CN113346076A - Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof - Google Patents

Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof Download PDF

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CN113346076A
CN113346076A CN202110528798.7A CN202110528798A CN113346076A CN 113346076 A CN113346076 A CN 113346076A CN 202110528798 A CN202110528798 A CN 202110528798A CN 113346076 A CN113346076 A CN 113346076A
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graphite
lithium ion
modified graphite
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ion battery
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王宏栋
李琳慈
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Shanxi New Innovation Materials Co.,Ltd.
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Qinxin Group Tianjin New Energy Technology Research Institute Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a surface modified graphite cathode material of a lithium ion battery and a preparation method thereof, wherein the graphite cathode material is prepared by the following steps: heating the graphite material to a certain temperature in an air isolation mode, preserving heat for a period of time, adding the heated graphite into deionized water for rapid cooling, and filtering and drying the cooled graphite material to obtain the surface modification material. The modified graphite material obtained by the method has better surface characteristics, the surface oxygen-containing groups are reduced, the micropore channels are increased, and the multiplying power charge-discharge performance and the first effect of the material are improved under the condition of ensuring that the charge capacity of the material is not changed. Because graphite material molecule is in active state under high temperature state, the surface stress that the quick cooling produced can make the outermost ink sheet face of material overcome the inter-laminar van der Waals' force and break away from the base member, nevertheless because the base member heat is higher, the ink sheet face that breaks away from can adsorb on the base member fast, forms the effect of normal position cladding, effectively improves material surface state, and this position vacancy becomes the micropore passageway after ink sheet face breaks away from original position simultaneously, is favorable to lithium ion to take off and inlays.

Description

Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the field of preparation of lithium battery materials, and particularly relates to a lithium ion battery surface modified graphite negative electrode material and a preparation method thereof.
Background
Lithium ion batteries are increasingly used in human production and life, and include electronic products such as mobile phones, notebook computers and charge pal and electric automobiles, electric buses, serving trolleys and logistics vehicles, etc. all use the lithium ion batteries as power supplies. The negative electrode material is an important component of the lithium ion battery, and the performance of the negative electrode material has great influence on the performance of the lithium ion battery. The particle size, the true density, the morphology, the compacted density and the like of the negative electrode material have influence on the capacity, the multiplying power and the cycle performance of the lithium ion battery, and in order to enable the lithium ion battery to have higher energy density, better multiplying power performance and better cycle performance, the negative electrode material is increasingly modified in all aspects. In studies on modification of negative electrode materials, modification by adding silicon for increasing capacity, modification by surface oxidation for improving cycle performance, and modification of graphite surfaces including coating modification and redox modification have been studied.
The purpose of graphite surface modification is to improve the surface state and improve the material performance. Because some groups, impurities and micropores exist on the surface of the graphite, the surface smoothness is poor, the edges and corners are more, the capacity, the first effect, the multiplying power and the cycling stability of the lithium ion battery are greatly influenced, carbon coating or other modification treatment is carried out on the graphite, surface active sites are reduced, the surface smoothness of particles is improved, the edges and corners of the particles are modified, and the electrical property of the material is favorably improved.
Most of the current graphite surface modification aims at a negative electrode material with high specific surface area and poor morphology, and aiming at a negative electrode material with small specific surface area and regular morphology, the surface performance of the material is difficult to further improve.
Disclosure of Invention
Aiming at the problems, the invention provides a lithium ion battery surface modified graphite cathode material and a preparation method thereof, and the technical scheme adopted by the invention is as follows:
heating the graphite material to a certain temperature in an air isolation mode, preserving heat for a period of time, adding the heated graphite into deionized water for rapid cooling treatment, and filtering and drying the graphite material subjected to cooling treatment to obtain the surface modified material. The modified graphite material obtained by the method has better surface characteristics, the surface oxygen-containing groups are reduced, the micropore channels are increased, and the multiplying power charge-discharge performance and the first effect of the material are improved under the condition of ensuring that the charge capacity of the material is not changed. Because graphite material molecule is in active state under high temperature state, the surface stress that the quick cooling produced can make the outermost ink sheet face of material overcome the inter-laminar van der Waals' force and break away from the base member, nevertheless because the base member heat is higher, the ink sheet face that breaks away from can adsorb on the base member fast, forms the effect of normal position cladding, effectively improves material surface state, and this position vacancy becomes the micropore passageway after ink sheet face breaks away from original position simultaneously, is favorable to lithium ion to take off and inlays.
Preferably, the graphite heating process must be performed in an oxygen-isolated or inert gas atmosphere, and the inert gas may be argon, nitrogen or argon-nitrogen mixture.
Preferably, the heating temperature of the graphite is 1000 +/-200 ℃, and the heat preservation time is 0.5-3 h.
Preferably, the time from the high-temperature state to the rapid cooling heat treatment of the graphite is 10-30S.
Preferably, the temperature of deionized water for rapidly cooling the graphite is 0-100 ℃.
The invention has the beneficial effects that:
the graphite cathode material with the reduced specific surface area and the reduced surface active groups provides a beneficial mode for improving the surface state due to the small specific surface area, the fewer surface groups and the better appearance, and the method has the advantages of simple operation, fewer process steps and strong practicability.
Drawings
FIG. 1 is a schematic view of the surface of an untreated graphite particle;
FIG. 2 is a schematic view showing the state of the surface of graphite particles after being heated at a high temperature and rapidly cooled;
FIG. 3 is a plot of charging and discharging curves for untreated graphite material;
FIG. 4 is a graph showing charging and discharging curves of modified graphite material;
FIG. 5 is a comparative XRD plot of graphite material before and after modification;
FIG. 6 is a comparison graph of 10C-rate charge-discharge curves of the graphite material before and after modification;
FIG. 7 is a cyclic voltammogram of the graphite anode material before modification;
FIG. 8 is a cyclic voltammetry graph of a modified graphite anode material;
fig. 9 is a graph comparing infrared curves of the graphite anode material before and after modification.
Detailed Description
Example 1
The artificial graphite cathode material XC-7 is prepared by purifying, shaping and graphitizing coal-based coke, and has the specific surface area of 1.76m2(g), capacity of 330mAh/g, first effect of 92.5%, and compacted density of 1.37g/cm3The porosity of the pole piece is 31%, and the charge-discharge capacity retention rate of 10C under a lithium iron system is 86.1%. Taking a certain amount of XC-7, putting the XC-7 into a test crucible, covering a crucible cover, filling coke particles at the edge of the outer surface of the cover, putting the XC-7 into a muffle furnace, isolating air, heating at the high temperature of 900 ℃, keeping the temperature for 1 hour, taking a certain amount of deionized water by using a glass beaker, wherein the amount of water needs to be completely immersed in graphite, controlling the water temperature to be 15 ℃, quickly taking out the crucible after heating, removing the coke particles at the periphery of the cover, opening the cover, quickly pouring the heated graphite into the deionized water, and quickly stirring to uniformly and quickly cool the graphite, wherein the whole operation time is controlled within 15 seconds. Filtering the cooled graphite water solution, taking the filtered graphite as XC-7S, placing the filtered graphite into a vacuum drying oven, drying at 150 ℃ for 12h, and performing physical property test after drying to obtain a specific surface area of 1.52m2(g), reversible capacity of 331mAh/g, first effect of 92.8%, and compacted density of 1.37g/cm3The porosity of the pole piece is 33%, and the 10C charge-discharge capacity retention rate under the lithium iron system is 88.3%. The specific surface area of the modified graphite anode material XC-7 is reduced by 0.24m2The porosity of the pole piece is increased by 2%, and the charge-discharge rate performance of 10C is improved by 2.2%.
Example 2
The artificial graphite cathode material XC-7 is prepared by purifying, shaping and graphitizing coal-based coke, and has the specific surface area of 1.76m2(g), capacity of 330mAh/g, first effect of 92.5%, and compacted density of 1.37g/cm3The porosity of the pole piece is 31%, and the charge-discharge capacity retention rate of 10C under a lithium iron system is 86.1%. Placing a certain amount of XC-7 into a test crucible, covering the crucible cover, filling coke particles on the outer edge of the cover, placing the cover into a muffle furnace, isolating air, heating at 1200 ℃ under the protection of nitrogen, keeping the temperature for 0.5 h, taking a certain amount of deionized water by using a glass beaker, adding the heated graphite into the deionized water, and rapidly stirring to uniformly and rapidly cool the graphite, wherein the whole operation time is controlled within 30 seconds. Filtering the cooled graphite water solution, taking the filtered graphite as XC-7S1, drying in a vacuum drying oven at 120 deg.C for 12h, and testing physical properties with specific surface area of 1.49m2A content of 332mAh/g, a first effect of 93.1%, and a compacted density of 1.38g/cm3The porosity of the pole piece is 34%, and the 10C charge-discharge capacity retention rate under a lithium iron system is 88.9%. The specific surface area of the modified graphite anode material XC-7 is reduced by 0.27m2The porosity of the pole piece is increased by 3%, and the charge-discharge rate performance of 10C is improved by 2.9%.
Example 3
The artificial graphite cathode material XC-7 is prepared by purifying, shaping and graphitizing coal-based coke, and has the specific surface area of 1.76m2(g), capacity of 330mAh/g, first effect of 92.5%, and compacted density of 1.37g/cm3The porosity of the pole piece is 31%, and the charge-discharge capacity retention rate of 10C under a lithium iron system is 86.1%. Taking a certain amount of XC-7, putting the XC-7 into a test crucible, covering the crucible cover, filling coke particles on the outer edge of the cover, putting the cover into a muffle furnace, isolating air, heating at the high temperature of 800 ℃ under the protection of nitrogen, keeping the temperature for 3 hours, taking out the crucible quickly after the heating is finished, removing the coke particles on the periphery of the cover, opening the cover, pouring the heated graphite into deionized water quickly, stirring quickly, and cooling the graphite uniformly and quickly. Filtering the cooled graphite aqueous solution, taking the filtered graphite as XC-7S2, putting the filtered graphite into a vacuum drying oven, drying for 12h at 120 ℃, and dryingThe specific surface area is 1.55m in the physical property test2Per g, capacity of 330mAh/g, first effect of 92.9%, and compacted density of 1.36g/cm3The porosity of the pole piece is 33.5%, and the charge-discharge capacity retention rate of 10C under a lithium iron system is 88.5%. The specific surface area of the modified graphite anode material XC-7 is reduced by 0.21m2The porosity of the pole piece is increased by 2.5 percent, and the charge-discharge rate performance of 10C is improved by 2.4 percent.
The negative electrode materials prepared in the above examples were assembled into a lithium ion battery, and electrochemical performance tests were performed, and the results are shown in the following table:
Figure BDA0003066300700000041
as can be seen from the particle size and tap density, the particle size and tap density before and after modification hardly changed, and as can be seen from the specific surface area, the specific surface area after modification was reduced by 0.21-0.27m2/g。
According to the electricity deduction data, the gram specific capacity is not improved after modification, and the first coulombic efficiency is improved by 0.2-0.6%.
As can be seen from the porosity data, the porosity after modification is increased by 2-3%, and the porosity test method comprises the following steps: take 1cm2Weighing the negative pole piece, recording as m1, dripping sufficient amount of hexadecane, standing for 12h, sucking off excessive liquid by using oil absorption paper, weighing, recording as m2, and calculating the volume V of the sucked hexadecaneHole(s)=(m2-m1)/ρHexadecane (Hexadecane)The porosity n, n ═ V, is the volume of the pores divided by the volume of the pole piece dressingHole(s)/VMaterial
As can be seen from the 10C multiplying power charge-discharge data, the multiplying power is improved by 2.2-2.9% after modification.
As can be seen from the XRD comparison graph, XC-7 has a diffraction pattern which is basically the same as that of XC-7S of the modified material, and has a strong (002) diffraction peak at 26.4 degrees of 2 theta, which corresponds to the diffraction pattern
Figure BDA0003066300700000042
Indicating that they all have a complete graphite crystal structure.
As can be seen from the cyclic voltammetry curve, XC-7 and XC-7S both conform to the characteristics of a graphite CV curve, and the oxidation peak of XC-7S after modification is obviously enlarged, which indicates that modification treatment eliminates some irregular structures on the graphite surface, so that the graphite surface is more uniform, the irreversible capacity of the material is reduced, oxidation can form some nano channels on the graphite surface, the nano channels can only allow lithium ions to be reversibly inserted and removed, and solvated ions or solvent molecules cannot be inserted, thereby improving the reversible lithium storage capacity of the graphite material.
As can be seen from the infrared spectrogram, XC-7S of the modified material is 3436.50cm-1The absorption peak disappears, and the surface hydroxyl functional groups are reduced, which shows that the modification improves the surface state of the material, reduces the surface functional groups of the material and is beneficial to improving the processing performance and the electrical performance of the material.

Claims (9)

1. The surface modified graphite cathode material of the lithium ion battery is prepared by modifying a graphite cathode material, and the graphite cathode material has a specific surface area of 1.3-2.0m2G, compacted density of 1.3-1.45g/cm3The particle size and distribution D10 is 6.5-7.5 μm, D50 is 14-16 μm, D90 is 27-30 μm, 2 theta is 26.4 DEG in XRD diffractogram has a strong (002) diffraction peak,
Figure FDA0003066300690000011
the infrared spectrogram is 3436.50cm-1Has an absorption peak, and is characterized in that: the infrared spectrogram of the surface modified graphite cathode material is 3436.50cm-1No absorption peak, and reduced surface hydroxyl functional groups after modification.
2. The surface-modified graphite anode material for lithium ion batteries according to claim 1, wherein the CV curve oxidation peak of the surface-modified graphite anode material is larger than that of the graphite anode material.
3. The surface-modified graphite negative electrode material for the lithium ion battery of claim 1, wherein the specific surface area of the surface-modified graphite negative electrode material is reduced by 0.21-0.27%, the porosity of a negative electrode material pole piece is increased by at least 2%, and the 10C discharge rate is increased by at least 2.2%.
4. The surface-modified graphite anode material for the lithium ion battery of claim 1, wherein the first coulombic efficiency of the surface-modified graphite anode material is improved by at least 0.3%.
5. The preparation method of the lithium ion battery surface modified graphite negative electrode material of claims 1 to 4, characterized in that: the graphite cathode material is isolated from air and heated to a certain temperature and is kept warm for a period of time, then the heated graphite cathode material is added into deionized water for rapid cooling treatment, and the cooled graphite cathode material is filtered and dried to obtain the surface modified graphite cathode material.
6. The surface-modified graphite negative electrode material for lithium ion batteries and the preparation method thereof according to claim 5, characterized in that the heating process of the graphite negative electrode material must be carried out in an oxygen-isolated or inert gas-protected environment.
7. The surface-modified graphite anode material for the lithium ion battery and the preparation method of the surface-modified graphite anode material are characterized in that the heating temperature of the anode material is 1000 +/-200 ℃, and the heat preservation time is 0.5-3 h.
8. The surface-modified graphite anode material for the lithium ion battery and the preparation method of the surface-modified graphite anode material are characterized in that the time from a high-temperature state to rapid cooling heat treatment of the anode material is 10-30S.
9. The lithium ion battery surface modified graphite negative electrode material and the preparation method thereof according to claim 5, characterized in that deionized water is adopted to rapidly cool the negative electrode material at a temperature of 0-100 ℃.
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CN114804095A (en) * 2022-04-27 2022-07-29 中南大学 Graphite negative electrode active material prepared from spheroidized graphite micro powder waste material, and preparation method and application thereof

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CN114804095B (en) * 2022-04-27 2023-12-12 中南大学 Graphite negative electrode active material prepared from spheroidized graphite micropowder waste, and preparation method and application thereof

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