CN111740082A - Modified graphite material, graphite negative electrode material, preparation methods of modified graphite material and graphite negative electrode material, and lithium battery - Google Patents

Modified graphite material, graphite negative electrode material, preparation methods of modified graphite material and graphite negative electrode material, and lithium battery Download PDF

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CN111740082A
CN111740082A CN202010451699.9A CN202010451699A CN111740082A CN 111740082 A CN111740082 A CN 111740082A CN 202010451699 A CN202010451699 A CN 202010451699A CN 111740082 A CN111740082 A CN 111740082A
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graphite
negative electrode
modified graphite
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tap density
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高娇阳
马美品
李海军
蔡惠群
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Yinlong New Energy Co Ltd
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Abstract

The invention provides a modified graphite material, a graphite cathode material, respective preparation methods and a lithium battery. The preparation method comprises the following steps: step S1, carrying out oxidation layer-expanding treatment on the pyrolytic carbon particles by using an oxidation layer-expanding agent to obtain a layer-expanded material; and step S2, mixing the asphalt and the expanded material, and then carrying out isostatic pressing and roasting treatment to obtain the modified graphite material. The modified graphite material is used as a graphite cathode material for preparing a lithium ion battery, and can be Li+The de-intercalation provides more sufficient channels, and improves the specific capacity, the compaction density, the tap density and the first efficiency of the lithium ion battery, thereby improving the energy density of the lithium ion battery.

Description

Modified graphite material, graphite negative electrode material, preparation methods of modified graphite material and graphite negative electrode material, and lithium battery
Technical Field
The invention relates to the technical field of batteries, in particular to a modified graphite material, a graphite negative electrode material, preparation methods of the modified graphite material and the graphite negative electrode material, and a lithium battery.
Background
The lithium ion battery, as a rechargeable secondary battery with good performance, has the advantages of high energy density, high working voltage, rapid charge and discharge, long cycle life, good safety performance and the like, and is widely used in a plurality of fields such as electronic equipment, electric vehicles, national defense and the like. With the technical development of lithium ion batteries, the performance requirements of various industries are higher and higher, including long cycle, high rate, high energy density and the like, and the improvement of the energy density becomes one of the important development directions of the lithium ion batteries.
The energy density of the battery is improved mainly by improving the specific capacity and the compaction density of raw materials, optimizing a formula or improving the platform voltage. Currently, the negative electrode of the commercial lithium ion battery is mainly made of conventional carbon materials, especially graphite materials, including natural graphite and artificial graphite. The natural graphite is generally subjected to surface coating modification treatment, so that the cost is low, the gram volume is high, and more applications are available for Japanese and Korean enterprises, but the natural graphite has poor compatibility with electrolyte, high cyclic expansion rate and poor performance, and is less applied to the domestic battery industry; the artificial graphite has good compatibility with electrolyte, long cycle life and excellent comprehensive performance, and is still the main negative electrode material applied to the lithium ion battery at present.
However, the graphite negative electrode material is not perfect, the problems of low theoretical specific capacity, low compaction density and the like become bottlenecks that hinder further development of the graphite negative electrode material, and as the energy density requirement of the battery is higher and higher, the research on the graphite modification technology for improving the performance of the graphite is more and more important.
Chinese patent application publication No. CN108232146A discloses a preparation method of a lithium ion battery negative electrode material: adding sodium nitrate into concentrated sulfuric acid, adding flake graphite powder, stirring in an ice-water bath, adding potassium permanganate, stirring and mixing in the ice-water bath, and stirring at 30-40 ℃ to obtain a mixed solution; adding deionized water into the mixed solution, stirring and mixing, adding deionized water and a hydrogen peroxide solution, stirring and mixing, filtering, cleaning, adding into a dispersing agent, and performing ultrasonic dispersion to obtain a graphene oxide dispersion solution; adding aluminum powder into the graphene oxide dispersion liquid, adding a reducing agent after stirring, stirring and mixing, filtering, cleaning and drying to obtain an aluminum-reduced graphene oxide compound; adding graphite into a dispersing agent, uniformly mixing to obtain a graphite dispersion liquid, adding an aluminum-reduced graphene oxide compound into the graphite dispersion liquid, uniformly mixing, and evaporating the dispersing agent to obtain the negative electrode material. The preparation method has a complex process flow, is not suitable for industrial production, and is seen from a charge-discharge curve of the material, the material does not have a charge-discharge platform of the traditional graphite, the first discharge specific capacity is 710mAh/g, the first charge specific capacity is 600mAh/g, the calculated first efficiency is approximately equal to 84.5 percent, and the difference with the first efficiency index requirement of the industrial graphite cathode material is too large, so that the battery performance is seriously influenced.
Disclosure of Invention
The invention mainly aims to provide a modified graphite material, a graphite negative electrode material, respective preparation methods and a lithium battery, and aims to solve the problems of low specific capacity, low compaction density and low first efficiency of the graphite negative electrode material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a modified graphite material, including step S1 of subjecting pyrolytic carbon particles to oxidation layer-expanding treatment with an oxidation layer-expanding agent to obtain a layer-expanded material; and step S2, mixing the asphalt and the expanded material, and then carrying out isostatic pressing and roasting treatment to obtain the modified graphite material.
Further, in the step S2, the mass ratio of the expanded material to the asphalt is 100: 1-20, preferably the coking value of the asphalt is 30-50%, preferably the isostatic pressure is 0.5-1.0 MPa, preferably the isostatic time is 20-60 min, preferably the roasting temperature is 500-800 ℃, and preferably the roasting time is 10-50 h.
Further, in the step S1, the oxidation layer-expanding agent is selected from H2O2One or more of oxalic acid and potassium permanganate, preferably the temperature of the oxidation layer expansion treatment is 50-120 ℃,the time of the oxidation layer expanding treatment is preferably 4-12 h, and the mass ratio of the oxidation layer expanding agent to the pyrolytic carbon particles is preferably 1-10: 100.
Further, before the above step S1, the preparation method further includes: crushing pyrolytic carbon to obtain crushed carbon particles; acid washing the crushed carbon particles by acid to obtain pyrolytic carbon particles; the particle size of the crushed carbon particles is preferably 5 to 30 μm, and the tap density of the crushed carbon particles is preferably 0.5 to 1.0g/cm3(ii) a The mass ratio of the crushed carbon particles to the acid is preferably 1: 0.01-1: 0.1, the hydrogen ion concentration of the acid is preferably 2-5 mol/L, the acid is preferably one or more selected from hydrochloric acid, sulfuric acid and nitric acid, the acid washing temperature is preferably 30-100 ℃, and the acid washing time is preferably 5-24 hours.
According to another aspect of the present invention, there is provided a modified graphite material prepared by any one of the aforementioned preparation methods.
Further, the particle size of the modified graphite material is 5-30 μm, and the specific surface area of the modified graphite material is preferably 2-15 m2The tap density of the preferred modified graphite material is 0.3-1.0 g/cm3。
According to still another aspect of the present invention, there is provided a method for preparing a graphite anode material, the method comprising: step A, shaping the modified graphite material to obtain a shaped material; and B, performing carbon coating treatment on the shaped material by using a coating agent to obtain a graphite cathode material, wherein the particle size of the shaped material is preferably 5-30 mu m, and the specific surface area of the shaped material is preferably 2-10 m2(iv) g, preferably the tap density of the shaped material is 0.5 to 1.0g/cm3Preferably, the shaped material is subjected to carbon coating treatment by adopting a coating agent in an inert atmosphere or nitrogen; the mass ratio of the shaped material to the coating agent is preferably 100: 1-20 ℃, more preferably the temperature of the carbon coating treatment is 800-1500 ℃, preferably the time of the carbon coating treatment is 5-30 h, and preferably the coating agent is one or more selected from asphalt, phenolic resin, furan resin and ethylene ethyl acrylate resin.
Further, the preparation method further comprises the following steps: and (3) demagnetizing the graphite negative electrode material at the temperature of below 60 ℃.
According to still another aspect of the present invention, there is provided a graphite anode material prepared by the foregoing preparation method.
Further, the compacted density of the graphite negative electrode material is 1.75-1.80 g/cm3Preferably, the specific surface area of the graphite negative electrode material is less than or equal to 2.5m2/g。
According to still another aspect of the present invention, there is provided a lithium battery comprising an anode and a cathode, the anode being the aforementioned graphite anode material.
By applying the technical scheme of the invention, the pyrolytic carbon particles with the graphite structure are subjected to oxidation layer expansion treatment, so that the surface and internal pores of the pyrolytic carbon particles are enriched, the specific capacity and tap density of the material are improved, and a foundation is laid for further modification and application of the graphite material; the expanded material is subjected to isostatic pressing and roasting treatment through asphalt, and the isostatic pressing treatment can uniformly extrude the asphalt into the pores of the expanded material on one hand and carbonize the asphalt after roasting, so that the inner pores of the expanded material are filled, and the tap density of the material is improved; therefore, the modified graphite material is used as a graphite negative electrode material for preparing a lithium ion battery, and can be Li+The de-intercalation provides more sufficient channels, and improves the specific capacity, the compaction density, the tap density and the first efficiency of the lithium ion battery, thereby improving the energy density of the lithium ion battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows an SEM image of a graphite anode material provided according to example 1 of the present invention;
fig. 2 shows an SEM image of a negative electrode sheet including a graphite negative electrode material 1 after rolling according to the present invention; and
fig. 3 shows a charge-discharge curve diagram of a button cell comprising a graphite anode material 1 according to the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the problems of low specific capacity, low compaction density and low first efficiency of the graphite negative electrode material exist in the prior art, and in order to solve the problems, the invention provides a modified graphite material, a graphite negative electrode material, respective preparation methods and a lithium battery.
In an exemplary embodiment of the present application, there is provided a method of preparing a modified graphite material, the method comprising: step S1, carrying out oxidation layer-expanding treatment on the pyrolytic carbon particles by using an oxidation layer-expanding agent to obtain a layer-expanded material; and step S2, mixing the asphalt and the expanded material, and then carrying out isostatic pressing and roasting treatment to obtain the modified graphite material.
According to the method, the pyrolytic carbon particles with the graphite structures are subjected to oxidation layer expansion treatment, so that the surface and internal pores of the pyrolytic carbon particles are enriched, the specific capacity and tap density of the material are improved, and a foundation is laid for further modification and application of the graphite material; the expanded material is subjected to isostatic pressing and roasting treatment through asphalt, and the isostatic pressing treatment can uniformly extrude the asphalt into the pores of the expanded material on one hand and carbonize the asphalt after roasting, so that the inner pores of the expanded material are filled, and the tap density of the material is improved; therefore, the modified graphite material is used as a graphite negative electrode material for preparing a lithium ion battery, and can be Li+The de-intercalation provides more sufficient channels, and improves the specific capacity, the compaction density, the tap density and the first efficiency of the lithium ion battery, thereby improving the energy density of the lithium ion battery.
In an embodiment of the present application, in step S2, the mass ratio of the expanded material to the asphalt is 100: 1-20, preferably the coking value of the asphalt is 30-50%, preferably the isostatic pressure is 0.5-1.0 MPa, preferably the isostatic time is 20-60 min, preferably the roasting temperature is 500-800 ℃, and preferably the roasting time is 10-50 h.
The asphalt in the proportion is more beneficial to carrying out sufficient pore filling treatment on the expanded material to reduce the specific surface area of the expanded material, meanwhile, the pressure and the time of isostatic pressing are beneficial to improving the pore filling uniformity of the asphalt and improving the tap density of the modified graphite material, and the coking value and the roasting temperature and the time of the asphalt are beneficial to better carbonizing the asphalt so as to fill pores in the expanded material.
In order to enhance the effect of the oxidation layer-expanding treatment, it is preferable that in the step S1, the oxidation layer-expanding agent is selected from H2O2One or more of oxalic acid and potassium permanganate, preferably, the temperature of oxidation layer expanding treatment is 50-120 ℃, the time of oxidation layer expanding treatment is 4-12 h, and the mass ratio of an oxidation layer expanding agent to pyrolytic carbon particles is 1-10: 100.
in an embodiment of the present application, before the step S1, the preparing further includes: crushing pyrolytic carbon to obtain crushed carbon particles; acid washing the crushed carbon particles by acid to obtain pyrolytic carbon particles; the particle size of the crushed carbon particles is preferably 5 to 30 μm, and the tap density of the crushed carbon particles is preferably 0.5 to 1.0g/cm3(ii) a The mass ratio of the crushed carbon particles to the acid is preferably 1: 0.01-1: 0.1, the hydrogen ion concentration of the acid is preferably 2-5 mol/L, the acid is preferably one or more selected from hydrochloric acid, sulfuric acid and nitric acid, the acid washing temperature is preferably 30-100 ℃, and the acid washing time is preferably 5-24 hours.
The pyrolytic carbon is crushed into the crushed carbon particles with the compacted density, impurity removal and subsequent oxidation layer expansion are facilitated, and the acid with the type and the amount is beneficial to effectively removing metal impurities and the like in the crushed carbon particles, so that high-purity pyrolytic carbon particles are obtained.
In another exemplary embodiment of the present application, there is provided a modified graphite material prepared by any one of the aforementioned preparation methods.
According to the method, the pyrolytic carbon particles with the graphite structures are subjected to oxidation layer expansion treatment, so that the surface and internal pores of the pyrolytic carbon particles are enriched, the specific capacity and tap density of the material are improved, and a foundation is laid for further modification and application of the graphite material; the expanded material is subjected to isostatic pressing and roasting treatment through asphalt, and the isostatic pressing treatment can uniformly extrude the asphalt into the pores of the expanded material on one hand and carbonize the asphalt after roasting, so that the inner pores of the expanded material are filled, and the tap density of the material is improved; therefore, the modified graphite material is used as a graphite negative electrode material for preparing a lithium ion battery, and can be Li+The de-intercalation provides more sufficient channels, and improves the specific capacity, the compaction density, the tap density and the first efficiency of the lithium ion battery, thereby improving the energy density of the lithium ion battery.
In one embodiment of the present application, the particle size of the modified graphite material is 5 to 30 μm, and the specific surface area of the modified graphite material is preferably 2 to 15m2The tap density of the preferred modified graphite material is 0.3-1.0 g/cm3。
The modified graphite material with the parameter value range has more excellent performance, and is easier to obtain the material with more excellent performance through simple treatment.
In still another exemplary embodiment of the present application, there is provided a method of preparing a graphite anode material, the method including: step A, shaping the modified graphite material to obtain a shaped material; and step B, performing carbon coating treatment on the shaped material by using a coating agent to obtain the graphite cathode material.
Through the shaping treatment and the surface carbon coating treatment of the modified graphite material, the surface defects of the modified graphite material can be further modified, so that the active sites and the specific surface area of the surface of the modified graphite material are reduced, and the problems of low first coulomb efficiency, poor long cycle performance of the battery and the like caused by more lithium loss and poor compatibility due to overlarge specific surface area of the material during the formation of the battery are solved.
The particle size of the material after the shaping is preferably 5-30 μm, and the specific surface area of the material after the shaping is preferably 2-10 m2(iv) g, preferably the tap density of the shaped material is 0.5 to 1.0g/cm3Preferably, a coating agent is adopted in an inert atmosphere to carry out carbon coating treatment on the shaped material; the mass ratio of the shaped material to the coating agent is preferably 100: 1-20 ℃, more preferably the temperature of the carbon coating treatment is 800-1500 ℃, preferably the time of the carbon coating treatment is 5-30 h, and preferably the coating agent is one or more selected from asphalt, phenolic resin, furan resin and ethylene ethyl acrylate resin.
The shaping treatment can be carried out by referring to the prior art, and in order to improve the shaping treatment effect, the modified graphite material is preferably milled and shaped by adopting an air flow mill; the specific carbon coating treatment step can refer to the prior art, and in order to improve the carbon coating effect, the coating agent and the shaped material are preferably uniformly mixed in a stirring tank and then are put into a crucible, and the mixture is put into a tunnel kiln, the temperature is increased by adopting the program of 15 ℃/min to 800-1500 ℃, and the temperature is increased by N2Sintering for 5-30 h in the atmosphere. The control of the carbon coating treatment conditions is beneficial to increasing the interlayer spacing of the carbonized coating layer, improving the isotropy and simultaneously being beneficial to improving the multiplying power and the low-temperature performance of the lithium ion battery.
In order to further optimize the performance of the graphite negative electrode material and reduce the influence of the magnetic impurities on the performance of the negative electrode material, the preparation method preferably further comprises the following steps: and (3) demagnetizing the graphite negative electrode material at the temperature of below 60 ℃.
In yet another exemplary embodiment of the present application, a graphite anode material prepared by the foregoing preparation method is provided.
The graphite cathode material obtained by the preparation method has high compaction density, high specific capacity and high first efficiency, is low in rebound rate, is quick in electrolyte infiltration under a high compaction condition when being used as a cathode material of a lithium ion battery, shows excellent electrochemical performance, and meets the requirement of the high energy density lithium ion battery on the cathode material.
In one embodiment of the present application, the graphite negative electrode described aboveThe compacted density of the material is 1.75-1.80 g/cm3Preferably, the specific surface area of the graphite negative electrode material is less than or equal to 2.5m2/g。
The graphite negative electrode material with the compacted density and the specific surface area has more excellent processing performance and electrochemical performance.
In yet another exemplary embodiment of the present application, there is provided a lithium battery including a negative electrode and a positive electrode, the negative electrode being the aforementioned graphite negative electrode material.
Because the graphite negative electrode material has the excellent performances of high tap density, high specific capacity and high primary efficiency, the graphite negative electrode material is used as the negative electrode material of the lithium ion battery, so that the lithium ion battery has the characteristics of high capacity and high primary efficiency, and the requirement of the high-energy density lithium ion battery on the negative electrode material is met.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Selecting 1000g of high-crystallinity pyrolytic carbon of coal mine extraction product as raw material, mechanically crushing the pyrolytic carbon to particle size of 15 mu m and tap density of 0.6g/cm3The crushed carbon granules; washing the crushed carbon particles with 2mol/L hydrochloric acid at 50 ℃ for 4h to remove impurities, filtering, washing and drying to obtain pyrolytic carbon particles, wherein the mass ratio of the crushed carbon particles to the hydrochloric acid is 1: 0.01;
at a temperature of 60 ℃ with 40g H2O2And carrying out oxidation layer expanding treatment on the pyrolytic carbon particles for 5 hours by 40g of oxalic acid to obtain a layer expanded material.
Selecting asphalt with a coking value of 30% as a pore-filling agent, wherein the mass ratio of the expanded material to the asphalt is 100: and 3, carrying out isostatic pressing treatment for 40min at the normal temperature under the pressure of 0.7MPa, and roasting for 20h at the temperature of 600 ℃ to obtain the modified graphite material. The particle diameter of the modified graphite material is 20 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.68g/cm3。
The modified graphite material is milled and shaped by airflow to obtain a shaped material with the particle size of 18.5 mu m and the specific surface area of2.0m2(g) tap density of 0.7g/cm3。
Adopting petroleum asphalt to carry out carbon coating treatment on the shaped material, wherein the mass ratio of the shaped material to the petroleum asphalt is 100:5, uniformly mixing the mixture in a stirring tank, then loading the mixture into a crucible, loading the crucible into a tunnel kiln, adopting programmed temperature rise of 15 ℃/min to 1300 ℃, and carrying out N2Sintering for 24 hours in the atmosphere, cooling to below 60 ℃ along with the crucible, screening and demagnetizing to obtain the graphite cathode material 1. The surface topography of the graphite anode material 1 is detected, and a corresponding SEM image is shown in FIG. 1.
Example 2
Example 2 differs from example 1 in that,
the coking value of the asphalt is 40%, pyrolytic carbon 1000 is selected as a raw material, and the raw material is mechanically crushed to the particle size of 5 mu m, and the tap density is 0.5g/cm3The crushed carbon granules; washing the crushed carbon particles with 5mol/L nitric acid at the temperature of 30 ℃ for 5 hours to remove impurities, filtering, washing and drying to obtain pyrolytic carbon particles, wherein the mass ratio of the crushed carbon particles to the nitric acid is 1: 0.1;
adopting petroleum asphalt to carry out carbon coating treatment on the shaped material, wherein the mass ratio of the shaped material to the petroleum asphalt is 100:1, uniformly mixing the mixture in a stirring tank, then loading the mixture into a crucible, loading the crucible into a tunnel kiln, adopting programmed temperature rise of 15 ℃/min to 800 ℃, and carrying out N-ray sintering at the temperature of N2Sintering for 5h in the atmosphere, cooling to below 60 ℃ along with the crucible, screening and demagnetizing to obtain the graphite cathode material 2.
Example 3
Example 3 differs from example 1 in that,
the coking value of the asphalt is 50%, 1000g of high-crystallinity pyrolytic carbon of a coal mine extraction product is selected as a raw material, and the raw material is mechanically crushed to the particle size of 30 mu m and the tap density of 1.0g/cm3The crushed carbon granules; washing the crushed carbon particles with hydrochloric acid at 100 ℃ for 24h to remove impurities, filtering, washing and drying to obtain pyrolytic carbon particles, wherein the mass ratio of the crushed carbon particles to the hydrochloric acid is 1: 0.05;
adopting phenolic resin to carry out carbon coating treatment on the shaped material, wherein the mass ratio of the shaped material to the phenolic resin is 100:20, and mixingThe materials are uniformly mixed in a stirring tank and then are put into a crucible, and the mixture is put into a tunnel kiln, and the temperature is raised by adopting the program of 15 ℃/min to 1500 ℃ in N2Sintering for 30h in the atmosphere, cooling to below 60 ℃ along with the crucible, screening and demagnetizing to obtain the graphite cathode material 3.
Example 4
Example 4 differs from example 1 in that,
selecting 1000g of high-crystallinity pyrolytic carbon of coal mine extraction product as raw material, mechanically crushing the pyrolytic carbon to 32 mu m of particle size and 0.45g/cm of tap density3The crushed carbon granules; washing the crushed carbon particles with 3mol/L hydrochloric acid at 100 ℃ for 24h to remove impurities, filtering, washing and drying to obtain pyrolytic carbon particles, wherein the mass ratio of the crushed carbon particles to the hydrochloric acid is 1: 0.008;
adopting phenolic resin to carry out carbon coating treatment on the shaped material, wherein the mass ratio of the shaped material to the phenolic resin is 100:20, uniformly mixing the mixture in a stirring tank, then loading the mixture into a crucible, loading the crucible into a tunnel kiln, adopting a program to heat up the mixture at 15 ℃/min to 1550 ℃ in N2Sintering for 30h in the atmosphere, cooling to below 60 ℃ along with the crucible, screening and demagnetizing to obtain the graphite cathode material 4.
Example 5
Example 5 differs from example 1 in that,
the temperature of the oxidation layer-expanding treatment is 50 ℃, the particle size of the obtained modified graphite material is 18 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.0 μm and a specific surface area of 2.1m2(ii)/g, tap density 0.71g/cm3And obtaining the graphite negative electrode material 5.
Example 6
Example 6 differs from example 1 in that,
the temperature of the oxidation layer-expanding treatment is 120 ℃, the particle diameter of the obtained modified graphite material is 17.5 mu m, and the specific surface area of the modified graphite material is 2.3m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.2 μm and a specific surface area of 2.2m2(ii)/g, tap density 0.73g/cm3And obtaining the graphite negative electrode material 6.
Example 7
Example 7 differs from example 1 in that,
the temperature of the oxidation layer-expanding treatment is 40 ℃, the particle size of the obtained modified graphite material is 17 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.8 μm and a specific surface area of 2.0m2(ii)/g, tap density 0.70g/cm3And obtaining the graphite negative electrode material 7.
Example 8
Example 8 differs from example 1 in that,
using 50gH2O250g oxalic acid is used for carrying out oxidation layer expanding treatment on the pyrolytic carbon granules to obtain a modified graphite material with the grain diameter of 17.5 mu m and the specific surface area of 2.4m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.1 μm and a specific surface area of 2.2m2(ii)/g, tap density 0.72g/cm3And obtaining the graphite negative electrode material 8.
Example 9
Example 9 differs from example 1 in that,
using 5gH2O2And 5g of oxalic acid to carry out oxidation layer-expanding treatment on the pyrolytic carbon granules to obtain a modified graphite material with the particle size of 17.0 mu m and the specific surface area of 2.2m2The tap density of the modified graphite material is 0.66g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtainThe particle diameter of the shaped material is 16.9 μm, and the specific surface area is 2.1m2(ii)/g, tap density 0.71g/cm3And obtaining the graphite negative electrode material 9.
Example 10
Example 10 differs from example 1 in that,
using 70gH2O2And 70g of oxalic acid to carry out oxidation layer-expanding treatment on the pyrolytic carbon granules to obtain a modified graphite material with the particle size of 18 mu m and the specific surface area of 2.2m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.5 μm and a specific surface area of 2.8m2(g) tap density of 0.6g/cm3To obtain the graphite negative electrode material 10.
Example 11
Example 11 differs from example 1 in that,
the time of oxidation layer-expanding treatment is 4h, the particle diameter of the obtained modified graphite material is 17.5 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.3 μm and a specific surface area of 1.8m2(ii)/g, tap density 0.72g/cm3And obtaining the graphite negative electrode material 11.
Example 12
Example 12 differs from example 1 in that,
the time of oxidation layer expansion treatment is 12h, the particle diameter of the obtained modified graphite material is 17.7 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.8 μm and a specific surface area of 2.1m2(ii)/g, tap density 0.70g/cm3And obtaining the graphite cathode material 12.
Example 13
Example 13 differs from example 1 in that,
the time of oxidation layer expansion treatment is 3h, the particle size of the obtained modified graphite material is 17.0 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.55g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.0 μm and a specific surface area of 2.0m2(ii)/g, tap density 0.65g/cm3To obtain the graphite negative electrode material 13.
Example 14
Example 14 differs from example 1 in that,
using 100gH2O2The particle diameter of the modified graphite material obtained by oxidizing and spreading the pyrolytic carbon particles is 17.1 mu m, and the specific surface area of the modified graphite material is 2.2m2The tap density of the modified graphite material is 0.9g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.1 μm and a specific surface area of 2.0m2(ii)/g, tap density 1.0g/cm3To obtain the graphite negative electrode material 14.
Example 15
Example 15 differs from example 1 in that,
the mass ratio of the expanded material to the asphalt is 100:1, the particle diameter of the obtained modified graphite material is 17.2 mu m, and the specific surface area of the modified graphite material is 15m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.2 μm and a specific surface area of 10m2(ii)/g, tap density 0.72g/cm3To obtain the graphite negative electrode material 15.
Example 16
Example 16 differs from example 1 in that,
material and asphaltene after layer expansionThe quantity ratio is 100:20, the particle diameter of the obtained modified graphite material is 18.2 mu m, and the specific surface area of the modified graphite material is 10m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.0 μm and a specific surface area of 8m2(g) tap density of 0.7g/cm3To obtain the graphite negative electrode material 16.
Example 17
Example 17 differs from example 1 in that,
the mass ratio of the expanded material to the asphalt is 100: 0.5, the particle diameter of the obtained modified graphite material is 17.3 mu m, and the specific surface area of the modified graphite material is 12m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.4 μm and a specific surface area of 10m2(ii)/g, tap density 0.68g/cm3To obtain the graphite negative electrode material 17.
Example 18
Example 18 differs from example 1 in that,
the isostatic pressure was 0.5MPa, the particle size of the resulting modified graphite material was 17.3. mu.m, and the specific surface area of the modified graphite material was 2.0m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.4 μm and a specific surface area of 1.9m2(ii)/g, tap density 0.70g/cm3To obtain the graphite negative electrode material 18.
Example 19
Example 19 differs from example 1 in that,
the isostatic pressure was 1.0MPa, the particle size of the resulting modified graphite material was 17.2 μm, and the specific surface area of the modified graphite material was 2.0m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.2 μm and a specific surface area of 1.8m2(ii)/g, tap density 0.72g/cm3To obtain the graphite negative electrode material 19.
Example 20
Example 20 differs from example 1 in that,
the isostatic pressure is 0.3MPa, the particle diameter of the obtained modified graphite material is 30 μm, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 29.0 μm and a specific surface area of 2.5m2(ii)/g, tap density 0.65g/cm3To obtain the graphite negative electrode material 20.
Example 21
Example 21 differs from example 1 in that,
the isostatic pressing time is 20min, the particle diameter of the obtained modified graphite material is 16.8 μm, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.75g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.2 μm and a specific surface area of 2.1m2(g) tap density of 0.85g/cm3To obtain a graphite negative electrode material 21.
Example 22
Example 22 differs from example 1 in that,
the isostatic pressing time is 60min, the particle diameter of the obtained modified graphite material is 17.0 μm, and the specific surface area of the modified graphite material is 2.1m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.5 μm and a specific surface area of 2.0m2(ii)/g, tap density 0.72g/cm3To obtain the graphite anode material 22.
Example 23
Example 23 differs from example 1 in that,
the isostatic pressing time is 80min, the particle diameter of the obtained modified graphite material is 18.0 μm, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.3 μm and a specific surface area of 1.8m2(ii)/g, tap density 0.70g/cm3To obtain a graphite negative electrode material 23.
Example 24
Example 24 differs from example 1 in that,
the roasting temperature is 500 ℃, the particle size of the obtained modified graphite material is 16.0 mu m, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 15.9 μm and a specific surface area of 2.1m2(ii)/g, tap density 0.72g/cm3To obtain the graphite negative electrode material 24.
Example 25
Example 25 differs from example 1 in that,
the roasting temperature is 800 ℃, the particle size of the obtained modified graphite material is 18.2 mu m, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.75g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 17.0 μm and a specific surface area of 1.8m2(g) tap density of 0.8g/cm3To obtain the graphite negative electrode material 25.
Example 26
Example 26 differs from example 1 in that,
the roasting temperature is 300 ℃, the particle size of the obtained modified graphite material is 17.0 mu m, and the ratio table of the modified graphite materialArea of 2.0m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.0 μm and a specific surface area of 2.4m2(ii)/g, tap density 0.68g/cm3To obtain the graphite negative electrode material 26.
Example 27
Example 27 differs from example 1 in that,
the roasting time is 10h, the particle size of the obtained modified graphite material is 17.2 mu m, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.70g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.2 μm and a specific surface area of 1.9m2(ii)/g, tap density 0.75g/cm3To obtain a graphite negative electrode material 27.
Example 28
Example 28 differs from example 1 in that,
the roasting time is 50h, the particle size of the obtained modified graphite material is 17.3 mu m, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.68g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.7 μm and a specific surface area of 2.2m2(g) tap density of 0.85g/cm3To obtain the graphite negative electrode material 28.
Example 29
Example 29 differs from example 1 in that,
the roasting time is 8h, the particle size of the obtained modified graphite material is 16.8 mu m, and the specific surface area of the modified graphite material is 2.0m2The tap density of the modified graphite material is 0.65g/cm3。
The obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.2 μm and a specific surface area of 2.5m2(ii)/g, tap density 0.68g/cm3To obtain the graphite negative electrode material 29.
Comparative example 1
Comparative example 1 is different from example 1 in that,
comparative example 1 No isostatic pressing and calcination treatment were performed, and the obtained modified graphite material was shaped by the process of example 1 to obtain a shaped material having a particle size of 16.1 μm and a specific surface area of 3.0m2(g) tap density of 0.60g/cm3To obtain the graphite negative electrode material 30.
Comparative example 2
Comparative example 2 differs from example 1 in that,
comparative example 2 No oxidation spreading treatment, the modified graphite material obtained after shaping by the process of example 1 had a particle size of 16.0. mu.m and a specific surface area of 1.5m2(g) tap density of 0.8g/cm3To obtain the graphite negative electrode material 31.
Comparative example 3
Pulverizing needle coke into 10 μm powder with tap density of 0.75g/cm3Uniformly mixing the raw material powder and the auxiliary material asphalt according to the mass ratio of 100:5 to obtain a mixture; carrying out heat treatment on the mixture in a vertical kettle at 65 ℃ for 10 hours for secondary granulation; and (3) loading the granulated material into a graphitization furnace, heating to 3200 ℃ for graphitization treatment for 45h, and screening to remove magnetism to obtain the graphite cathode material 32.
The surface appearance of the rolled negative plate prepared from the graphite negative material 1 is detected, and the compaction density is 1.78g/cm3The corresponding SEM image is shown in fig. 2.
Button half-cells respectively made of the graphite negative electrode materials 1 to 32: preparing a graphite negative electrode material, a conductive agent SP, CMC and SBR (solid content is 15%) according to a mass ratio of 95:1.5:1.5:2.0, adding deionized water to prepare slurry, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven for 12 hours to prepare a negative electrode sheet; the electrolyte is prepared by using a mixture of EC, EMC and DEC in a volume ratio of 1:1:1 as a solvent, using VC accounting for 2% of the volume of the solvent as an additive, respectively testing specific capacity and first efficiency by assembling the button half cells according to the prior art, respectively standing the button half cells for 12h, and calculating the specific capacity of the materials by using the following formula: ca/[ (M electrode-M copper foil) × active material percentage ], where C: the specific capacity of the negative electrode material mAh/g; ca: average discharge capacity mAh of the button cell; m electrode: weight g of the negative plate; m copper foil: weight g of copper foil.
The particle sizes of the graphite cathode materials 1 to 32 were respectively measured by a laser particle sizer.
And respectively testing the tap densities of the graphite cathode materials 1 to 32 by using a tap density instrument.
The specific surface areas of the graphite anode materials 1 to 32 were respectively tested by using a specific surface area meter.
The compacted densities of the negative electrode sheets respectively made of the graphite negative electrode materials 1 to 32 were respectively measured by a compacted density meter.
The test results and other performance parameters such as specific surface area are shown in Table 1.
TABLE 1
Figure BDA0002507832370000131
Figure BDA0002507832370000141
As can be seen from FIG. 1, the morphology is mainly spherical-like with smooth appearance, and the uniformity of the whole material is better; as can be seen from FIG. 2, at this compaction density, the surface of the pole piece had many pores and no overpressure was observed; as can be seen from FIG. 3, the first discharge specific capacity of the graphite anode material 1 is 388.5mAh/g, and the first charge specific capacity is 367.5 mAh/g.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the method, the pyrolytic carbon particles with the graphite structures are subjected to oxidation layer expansion treatment, so that the surface and internal pores of the pyrolytic carbon particles are enriched, the specific capacity and tap density of the material are improved, and a foundation is laid for further modification and application of the graphite material; then the expanded material is subjected to isostatic pressing and roasting treatment by asphalt, and the isostatic pressing treatment is carried out on the one handThe asphalt can be uniformly extruded into the pores of the expanded material and then carbonized after being roasted, so that the internal pores of the expanded material are filled, and the tap density of the material is improved; therefore, the modified graphite material is used as a graphite negative electrode material for preparing a lithium ion battery, and can be Li+The de-intercalation provides more sufficient channels, and improves the specific capacity, the compaction density, the tap density and the first efficiency of the lithium ion battery, thereby improving the energy density of the lithium ion battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A preparation method of a modified graphite material is characterized by comprising the following steps:
step S1, carrying out oxidation layer-expanding treatment on the pyrolytic carbon particles by using an oxidation layer-expanding agent to obtain a layer-expanded material;
and step S2, mixing the asphalt and the expanded material, and then carrying out isostatic pressing and roasting treatment to obtain the modified graphite material.
2. The method according to claim 1, wherein in the step S2, the mass ratio of the layer-expanded material to the asphalt is 100: 1-20, preferably the coking value of the asphalt is 30-50%, preferably the pressure of the isostatic pressing is 0.5-1.0 MPa, preferably the time of the isostatic pressing is 20-60 min, preferably the roasting temperature is 500-800 ℃, and preferably the roasting time is 10-50 h.
3. The method according to claim 1, wherein in step S1, the oxidation layer-expanding agent is selected from H2O2One or more of oxalic acid and potassium permanganate, preferably, the temperature of the oxidation layer expanding treatment is 50-120 ℃, preferablyThe time for the oxidation layer expanding treatment is selected to be 4-12 hours, and the mass ratio of the oxidation layer expanding agent to the pyrolytic carbon particles is preferably 1-10: 100.
4. The method of claim 1, wherein prior to the step S1, the method further comprises:
crushing pyrolytic carbon to obtain crushed carbon particles;
acid washing the crushed carbon particles by using acid to obtain pyrolytic carbon particles;
the particle size of the crushed carbon particles is preferably 5 to 30 μm, and the tap density of the crushed carbon particles is preferably 0.5 to 1.0g/cm3(ii) a The mass ratio of the crushed carbon particles to the acid is preferably 1: 0.01-1: 0.1, the hydrogen ion concentration of the acid is preferably 2-5 mol/L, the acid is preferably one or more selected from hydrochloric acid, sulfuric acid and nitric acid, the acid washing treatment temperature is preferably 30-100 ℃, and the acid washing treatment time is preferably 5-24 hours.
5. A modified graphite material, characterized in that it is produced by the production method according to any one of claims 1 to 4.
6. The modified graphite material according to claim 5, wherein the particle size of the modified graphite material is 5 to 30 μm, and preferably the specific surface area of the modified graphite material is 2 to 15m2The tap density of the modified graphite material is preferably 0.3-1.0 g/cm3。
7. A preparation method of a graphite negative electrode material is characterized by comprising the following steps:
a, shaping the modified graphite material of claim 5 or 6 to obtain a shaped material;
step B, adopting a coating agent to carry out carbon coating treatment on the shaped material to obtain a graphite cathode material,
the particle size of the reshaped material is preferably5 to 30 μm, preferably the specific surface area of the shaped material is 2 to 10m2(iv)/g, preferably the tap density of the shaped material is 0.5 to 1.0g/cm3Preferably, a coating agent is adopted in inert atmosphere or nitrogen to carry out carbon coating treatment on the shaped material; preferably, the mass ratio of the reshaped material to the coating agent is 100: 1-20 ℃, more preferably, the temperature of the carbon coating treatment is 800-1500 ℃, preferably, the time of the carbon coating treatment is 5-30 h, and preferably, the coating agent is one or more selected from asphalt, phenolic resin, furan resin and ethylene ethyl acrylate resin.
8. The method of manufacturing according to claim 7, further comprising:
and (3) carrying out demagnetization treatment on the graphite negative electrode material at the temperature of below 60 ℃.
9. A graphite negative electrode material, characterized in that it is prepared by the preparation method of claim 7 or 8.
10. The graphite anode material as claimed in claim 9, wherein the compacted density of the graphite anode material is 1.75-1.80 g/cm3Preferably, the specific surface area of the graphite negative electrode material is less than or equal to 2.5m2/g。
11. A lithium battery comprising a negative electrode and a positive electrode, wherein the negative electrode is the graphite negative electrode material according to claim 9 or 10.
CN202010451699.9A 2020-05-25 2020-05-25 Modified graphite material, graphite negative electrode material, preparation methods of modified graphite material and graphite negative electrode material, and lithium battery Pending CN111740082A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645301A (en) * 2020-12-23 2021-04-13 福建杉杉科技有限公司 Particle surface in-situ oxidation and carbon coating modified graphite negative electrode material and preparation method thereof
CN113113572A (en) * 2021-03-11 2021-07-13 广东海洋大学 High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof
CN117397056A (en) * 2023-06-28 2024-01-12 贝特瑞新材料集团股份有限公司 Negative electrode material and battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645301A (en) * 2020-12-23 2021-04-13 福建杉杉科技有限公司 Particle surface in-situ oxidation and carbon coating modified graphite negative electrode material and preparation method thereof
CN112645301B (en) * 2020-12-23 2023-08-15 福建杉杉科技有限公司 Particle surface in-situ oxidation and carbon coated modified graphite negative electrode material and preparation method thereof
CN113113572A (en) * 2021-03-11 2021-07-13 广东海洋大学 High-rate natural graphite-based composite material for lithium ion battery and preparation method and application thereof
CN117397056A (en) * 2023-06-28 2024-01-12 贝特瑞新材料集团股份有限公司 Negative electrode material and battery

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