CN115881952A - Negative electrode material and battery - Google Patents
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- CN115881952A CN115881952A CN202211657898.0A CN202211657898A CN115881952A CN 115881952 A CN115881952 A CN 115881952A CN 202211657898 A CN202211657898 A CN 202211657898A CN 115881952 A CN115881952 A CN 115881952A
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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
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- 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
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- 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
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- 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
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a negative electrode material and a battery, wherein the graphite negative electrode material comprises graphitized carbon particles and satisfies the formula V multiplied by S/OI =1.74 multiplied by 10 7 cm 5 /kg 2 ～6.1×10 7 cm 5 /kg 2 (ii) a Wherein V is the pore volume of the anode material and has a unit of cm 3 (iv) kg; s is the specific surface area of the negative electrode material and has a unit of m 2 (iv) g; and OI is the orientation degree of the negative electrode material. The pore volume, the specific surface area and the orientation degree of the graphite cathode material are adjusted to ensure that the graphite cathode material meets V S/OI =1.74 multiplied by 10 7 cm 5 /kg 2 ～6.1×10 7 cm 5 /kg 2 And further, the multiplying power performance of the negative electrode material is improved, and the graphite negative electrode material with relatively excellent quick charging performance is obtained.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of ion batteries, in particular to a negative electrode material and a battery.
Background
The rapid development of the electric automobile industry puts higher requirements on the quick charging capability of the lithium ion battery, and the design of the quick charging battery aims at the improvement of an electrode structure, such as the adoption of positive and negative electrode materials with better rate capability. The multiplying power performance expresses the ratio of the charging and discharging current of the battery core, the charging and discharging capacity of the battery is influenced, the charging rate is greatly influenced, lithium is easily separated from the negative electrode if the ordinary battery is quickly charged, the performance attenuation of the battery is accelerated, the internal short circuit of the battery can be caused in serious conditions, the ignition and explosion occur, and the multiplying power performance of the battery can be improved to a certain extent.
For a graphite negative electrode, generally speaking, what is easy to think about the improvement of the rate capability is to create more lithium ion diffusion channels for a graphite material by constructing a microporous structure so as to promote the diffusion of lithium ions in a solid-liquid interface and a solid phase; in addition, the graphite material has a large specific surface area, contains a large number of active sites, increases the reaction area, and tends to exhibit high rate performance. In fact, at the present stage when graphite materials have been developed well, by improving one parameter only, the rate capability is not necessarily optimal. At present, intensive research is needed to be carried out from the synergistic effect among various factors, so that the rate capability of the graphite can be improved to the maximum extent.
Disclosure of Invention
In view of the above, the present application provides a new anode material and a battery using the same, which overcome the problem that the existing anode material does not consider the interaction of pore volume V, specific surface area S and orientation degree OI on the graphite anode material, resulting in relatively poor performance of the graphite anode material, especially fast charge performance.
The invention is realized by the following steps:
in a first aspect, the present invention provides an anode material comprising a graphite material and filled withFoot formula V × S/OI =1.74 × 10 7 cm 5 /kg 2 ～6.1×10 7 cm 5 /kg 2 (ii) a Wherein V is the pore volume of the negative electrode material in cm 3 Per kg; s is the specific surface area of the negative electrode material and has the unit of m 2 (ii)/g; OI is the degree of orientation of the negative electrode material,
the pore volume is tested by American Mike ASAP2460 equipment, and is modeled by BJH Desorption cumulative volume of places
And calculating the aperture range.
In an alternative embodiment, the anode material satisfies: v × S/OI =2.1 × 10 7 cm 5 /kg 2 ～3.17×10 7 cm 5 /kg 2 。
In alternative embodiments, the pore volume V is 5.0cm 3 /kg～8.0cm 3 /kg。
In an alternative embodiment, the specific surface area S is 1.8m 2 /g～3.0m 2 /g。
In an alternative embodiment, the degree of orientation OI is between 3.8 and 5.4.
In an alternative embodiment, the pore size distribution of the anode material is in the range of
In an alternative embodiment, the negative electrode material has a median particle diameter of 10 to 30 μm.
In an alternative embodiment, the degree of graphitization of the graphite material is 91 to 95%.
In an alternative embodiment, the anode material further comprises amorphous carbon.
In an alternative embodiment, the amorphous carbon content in the anode material is less than 5% by mass.
In an alternative embodiment, the graphite material comprises artificial graphite.
In a second aspect, the present invention provides a battery comprising the negative electrode material of the first aspect.
The invention has the following beneficial effects:
the application provides a negative electrode material, which comprises a graphite material, wherein the interior and/or the surface of the graphite material is provided with pores, the pore volume of the negative electrode material is V, the specific surface area is S, and the orientation value is OI, wherein V is S/OI =1.74 × 10 7 cm 5 /kg 2 ～6.1×10 7 cm 5 /kg 2 . The pore volume in a certain range in the graphite material can increase the diffusion channel of lithium ions, promote the diffusion of the lithium ions in a solid-liquid interface and a solid phase, reduce concentration polarization and be beneficial to improving the rate capability of the cathode material. Meanwhile, the specific surface area within a certain range can ensure an enough electrochemical reaction interface, promote the diffusion of lithium ions in a solid-liquid interface and a solid phase, reduce concentration polarization and be beneficial to improving the rate capability of the cathode material. The applicant researches on how to further improve the rate capability of the graphite material on the basis of the above, and purposefully searches among a plurality of considerations, and finds that the combination of the orientation degree OI of the graphite negative electrode, the specific surface area and the pore volume can greatly improve the lithium ion migration rate, and the reason is presumed that the diffusion of lithium ions in the graphite material has strong directionality, namely, the lithium ions can only be inserted into 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, the pore volume and the specific surface area are improved once, a large number of lithium ion non-insertable interfaces exist, which is not beneficial to the improvement of the rate capability, and the OI value represents the orientation degree of the graphite and represents the number of the end faces perpendicular to the c-axis direction of the graphite crystal to a certain extent. The application controls the V S/OI of the negative electrode material in the range, thereby being beneficial to improving the effective lithium ion extraction interface and improving the multiplying power performance of the material.
The application provides a cathode material forms through continuous graphitization technology production and processing for the continuous feeding of all materials and continuous ejection of compact, and then the time and the temperature through high-temperature region keep unanimous, and the graphitization process is through the control to heating and cooling speed, make in the material volatile, matters such as impurity element can even rapid escape, and simultaneously, through twice die mould technology, and to the regulation to die mould pressure size, the realization is to the accurate control of graphite pore volume, specific surface area and orientation degree. The synergistic use of the process method overcomes the problems that the materials are heated unevenly due to the temperature gradient existing at different positions in the traditional graphitization furnace, the indexes of the specific surface area, the pore volume, the orientation degree and the like of the produced and processed products are greatly fluctuated and are not controlled, and the like, so that the pore volume, the specific surface area and the orientation degree of the processed materials meet the ideal regulation and control design requirements.
The cathode material provided by the application uses a continuous graphitization process, so that the energy consumption in unit mass is low, the cost and the production period have obvious advantages, and the cathode material is environment-friendly.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is an SEM image of a graphite negative electrode material in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the field of negative electrode materials, development of continuous graphitization equipment lasts for decades, and a patent (US 06619591) is published as early as 1987 and discloses equipment capable of continuously graphitizing carbon-containing materials, and in recent years, an applicant is continuously developing continuous graphitization equipment, for example, a patent with an authorization publication number of CN211425033U applied in 2019 discloses a vertical continuous furnace for producing a negative electrode material of a lithium battery, which can realize continuous discharge from a discharge port and continuous feeding from a material pipeline. Compared with the conventional process, the continuous graphitization process shortens the graphitization time from several days to several hours, so that the energy consumption is remarkably reduced, but the continuous graphitization process greatly shortens the graphitization time, so that compared with the conventional graphite material, the microstructure of the graphite material is changed, particularly the internal pore structure of the graphite material, the crystal form and the like are changed. It has long been verified in the industry that such changes are difficult to meet and improve upon the performance requirements of graphite materials, and therefore continuous graphitized graphite products have not been a precedent for successful mass production over the three-forty years even though continuous graphitizing equipment has been available.
In recent years, with the further energy shortage, in order to further reduce the cost of graphite materials, the applicant continuously develops the application of continuous graphitization equipment, and aims to develop a graphite negative electrode material which has performance equivalent to or even better than that of the conventional graphitization negative electrode material at present, so as to reduce the energy consumption of the graphite negative electrode material and further reduce the cost. Through development of a large number of preparation processes, the applicant develops various means capable of improving adverse changes brought to graphite products by rapid temperature rise and drop, and obtains a series of graphite cathode materials with different models through screening of the products. Although the microstructure of the graphite cathode material is different from that of the conventional graphite product, the graphite cathode material has the electrical property basically equivalent to that of the conventional graphite product, even the electrical property and the processing property in certain aspects are more excellent or stable, and the graphite cathode material has the condition of replacing the conventional graphite product.
The following description will be made in further detail by taking one of the processes developed by the applicant as an example.
The graphite cathode material in the application adopts the continuous graphitization device to realize the graphitization process of the graphite material, and the power-off is not needed in the production process, so that the continuous production is realized. Specifically, the following method can be adopted:
(1) Calcining green coke at 500-1000 ℃ for 45-55 h, and cooling to obtain low calcined coke;
(2) Crushing the low-calcined coke obtained in the step (1) and shaping the crushed low-calcined coke by a shaping device to obtain crushed and shaped coke powder;
(3) Mixing the coke powder obtained in the step (2) with a binder according to a mass ratio of 100: (2-5) mixing to obtain a precursor mixture A;
(4) Performing primary compression on the precursor mixture A in the step (3) at a low pressure of 5-15 MPa, and performing secondary compression at a high pressure of 15-30 MPa to obtain a precursor B, wherein the difference of the pressures used by the secondary compression and the primary compression is 10-20 MPa, and standing for 1-5 h between the two compression;
(5) And (5) treating the precursor B in the step (4) through a continuous graphitizing furnace at the high temperature of 3000-3200 ℃ to obtain a graphitized product C, wherein the temperature rise curve is as follows: heating from the initial temperature to 3000-3200 ℃ at a heating rate of 12-17 ℃/min, preserving the heat at 3000-3200 ℃ for 3-4 h, and cooling to 25 ℃ at a cooling rate of 16-25 ℃/min after preserving the heat.
According to the preparation method of the negative electrode material, the coke powder and the binder are mixed and then subjected to secondary compression, compared with primary compression, the orientation degree of the material can be better reduced through secondary compression, and the compression strength and compactness can be better controlled through secondary compression, so that the purpose of regulating and controlling the pore volume is achieved; in the continuous graphitization process, a rapid heating mode is adopted, and in the growth process of graphite microcrystals, volatile components, impurity atoms and the like rapidly escape from graphite particles, so that a certain pore structure can be formed in the graphite; the rapid cooling can reduce the oxidation of materials, maintain the stability of a microporous structure, and only a few hours are needed from the process of feeding the materials into the furnace to the process of discharging the materials from the furnace in the graphitization process, thereby improving the production efficiency to a certain extent.
In some embodiments, the green coke may be any one of petroleum coke, needle coke, pitch coke, isotropic coke; the physical and chemical properties of the coke powder can be changed to a certain degree through calcination treatment, and the capacity performance is improved.
In some embodiments, the binder may be at least one of asphalt, liquid asphalt, phenolic resin, potato starch, corn starch, tapioca flour.
In some embodiments, the pressure of the primary press may be 5MPa, 8MPa, 10MPa, 12MPa, 15MPa, the primary press may serve the purpose of pre-pressing and not pressing too much, the pressure of the secondary press may be 15MPa, 18MPa, 20MPa, 22MPa, 25MPa, 28MPa, 30MPa, and the secondary press functions to regulate the strength of the press to a desired level. The method is characterized in that the small-pressure compression is firstly used, the large-pressure compression is used after standing, the process from agglomeration to dispersion is carried out in the middle, the distribution of the binder in the coke powder can be more uniform, so that the particle orientation degree difference caused by excessive binder content at a certain position in the compression process is avoided, in addition, the pore volume unevenness caused by binder volatilization in the subsequent heat treatment process can also be avoided, the accurate regulation and control of the orientation degree and the pore volume are realized, the pressure difference used by the secondary compression and the primary compression is ensured to be within the range of 10 MPa-20 MPa, specifically 10MPa, 12MPa, 15MPa, 18MPa or 20MPa, and the like, and the limitation is not required. If the pressure difference is too small, the front and back compression effects are equivalent, which is almost equal to one-time compression, the process from agglomeration to dispersion of the raw materials cannot be completed, the binder is not uniformly distributed, uniform holes and orientation degree are not generated, and if the pressure difference is too large, the materials are easy to loosen and cannot achieve the purpose of precise regulation.
In some embodiments, the standing time between the primary pressing and the secondary pressing can be 1h, 2h, 3h, 4h, 5h and the like, the binder and the coke powder are slightly fused during the standing, the binder slowly performs the binding action, an interaction force is formed between the binder and the coke powder, and the binder has certain strength and provides necessary conditions for the secondary pressing.
In some embodiments, the temperature of the graphitization treatment may be 3000 ℃, 3100 ℃, 3200 ℃, or the like, without limitation. The heating rate can be 12 ℃/min, 13 ℃/min, 14 ℃/min, 15 ℃/min, 16 ℃/min or 17 ℃/min, etc., without limitation. The cooling rate can be 16 ℃/min, 18 ℃/min, 20 ℃/min, 22 ℃/min, 24 ℃/min or 25 ℃/min, etc., without limitation. The advantage of such a design is that it facilitates the rapid escape of volatile materials within the coke feedstock, facilitating the formation of pore structures in the product.
In some embodiments, the graphitization treatment of step (7) is followed by at least one of pulverization, sieving, and demagnetization. Preferably, after the carbonization treatment, the steps of crushing, demagnetizing and screening are also sequentially carried out.
In some embodiments, the pulverization is any one of a mechanical pulverizer, a jet pulverizer, and a cryogenic pulverizer.
In some embodiments, the screening manner is any one of a fixed screen, a drum screen, a resonance screen, a roller screen, a vibrating screen and a chain screen, the screening mesh number is 100 to 500 meshes, specifically, the screening mesh number may be 100 meshes, 200 meshes, 250 meshes, 325 meshes, 400 meshes, 500 meshes, and the like, and the particle size of the negative electrode material is controlled in the above range, which is beneficial to improving the processability of the negative electrode material.
In some embodiments, the demagnetizing device is any one of a permanent magnet drum magnetic separator, an electromagnetic iron remover and a pulsating high gradient magnetic separator, and the demagnetizing is to finally control the content of the magnetic substance in the negative electrode material, so as to avoid the discharging effect of the magnetic substance on the lithium ion battery and the safety of the battery during the use process.
The application provides a negative electrode material, which comprises a graphite material and satisfies the formula V multiplied by S/OI =1.74 multiplied by 10 7 ～6.1×10 7 cm 5 /kg 2 (ii) a Wherein V is the pore volume of the anode material and has a unit of cm 3 (iv) kg; s is the specific surface area of the negative electrode material and has the unit of m 2 (iv) g; OI is the degree of orientation of the negative electrode material,
the pore volume is tested by adopting ASAP2460 equipment of American Mike company, and a BJH Desorption cumulative volume of places model is adopted
And calculating the aperture range.
The application provides a negative electrode material forms through continuous graphitization technology production and processing for the continuous feeding of all materials and continuous ejection of compact, and then the time and the temperature through high temperature zone keep unanimous, and the graphitization process is through the control to the speed of rising and falling temperature, and matters such as volatile in the material, impurity element can evenly escape fast, simultaneously, through secondary die mould technology, and the control is to the regulation of the pressure size of die mould, realizes the accurate control to the orientation degree. The synergistic use of the process method overcomes the problems that the materials are heated unevenly due to the temperature gradient existing at different positions in the traditional graphitization furnace, the indexes of the specific surface area, the pore volume, the orientation degree and the like of the produced and processed products are greatly fluctuated and are not controlled, and the like, so that the pore volume, the specific surface area and the orientation degree of the processed materials meet the ideal regulation and control design requirements.
The pore volume in a certain range in the graphite material can increase the diffusion channel of lithium ions, promote the diffusion of the lithium ions in a solid-liquid interface and a solid phase, reduce concentration polarization and be beneficial to improving the rate capability of the cathode material. Meanwhile, the specific surface area within a certain range can ensure an enough electrochemical reaction interface, promote the diffusion of lithium ions in a solid-liquid interface and a solid phase, reduce concentration polarization and be beneficial to improving the rate capability of the cathode material. The applicant researches how to further improve the rate capability of the graphite material on the basis of the above, and purposefully explores in a plurality of considerations, and finds that the combination of the orientation degree OI of the graphite negative electrode, the specific surface area and the pore volume can greatly improve the lithium ion migration rate, and the reason is presumed that the lithium ion diffusion in the graphite material has strong directionality, namely the lithium ion diffusion can only insert into 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, the pore volume and the specific surface area are improved once, a large number of lithium ion non-releasable interfaces exist, which are not beneficial to the improvement of the rate capability, and the OI value represents the orientation degree of the graphite and represents the number of the end faces perpendicular to the c-axis direction of the graphite crystal to a certain extent. The V S/OI of the negative electrode material is controlled within the range, so that the effective lithium ion deintercalation interface is improved, and the multiplying power performance of the material is improved.
In some embodiments, the anode material satisfies: vxs/OI =2.1 × 10 7 cm 5 /kg 2 ～3.17×10 7 cm 5 /kg 2 。
In some embodiments, the pore volume V is from 5.0 to 8.0cm 3 /kg。
In some embodiments, the specific surface area S is 1.8m 2 /g～3.0m 2 /g。
In some embodiments, the degree of orientation OI is between 3.8 and 5.4.
In order to improve the quick charge performance of the graphite negative electrode material and comprehensively consider the capacity, the cycle performance and the like of the graphite negative electrode, the pore volume V, the specific surface area S and the orientation degree OI of the negative electrode material are limited.
In some embodiments, the anode material has a pore size distribution ranging from
In some embodiments, the anode material has a median particle diameter of 10 to 30 μm.
The median particle size of the graphite material has an effect on the specific surface area of the electrode and the proportion of edge atoms, thereby affecting the capacity performance.
In some embodiments, the degree of graphitization of the negative electrode material is 91 to 95%.
The graphitization degree can influence the layered structure, the distance between adjacent crystal layers, the resistivity and the like of the graphite material, and the higher the graphitization degree is, the closer to ideal graphite is, the better the theoretical capacity is.
In some embodiments, the anode material further comprises amorphous carbon;
in some embodiments, the mass content of the amorphous carbon in the anode material is less than 5%.
The adhesive is difficult to convert into graphitized carbon after graphitizing treatment, the part which cannot be converted into graphitized carbon exists in the form of amorphous carbon, and the existence of a certain amount of amorphous carbon can increase the conductivity of the material and improve the electrochemical performance.
Another embodiment of the present application provides an application of the graphite negative electrode material described in the foregoing embodiment in a lithium ion battery.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a graphite anode material, which comprises the following specific preparation steps:
(1) Calcining petroleum coke green coke at 800 ℃ for 50h, and cooling to obtain low calcined coke;
(2) Crushing the low calcined coke obtained in the step (1) and shaping the crushed low calcined coke by a shaping device to obtain crushed and shaped coke powder, wherein the median particle size is controlled to be 16um;
(3) Mixing the coke powder obtained in the step (2) with corn starch according to the mass ratio of 100:5, mixing to obtain a precursor mixture A;
(4) Performing primary compression on the precursor mixture A in the step (3) at low pressure of 10MPa, performing secondary compression at high pressure of 25MPa, and standing for 2 hours between the primary compression and the secondary compression to obtain a precursor B;
(5) And (5) treating the precursor B in the step (4) at 3000 ℃ in a continuous graphitizing furnace to obtain a graphitized product C, wherein the temperature rise curve is as follows: heating to 3000 ℃ according to the heating rate of 15 ℃/min, preserving heat for 3h at 3000 ℃, and cooling to 100 ℃ according to the cooling rate of 22 ℃/min after preserving heat;
(6) And (5) treating the graphitized product C in the step (5) through the working procedures of scattering, demagnetizing, screening and the like to obtain the graphite negative electrode material.
When the graphite negative electrode material obtained in this example was observed with a scanning electron microscope from hitachi corporation S4800, the surface morphology is as shown in fig. 1, and it can be seen that the artificial graphite mainly consists of artificial graphite, and the artificial graphite includes primary particles and secondary particles, of which primary particles are predominant.
Examples 2 to 20 and comparative examples 1 to 3
The preparation methods of the graphite anode materials in examples 2 to 20 and comparative examples 1 to 3 are shown in table 1, wherein S2 represents example 2, S3 represents example 3, and so on, D1 represents comparative example 1, D2 represents comparative example 2, and D3 represents comparative example 3.
Table 1 preparation method of graphite anode material in examples 2 to 20 and comparative examples 1 to 3
The anode materials prepared in the above examples 1 to 20 and comparative examples 1 to 3 include artificial graphite, and the test parameters and the electrochemical performance test results thereof are shown in tables 2 and 3.
Test example:
the graphite negative electrode materials obtained in the above examples and comparative examples and the batteries including the graphite negative electrode materials were tested for their performance according to the following test methods, and the test results are shown in table 2.
1. The pore volume V, specific surface area S, and orientation degree OI values of the graphite anode materials obtained in the above examples and comparative examples of the present application were measured by the following specific methods:
(1) the pore volume V is tested by ASAP2460 equipment of Michmark company in America, and is calculated by applying a BJH Desorption cumulative pore volume of sites model, and the pore diameter distribution range of the graphite cathode material is
Unit is cm 3 /kg；
(2) The specific surface area S is tested by a dynamic specific surface area rapid tester JW-DX of Beijing Jingwei Gaobaokou science and technology Limited company, and the unit is m 2 /g；
(3) The OI value is tested by an X' pert PRO model X-ray diffractometer from Netherlands to Parnaceae, and the OI value is calculated as the intensity ratio of 004 peak to 110 peak after the OI value is pressed into tablets at 9.0T and rebounded for 8H.
2. The graphite negative electrode materials prepared in the above examples 1 to 20 and comparative examples 1 to 3 were applied to batteries, and the obtained batteries were tested for their performance by the following specific method:
the sample, the SP, the CMC, the SBR were magnetically stirred in deionized water for 8 hours in a mass ratio of 95.5. The slurry obtained by mixing was coated on a copper foil, and dried in vacuum at 60 ℃ to obtain a working electrode. The method comprises the steps of adopting metal lithium as a counter electrode and a reference electrode, adopting a diaphragm Celgard2325, adopting an electrolyte of 1 mol.L-1 LiPF 6-EC (ethylene carbonate)/DMC (dimethyl carbonate)/EMC (ethyl methyl carbonate) (the volume ratio is 1.
The first discharge capacity and the first discharge efficiency are tested on a LAND battery tester, and the charge and discharge conditions are as follows: standing for 2h; discharging: 0.1C to 0.005V,0.09C,0.08C 8230; 0.02C to 0.001V; standing for 15min; charging: 0.1C to 1.5V; standing for 15min.
And (3) testing charge and discharge conditions by using a charge multiplying power: (1) 0.1 ℃ is released to 0.01V, and the pressure is kept constant for 5h;0.1C to 1.5V; (2) 0.2C to 0.01V, and constant pressure is 0.01C; charging 0.2C to 1.5V; (3) 0.2C to 0.01V, and constant pressure is 0.01C;2C to 1.5V,0.2C to 1.5V; (4) 0.2C to 0.01V, and constant pressure is 0.01C;0.2C to 1.5V; (5) 1C is put to 0.01V, and the constant pressure is 0.01C; charging 0.2C to 1.5V; (6) 2C to 0.01V.
Low-temperature discharge performance test conditions: after the battery is fully charged at the normal temperature according to 0.5 ℃, the battery is placed for 16 hours at the specified temperature (-10 ℃) and the capacity percentage which can be discharged to the termination voltage according to the 0.5 ℃ is the capacity retention ratio of-10 ℃/25 ℃.
High-temperature storage performance test conditions: the battery capacity retention rate was tested after storing the battery at 60 ℃ for 7 days.
Normal temperature cycle performance test conditions: the capacity retention of the battery was tested after cycling the battery at room temperature (25 ℃) for 500 cycles at 1C.
TABLE 2 parameters of anode materials in examples and comparative examples
Table 3 results of tests performed on lithium ion batteries using negative electrode materials obtained in examples and comparative examples
From the test data of examples 1 to 20, it can be seen that V.S/OI was controlled to 1.74X 10 7 ～6.1×10 7 cm 5 /kg 2 In the range, not only lithium ions have sufficient diffusion channels and reaction sites, but also an effective lithium ion extraction interface is improved, the diffusion rate of the lithium ions is guaranteed, and therefore the cathode material with better rate capability is obtained.
Comparative example 1 the negative electrode material prepared by the discontinuous graphitization process has too small specific surface area and too large orientation degree, V S/OI is out of the range, and the rate capability of the material is obviously reduced compared with that of example 1.
Comparative example 2 is the negative electrode material prepared by the discontinuous graphitization process, the pore volume V of the graphite material is too large, the orientation degree is too small, V S/OI is out of the range, electrolyte consumed by the graphite material as the negative electrode material in the lithium desorption reaction is increased, and the rate capability of the material is obviously reduced.
Comparative example 3 although the negative electrode material was prepared by the continuous graphitization process, the rate capability was inferior to that of example 1 because the pressing was performed only once, which resulted in the deviation of V × S/OI from the above range.
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 (10)
1. An anode material characterized in that: comprises a graphite material and satisfies the formula V × S/OI =1.74 × 10 7 cm 5 /kg 2 ～6.1×10 7 cm 5 /kg 2 (ii) a Wherein V is the pore volume of the negative electrode material in cm 3 (iv) kg; s is the specific surface area of the negative electrode material and has a unit of m 2 (iv) g; OI is the degree of orientation of the negative electrode material,
the pore volume is tested by American Mike ASAP2460 equipment, and is modeled by BJH Desorption cumulative volume of places
And calculating the aperture range.
2. The negative electrode material according to claim 1, characterized in that: v × S/OI =2.1 × 10 7 cm 5 /kg 2 ～3.17×10 7 cm 5 /kg 2 。
3. The anode material according to claim 1, characterized in that: the pore volume V is 5.0cm 3 /kg～8.0cm 3 /kg。
4. The anode material according to claim 1, characterized in that: the specific surface area S is 1.8m 2 /g～3.0m 2 /g。
5. The anode material according to claim 1, characterized in that: the orientation degree OI is 3.8-5.4.
6. The anode material according to claim 1, characterized in that: the pore diameter distribution range of the negative electrode material is
7. The negative electrode material according to claim 1, characterized in that: the median particle size of the negative electrode material is 10-30 μm.
8. The negative electrode material according to claim 1, characterized in that: the graphitization degree of the graphite material is 91-95%.
9. The anode material according to claim 1, characterized in that: the anode material satisfies at least one of the following characteristics:
(1) The anode material further comprises amorphous carbon;
(2) The negative electrode material also comprises amorphous carbon, and the mass content of the amorphous carbon in the negative electrode material is less than 5%;
(3) The graphite material comprises artificial graphite.
10. A battery comprising the negative electrode material of any one of claims 1-9.
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| WO2024131202A1 (en) * | 2022-12-22 | 2024-06-27 | 开封瑞丰新材料有限公司 | Negative electrode material and battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210273223A1 (en) * | 2019-02-01 | 2021-09-02 | Lg Chem, Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery comprising the same |
| CN115377393A (en) * | 2022-09-23 | 2022-11-22 | 深圳市贝特瑞新能源技术研究院有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN115472829A (en) * | 2021-06-10 | 2022-12-13 | 国家能源投资集团有限责任公司 | Negative electrode material, preparation method and application thereof, negative electrode plate and application thereof |
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| CN107706387B (en) * | 2017-10-09 | 2021-11-05 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN109713303B (en) * | 2018-12-29 | 2021-12-21 | 蜂巢能源科技有限公司 | Method for preparing negative electrode material, negative electrode material and power battery |
| CN110642247B (en) * | 2019-09-30 | 2021-05-25 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery |
| CN110600715B (en) * | 2019-10-17 | 2021-06-04 | 石家庄尚太科技股份有限公司 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210273223A1 (en) * | 2019-02-01 | 2021-09-02 | Lg Chem, Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery comprising the same |
| CN115472829A (en) * | 2021-06-10 | 2022-12-13 | 国家能源投资集团有限责任公司 | Negative electrode material, preparation method and application thereof, negative electrode plate and application thereof |
| CN115377393A (en) * | 2022-09-23 | 2022-11-22 | 深圳市贝特瑞新能源技术研究院有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
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| WO2024131202A1 (en) * | 2022-12-22 | 2024-06-27 | 开封瑞丰新材料有限公司 | Negative electrode material and battery |
| 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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