CN114975925A - Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof - Google Patents
Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof Download PDFInfo
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a phosphorus-graphene doped composite graphite cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: adding a phosphorus source and graphene into an organic solvent to obtain a mixed solution A; adding the mixed solution A and graphite into a mixing device to obtain mixed solution B; putting the mixed solution B into heat treatment equipment for heat treatment to obtain a treated material C; and (4) loading the treated material C into graphite equipment for heat treatment to obtain the graphite cathode material. According to the preparation method, the phosphorus source is combined with the graphene, so that the defects of low initial efficiency, small tap density and the like of the graphene are overcome, the advantages of high conductivity, large mechanical strength and the like of the graphene are utilized, the multiplying power performance and the cycle stability of the cathode material can be effectively improved through the doping mode of the non-metal elements of the phosphorus source, the problems of low ionic conductivity, large resistance and the like of nitrogen-doped graphite in the traditional technology are solved, and the multiplying power performance and the cycle stability of the cathode material can be further improved.
Description
Technical Field
The invention relates to the technical field of new energy lithium ion battery cathode materials, in particular to a phosphorus-graphene doped composite graphite cathode material and a preparation method thereof.
Background
The traditional graphite cathode can not meet the increasing demand of high-performance power supply, therefore, the method for modifying graphite is actively explored at home and abroad to improve the capacity, the cycling stability and the high rate performance of the graphite cathode. Many factors have been shown to affect the behavior of graphite electrodes.
Proper elements are selected for doping in the graphite cathode so as to regulate and control the microstructure and the electronic structure of the graphite, the electron and ion transfer efficiency of the graphite is effectively improved, and element doping can be divided into metal element doping and non-metal element doping according to element types. At present, the commonly used metal elements include Fe, Co, Ni, Cu, Zn, Ag, etc. The doping of metal elements can improve the electronic conductivity of the graphite cathode, and some metal elements such as Sn can form an active composite material with graphite to increase lithium ion storage active sites, thereby improving the capacity. Besides metal elements, there are also some doping of non-metal elements, such as B, N, P, S, Si, etc.; there are related researchers using H 3 BO 3 B doping is carried out, the first coulombic efficiency is effectively improved, and a plurality of researchers use Si doping to prepare graphite nanosheets, so that the reversible capacity of the electrode can be greatly improved. Therefore, the doping of the non-metal elements can effectively improve the rate capability, the cycling stability and the capacity of the electrode.
Phosphorus has a high theoretical specific capacity (2596 mA.hg) -1 ，6075mAh.cm -3 ) And the advantages of moderate and safe lithium intercalation potential (0.7Vvs. Li +/Li) make it an ideal fast-charging type power battery cathode material.
Phosphorus has also been studied recently by related researchers, and the high theoretical specific capacity and excellent electronic conductivity of black phosphorus make black phosphorus considered as an excellent lithium ion battery negative electrode material, and show great potential in preparing high-capacity and high-rate lithium ion batteries. However, in practical applications it was found that with Li + The black phosphorus is easy to expand due to continuous insertion and separation, resulting in fast capacity attenuation, low coulombic efficiency and reversible capacityThe amount is small, and the like. Consequently, researchers have attempted to combine black phosphorus with other materials to build black phosphorus-based composites to address the problem of volume expansion during cycling.
Graphene is a novel negative electrode material developed in recent years, has the advantages of high conductivity, high mechanical strength and the like, is applied to the fields of lithium ion battery negative electrode materials, conductive agents and the like, but has the defects of low efficiency, low tap density and the like for the first time, and limits the application of graphene in the aspect of lithium ion batteries. At present, graphite doped with non-metallic elements such as phosphorus and the like, namely graphene, is not available, and a high-performance graphite negative electrode material is prepared.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the present invention is to provide a preparation method of a phosphorus-graphene doped composite graphite negative electrode material, wherein a non-metallic element and graphene are mixed and then doped into graphite, so that the obtained graphite negative electrode material has high cycle performance and high rate.
The invention also aims to provide the phosphorus-graphene doped composite graphite negative electrode material prepared by the preparation method.
One of the purposes of the invention is realized by adopting the following technical scheme:
a preparation method of a phosphorus-graphene doped composite graphite negative electrode material comprises the following preparation steps:
s1: adding a phosphorus source and graphene into an organic solvent, and uniformly mixing to obtain a mixed solution A;
s2: adding the mixed solution A and graphite into a mixing device, and uniformly dispersing to obtain a mixed solution B;
s3: putting the mixed solution B into heat treatment equipment for heat treatment or putting the mixed solution B into carbonization equipment for direct carbonization to obtain a treated material C;
s4: loading the treated material C into graphite equipment, and carrying out graphitization treatment in a graphitization furnace to obtain a graphitized material D;
s5: and screening the graphitized material D to obtain the graphite cathode material.
According to the invention, the phosphorus source is combined with the graphene, so that the defects of low first efficiency, small tap density and the like of the graphene are overcome, the advantages of high conductivity, large mechanical strength and the like of the graphene are utilized, the multiplying power performance and the cycling stability of the cathode material can be effectively improved through the doping mode of the non-metal element of the phosphorus source, meanwhile, the problems of low ionic conductivity, large resistance and the like of nitrogen-doped graphite in the traditional technology are solved through the combination of the phosphorus source and the graphene, and the multiplying power performance and the cycling stability of the cathode material can be further improved.
Further, in step S1, the phosphorus source is one or more of phosphonitrile trimer chloride, adenosine triphosphate, adenosine diphosphate, phosphoenone acetonic acid, phosphate ester, tetrakis hydroxymethyl phosphonium chloride, dimethyl vinylphosphate, hexachlorocyclotriphosphazene, polydichlorophosphazene, polyalkoxyphosphazene, polyaryloxy phosphazene, and polyfluorinated epoxy phosphazene. For example, phosphorus sources for combinations of phosphonitrilic trichloride, adenosine triphosphate, adenosine diphosphate, and phosphoenonylpyruvic acid, phosphorus sources for combinations of dimethyl vinylphosphate and hexachlorocyclotriphosphazene, phosphorus sources for combinations of dimethyl vinylphosphate, hexachlorocyclotriphosphazene, polydichlorophosphazene, and polyalkoxyphosphazene, phosphorus sources for combinations of adenosine diphosphate, phosphoenonylpyruvic acid, phosphate esters, tetrakis hydroxymethyl phosphonium chloride, and dimethyl vinylphosphate.
Further, in step S1, the organic solvent is one or more of an oil solvent, an alcohol solvent, a ketone solvent, an alkane solvent, N-methylpyrrolidone, tetrahydrofuran, and toluene.
Further, the oil solvent is one or more than two of kerosene, mineral oil and vegetable oil; the alcohol solvent is one or more than two of ethanol, methanol, ethylene glycol, isopropanol, n-octanol, allyl alcohol and octanol; the ketone solvent is one or more than two of acetone, methyl butanone, methyl isobutyl ketone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone and methyl hexyl ketone; the alkane solvent is one or more than two of cyclohexane, normal hexane, isoheptane, 3-dimethylpentane and 3-methylhexane.
Further, in step S1, the weight ratio of the phosphorus source, the graphene, and the organic solvent is (0.3-0.4): (0.1-0.3): (1-2).
Further, in step S2, the graphite is artificial graphite and/or natural graphite.
Further, in step S2, the weight ratio of the mixed solution A to graphite is (0.1-0.3): 1.
Further, in step S2, the mixing device is a fusion machine or a VC100 mixer, the rotating speed is 300r/min-500r/min, and the mixing time is 1min-10 min.
Further, in step S3, the heat treatment equipment is one of a vertical kettle, a horizontal kettle, and a roller furnace, the heat treatment mode is to perform temperature rise coating by using a 400-800 ℃ curve, and the rotation frequency is 5 HZ-50 HZ; the carbonization equipment is a carbonization furnace, and the carbonization temperature is 800-1150 ℃.
Further, in step S4, the graphite equipment is an acheson graphitization furnace, and the temperature of the graphitization furnace is 2400 ℃ to 3000 ℃.
Further, in step S2, the graphite has an average particle diameter of 8.0 to 11 μm; in step S5, the graphite negative electrode material has an average particle diameter of 9.0 to 15 μm.
The second purpose of the invention is realized by adopting the following technical scheme:
the phosphorus-graphene doped composite graphite negative electrode material is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the defects of low first-time efficiency, small tap density and the like of the graphene are overcome by combining the phosphorus source with the graphene, the advantages of high conductivity, large mechanical strength and the like of the graphene are utilized, the multiplying power performance and the cycle stability of the cathode material can be effectively improved by the doping mode of the non-metal elements of the phosphorus source, meanwhile, the problems of low ionic conductivity, large resistance and the like of nitrogen-doped graphite in the traditional technology are solved by combining the phosphorus source with the graphene, and the multiplying power performance and the cycle stability of the cathode material can be further improved.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
Example 1
A preparation method of a phosphorus-graphene doped composite graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of artificial graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding a phosphorus source of a combination of vinyl dimethyl phosphate and hexachlorocyclotriphosphazene in a ratio of 1:1 and graphene into N-methylpyrrolidone, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the phosphorus source to the graphene to the N-methyl pyrrolidone is 0.3:0.2: 1;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.1:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a vertical kettle for heat treatment, and heating and coating according to a curve of 400-800 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Example 2
A preparation method of a phosphorus-graphene doped composite graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of natural graphite mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding a phosphorus source of a combination of adenosine diphosphate, phosphoketene pyruvic acid, phosphate, tetrakis (hydroxymethyl) phosphonium chloride and dimethyl vinylphosphate in a ratio of 1:1:1:1:1, and graphene into methyl isobutyl ketone, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the phosphorus source to the graphene to the methyl isobutyl ketone is 0.4:0.2: 1.5;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.2:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a vertical kettle for heat treatment, and heating and coating according to a curve of 400-800 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Example 3
A preparation method of a phosphorus-graphene doped composite graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of artificial graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding hexachlorocyclotriphosphazene and graphene into cyclohexane, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the hexachlorocyclotriphosphazene to the graphene to the cyclohexane is 0.3:0.1: 2;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.3:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a vertical kettle for heat treatment, and heating and coating according to a curve of 400-800 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Example 4
A preparation method of a phosphorus-graphene doped composite graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of artificial graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding phosphate and graphene into allyl alcohol, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the phosphate to the graphene to the allyl alcohol is 0.4:0.3: 2;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.2:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a carbonization furnace for direct carbonization at the temperature of 1000 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Comparative example 1
A preparation method of a graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of natural graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: putting graphite powder into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s3: and screening the graphitized material D to obtain the graphite cathode material.
Comparative example 2
A preparation method of a graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of artificial graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding phosphate into allyl alcohol, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the phosphate to the allyl alcohol is 0.4: 2;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.2:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a carbonization furnace for direct carbonization at the carbonization temperature of 1000 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Comparative example 3
A preparation method of a graphite negative electrode material comprises the following preparation steps:
s1: grinding 300g of artificial graphite material mechanically to obtain graphite powder with the average particle size of 8.0-11 mu m;
s2: adding graphene into allyl alcohol, and uniformly mixing to obtain a mixed solution A; wherein the weight ratio of the graphene to the allyl alcohol is 0.3: 2;
s3: adding the mixed solution A and graphite powder into a fusion machine according to the weight ratio of 0.2:1 to uniformly disperse the mixed solution A and the graphite powder, wherein the rotating speed is 500r/min, and the mixing time is 5min to obtain mixed solution B;
s4: putting the mixed solution B into a carbonization furnace for direct carbonization at the carbonization temperature of 1000 ℃ to obtain a treated material C;
s5: loading the treated material C into an Acheson graphitizing furnace, and carrying out heat treatment in the graphitizing furnace at the temperature of 2800 ℃ to obtain a graphitized material D;
s6: and screening the graphitized material D to obtain the graphite negative electrode material with the average particle size of 9.0-15 mu m.
Performance testing
The materials prepared in the comparative examples and examples were tested for capacity retention at 0.5 cycles for 50 cycles and at 3C versus 0.1C.
The test method comprises the following steps: the test was carried out by a half cell test method in which N-methylpyrrolidone (NMP) was added to the negative electrode material and polyvinylidene fluoride (PVdF) of the above examples and comparative examples at a mass ratio of 9:1 to prepare a slurry, which was coated on a copper foil, dried, and then dried,And punching and pressing the film to prepare the negative plate. The metal lithium foil is used as a counter electrode, and the electrolyte is 1MLiPF 6 And (PC + DMC) ═ 1:1, and a polypropylene membrane (Celgard 2325) is a diaphragm to assemble the battery. The charging and discharging voltage is 0-1.5V, the charging and discharging speed is 0.1C and 0.5C, the battery performance is tested, and the test results are shown in the following table.
TABLE 1
| Item | First coulombic efficiency (%) | 5C Capacity Retention (%) |
| Example 1 | 97.66 | 58.22 |
| Example 2 | 97.21 | 59.65 |
| Example 3 | 98.41 | 58.03 |
| Example 4 | 96.92 | 59.22 |
| Comparative example 1 | 95.21 | 51.24 |
| Comparative example 2 | 95.93 | 55.20 |
| Comparative example 3 | 94.36 | 48.68 |
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (10)
1. A preparation method of a phosphorus-graphene doped composite graphite negative electrode material is characterized by comprising the following preparation steps:
s1: adding a phosphorus source and graphene into an organic solvent, and uniformly mixing to obtain a mixed solution A;
s2: adding the mixed solution A and graphite into a mixing device, and uniformly dispersing to obtain a mixed solution B;
s3: putting the mixed solution B into heat treatment equipment for heat treatment or putting the mixed solution B into carbonization equipment for direct carbonization to obtain a treated material C;
s4: loading the treated material C into graphite equipment, and carrying out graphitization treatment in a graphitization furnace to obtain a graphitized material D;
s5: and screening the graphitized material D to obtain the graphite cathode material.
2. The method for preparing the phosphorus-graphene doped composite graphite negative electrode material of claim 1, wherein in step S1, the phosphorus source is one or more of phosphonitrile trimer chloride, adenosine triphosphate, adenosine diphosphate, phosphoenone pyruvic acid, phosphate ester, tetrakis hydroxymethyl phosphonium chloride, dimethyl vinylphosphate, hexachlorocyclotriphosphazene, polydichlorophosphazene, polyalkoxyphosphazene, polyaryloxy phosphazene, and polyfluorooxyphosphazene.
3. The method for preparing the phosphorus-graphene doped composite graphite anode material according to claim 1, wherein in step S1, the organic solvent is one or more of an oil solvent, an alcohol solvent, a ketone solvent, an alkane solvent, N-methylpyrrolidone, tetrahydrofuran, and toluene.
4. The preparation method of the phosphorus-graphene doped composite graphite anode material according to claim 3, wherein the oil solvent is one or more than two of kerosene, mineral oil and vegetable oil; the alcohol solvent is one or more than two of ethanol, methanol, ethylene glycol, isopropanol, n-octanol, allyl alcohol and octanol; the ketone solvent is one or more than two of acetone, methyl butanone, methyl isobutyl ketone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone and methyl hexyl ketone; the alkane solvent is one or more than two of cyclohexane, normal hexane, isoheptane, 3-dimethylpentane and 3-methylhexane.
5. The method for preparing the phosphorus-graphene doped composite graphite anode material according to claim 1, wherein in step S1, the weight ratio of the phosphorus source, the graphene and the organic solvent is (0.3-0.4): (0.1-0.3): (1-2).
6. The method for preparing the phosphorus-graphene doped composite graphite anode material according to claim 1, wherein in step S2, the graphite is artificial graphite and/or natural graphite.
7. The method for producing a phosphorus-graphene doped composite graphite anode material according to claim 1, wherein in step S2, the weight ratio of the mixed solution a to graphite is (0.1-0.3): 1.
8. The preparation method of the phosphorus-graphene doped composite graphite anode material as claimed in claim 1, wherein in step S2, the mixing device is a fusion machine or a VC100 mixer, the rotation speed is 300r/min to 500r/min, and the mixing time is 1min to 10 min.
9. The method for preparing the phosphorus-graphene doped composite graphite anode material according to claim 1, wherein in step S3, the heat treatment equipment is one of a vertical kettle, a horizontal kettle and a roller furnace, the heat treatment mode is to perform temperature rise coating by using a curve of 400-800 ℃, and the rotation frequency is 5 HZ-50 HZ; the carbonization equipment is a carbonization furnace, and the carbonization temperature is 800-1150 ℃; in step S4, the graphite equipment is an acheson graphitization furnace, and the temperature of the graphitization furnace is 2400 ℃ to 3000 ℃.
10. A phosphorus-graphene doped composite graphite negative electrode material, characterized in that the graphite negative electrode material is prepared by the preparation method according to any one of claims 1 to 9.
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