WO2021217620A1 - 负极活性材料及其制备方法、二次电池和包含二次电池的装置 - Google Patents
负极活性材料及其制备方法、二次电池和包含二次电池的装置 Download PDFInfo
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Definitions
- Secondary batteries are widely used because of their reliable performance, no pollution, no memory effect, etc. For example, with increasing attention to environmental protection issues and the increasing popularity of new energy vehicles, the demand for power-type secondary batteries will show explosive growth. However, as the application range of the secondary battery becomes wider and wider, the performance of the secondary battery also poses a severe challenge. Energy density affects the endurance of the secondary battery (that is, the use time after a charge). Therefore, the development of secondary battery technology requires high energy density as a prerequisite. However, the inventor found that when the energy density of the battery is high, the fast charging performance and cycle life are generally relatively poor.
- the first aspect of the present application provides a negative electrode active material, which includes a core and a coating layer covering the surface of the core, the core includes artificial graphite, the coating layer includes amorphous carbon, and the negative electrode is active
- the surface area average particle size D(3,2) of the material is denoted as A
- the surface area average particle size D(3,2) of the negative electrode active material after powder compaction under a pressure of 20kN is denoted as B
- the negative electrode active material satisfies: 72% ⁇ B/A ⁇ 100% ⁇ 82%.
- a second aspect of the present application provides a secondary battery, which includes a negative pole piece, and the negative pole piece includes the negative electrode active material described in the first aspect of the present application.
- a third aspect of the present application provides a device including the secondary battery described in the second aspect of the present application.
- the fourth aspect of the present application provides a method for preparing a negative electrode active material, which includes the following steps:
- the volume average particle size D v 50 of the coke raw material is 7 ⁇ m-12 ⁇ m, and the volatile content C 1 of the coke raw material satisfies 1% ⁇ C 1 ⁇ 12%;
- the negative electrode active material provided in the present application includes a core and a coating layer covering the surface of the core, the core includes artificial graphite, the coating layer includes amorphous carbon, and the negative electrode active material is exposed to The D(3,2) before and after the 20kN pressure powder compaction meets a specific relationship, which enables the negative electrode active material to have a higher gram capacity while greatly improving the ability of the negative electrode active material to rapidly transmit active ions, and The stability of the structure under pressure (such as the cyclic expansion force of the negative electrode, etc.). Therefore, the use of the negative electrode active material of the present application can enable the secondary battery to have a higher energy density and improve the fast charging capability and cycle life.
- the device of the present application includes the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
- FIG. 1 is a scanning electron microscope (SEM) image of an embodiment of artificial graphite.
- Fig. 2 is a schematic diagram of an embodiment of a secondary battery.
- Fig. 3 is an exploded view of Fig. 2.
- Fig. 4 is a schematic diagram of an embodiment of a battery module.
- Fig. 5 is a schematic diagram of an embodiment of a battery pack.
- Fig. 6 is an exploded view of Fig. 5.
- Fig. 7 is a schematic diagram of an embodiment of a device in which a secondary battery is used as a power source.
- any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
- every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit in combination with any other point or single numerical value or in combination with other lower or upper limits to form an unspecified range.
- An embodiment of the first aspect of the present application provides a negative active material
- the negative active material includes a core and a coating layer covering the surface of the core, the core includes artificial graphite, and the coating layer includes amorphous carbon
- the surface area average particle size D(3,2) of the negative electrode active material is denoted as A
- the surface area average particle size D(3,2) of the negative electrode active material after powder compaction under a pressure of 20kN is denoted as B
- the negative electrode The active material satisfies: 72% ⁇ B/A ⁇ 100% ⁇ 82%.
- the negative electrode active material provided in the present application includes a core and a coating layer covering the surface of the core, the core includes artificial graphite, the coating layer includes amorphous carbon, and the negative electrode active material is The latter D(3,2) satisfies a specific relationship, which enables the negative electrode active material to have a higher gram capacity, while greatly improving the ability of the negative electrode active material to rapidly transmit active ions, and the structure is stable under stress sex.
- the term "forced” includes the huge internal stress (referred to as the cyclic expansion force) caused by the negative electrode active material being repeatedly contracted and expanded during the battery cycle charging and discharging process. Therefore, the use of the negative electrode active material of the present application can enable the secondary battery to improve the fast charging capability and cycle life under the premise of a higher energy density, so that the secondary battery can simultaneously take into account higher energy density, fast charging performance and Cycle performance.
- artificial graphite has a layered structure formed by multiple graphite layers (Graphene layers) arranged along the c-axis direction, and its surface includes a basal plane and an edge plane.
- Active ions are mainly embedded and extracted from the end surface of artificial graphite, so the higher the ratio of the end surface to the base surface, the more conducive to the rapid transmission of active ions.
- the inventors have surprisingly found that when the negative electrode active material satisfies an appropriate relationship between D(3,2) before and after being compressed by 20kN pressure, it can have a higher structural stability and a higher The ratio of the end surface to the base surface.
- the negative electrode active material has a longer cycle life and higher active ion rapid transport performance, so that the secondary battery using it has a higher energy density. At the same time, it takes into account a longer cycle life and a better fast charging capability.
- the negative electrode active material may satisfy: 72% ⁇ B/A ⁇ 100% ⁇ 80%, 74% ⁇ B/A ⁇ 100% ⁇ 82%, 74.5% ⁇ B/A ⁇ 100% ⁇ 79% , 75.5% ⁇ B/A ⁇ 100% ⁇ 81%, 76% ⁇ B/A ⁇ 100% ⁇ 82% or 77% ⁇ B/A ⁇ 100% ⁇ 80%, etc.
- the negative active material satisfies 74% ⁇ B/A ⁇ 100% ⁇ 80%.
- the B/A value of the negative electrode active material is in an appropriate range, which is more conducive to making the battery take into account both high rapidity and sufficient capacity and cycle life.
- 80% to 100% of the surface of the core may be covered with an amorphous carbon coating layer. More preferably, 90% to 100% of the surface of the core may be covered with an amorphous carbon coating layer.
- the amorphous carbon coating layer may be formed by carbonization of an organic carbon source.
- the organic carbon source can be selected from high molecular polymers, such as coal tar pitch, petroleum pitch, phenolic resin and other high molecular materials.
- Amorphous carbon has a disordered structure and a relatively high interlayer spacing. Therefore, the use of amorphous carbon to coat the core material can enable active ions to diffuse faster in the negative electrode active material particles, thereby improving the rapid charging ability of the material. At the same time, the amorphous carbon coating layer can also protect the core material, greatly reducing the graphite layer peeling caused by the solvent co-embedding of the core material, so that the negative electrode active material has higher structural stability. Therefore, the negative electrode active material can have higher capacity development and cycle life.
- the inventors have found through in-depth research that when the anode active material of the present application satisfies the above conditions, if one or more of the following design conditions are optionally satisfied, the performance of the secondary battery can be further improved.
- D(3,2) (ie, A) of the negative active material may satisfy: 9 ⁇ m ⁇ A ⁇ 15 ⁇ m.
- the D(3,2) of the negative electrode active material is in an appropriate range, so that the active ions and electrons have a shorter diffusion path in the particles, thereby improving the active ion diffusion rate and electronic conductivity of the negative electrode active material, and thus can improve the battery’s performance.
- the negative electrode active material with appropriate D(3,2) has a higher gram capacity, and at the same time can enable the pole piece using it to obtain a higher compaction density, so it can also increase the energy density of the battery.
- the active specific surface area of the negative electrode active material is small, thereby reducing the side reaction of the electrolyte on the surface thereof, thereby enabling the battery to have high cycle performance.
- the negative electrode active material volume average particle size D v 50 satisfy: 10 ⁇ m ⁇ D v 50 ⁇ 16 ⁇ m.
- the negative electrode active material D v 50 can ⁇ 10.5 ⁇ m, ⁇ 11 ⁇ m, ⁇ 11.5 ⁇ m, ⁇ 12 ⁇ m, or ⁇ 12.5 ⁇ m; further, the negative electrode active material D v 50 can ⁇ 15.5 ⁇ m, ⁇ 15 ⁇ m, ⁇ 14.5 ⁇ m , ⁇ 14 ⁇ m, ⁇ 13.5 ⁇ m, or ⁇ 13 ⁇ m. More preferably, 12 ⁇ m ⁇ D v 50 ⁇ 14 ⁇ m.
- the D v 50 of the negative electrode active material is suitable for making it have higher active ions and fast electron transport performance, and at the same time, it can also reduce the side reaction of the electrolyte in the negative electrode.
- a negative electrode active material with a proper D v 50 is also beneficial to increase its powder compaction density, so that the pole piece using it can obtain a higher compaction density, thereby increasing the energy density of the battery.
- the negative active material may simultaneously satisfy 9 ⁇ m ⁇ A ⁇ 14 ⁇ m and 10 ⁇ m ⁇ D v 50 ⁇ 15 ⁇ m. More preferably, the negative active material may simultaneously satisfy 11 ⁇ m ⁇ A ⁇ 13 ⁇ m and 12 ⁇ m ⁇ D v 50 ⁇ 14 ⁇ m.
- the negative electrode active material satisfies both A and D v 50 in an appropriate range, so that the negative electrode active material has a better surface structure and particle size distribution. Therefore, the negative electrode active material can also have higher electrochemical kinetic performance and higher
- the surface stability of the battery can further improve the fast charging ability and cycle performance of the battery.
- the particles can form close contact with each other, and at the same time, a good pore structure can be formed, so that the pole piece has high active ion solid-phase diffusion performance and liquid-phase conductivity. Thereby, the fast charging capability of the battery is further improved.
- the particle size distribution (D v 90-D v 10)/D v 50 of the negative active material satisfies: 1.0 ⁇ (D v 90-D v 10)/D v 50 ⁇ 1.35.
- the (D v 90-D v 10)/D v 50 of the negative active material may be 1.1, 1.15, 1.18, 1.2, 1.25, or 1.3. More preferably, 1.15 ⁇ (D v 90-D v 10)/D v 50 ⁇ 1.25.
- Proper particle size distribution makes the negative electrode active material contain an appropriate amount of larger particles and smaller particles.
- the negative electrode film prepared by the negative electrode active material can obtain a higher compaction density, and the material particles can have a larger
- the contact area can enable the negative pole piece to have a higher reversible capacity, and at the same time improve the solid phase diffusion performance of active ions in the negative electrode film layer and the electronic conductivity performance.
- the particle size distribution of the negative electrode active material also allows the negative electrode film to form an unobstructed pore structure, especially the active ion liquid phase conduction path is short and the impedance is small. Therefore, the battery can obtain a higher fast charging capability and energy density.
- the particle size distribution of the negative electrode active material is within an appropriate range, and the negative electrode film layer also has higher cohesion, which can reduce the cycle expansion force of the battery.
- the number of small particles in the negative electrode active material is small, which can reduce side reactions in the battery. Therefore, the cycle life of the battery can be further improved.
- the negative electrode active material which can meet 10 ⁇ m ⁇ D v 50 ⁇ 16 ⁇ m and 1.0 ⁇ (D v 90-D v 10) / D v 50 ⁇ 1.35. More preferably, the negative active material may satisfy 12 ⁇ m ⁇ D v 50 ⁇ 14 ⁇ m and 1.1 ⁇ (D v 90-D v 10) / D v 50 ⁇ 1.3.
- the volume of the negative electrode active material a particle size distribution satisfying D v 90: 18 ⁇ m ⁇ D v 90 ⁇ 26 ⁇ m. More preferably, 20 ⁇ m ⁇ D v 90 ⁇ 24 ⁇ m. If the D v 90 of the negative electrode active material is in an appropriate range, the content of large particles in the negative electrode active material can be further reduced, and the rapid transmission performance of active ions and electrons can be improved, thereby further improving the rapid charging ability of the battery. In addition, the negative electrode active material contains fewer large particles, which is beneficial to uniformly distribute the negative electrode active material in the film layer, which can further improve the active ion and electron transport performance of the film layer, and reduce the battery polarization, so that the battery can obtain High fast charging capacity and cycle performance.
- the tap density of the negative electrode active material may be 0.9 g/cm 3 to 1.15 g/cm 3 , more preferably 0.95 g/cm 3 to 1.05 g/cm 3 .
- the tap density of the negative electrode active material is within an appropriate range, which enables the negative electrode active material to have higher active ion and electron rapid transport capabilities.
- the negative electrode active material has a small degree of secondary particles, which can make it also have a higher gram capacity and lower side reactions. Therefore, an appropriate tap density can improve the battery's rapid charging capability, energy density, and cycle life.
- the negative active material can simultaneously satisfy 10 ⁇ m ⁇ D v 50 ⁇ 15 ⁇ m and the tap density can be 0.9 g/cm 3 ⁇ 1.15 g/cm 3 .
- the negative active material may satisfy 12 ⁇ m ⁇ D v 50 ⁇ 14 ⁇ m and 0.95g / cm 3 ⁇ 1.05g / cm 3.
- the negative electrode active material satisfies both D v 50 and tap density in an appropriate range, which can make it have higher bulk structure stability and surface stability, and at the same time have a higher end-to-base ratio and shorter activity Ion and electron transport path. Therefore, the use of the negative electrode active material can enable the battery to have higher cycle performance, and at the same time, further improve the fast charging ability of the battery.
- the graphitization degree of the negative electrode active material may be 90%-96%, more preferably 92%-95%.
- the graphitization degree of the negative electrode active material is within an appropriate range, which can make it have a smaller powder resistivity while also having a larger interlayer spacing, reducing the resistance to solid diffusion of active ions in the particles, thereby increasing its resistance. Fast charging capability.
- having an appropriate degree of graphitization can also prevent the artificial graphite from being co-embedded with solvents during the battery cycle, so that the graphite layer is not easily peeled off, which improves the structural stability of the negative electrode active material.
- the powder OI value of the negative active material may be 2.0-5.0, more preferably 2.1-4.0, and particularly preferably 2.5-3.5.
- the powder OI value of the negative electrode active material is within an appropriate range, which can make it have a higher degree of isotropy, so that the active ions can be extracted/intercalated in different directions, shorten the ion migration path, and reduce the ion diffusion resistance. Improve the fast charging capability of the battery. At the same time, the expansion of the negative electrode active material for ion intercalation can be dispersed in all directions, thereby reducing the cyclic expansion of the pole piece and the battery, and improving the cycle life.
- the gram capacity C of the negative electrode active material satisfies: 350mAh/g ⁇ C ⁇ 356mAh/g, more preferably 352mAh/g ⁇ C ⁇ 354mAh/g. While the negative electrode active material has a higher gram capacity, it can reduce the migration path of active ions therein and increase the solid phase diffusion rate of the active ions, so that the battery has a higher energy density and rapid charging ability. In addition, the negative electrode active material can also have high structural stability, it is not easy to disintegrate during the stress process, and it enables the particles in the pole piece to have a high cohesion force, so that the battery has a high cycle life. .
- the surface area average particle size D (3, 2) of the negative active material has a well-known meaning in the art, and can be tested by methods known in the art. For example, it can be measured with a laser diffraction particle size distribution measuring instrument (such as Mastersizer 3000) with reference to the standard GB/T 19077.1-2016. In this application, it can be tested in accordance with the following methods:
- D v 10, D v 50, and D v 90 of the negative electrode active material are all well-known meanings in the art, and can be tested by methods known in the art. For example, it can be measured with a laser particle size analyzer (such as Malvern Mastersizer 3000) with reference to the standard GB/T 19077.1-2016.
- a laser particle size analyzer such as Malvern Mastersizer 3000
- D v 10, D v 50, and D v 90 are as follows:
- D v 10 the particle size corresponding to the cumulative volume distribution percentage of the negative active material reaches 10%
- D v 50 the particle size corresponding to the cumulative volume distribution percentage of the negative active material reaches 50%
- D v 90 the particle size corresponding to when the cumulative volume distribution percentage of the negative electrode active material reaches 90%.
- the tap density of the negative electrode active material has a well-known meaning in the art, and can be tested by methods known in the art. For example, you can refer to the standard GB/T 5162-2006 and use a powder tap density tester for measurement. For example, if the FZS4-4B tap density meter of Beijing Iron and Steel Research Institute is used, the test parameters are as follows: vibration frequency: 250 ⁇ 15 times/min, amplitude: 3 ⁇ 0.2mm, number of vibrations: 5000 times, measuring cylinder: 25mL.
- the degree of graphitization of the negative electrode active material is a well-known meaning in the art, and can be tested by methods known in the art.
- the degree of graphitization can be tested with an X-ray diffractometer (such as Bruker D8 Discover).
- a copper target can be used as the anode target
- CuK ⁇ rays are used as the radiation source
- the ray wavelength The scanning 2 ⁇ angle range is 20° ⁇ 80°, and the scanning rate is 4°/min.
- X-ray diffraction analysis can refer to the standard JISK 0131-1996, and use an X-ray diffractometer (for example, Bruker D8 Discover X-ray diffractometer) for testing.
- a copper target can be used as the anode target
- CuK ⁇ rays are used as the radiation source
- the ray wavelength The scanning 2 ⁇ angle range is 20° ⁇ 80°, and the scanning rate is 4°/min.
- the amount of binder C 2 added in the granulation process satisfies 0% ⁇ C 2 ⁇ 16%, and the C 1 and the C 2 satisfies 10% ⁇ C 1 +C 2 ⁇ 16%, preferably 12% ⁇ C 1 +C 2 ⁇ 14%.
- the coke raw material in step S10, can be directly purchased commercially or obtained by crushing the coke material.
- the coke material is crushed to obtain coke raw material.
- the morphology of the coke raw material obtained after crushing preferably includes one or more of block, spherical, and spherical-like shapes. In this way, the coke raw material can obtain a higher ratio of the end surface to the base surface, so that the negative electrode active material can have a higher ratio of the end surface to the base surface.
- the D v 50 of the coke raw material obtained by crushing is 7 ⁇ m to 12 ⁇ m, and preferably, the D v 50 of the coke raw material obtained after crushing is 7 ⁇ m to 10 ⁇ m. If the D v 50 of the coke raw material is in an appropriate range, the subsequent granulation process can be improved, so that the obtained negative electrode active material has an appropriate degree of secondary particles and D v 50. In particular, the D v 50 of the coke raw material can make it have a higher ratio of end face to base face.
- the volatile matter content of raw coke C 1 satisfies 1% ⁇ C 1 ⁇ 12%.
- the volatile content C 1 of the coke raw material can be ⁇ 1%, ⁇ 3%, ⁇ 5%, ⁇ 6%, ⁇ 7%, or ⁇ 8%; furthermore, it can be ⁇ 12%, ⁇ 11%, ⁇ 10%, Or ⁇ 9%.
- the appropriate volatile content of the coke raw material can make the prepared artificial graphite have a higher structural strength, which is beneficial to keep the B/A of the negative electrode active material within the aforementioned range.
- the volatile content of the coke raw material can be tested using methods known in the art. For example, refer to SH/T 0226-1990 for measurement.
- the weight percentage of sulfur in the coke feedstock may be ⁇ 4%, for example, ⁇ 1% or ⁇ 0.5%.
- the coke raw material includes one or more of petroleum-based non-needle coke, petroleum-based needle coke, coal-based non-needle coke, and coal-based needle coke.
- the coke raw material is selected from one or more of petroleum-based non-needle coke (such as petroleum calcined coke, petroleum-based green coke, etc.) and petroleum-based needle coke. More preferably, the coke raw material includes petroleum-based green coke. Using appropriate coke raw materials can make the prepared negative electrode active material have both higher structural stability and end-to-base ratio, which is beneficial to keep B/A within the aforementioned range.
- petroleum-based non-needle coke such as petroleum calcined coke, petroleum-based green coke, etc.
- the coke raw material includes petroleum-based green coke.
- the raw materials can be crushed using equipment and methods known in the art, such as jet mill, mechanical mill or roller mill.
- the crushing process often produces too many small particles, sometimes there are too large particles, so after crushing, it can be classified according to requirements to remove the too small and large particles in the powder after crushing.
- After the classification treatment a coke raw material with a better particle size distribution can be obtained, which is convenient for the subsequent shaping and granulation process.
- the classification treatment can be carried out using equipment and methods known in the art, such as a classification screen, a gravity classifier, a centrifugal classifier, and the like.
- step S20 the edges and corners of the coke raw material particles are polished by shaping.
- the greater the degree of shaping the closer the particles are to the spherical shape, which can increase the ratio of the end surface to the base surface.
- the shaping treatment is also conducive to the subsequent granulation process, so that the secondary particles in the negative active material obtained have higher structural stability.
- the amount of binder C 2 added in the granulation process of step S30 and the volatile content C 1 of the coke raw material satisfies 10% ⁇ C 1 +C 2 ⁇ 16%. Preferably, 12% ⁇ C 1 +C 2 ⁇ 14%.
- the aforementioned binder amount C 2 is the percentage of the weight of the binder added in the granulation process to the total weight of the coke raw material.
- the degree of granulation of the negative electrode active material particles can be improved, which is beneficial to make A and B The value of is within the range described above. In addition, this can further increase the gram capacity of the negative electrode active material, and is beneficial to improve the overall structural strength of the negative electrode active material particles.
- the binder is preferably selected from asphalt.
- step S30 equipment known in the art can be used for granulation, such as a granulator.
- the granulator usually includes a stirred reactor and a module for temperature control of the reactor.
- the degree of granulation and the structural strength of the granules can be controlled, which is beneficial to make the obtained negative electrode active material have a higher gram capacity, but also It has higher structural stability and higher ratio of end face to base face.
- the volume average particle size D v 50 of the granulated product can be made within the required range, and more preferably, the D v 10, D v 50 and D v 90 of the granulated product can be equalized. Within the required range.
- step S40 the granulated product obtained in step S30 is graphitized at a temperature of 2800° C. to 3200° C. to obtain artificial graphite with an appropriate degree of graphitization.
- the temperature for graphitization in step S40 is preferably 2900°C to 3100°C.
- step S40 graphitization can be performed using equipment known in the art, such as a graphitization furnace, and further, for example, an Acheson graphitization furnace.
- a small amount of oversized particles formed by the agglomeration of the granulated product during the high-temperature graphitization process can be removed by sieving. This can prevent oversized particles from affecting material processing properties, such as slurry stability and coating properties.
- step S50 mixing the artificial graphite obtained in step S40 with an organic carbon source, so that the organic carbon source is coated on at least a part of the surface of the artificial graphite;
- the organic carbon source is carbonized to form an amorphous carbon coating layer on at least a part of the surface of the artificial graphite to obtain a negative electrode active material.
- the temperature of the heat treatment is 1000°C to 1300°C.
- the amount of organic carbon source C 3 added in the coating process satisfies 13% ⁇ C 1 + C 2 + C 3 ⁇ 18% between C 1 and C 2. And the organic carbon source satisfies 1.5% ⁇ C 3 ⁇ carbon residue rate ⁇ 3.5%.
- the amount C 3 of the organic carbon source is the percentage of the weight of the organic carbon source added in the coating process to the total weight of the artificial graphite.
- the carbon residue rate is the carbon residue rate of the organic carbon source, which can be measured by the LP-5731 coal pitch coking value tester. The test can refer to GB/T268 "Determination of Carbon Residue in Petroleum Products", GB/T8727-2008 “Coal Pitch" Method for determination of product coking value.”
- the amount of the organic carbon source added in the coating process satisfies the above relationship, and can improve the granulation degree of the negative electrode active material particles, thereby helping to keep the values of A and B within the aforementioned ranges.
- the coating layer has an appropriate proportion in the negative electrode active material, which enables the negative electrode active material to have both higher dynamic performance and longer cycle life.
- the organic carbon source satisfies 1.5% ⁇ C 3 ⁇ carbon residue rate ⁇ 2.5%. More preferably, 13% ⁇ C 1 + C 2 + C 3 ⁇ 17%, and 1.8% ⁇ C 3 ⁇ carbon residue rate ⁇ 2.4%.
- 2% ⁇ C 3 ⁇ 8% such as C 3 3%, 4%, 5%, 6% or 7%.
- the organic carbon source may be selected from one or more of coal pitch, petroleum pitch, phenolic resin, coconut shell, etc., preferably coal pitch.
- the implementation of the second aspect of the present application provides a secondary battery.
- the secondary battery includes a negative pole piece, and the negative pole piece includes the negative electrode active material described in the first aspect of the present application.
- the secondary battery of the present application adopts the negative electrode active material of the first aspect of the present application, it can simultaneously take into account higher energy density, cycle life, and rapid charge and discharge capabilities.
- the secondary battery also includes a positive pole piece and an electrolyte.
- active ions are inserted and extracted back and forth between the positive pole piece and the negative pole piece.
- the electrolyte conducts ions between the positive pole piece and the negative pole piece.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode membrane provided on at least one surface of the negative electrode current collector, and the negative electrode membrane includes the negative electrode active material described in the first aspect of the present application.
- the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film is laminated on either or both of the two opposite surfaces of the negative electrode current collector.
- the negative electrode current collector can be made of materials with good electrical conductivity and mechanical strength to play the role of conduction and current collection.
- copper foil may be used as the negative electrode current collector.
- the negative electrode membrane may also optionally include a binder.
- the binder may be selected from polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), sodium alginate (SA), One or more of polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
- the negative electrode membrane may optionally include a thickener.
- the thickener may be sodium carboxymethyl cellulose (CMC-Na).
- the negative electrode film may also optionally include a conductive agent.
- the conductive agent used for the negative electrode film may be selected from one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
- other negative electrode active materials may also be included in the negative electrode membrane.
- the other negative electrode active material can be selected from one or more of other graphite materials (such as artificial graphite, natural graphite, etc. different from the first aspect of the present application), soft carbon, hard carbon, silicon-based materials, and tin-based materials.
- the negative pole piece can be prepared according to methods known in the art. As an example, disperse the negative electrode active material, binder, and optional thickener and conductive agent in a solvent.
- the solvent can be deionized water to form a uniform negative electrode slurry; the negative electrode slurry is coated on the negative electrode collector. On the fluid, after drying, cold pressing and other processes, the negative pole piece is obtained.
- the positive electrode sheet includes a positive electrode current collector and a positive electrode membrane provided on at least one surface of the positive electrode current collector.
- the positive electrode current collector has two opposite surfaces in its own thickness direction, and the positive electrode film is laminated on either or both of the two opposite surfaces of the positive electrode current collector.
- the positive electrode current collector can be made of materials with good electrical conductivity and mechanical strength.
- aluminum foil may be used as the positive electrode current collector.
- the positive electrode membrane includes a positive electrode active material.
- This application does not specifically limit the specific types of positive electrode active materials, and materials known in the art that can be used for secondary battery positive electrodes can be used, and those skilled in the art can make selections according to actual needs.
- the secondary battery may be a lithium ion secondary battery.
- the positive electrode active material may include one or more of lithium transition metal oxides, lithium-containing phosphates with an olivine structure, and their respective modified compounds.
- lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide One or more of the compounds, lithium nickel cobalt aluminum oxide and its modified compounds.
- lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate, lithium iron phosphate and carbon composite material, lithium manganese phosphate, lithium manganese phosphate and carbon composite material, lithium iron manganese phosphate, lithium iron manganese phosphate
- One or more of the composite materials with carbon and its modified compounds may be used. The present application is not limited to these materials, and other conventionally known materials that can be used as positive electrode active materials for secondary batteries can also be used.
- M is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn 0.5 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1, 1 ⁇ e ⁇ 2, 0 ⁇ f ⁇ 1, M is selected from Mn, Al, Zr
- Zn is selected from Mn, Al, Zr
- Zn is selected from Cu, Cr, Mg, Fe, V, Ti and B
- A is selected from one or more of N, F, S and Cl.
- the modification compound of each of the above-mentioned materials may be doping modification and/or surface coating modification of the material.
- the positive electrode membrane may optionally include a binder.
- a binder There is no specific restriction on the type of binder, and those skilled in the art can make a selection according to actual needs.
- the binder used for the positive electrode membrane may include one or more of polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
- the positive pole piece can be prepared according to methods known in the art.
- the positive electrode active material, conductive agent, and binder can be dispersed in a solvent (for example, N-methylpyrrolidone, NMP for short) to form a uniform positive electrode slurry; the positive electrode slurry can be coated on the positive electrode current collector, After drying, cold pressing and other processes, a positive pole piece is obtained.
- a solvent for example, N-methylpyrrolidone, NMP for short
- the electrolyte conducts ions between the positive pole piece and the negative pole piece.
- the type of electrolyte in this application can be selected according to requirements.
- the electrolyte may be selected from at least one of solid electrolytes and liquid electrolytes (ie, electrolytes).
- the electrolyte uses an electrolytic solution.
- the electrolyte includes an electrolyte salt and a solvent.
- the electrolyte may also optionally include additives.
- the additives can include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery performance, such as additives that improve battery overcharge performance, additives that improve battery high-temperature performance, and battery low-temperature performance. Additives, etc.
- the positive pole piece, the negative pole piece, and the separator can be made into an electrode assembly through a winding process or a lamination process.
- the secondary battery may include an outer package.
- the outer packaging can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
- the outer packaging of the secondary battery may be a hard case, such as a hard plastic case, aluminum case, steel case, or the like.
- the outer packaging of the secondary battery may also be a soft bag, such as a pouch type soft bag.
- the material of the soft bag can be plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.
- Fig. 2 shows a secondary battery 5 with a square structure as an example.
- the outer package may include a housing 51 and a cover 53.
- the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
- the housing 51 has an opening communicating with the accommodating cavity, and a cover plate 53 can cover the opening to close the accommodating cavity.
- the electrode assembly 52 is packaged in the receiving cavity.
- the electrolyte may be an electrolyte, and the electrolyte is infiltrated in the electrode assembly 52.
- the number of electrode assemblies 52 included in the secondary battery 5 can be one or several, which can be adjusted according to requirements.
- the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
- Fig. 4 is a battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
- the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
- FIGS 5 and 6 show the battery pack 1 as an example.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
- the battery box includes an upper box body 2 and a lower box body 3.
- the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
- a plurality of battery modules 4 can be arranged in the battery box in any manner.
- a second aspect of the present application provides a device including the secondary battery of the first aspect of the present application.
- the secondary battery can be used as a power source of the device, and can also be used as an energy storage unit of the device.
- the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
- Fig. 7 is a device as an example.
- the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.
- a battery pack or a battery module can be used.
- the device may be a mobile phone, a tablet computer, a notebook computer, and the like.
- the device is generally required to be thin and light, and a secondary battery can be used as a power source.
- a shaping machine is used to shape the coke raw material obtained in step 1), and then a classification process is performed to obtain a precursor with a particle size distribution (D v 90-D v 10)/D v 50 of 1.51.
- step 2) The precursor obtained in step 2) is mixed with a binder, and the precursor is granulated using a granulator.
- step 5) Coating: the artificial graphite obtained in step 4) is mixed with organic carbon source coal pitch, and heat-treated at 1050° C. to obtain a negative electrode active material.
- the negative active material, the conductive agent carbon black (Super P), the binder styrene-butadiene rubber (SBR), and the thickener sodium carboxymethyl cellulose (CMC-Na) prepared above are adjusted according to 96.4:1:1.2:1.4
- the mass ratio is fully stirred and mixed in an appropriate amount of deionized water to form a uniform negative electrode slurry; the negative electrode slurry is coated on the surface of the negative electrode current collector copper foil, dried and cold pressed to obtain a negative electrode pole piece.
- the compacted density of the negative pole piece is 1.65 g/cm 3 , and the areal density is 11 mg/cm 2 .
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- the electrode assembly is obtained.
- the electrode assembly is packed into the outer package, and the above electrolyte is added. After packaging, standing, forming, aging, etc. , Get a secondary battery.
- the batteries prepared in the examples and comparative examples were charged to 80% SOC (State of Charge) in 30 minutes, fully charged to 100% SOC at 0.33C, and fully discharged at 1C, repeated 10 times After that, charge the battery to 80% SOC in 30 minutes, and fully charge it to 100% SOC at 0.33C, then disassemble the negative pole piece, and observe the lithium evolution on the surface of the negative pole piece. If no lithium is deposited on the surface of the negative electrode, the time to charge to 80% SOC is decreased by 1 min and the test is repeated until lithium is deposited on the surface of the negative electrode. Stop the test. At this time, the charging time to 80% SOC (min) + 1 min is The maximum charging capacity of the battery.
- SOC State of Charge
- the negative electrode active material provided by the present application includes a core and an amorphous carbon coating layer coated on at least a part of the surface of the core, and the core includes artificial Graphite, and the negative electrode active material meets a specific relationship between D(3,2) before and after powder compaction under 20kN pressure, which can enable the negative electrode active material to have a higher gram capacity while greatly improving the rapid transfer of the negative electrode active material
- the ability of active ions and the structural stability under stress enable the secondary battery using it to improve the fast charging ability and cycle life under the premise of higher energy density. Therefore, the secondary battery can simultaneously take into account higher energy density, fast charging performance and cycle performance.
- the negative active material of Comparative Example 1 has a high B/A value, and the material has poor kinetic performance, and cannot achieve fast charging.
- the negative active material of Comparative Example 2 has a low B/A value, and the material has poor stability during battery cycling, which reduces the cycling performance of the battery.
- the coke raw materials in Table 3 are all petroleum-based needle coke.
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Abstract
Description
Claims (14)
- 一种负极活性材料,包括核和覆盖在所述核表面的包覆层,所述核包括人造石墨,所述包覆层包括无定形碳,所述负极活性材料的表面积平均粒径D(3,2)记为A,所述负极活性材料在20kN压力下粉压后的表面积平均粒径D(3,2)记为B,所述负极活性材料满足:72%≤B/A×100%≤82%。
- 根据权利要求1所述的负极活性材料,其中,所述负极活性材料满足:74%≤B/A×100%≤80%。
- 根据权利要求1或2所述的负极活性材料,其中,9μm≤A≤15μm,优选地,11μm≤A≤13μm。
- 据权利要求1-3任一项所述的负极活性材料,其中,所述负极活性材料的体积平均粒径D v50满足:10μm≤D v50≤16μm,优选地,12μm≤D v50≤14μm。
- 根据权利要求1-4任一项所述的负极活性材料,其中,所述负极活性材料的粒径分布(D v90-D v10)/D v50满足:1.0≤(D v90-D v10)/D v50≤1.35,优选地,1.15≤(D v90-D v10)/D v50≤1.25。
- 根据权利要求1-5任一项所述的负极活性材料,其中,所述负极活性材料的体积粒径分布D v90满足:18μm≤D v90≤26μm,优选地,20μm≤D v90≤24μm。
- 根据权利要求1-6任一项所述的负极活性材料,其中,所述负极活性材料的振实密度为0.9g/cm 3~1.15g/cm 3,优选为0.95g/cm 3~1.05g/cm 3。
- 根据权利要求1-7任一项所述的负极活性材料,其中,所述负极活性材料的石墨化度为90%~96%,优选为92%~95%。
- 根据权利要求1-8任一项所述的负极活性材料,其中,所述负极活性材料的粉体OI值为2.0~5.0,优选为2.1~4.0。
- 根据权利要求1-8任一项所述的负极活性材料,其中,所述负极活性材料的克容量C满足:350mAh/g≤C≤356mAh/g,优选地,352mAh/g≤C≤354mAh/g。
- 一种二次电池,包括负极极片,所述负极极片包括根据权利要求1-10任一项所述的负极活性材料。
- 一种装置,包括根据权利要求11所述的二次电池。
- 一种负极活性材料的制备方法,包括以下步骤:a)提供焦原料,所述焦原料的体积平均粒径D v50为7μm~12μm,所述焦原料的挥发份含量C 1满足1%≤C 1≤12%,优选地,5%≤C 1≤9%;b)对所述焦原料进行整形、分级处理,得到粒径分布(D v90-D v10)/D v50为1.0~1.55的前驱体;c)对所述前驱体进行造粒,所述造粒过程加入的粘结剂用量C 2满足0%≤C 2≤16%,且所述C 1和所述C 2满足10%≤C 1+C 2≤16%,优选地,12%≤C 1+C 2≤14%;d)对造粒产物在2800℃~3200℃的温度下进行石墨化处理,得到人造石墨;e)采用有机碳源对所述人造石墨进行包覆,经热处理,以在所述人造石墨的至少一部分表面形成无定形碳包覆层,得到负极活性材料,所述包覆过程加入的有机碳源用量C 3与所述C 1和所述C 2之间满足13%≤C 1+C 2+C 3≤18%,且1.5%≤C 3×残炭率≤3.5%;其中,所述负极活性材料的表面积平均粒径D(3,2)记为A,所述负极活性材料在20kN压力下粉压后的表面积平均粒径D(3,2)记为B,所述负极活性材料满足:72%≤B/A×100%≤82%。
- 根据权利要求13所述的制备方法,其中,所述焦原料还满足如下中的至少之一:1)所述焦原料包括石油系非针状焦、石油系针状焦中的一种或几种;优选地,所述焦原料包括石油系生焦;2)所述焦原料的粒径分布(D v90-D v10)/D v50为1.2~1.7。
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CN202080005589.8A CN114223072B (zh) | 2020-04-30 | 2020-04-30 | 负极活性材料及其制备方法、二次电池和包含二次电池的装置 |
KR1020227018158A KR20220092566A (ko) | 2020-04-30 | 2020-04-30 | 부극 활성 재료 및 이의 제조 방법, 이차 전지, 및 이차 전지를 포함하는 장치 |
JP2022534656A JP7263627B2 (ja) | 2020-04-30 | 2020-04-30 | 負極活性材料及びその製造方法、二次電池及び二次電池を含む装置 |
PCT/CN2020/088426 WO2021217620A1 (zh) | 2020-04-30 | 2020-04-30 | 负极活性材料及其制备方法、二次电池和包含二次电池的装置 |
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CN114050264A (zh) * | 2021-11-15 | 2022-02-15 | 珠海冠宇电池股份有限公司 | 一种负极材料及包含该负极材料的负极片 |
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CN114223072A (zh) | 2022-03-22 |
EP3955348B1 (en) | 2023-04-19 |
EP3955348A1 (en) | 2022-02-16 |
CN114223072B (zh) | 2024-07-12 |
JP7263627B2 (ja) | 2023-04-24 |
JP2022554030A (ja) | 2022-12-27 |
US20220166009A1 (en) | 2022-05-26 |
US11569498B2 (en) | 2023-01-31 |
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EP3955348A4 (en) | 2022-07-27 |
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