WO2024131202A1 - Matériau d'électrode négative et batterie - Google Patents

Matériau d'électrode négative et batterie Download PDF

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Publication number
WO2024131202A1
WO2024131202A1 PCT/CN2023/122281 CN2023122281W WO2024131202A1 WO 2024131202 A1 WO2024131202 A1 WO 2024131202A1 CN 2023122281 W CN2023122281 W CN 2023122281W WO 2024131202 A1 WO2024131202 A1 WO 2024131202A1
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Prior art keywords
negative electrode
electrode material
graphite
temperature
material according
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English (en)
Chinese (zh)
Inventor
张宝煊
黄健
李东东
杨书展
任建国
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Kaifeng Ruifeng New Material Co Ltd
BTR New Material Group Co Ltd
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Kaifeng Ruifeng New Material Co Ltd
BTR New Material Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to the technical field of negative electrode materials for ion batteries, and in particular to negative electrode materials and batteries.
  • Rate performance refers to the ratio of the charge and discharge current of the battery cell, which not only affects the charge and discharge capacity of the battery, but also has a great impact on the charging rate. If ordinary batteries are fast-charged, it is easy to cause lithium deposition at the negative electrode, resulting in accelerated battery performance degradation. In severe cases, it can cause internal short circuits in the battery, causing fire and explosion. Improving the rate performance of the battery can improve this problem to a certain extent.
  • the easiest way to improve rate performance is to create more lithium ion diffusion channels for graphite materials by building microporous structures, promoting the diffusion of lithium ions at the solid-liquid interface and in the solid phase; in addition, graphite materials have a large specific surface area, contain more active sites, and have a larger reaction area, which tends to show high rate performance. In fact, at the current stage when graphite materials have been developed to a very mature stage, improving a single parameter may not necessarily achieve the optimal rate performance.
  • the pore volume was measured using the ASAP2460 equipment of the American Micromeritics Company and the BJH Desorption cumulative volume of pores model. Calculated within the aperture range.
  • the pore volume V is 5.0 cm 3 /kg to 8.0 cm 3 /kg.
  • the specific surface area S is 1.8 m 2 /g to 3.0 m 2 /g.
  • the orientation degree OI is 3.8 to 5.4.
  • the pore size distribution range of the negative electrode material is
  • the median particle size of the negative electrode material is 10 to 30 ⁇ m.
  • the graphite material has a graphitization degree of 91-95%.
  • the negative electrode material also includes amorphous carbon.
  • the mass content of the amorphous carbon in the negative electrode material is less than 5%.
  • the graphite material comprises artificial graphite.
  • the present disclosure also provides a method for preparing the above-mentioned negative electrode material, the method comprising:
  • step (2) crushing the low calcined coke obtained in step (1) and shaping it through shaping equipment to obtain crushed and shaped coke powder;
  • step (3) mixing the coke powder obtained in step (2) with a binder in a mass ratio of 100:(2-5) to obtain a precursor mixture A;
  • step (3) The precursor mixture A in step (3) is subjected to a primary pressing at a low pressure of 5 MPa to 15 MPa, and then subjected to a secondary pressing at a high pressure of 15 MPa to 30 MPa, to obtain a precursor B, wherein the difference between the pressure used for the secondary pressing and the pressure used for the primary pressing is 10 to 20 MPa, and the two pressings are allowed to stand for 1 to 5 hours;
  • the precursor B in step (4) is graphitized at a high temperature of 3000-3200° C. in a continuous graphitization furnace, and the temperature curve of the graphitization treatment is as follows: the temperature is increased from the initial temperature to 3000-3200° C. at a heating rate of 12-17° C./min, and the temperature is kept at 3000-3200° C. for 3-4 hours. After the temperature is kept, the temperature is cooled to 25° C. at a cooling rate of 16-25° C./min to obtain the negative electrode material.
  • the present disclosure also provides a battery, which comprises the aforementioned negative electrode material or the negative electrode material prepared by the aforementioned preparation method.
  • FIG. 1 is a SEM image of the negative electrode material in Example 1 of the present application.
  • graphitization degree refers to the degree to which non-graphite carbon of a negative electrode material is transformed into graphite-like carbon at high temperature or during secondary heating, and is one of the detection items of microscopic analysis of negative electrode materials.
  • specific capacity refers to mass specific capacity, that is, the amount of electricity that can be discharged by a unit mass of a battery or active material.
  • first-cycle coulombic efficiency refers to the ability of electrons to reach reactants in a solution from an electrode in an electrochemical reaction. It is an important parameter in an electrochemical reaction and can be used to evaluate the efficiency and feasibility of an electrochemical reaction.
  • the negative electrode material in the present disclosure uses a continuous graphitization device to realize the graphitization process of the graphite material, and there is no need to cut off the power during the production process to achieve continuous production.
  • the following method can be used:
  • step (2) crushing the low calcined coke obtained in step (1) and shaping it through shaping equipment to obtain crushed and shaped coke powder;
  • step (3) mixing the coke powder obtained in step (2) with a binder in a mass ratio of 100:(2-5) to obtain a precursor mixture A;
  • step (3) The precursor mixture A in step (3) is subjected to a primary pressing at a low pressure of 5 MPa to 15 MPa, and then subjected to a secondary pressing at a high pressure of 15 MPa to 30 MPa, to obtain a precursor B, wherein the difference between the pressure used for the secondary pressing and the pressure used for the primary pressing is 10 to 20 MPa, and the two pressings are allowed to stand for 1 to 5 hours;
  • the precursor B in step (4) is graphitized at a high temperature of 3000-3200°C in a continuous graphitization furnace to obtain a graphitized product C.
  • the temperature curve of the graphitization treatment is as follows: the temperature is increased from the initial temperature to 3000-3200°C at a heating rate of 12-17°C/min, and the temperature is kept at 3000-3200°C for 3-4h. After the temperature is kept, the temperature is cooled to 25°C at a cooling rate of 16-25°C/min to obtain the graphite negative electrode material disclosed in the present invention.
  • the preparation method of the negative electrode material provided by the present disclosure comprises a process of performing a secondary pressing after mixing coke powder and a binder.
  • the double pressing can better reduce the orientation degree of the material and can better control the strength and density of the pressing, thereby achieving the purpose of regulating the pore volume.
  • the continuous graphitization process adopts a rapid heating method. During the growth of graphite microcrystals, volatiles and impurity atoms quickly escape from the graphite particles, so that a certain pore structure can be formed inside the graphite. Rapid cooling can reduce the oxidation of the material and maintain the stability of the microporous structure.
  • the graphitization process only takes a few hours from the material entering the furnace to the material leaving the furnace, thereby improving the production efficiency of the negative electrode material to a certain extent.
  • the green coke may be any one of petroleum coke, needle coke, pitch coke, and isotropic coke.
  • the calcination temperature may be 700°C to 900°C, such as 750°C, 800°C, 850°C or 900°C, or a range consisting of any two of these values, which is not limited here.
  • the calcination temperature may be 750°C to 850°C, etc.
  • the calcination time may be 48 to 52h, such as 49h, 50h or 51h, etc., or a range consisting of any two of these values, which is not limited here.
  • the calcination time may be 49h to 51h, etc.
  • Calcination treatment can change the physical and chemical properties of coke powder to a certain extent and improve the capacity performance of the negative electrode material.
  • the binder may be at least one of asphalt, liquid asphalt, phenolic resin, potato starch, corn starch, and tapioca flour.
  • the pressure of the first press can be 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, etc., or a range consisting of any two of these values, which is not limited here.
  • the pressure of the first press can be 8MPa-10MPa, 8MPa-12MPa, or 10MPa-12MPa.
  • the first press can serve the purpose of pre-pressing.
  • the pressure of the secondary pressing can be 15MPa, 18MPa, 20MPa, 22MPa, 25MPa, 28MPa, 30MPa, etc., or a range composed of any two of these values, which is not limited here.
  • the pressure of the secondary pressing can be 18MPa-28MPa, 20MPa-25MPa or 22MPa-22MPa.
  • the role of the secondary pressing is to adjust the strength of the pressing to the desired level. By pressing with a small pressure first, letting it stand and then pressing with a large pressure, the process from agglomeration to dispersion is experienced in the middle, which can make the distribution of the binder in the coke powder more uniform, thereby reducing the situation where the excessive binder content in a certain place leads to poor particle orientation during the pressing process. In addition, it can also reduce the uneven pore volume caused by the volatilization of the binder during the subsequent heat treatment, and achieve precise control of the orientation and pore volume.
  • the difference in pressure between the secondary pressing and the primary pressing is within the range of 10MPa to 20MPa, and may be 10MPa, 12MPa, 15MPa, 18MPa or 20MPa, or a range consisting of any two of these values, which is not limited here.
  • the difference in pressure between the secondary pressing and the primary pressing may be 12MPa to 18MPa, 15MPa to 18MPa.
  • the difference in pressure between the secondary pressing and the primary pressing is within the scope of the present disclosure, which can effectively complete the process from agglomeration to dispersion of the raw materials, and make the binder evenly distributed, thereby facilitating the production of uniform pores and orientation, while reducing the looseness of the material, and can achieve the purpose of precise control.
  • the pressure difference between the secondary pressing and the primary pressing is too small, the pressing effect before and after is equivalent, almost equivalent to the primary pressing, the raw materials cannot complete the process from agglomeration to dispersion, the binder is unevenly distributed, which is not conducive to the production of uniform pores and orientation, and if the pressure difference between the secondary pressing and the primary pressing is too large, the material is easy to loosen, and the purpose of precise control cannot be achieved.
  • the standing time between the primary pressing and the secondary pressing can be 1h, 2h, 3h, 4h, 5h, etc., or a range consisting of any two of these values, such as 2-4h, 2h-3h, or 3h-4h, etc., which are not limited here.
  • the binder and the coke powder are slightly fused, and the binder slowly exerts a bonding effect, forming an interaction force between the two, with a certain strength, which provides the necessary conditions for the secondary pressing.
  • the temperature of the graphitization treatment may be 3000°C, 3050°C, 3100°C, 3150°C or 3200°C, or a range consisting of any two of these values, such as 3000°C to 3200°C, 3050°C to 3100°C, which is not limited here.
  • the heating rate may be 12°C/min, 13°C/min, 14°C/min, 15°C/min, 16°C/min or 17°C/min, or a range consisting of any two of these values, such as 12°C/min to 16°C/min, 13°C/min to 15°C/min, which is not limited here. Not limited here.
  • the cooling rate can be 16°C/min, 18°C/min, 20°C/min, 22°C/min, 24°C/min or 25°C/min, or a range consisting of any two of these values, such as 16°C/min to 25°C/min, 18°C/min to 24°C/min or 20°C/min to 22°C/min, etc., which are not limited here.
  • the advantage of such a design is that it is conducive to the rapid escape of volatiles inside the coke raw material and the formation of a pore structure in the product.
  • step (7) after the graphitization treatment in step (7), at least one of pulverization, screening and demagnetization is further performed.
  • pulverization, demagnetization and screening are further performed in sequence.
  • the pulverization method is any one of a mechanical pulverizer, a jet pulverizer, and a low-temperature pulverizer.
  • the screening method is any one of a fixed screen, a drum screen, a resonance screen, a roller screen, a vibrating screen and a chain screen
  • the mesh number of the screening is 100 to 500 meshes
  • the mesh number of the screening can be 100 mesh, 200 mesh, 250 mesh, 325 mesh, 400 mesh, 500 mesh, etc. or a range composed of any two of these values, such as 200 to 400 mesh or 250 to 325 mesh, etc.
  • the particle size of the negative electrode material is controlled within the above range, which is conducive to improving the processing performance of the negative electrode material.
  • the demagnetization equipment is any one of a permanent magnetic drum magnetic separator, an electromagnetic iron remover and a pulsating high gradient magnetic separator.
  • the purpose of demagnetization is to ultimately control the magnetic substance content of the negative electrode material, reduce the discharge effect of the magnetic substance on the lithium-ion battery and the safety of the battery during use.
  • the pore volume was measured using the ASAP2460 equipment from Micromeritics, USA, and the BJH Desorption cumulative volume of pores model was used. Calculated within the aperture range.
  • the negative electrode material provided by the present disclosure is produced and processed by a continuous graphitization process, so that all materials are continuously fed and discharged, so that the time and temperature of all materials passing through the high temperature zone are consistent, and the graphitization process controls the heating and cooling rates, so that volatiles, impurity elements and other substances in the material can escape evenly and quickly.
  • the orientation degree can be accurately controlled.
  • the pore volume within a certain range in the negative electrode material can increase the diffusion channel of lithium ions, promote the diffusion of lithium ions at the solid-liquid interface and in the solid phase, reduce concentration polarization, and help improve the rate performance of the negative electrode material.
  • the specific surface area within a certain range can ensure sufficient electrochemical reaction interface, promote the diffusion of lithium ions at the solid-liquid interface and in the solid phase, reduce concentration polarization, and help improve the rate performance of the negative electrode material.
  • the diffusion of lithium ions in the negative electrode material has a strong directionality, that is, it can only be embedded along the end face perpendicular to the c-axis direction of the graphite crystal. If the end face perpendicular to the c-axis direction of the graphite crystal is not enough, blindly improving the pore volume and specific surface area will result in a large number of "lithium ion non-deintercalation interfaces", which is not conducive to the improvement of rate performance.
  • the OI value represents the orientation degree of graphite, which to a certain extent reflects the number of end faces perpendicular to the c-axis direction of the graphite crystal. Controlling the V ⁇ S/OI of the negative electrode material within the above range is conducive to improving the "effective lithium ion deintercalation interface" and improving the rate performance of the negative electrode material.
  • the pore volume V may be 5.0 to 8.0 cm 3 /kg.
  • it may be 5.0 cm 3 /kg, 5.5 cm 3 /kg, 6.0 cm 3 /kg, 6.5 cm 3 /kg, 7.0 cm 3 /kg, 7.5 cm 3 /kg or 8.0 cm 3 /kg, or a range consisting of any two of these values, which is not limited herein.
  • the pore volume V of the negative electrode material may be 5.5 cm 3 /kg to 8.0 cm 3 /kg, 6.0 cm 3 /kg to 7.5 cm 3 /kg or 6.5 cm 3 /kg to 7.0 cm 3 /kg, etc.
  • the pores create more lithium ion diffusion channels and electrochemical reaction interfaces for the negative electrode material, which can promote the diffusion of lithium ions at the solid-liquid interface and in the solid phase, reduce concentration polarization, and help improve the rate performance of the negative electrode material.
  • the specific surface area S may be 1.8 m 2 /g to 3.0 m 2 /g.
  • it may be 1.8 m 2 /g, 2.0 m 2 /g, 2.2 m 2 /g, 2.4 m 2 /g, 2.6 m 2 /g, 2.8 m 2 /g or 3.0 m 2 /g, or a range consisting of any two of these values, which is not limited here.
  • the specific surface area S may be 2.0 m 2 /g to 2.8 m 2 /g, 2.2 m 2 /g to 2.6 m 2 /g, 2.4 m 2 /g to 2.6 m 2 /g; and so on. Only a suitable specific surface area can enable the negative electrode material to reversibly deintercalate lithium ions to the maximum extent. A specific surface area that is too large or too small is not conducive to the reversible deintercalation of lithium ions.
  • the orientation degree OI may be 3.8 to 5.4, such as 4.0 to 5.0, 4.2 to 4.8, etc., which are not limited here.
  • a suitable orientation degree OI makes the negative electrode material have better rate performance and less expansion.
  • the pore volume V, specific surface area S, and orientation degree OI value of the negative electrode material are limited.
  • the average pore size distribution range of the negative electrode material is The pore size distribution range of the negative electrode material can be or Etc. Appropriate pore size distribution is conducive to lithium ion insertion and extraction, which helps to improve the rate performance of negative electrode materials.
  • the median particle size (D50) of the negative electrode material may be 10 to 30 ⁇ m.
  • the median particle size of the negative electrode material may be, for example, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m or 30 ⁇ m, etc., which is not limited here.
  • the median particle size of the negative electrode material has a certain influence on the specific surface area of the electrode and the ratio of edge atoms, thereby affecting the capacity performance of the battery.
  • the degree of graphitization of the negative electrode material is 91-95%.
  • it can be 91%, 92%, 93%, 94% or 95%, etc., which is not limited here.
  • the degree of graphitization of the negative electrode material can be 91%-94% or 92%-94%; etc.
  • the degree of graphitization can affect the layered structure, adjacent interlayer spacing, resistivity, etc. of the graphite material. The higher the degree of graphitization, the closer it is to ideal graphite, and the better the theoretical capacity of the negative electrode material.
  • the negative electrode material further comprises amorphous carbon
  • the mass content of amorphous carbon in the negative electrode material is less than 5%.
  • the graphite material comprises artificial graphite.
  • the part that cannot be converted into graphitized carbon exists in the form of amorphous carbon.
  • the presence of a certain amount of amorphous carbon can increase the electrical conductivity of the material and improve its electrochemical properties.
  • Another embodiment of the present disclosure provides an application of the negative electrode material of the aforementioned embodiment in a lithium ion battery.
  • Another embodiment of the present disclosure provides a battery, wherein the battery comprises the negative electrode material described in any one of the aforementioned embodiments or the negative electrode material prepared by the aforementioned preparation method.
  • the present disclosure provides a new negative electrode material and a battery using the negative electrode material, which overcomes the problem that the existing negative electrode materials do not consider the interaction between the pore volume V, specific surface area S and orientation degree OI on the negative electrode material, resulting in relatively poor performance of the negative electrode material, especially the fast charging performance.
  • the pore volume within a certain range in the graphite material can increase the diffusion channel of lithium ions, promote the diffusion of lithium ions at the solid-liquid interface and in the solid phase, reduce the concentration polarization of lithium ions, and help improve the rate performance of the negative electrode material.
  • the specific surface area within a certain range can ensure sufficient electrochemical reaction interface, promote the diffusion of lithium ions at the solid-liquid interface and in the solid phase, reduce the concentration polarization of lithium ions, and help improve the rate performance of the negative electrode material.
  • the applicant has studied how to further improve the rate performance of graphite materials, and purposefully explored many factors. It is found that combining the orientation degree OI of the negative electrode material with the specific surface area and pore volume can greatly improve the migration rate of lithium ions. The reason is speculated to be that the diffusion of lithium ions in graphite materials has a strong directionality, that is, it can only be embedded in the end face perpendicular to the c-axis direction of the graphite crystal.
  • the OI value represents the orientation degree of graphite, which to a certain extent reflects the number of end faces perpendicular to the c-axis direction of the graphite crystal.
  • the present disclosure controls the V ⁇ S/OI of the negative electrode material within the above range, which is conducive to improving the "effective lithium ion deintercalation interface" and improving the rate performance of the negative electrode material.
  • the negative electrode material provided by the present disclosure is produced and processed through a continuous graphitization process, so that all materials are continuously fed and discharged, and the time and temperature of the high temperature zone are kept consistent, and the graphitization process controls the heating and cooling rate, so that the volatile matter, impurity elements and other substances in the material can escape evenly and quickly.
  • the pore volume, specific surface area and orientation of the graphite material can be accurately controlled.
  • the negative electrode material provided by the present disclosure uses a continuous graphitization process, has low energy consumption per unit mass, has obvious advantages in cost and production cycle, and is environmentally friendly.
  • This embodiment provides a negative electrode material, and the preparation steps are as follows:
  • step (2) crushing the low calcined coke obtained in step (1) and shaping it through shaping equipment to obtain crushed and shaped coke powder, wherein the median particle size is controlled to be 16 ⁇ m;
  • step (3) mixing the char powder obtained in step (2) with corn starch in a mass ratio of 100:5 to obtain a precursor mixture A;
  • step (3) The precursor mixture A in step (3) is subjected to a first pressing at a low pressure of 10 MPa, and then subjected to a second pressing at a high pressure of 25 MPa, and is allowed to stand for 2 h between the first pressing and the second pressing, to obtain a precursor B;
  • the precursor B in step (4) is subjected to a high temperature treatment at 3000° C. in a continuous graphitization furnace to obtain a graphitized product C, and the heating curve is as follows: heating to 3000° C. at a heating rate of 15° C./min, keeping at 3000° C. for 3 h, and cooling to 100° C. at a cooling rate of 22° C./min after keeping.
  • the graphitized product C in step (5) is processed by processes such as breaking up, demagnetizing, and screening to obtain a negative electrode material.
  • the negative electrode material obtained in this embodiment was observed using a Hitachi S4800 scanning electron microscope.
  • the surface morphology is shown in FIG1 . It can be seen that the main component is artificial graphite, which includes primary particles and secondary particles, of which the main components are primary particles.
  • the negative electrode materials prepared in the above-mentioned Examples 1 to 20 and Comparative Examples 1 to 3 include artificial graphite, and their test parameters and electrochemical performance test results are shown in Tables 2 and 3.
  • the performance of the negative electrode materials and batteries including the negative electrode materials obtained in the above embodiments and comparative examples were tested.
  • the testing method is as follows.
  • the test results are shown in Table 2.
  • the pore volume V, specific surface area S, and orientation degree OI value of the negative electrode materials obtained in the above embodiments and comparative examples of the present disclosure are tested.
  • the testing method is as follows:
  • the pore volume V was measured using the ASAP2460 equipment from Micromeritics, USA, and calculated using the BJH Desorption cumulative volume of pores model.
  • the measurement range of this model is
  • the average pore size distribution range of the negative electrode material is The unit is cm 3 /kg;
  • the specific surface area S is measured by the dynamic specific surface area rapid determination instrument JW-DX of Beijing Jingwei Gaobo Science and Technology Co., Ltd., and the unit is m2 /g;
  • the OI value was tested using the X'pert PRO X-ray diffractometer from PANalytical, Netherlands. The OI value was 9.0T. The peak intensity ratio of 004 peak to 110 peak calculated after film preparation and rebound for 8 hours.
  • the sample, SP, CMC, and SBR were magnetically stirred in deionized water at a mass ratio of 95:1.5:1.5:2 for 8 hours to make them evenly mixed.
  • the mixed slurry was coated on copper foil and dried in vacuum at 60°C as a working electrode.
  • Metal lithium was used as the counter electrode and reference electrode, the diaphragm was Celgard2325, the electrolyte was 1mol ⁇ L ⁇ 1LiPF6 ⁇ EC (ethylene carbonate)/DMC (dimethyl carbonate)/EMC (ethyl methyl carbonate) (volume ratio of 1:1:1), and the CR2016 button cell was assembled in a glove box filled with high-purity argon, and 4 batteries were prepared for each group of samples.
  • the first discharge capacity and first discharge efficiency tests were carried out on a LAND battery tester, and the charge and discharge conditions were as follows: standing for 2 hours; discharge: 0.1C to 0.005V, 0.09C to 0.001V, 0.08C to 0.001V, 0.07 to 0.001V, 0.06 to 0.001V, 0.05 to 0.001V, 0.04 to 0.001V, 0.03 to 0.001V, 0.02C to 0.001V; standing for 15 minutes; charging: 0.1C to 1.5V; standing for 15 minutes.
  • the charging and discharging conditions of the withholding rate test are as follows: 10.1C discharge to 0.01V, constant voltage for 5h; 0.1C charge to 1.5V; 20.2C discharge to 0.01V, constant voltage 0.01C; 0.2C charge to 1.5V; 30.2C discharge to 0.01V, constant voltage 0.01C; 2C charge to 1.5V, 0.2C charge to 1.5V; 40.2C discharge to 0.01V, constant voltage 0.01C; 0.2C charge to 1.5V; 51C discharge to 0.01V, constant voltage 0.01C; 0.2C charge to 1.5V; 62C discharge to 0.01V.
  • Low temperature discharge performance test conditions After the battery is fully charged at 0.5C at room temperature, it is placed at the specified temperature (-10°C) for 16 hours and discharged at 0.5C to the termination voltage. The percentage of capacity that can be released is the -10°C/25°C capacity retention rate.
  • High temperature storage performance test conditions The battery capacity retention rate is tested after the battery is stored at 60°C for 7 days.
  • Normal temperature cycle performance test conditions The battery is cycled at room temperature (25°C) at 1C for 500 cycles and then the battery capacity retention rate is tested.
  • controlling the V ⁇ S/OI of the negative electrode material within the range of 1.74 ⁇ 10 7 to 6.1 ⁇ 10 7 cm 5 /kg 2 not only provides sufficient diffusion channels and reaction sites for lithium ions, but also improves the “effective lithium ion deintercalation interface” and ensures the lithium ion diffusion rate, thereby obtaining a negative electrode material with better rate performance.
  • Comparative Example 1 the negative electrode material prepared by a discontinuous graphitization process has too small a specific surface area, too large an orientation degree, and V ⁇ S/OI is out of the above range. The rate performance of the material is significantly reduced compared with that of Example 1.
  • the negative electrode material is prepared by a discontinuous graphitization process.
  • the pore volume V of the graphite material is too large, the orientation degree is too small, and the V ⁇ S/OI is out of the above range.
  • the graphite material used as the negative electrode material consumes more electrolyte in the lithium deintercalation reaction, and the rate performance of the material is significantly reduced.
  • Comparative Example 3 adopts a continuous graphitization process to prepare the negative electrode material, only one pressing process is performed, resulting in V ⁇ S/OI being out of the above range, and the rate performance is worse than that of Example 1.
  • the present disclosure provides a negative electrode material and a battery.
  • the negative electrode material provided by the present disclosure combines the pore volume of the graphite material with the specific surface area and the orientation degree to increase the migration rate of lithium ions to a greater extent. Therefore, the negative electrode material of the present disclosure allows lithium ions to migrate quickly and complete the electrochemical reaction, thereby obtaining a negative electrode material with better rate performance, and thus has excellent practicality.

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Abstract

L'invention concerne un matériau d'électrode négative et une batterie. Le matériau d'électrode négative comprend des particules de carbone graphitisées, et satisfait la formule V×S/OI=1,74×107cm5/kg2-6,1×107cm5/kg2, où V est le volume poreux du matériau d'électrode négative, et l'unité est le cm3/kg ; S est la surface spécifique du matériau d'électrode négative, et l'unité est le m2/g ; et OI est le degré d'orientation du matériau d'électrode négative. Le volume poreux, la surface spécifique et le degré d'orientation du matériau d'électrode négative sont ajustés, de telle sorte que le matériau d'électrode négative satisfait V×S/OI=1,74×107cm5/kg2-6,1×107cm5/kg2, ce qui permet d'améliorer les performances de taux du matériau d'électrode négative, et d'obtenir un matériau d'électrode négative présentant une performance de charge rapide relativement excellente.
PCT/CN2023/122281 2022-12-22 2023-09-27 Matériau d'électrode négative et batterie Ceased WO2024131202A1 (fr)

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CN117558917A (zh) * 2023-10-31 2024-02-13 贝特瑞新材料集团股份有限公司 负极材料及电池
CN121355254A (zh) * 2023-11-30 2026-01-16 贝特瑞新材料集团股份有限公司 负极材料及电池

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