmosphere;
(4) and ball-milling the carbonized sample in a ball mill at 400r/min for 1h, and then sieving the ball by a 400-mesh sieve. Obtaining the spherical natural graphite cathode material after oxidation coating modification.
Preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil; preparing 100mg/mL polyvinylidene fluoride solution by taking N-methylpyrrolidone as a solvent, mixing the oxidized modified spherical natural graphite negative electrode material prepared in the embodiment with carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry; uniformly coating the prepared electrode slurry on the treated copper foil, and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice; wrapping the electrode plate with the treated copper foil, placing in a flat, rigid and clean mold, press-molding under 10Mpa pressure, and assembling the button-type half cell in an argon-filled glove box.
Comparative example 1
This comparative example differs from examples 1-4 in that: preparation of only H2SO4After modificationThe spherical natural graphite cathode material does not contain H2SO4And coating the modified spherical natural graphite negative electrode material.
Preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil; preparing 100mg/mL polyvinylidene fluoride solution by taking N-methyl pyrrolidone as a solvent, and reacting H2SO4Mixing the modified spherical natural graphite negative electrode material with carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry; uniformly coating the prepared electrode slurry on the treated copper foil, and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice; wrapping the electrode plate with the treated copper foil, placing in a flat, rigid and clean mold, press-molding under 10Mpa pressure, and assembling the button-type half cell in an argon-filled glove box.
The batteries prepared in examples 1 to 4 and the battery prepared in comparative example 1 were respectively subjected to charge and discharge performance tests at a rate of 0.2C using the bond battery test system, and the results are shown in table 1.
Table 1 shows the charge and discharge performance test of the batteries of examples 1 to 4 and comparative example 1
The test data in the above table show that the present invention uses spherical natural graphite as a raw material and H2SO4Carrying out oxidation modification on the graphite, then carrying out coating modification on the graphite by using a precursor, and exploring the optimal coating conditions through the processes of pre-curing, carbonization, ball milling, sieving and the like to prepare the spherical natural graphite cathode material with improved high-temperature performance; the prepared oxidation modified spherical natural graphite cathode material is used as a raw material for preparing electrode slurry, the electrode slurry is coated on copper foil to prepare electrode slices, the electrode slices are assembled into a button cell, and tests show that when the mass of a precursor is sphericalUnder the condition that the mass of the natural graphite is 9%, the prepared modified spherical natural graphite cathode material has the best high-temperature performance, the first charge-discharge efficiency of the prepared battery reaches 94%, and the charge-discharge efficiency after 5 times of circulation is 99.41%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the acid modified spherical natural graphite negative electrode material is characterized by comprising the following steps of:
(1) placing spherical natural graphite in H2SO4In the water solution, the spherical natural graphite is fully dispersed in H by ultrasonic stirring for 2 to 12 hours2SO4In the aqueous solution, the prepared aqueous solution is placed at 0-120 ℃ and stirred for 2-12h, suction filtration is carried out, and a filter cake is taken and dried in a drying oven at 60-100 ℃ to obtain the acid modified spherical natural graphite cathode material;
(2) weighing a precursor, wherein the mass of the precursor is 1-20% of that of the spherical natural graphite, stirring and dissolving the precursor in absolute ethyl alcohol, stirring for 3-8h to completely dissolve the precursor, and performing suction filtration to obtain a filtrate;
(3) adding the acid-modified spherical natural graphite negative electrode material obtained in the step (1) into the filtrate obtained in the step (2), stirring for 3-12h, placing into a drying oven, and drying at 60-100 ℃;
(4) putting the dried sample into a tube furnace, and carbonizing at 600-1600 ℃ for 1-10h at a heating rate of 0.1-10 ℃/min under an argon atmosphere;
(5) and ball-milling the carbonized sample in a ball mill at 800r/min for 1-2h, and then sieving with a 200-600 mesh sieve to obtain the oxidation modified spherical natural graphite cathode material.
2. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: h in the step (1)2SO4The molar mass of the aqueous solution is 1-5M.
3. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: in the step (1), the mass of the acid solution is 5-50% of that of the spherical natural graphite.
4. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: and (2) in the step (1), the prepared aqueous solution is placed at 0 ℃ and stirred for 3-5 h.
5. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: the precursor in the step (2) comprises phenolic resin or coal pitch.
6. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: the ball milling speed in the step (5) is 300-500 r/min.
7. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: the ball milling time in the step (5) is 1-1.5 h.
8. The method for preparing the acid-modified spherical natural graphite negative electrode material according to claim 1, wherein the method comprises the following steps: and (5) sieving with a sieve of 400-600 meshes.
9. A lithium ion battery, characterized by: comprising an electrode slurry and a copper foil, the electrode slurry comprising the oxidized modified spherical natural graphite negative electrode material according to claim 1.
10. The lithium ion battery of claim 9, wherein the method of making the lithium ion battery comprises the steps of:
(a) preparing a plurality of copper foils with the diameter of 8mm and the thickness of 15 um; placing the copper foil in a dilute hydrochloric acid solution for ultrasonic cleaning for 3-5min, and then placing the copper foil in an acetone solution for ultrasonic cleaning for 3-5 min; taking out the copper foil from the acetone solution, respectively cleaning the copper foil by using deionized water and alcohol, and then drying and weighing the copper foil;
(b) preparing 100mg/mL polyvinylidene fluoride solution by taking N-methyl pyrrolidone as a solvent, mixing an oxidized modified spherical natural graphite negative electrode material, carbon black and polyvinylidene fluoride according to the mass ratio of 93:2:5, grinding to uniformly mix the materials, and preparing electrode slurry;
(c) uniformly coating the prepared electrode slurry on the copper foil treated in the step (a), and performing vacuum drying at 70 ℃ for 24 hours to prepare an electrode slice;
(d) and (c) vertically wrapping the electrode plate prepared in the step (c) by using the copper foil treated in the step (a), putting the electrode plate into a flat, rigid and clean die, performing compression molding under the pressure of 10Mpa, and then assembling the electrode plate into a battery in an argon-filled glove box.
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Application publication date: 20210716 |