CN117712376A - Graphite negative electrode active material, negative electrode sheet, secondary battery and device - Google Patents

Graphite negative electrode active material, negative electrode sheet, secondary battery and device Download PDF

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Publication number
CN117712376A
CN117712376A CN202311767284.2A CN202311767284A CN117712376A CN 117712376 A CN117712376 A CN 117712376A CN 202311767284 A CN202311767284 A CN 202311767284A CN 117712376 A CN117712376 A CN 117712376A
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Prior art keywords
graphite
active material
negative electrode
satisfies
particle graphite
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孟宪慧
马坤
陈帅
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Weilai Battery Technology Anhui Co ltd
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Weilai Battery Technology Anhui Co ltd
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Priority to CN202311767284.2A priority Critical patent/CN117712376A/en
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application discloses a graphite anode active material, an anode piece, a secondary battery and a device, wherein the anode active material comprises primary particle graphite and secondary particle graphite, and the oil absorption value of the primary particle graphite is 30mL/100 g-51 mL/100g; and/or the oil absorption value of the secondary particle graphite satisfies 40mL/100 g-65 mL/100g. The negative electrode active material not only has ultra-long cycle performance, but also can improve the charge and discharge capacity under the low-temperature condition, overcomes the influence caused by low temperature, and can meet various application scenes.

Description

Graphite negative electrode active material, negative electrode sheet, secondary battery and device
Technical Field
The application relates to a negative electrode active material, in particular to a negative electrode active material, a negative electrode plate, a secondary battery and a device, and belongs to the field of battery materials.
Background
The development of electric vehicles becomes one of the important ways of energy conservation and emission reduction, and a power battery is a core component of the electric vehicles. The quick charging can save time and realize quick energy supplementing. Therefore, the quick charge performance is one of important influencing factors considered by the majority of users when buying the vehicle. In addition, the battery attenuation problem of the electric automobile is widely focused, and the long-cycle performance is guaranteed that the electric automobile can be continuously used without power failure. In addition, the influence of temperature on the battery is huge, and particularly in winter, the activity of a chemical system is reduced along with the reduction of air temperature, so that the battery is difficult to charge and discharge in winter. Therefore, the problem of low temperature is a necessary way for pushing the electric automobile to the northern city.
Therefore, there is an urgent need to develop a graphite anode active material, and to apply the same to a power battery, capable of improving low-temperature fast charge performance and cycle performance of the battery.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a graphite negative electrode active material, a negative electrode plate, a secondary battery and a device. The relation between the ID/IG values of the primary particle graphite and the secondary particle graphite in the graphite negative electrode active material is adjusted, so that the quick charge performance and the circulation performance of the graphite negative electrode active material at low temperature are effectively improved.
The first aspect of the application provides a graphite anode active material, which comprises primary particle graphite and secondary particle graphite, wherein the oil absorption value of the primary particle graphite is 30mL/100 g-51 mL/100g; the oil absorption value of the secondary particle graphite meets 40mL/100 g-65 mL/100g.
A second aspect of the present application provides a negative electrode tab comprising a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector, the negative electrode material layer comprising the negative electrode active material of the first aspect.
A third aspect of the present application provides a secondary battery comprising the negative electrode tab and the positive electrode tab of the second aspect.
A fourth aspect of the present application provides an apparatus comprising the secondary battery according to the third aspect.
The negative electrode active material not only has ultra-long cycle performance, but also can improve the charge and discharge capacity under the low-temperature condition, overcomes the influence caused by low temperature, and can meet various application scenes.
Drawings
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized below, may be had by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than as described herein, and therefore the present invention is not limited to the specific embodiments disclosed below.
Fig. 1 is an SEM image of a graphite anode active material in example 1 of the present invention.
Detailed Description
For simplicity, this application discloses only a few numerical ranges specifically. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
Unless otherwise indicated, terms used in the present application have well-known meanings commonly understood by those skilled in the art. Unless otherwise indicated, the numerical values of the parameters set forth in this application may be measured by various measurement methods commonly used in the art (e.g., may be tested according to the methods set forth in the examples of this application).
The list of items to which the term "at least one of," "at least one of," or other similar terms are connected may mean any combination of the listed items. For example, if items a and B are listed, then the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single component or multiple components. Item B may comprise a single component or multiple components. Item C may comprise a single component or multiple components.
The term "Dv50" (also referred to as "median particle diameter") refers to a particle diameter of a material up to 50% by volume in a volume-based particle size distribution from the small particle diameter side, i.e., the volume of the material smaller than this particle diameter accounts for 50% of the total volume of the material.
The present application is further described below in conjunction with the detailed description. It should be understood that these specific embodiments are presented by way of example only and are not intended to limit the scope of the present application.
The negative electrode active material comprises primary particle graphite and secondary particle graphite, wherein the oil absorption value of the primary particle graphite is 30mL/100 g-51 mL/100g, and the oil absorption value of the secondary particle graphite is 40mL/100 g-65 mL/100g. The micropore distribution and the active point of the surface active layer of the artificial graphite anode active material meeting the relation range are in controllable active states, so that better embedded active points can be provided for lithium ions, meanwhile, electrolyte can be better absorbed and distributed, the electrolyte can uniformly infiltrate the anode active material, and the artificial graphite anode active material has better low-temperature dynamics and circulation performance. As can be seen from fig. 1, the negative electrode active material of the present application is a typical artificial graphite structure in which secondary particles and primary particles are mixed and the edges and corners are sharp and clear. Therefore, the inventor creatively mixes primary particles and secondary particles of different types, and the anode active material obtained after mixing not only has ultra-long cycle performance, but also is suitable for being used in a low-temperature environment, meets the low-temperature charge and discharge requirements, and overcomes the low-temperature problem of the lithium ion battery.
In some embodiments, the primary particulate graphite has an oil absorption value of 30mL/100g, 32mL/100g, 34mL/100g, 36mL/100g, 38mL/100g, 40mL/100g, 42mL/100g, 44mL/100g, 46mL/100g, 48mL/100g, 50mL/100g, 51mL/100g, or any range therebetween; if the oil absorption value of the primary particle graphite is too large or too small, the expected effect cannot be achieved. Specifically, the primary particle graphite is a main contributor to the cycle performance, and if the oil absorption value of the primary particle graphite is too large, the activity of the primary particle graphite is too high, and the secondary reaction with electrolyte is aggravated, so that the cycle performance is reduced; if the oil absorption value of the primary particle graphite is too small, the liquid absorption capacity of the primary particle graphite is reduced, and the electrolyte is more difficult to infiltrate so as to generate lithium precipitation; in some embodiments, the primary particulate graphite has an oil absorption value that satisfies 31mL/100g to 50mL/100g.
In some embodiments, the secondary particulate graphite has an oil absorption value of 40mL/100g, 42mL/100g, 44mL/100g, 46mL/100g, 48mL/100g, 50mL/100g, 52mL/100g, 54mL/100g, 56mL/100g, 58mL/100g, 60mL/100g, 62mL/100g, 64mL/100g, 65mL/100g, or any range therebetween; if the oil absorption value of the secondary particle graphite is too large or too small, the expected effect cannot be achieved. Specifically, the secondary particle graphite is a main contributor to the quick charging performance, if the oil absorption value of the secondary particle graphite is too large, electrolyte which should belong to the primary particle graphite is contended, so that electrolyte infiltration of the whole material is unbalanced, and a local dead lithium area appears; if the oil absorption value of the secondary particle graphite is too small, the liquid absorption amount is insufficient, the electrolyte cannot completely infiltrate the anode active material, and the quick charge performance is obviously reduced; the oil absorption value of the secondary particle graphite meets 44mL/100 g-63 mL/100g.
In some embodiments, the contact angle of the primary particle graphite satisfies 16.0 ° -20.0 °, the contact angle of the primary particle graphite directly reacts with the interaction relationship between the material and the electrolyte, and if the contact angle of the primary particle graphite is too large, the primary particle graphite can absorb the electrolyte in a large amount, so that the particles expand more, and the cycle performance is reduced; if the contact angle of the primary particle graphite is too small, the electrolyte absorption amount is insufficient, and the lithium storage performance of the primary particle graphite cannot be fully exerted, thereby reducing the cycle performance. In some embodiments, the ID/IG of the secondary particulate graphite is 16.0 °, 16.5 °, 17.0 °, 17.5 °, 18.0 °, 18.5 °, 19.0 °, 19.5 °, 20 °, or any range therebetween. The contact angle of the primary particle graphite satisfies 16.0 DEG to 19.0 deg.
In some embodiments, the contact angle of the secondary particle graphite satisfies 20.0 ° -41.0 °, the contact angle of the secondary particle graphite also directly reflects the interaction relationship between the material and the electrolyte, and if the contact angle of the secondary particle graphite is too large, the secondary particle graphite can absorb the electrolyte in a large amount, so that the particles expand greatly, and the cycle performance is reduced; if the contact angle of the secondary particle graphite is too small, the electrolyte absorption amount is insufficient, and the lithium storage performance of the secondary particle graphite cannot be fully exerted, thereby reducing the cycle performance. In some embodiments, the ID/IG of the secondary particulate graphite is 20.0 °, 23.0 °, 26.0 °, 29.0 °, 32.0 °, 35.0 °, 38.0 °, 41.0 °, or any range therebetween. In some embodiments, the contact angle of the secondary particulate graphite satisfies 22.0 ° to 40.0 °.
In some embodiments, dv50 of the primary particle graphite satisfies 5.0 μm to 11.0 μm, and if the particle size of the primary particle graphite is too small, it may cause a drastic decrease in cycle performance, and if the particle size of the primary particle graphite is too large, it may make the electrode sheet difficult to process, and the occurrence of irregularities may seriously affect battery performance. In some embodiments, the Dv50 of the primary particulate graphite is 5.0 μm, 6.0 μm, 7.0 μm, 8.0 μm, 9.0 μm, 10.0 μm, 11.0 μm, or any range therebetween; the Dv50 of the primary particle graphite satisfies 7.0 μm to 9.0 μm.
In some embodiments, the primary particle graphite has a tap density of 0.8g/cm 3 ～1.3g/cm 3 If the tap density of the primary particle graphite is too high, the materials are excessively densely packed, and electrolyte is difficult to infiltrate; if the tap density of the primary particle graphite is too small, the material is too fluffy, which affects electrode processing. In some embodiments, the primary particle graphite has a tap density of 0.8g/cm 3 、0.9g/cm 3 、1.0g/cm 3 、1.1g/cm 3 、1.2g/cm 3 、1.3g/cm 3 Or any range therebetween; in some embodiments, the primary particle graphite has a tap density of 0.9g/cm 3 ～1.2g/cm 3 。
In some embodimentsWherein the specific surface area of the primary particle graphite satisfies 1.2m 2 /g～1.8m 2 And/g, if the specific surface area of the primary particle graphite is too large, the initial efficiency of the battery is lowered, and if the specific surface area of the primary particle graphite is too small, the quick-charging performance of the material is insufficient. In some embodiments, the primary particle graphite has a tap density of 1.2m 2 /g、1.3m 2 /g、1.4m 2 /g、1.5m 2 /g、1.6m 2 /g、1.7m 2 /g、1.8m 2 G or any range therebetween; the specific surface area of the primary particle graphite satisfies 1.3m 2 /g～1.6m 2 /g。
In some embodiments, dv50 of the secondary particle graphite satisfies 11.0 μm to 17.0 μm, and if the particle size of the secondary particle graphite is too small, it may cause a drastic decrease in cycle performance, and if the particle size of the secondary particle graphite is too large, it may make the electrode tab difficult to process, and the occurrence of irregularities may seriously affect battery performance. In some embodiments, the Dv50 of the secondary particulate graphite is 11.0 μm, 12.0 μm, 13.0 μm, 14.0 μm, 15.0 μm, 16.0 μm, 17.0 μm, or any range therebetween; in some embodiments, the Dv50 of the secondary particulate graphite satisfies 12.0 μm to 16.0 μm.
In some embodiments, the secondary particulate graphite has a tap density of 0.9g/cm 3 ～1.3g/cm 3 If the tap density of the secondary particle graphite is too high, the materials are excessively densely packed, and electrolyte is difficult to infiltrate; if the tap density of the secondary particulate graphite is too small, the material may be too fluffy, affecting electrode processing. In some embodiments, the secondary particulate graphite has a tap density of 0.9g/cm 3 、1.0g/cm 3 、1.1g/cm 3 、1.2g/cm 3 、1.3g/cm 3 Or any range therebetween; in some embodiments, the secondary particulate graphite has a tap density of 1.0g/cm 3 ～1.2g/cm 3 。
In some embodiments, the specific surface area of the secondary particulate graphite satisfies 1.0m 2 /g～1.8m 2 /g m 2 And/g, if the specific surface area of the secondary particle graphite is too large, the initial efficiency of the battery is lowered, and if the specific surface area of the secondary particle graphite is too small, the quick-charging performance of the material is insufficient. In some embodiments, the secondary particulate graphite has a tap density of 1.0m 2 /g、1.1m 2 /g、1.2m 2 /g、1.3m 2 /g、1.4m 2 /g、1.5m 2 /g、1.6m 2 /g、1.7m 2 /g、1.8m 2 G or any range therebetween; the specific surface area of the secondary particle graphite is 1.1m 2 /g～1.4m 2 /g。
In some embodiments, the mass ratio of the primary particulate graphite to the secondary particulate graphite is (0.5-1.5): 1. if the mass ratio of the primary particle graphite is too high, the quick charge performance does not meet the expectations, and lithium can be separated out; if the mass ratio of the secondary particle graphite is too high, the cycle performance is greatly deteriorated, and it is difficult to realize a long cycle. In some embodiments, the mass ratio of the secondary particulate graphite to the primary particulate graphite is 0.5: 1. 0.7: 1. 0.9: 1. 1.1:1. 1.2: 1. 1.3: 1. 1.4:1. 1.5: 1. 1.6:1 or any range therebetween.
In some embodiments, the graphite anode active material has a Dv50 of 11.0 μm to 14.0 μm. In some embodiments, the Dv50 of the anode active material is 11.0 μm, 12.0 μm, 13.0 μm, 14.0 μm, or any value in between.
In some embodiments, the graphite anode active material has a tap density of 1.0g/cm 3 -1.3g/cm 3 . In some embodiments, the negative electrode active material has a tap density of 1.0g/cm 3 、1.1g/cm 3 、1.2g/cm 3 、1.3g/cm 3 Or any value therebetween.
In some embodiments, the graphite anode active material has a specific surface area of 1.2g/cm 2 -1.8g/cm 2 . The specific surface area of the active material reflects the surface state of the material, the specific surface area is larger, the surface reactivity of the material is higher, the active material is easy to react with electrolyte, and the performance of the whole battery is not beneficial to improvement, therefore, the stone is required to be usedThe specific surface area BET of the ink anode active particles is defined within the above-described suitable range. In some embodiments, the specific surface area of the anode active material is 1.2g/cm 2 、1.3g/cm 2 、1.4g/cm 2 、1.5g/cm 2 、1.6g/cm 2 、1.7g/cm 2 、1.8g/cm 2 Or any value therebetween.
In some embodiments, the graphite anode active material further comprises a silicon-based material. In some embodiments, the silicon-based material includes at least one of silicon, a silicon alloy, a silicon carbon compound, a silicon oxygen compound, or a composite of elemental silicon and graphite.
According to an embodiment of the present application, the preparation of the anode active material includes the steps of: 1. preparation of primary particle graphite: crushing a precursor (needle coke, pitch coke or petroleum coke, for example, can be selected according to the need), graphitizing (wherein the graphitizing temperature is more than or equal to 3000 ℃) and processing a finished product to prepare primary particle graphite; 2. preparation of secondary particle graphite: crushing a precursor (needle coke, pitch coke, petroleum coke and the like can be selected according to the need), graphitizing (the graphitizing temperature is more than or equal to 3000 ℃), coating and granulating (the content of a coating agent can be 2% -4%), and carbonizing (according to the actual need, coating and carbonizing can be not performed), so as to obtain secondary particle graphite; 3. preparation of graphite anode active material: mixing the primary particle graphite and the secondary particle graphite, wherein the mass ratio of the secondary particle graphite to the primary particle graphite is (0.3-1): 1. of course, the preparation method of the anode active particles is not limited thereto, but may also be prepared by other methods well known in the art.
In some embodiments, the preparation of the negative electrode active material of the present application includes the following steps:
1. preparation of primary particle graphite
(1) Crushing of raw materials
Pulverizing needle coke (volatile component is less than or equal to 2%, sulfur content is less than or equal to 0.6%, ash content is less than or equal to 0.4%, and water content is less than or equal to 0.5%) to obtain needle coke powder, wherein Dv50 of the obtained needle coke powder is 7.5-9.5 μm, and tap density is 0.4-0.8 g/cm3;
(2) Graphitization of
And (3) graphitizing the needle coke powder obtained in the step (1), wherein graphitizing equipment is an Acheson crucible furnace, the treatment temperature is more than or equal to 3000 ℃, and the treatment time is 30-60 h (preferably 50 h). The graphitization degree of the graphitized material is 92.5% -96%;
(3) Processing of finished products
And (3) carrying out finished product processing on the material obtained in the step (2) to obtain primary particles, wherein the Dv50 of the primary particles is 7.0-9.0 mu m, the tap density is 0.9-1.2 g/cm < 3 >, the specific surface area is 1.2m < 2 >/g-1.8 m < 2 >/g, the discharge capacity is 350-355mAh/g, and the first cycle efficiency is 92.0-96.0%.
2. Preparation of secondary particle graphite
(4) Crushing of raw materials
The petroleum coke (the volatile component is 8% -15%, the sulfur content is less than or equal to 3%, the ash content is less than or equal to 0.4%, and the moisture content is less than or equal to 15%) is crushed, wherein the Dv50 of the obtained petroleum coke powder is 8.5-9.5 mu m, and the tap density is 0.3-0.7 g/cm < 3 >.
(5) Graphitization of
And (3) graphitizing the petroleum coke powder obtained in the step (4) to obtain primary particle graphite, wherein equipment for graphitizing is an Acheson crucible furnace, the treatment temperature is more than or equal to 3000 ℃, and the treatment time is 30-60 h (preferably 50 h). The graphitization degree of the graphitized material is 92.5% -96%.
(6) Coating granulation
And (3) coating and granulating the primary particle graphite obtained in the step (5), wherein equipment adopted for coating can be one or more of a vertical coating kettle, a horizontal coating kettle, a roller furnace and a continuous rotary kiln, and a coating agent can be one or more of modified high-temperature asphalt with a softening point of 150-280 ℃ and a coking value of 45-95, or one or more of phenolic resin, starch, sucrose and the like. The content of the coating agent may be 2% -4%. And finally, carrying out high-temperature carbonization treatment on the material subjected to coating granulation. Wherein, the high-temperature carbonization equipment can be one or more of a roller kiln, a gas type tunnel kiln, a pusher kiln and a shuttle kiln, and the carbonization temperature is 800-1600 ℃.
(7) Processing of finished products
And (3) carrying out finished product processing on the carbonized material in the step (6) to obtain surface modified secondary particles, wherein the Dv50 of the secondary particles is 12.0-16.0 mu m, the Dv10 is 8.2 mu m, the tap density is 1.0g/cm < 3 > -1.2g/cm < 3 >, the specific surface area is 1.0m < 2 >/g-1.8 m < 2 >/g, the graphitization degree is 92.0% -94.0%, the discharge capacity is 345mAh/g-353mAh/g, and the first cycle efficiency is 91.5% -94%.
3. Preparation of graphite negative electrode active material
Mixing the secondary particle graphite obtained in the second step with the primary particle graphite obtained in the first step according to the mass ratio ((0.3-1): 1), and obtaining the graphite anode active material, wherein the Dv50 of the graphite anode active material is 11.0-14.0 mu m, the tap density is 1.0g/cm < 3 > -1.3g/cm < 3 >, the specific surface area is 1.2g/cm < 2 > -1.8g/cm < 2 >, the discharge capacity is 350mAh/g-354mAh/g, and the first cycle efficiency is 92% -95%. The preparation method of the graphite anode active material is simple, the reaction condition is controllable, the cost is low, and the industrial production is feasible.
In some embodiments, the positive electrode sheet includes a positive electrode active material layer including a positive electrode active material including at least one of a nickel-cobalt-based ternary material and a phosphate-based material.
In some embodiments, the nickel cobalt-based ternary material includes LiNi m Co n At least one of A (1-m-n) O2 materials, wherein A is selected from at least one of manganese, aluminum, magnesium, chromium, calcium, zirconium, molybdenum, silver or niobium, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.5, and m+n is more than or equal to 1.
In some embodiments, m is 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or a range consisting of any two of these values. In some embodiments, n is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or a range consisting of any two of these values.
In some embodiments, the nickel cobalt-based ternary material includes at least one of NCA, NCM111, NCM523, NCM622, NCM811, ni90, ni92, or Ni 95.
In some embodiments, the phosphate-based material comprises LiMn k B (1-k) PO 4 Wherein k is more than or equal to 0 and less than or equal to 1, and the B element is selected from at least one of iron, cobalt, magnesium, calcium, zinc, chromium or lead. In some embodiments, k is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or a range of any two of these values. In some embodiments, the phosphate-based material comprises lithium iron phosphate, liMn 0.6 Fe 0.4 PO 4 Or LiMn 0.8 Fe 0.2 PO 4 At least one of them.
In some embodiments, the positive electrode active material includes at least one of lithium nickel oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, lithium nickel manganese cobalt magnesium oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium iron phosphate, and lithium manganese iron phosphate.
In some embodiments, the positive electrode active material layer further includes a binder, and optionally includes a conductive material. The binder enhances the bonding of the positive electrode active material particles to each other and also enhances the bonding of the positive electrode active material to the current collector.
In some embodiments, the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive material includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the positive electrode further includes a positive electrode current collector, which may be a metal foil or a composite current collector. For example, aluminum foil may be used. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, or the like) on a polymer substrate.
In some embodiments, the negative electrode tab includes a negative electrode active particle layer including negative electrode active particles including a carbon-based material, or a mixture of a silicon-based material and at least one material selected from a carbon-based material, a tin-based material, a phosphorus-based material, and metallic lithium.
In some embodiments, the anode active particle layer further includes a binder and a conductive agent. In some embodiments, the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the negative electrode further comprises a negative electrode current collector comprising: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or any combination thereof.
In some embodiments, a separator is provided between the positive and negative electrodes to prevent shorting. The materials and shape of the release film that can be used in the embodiments of the present application are not particularly limited, and can be any of the techniques disclosed in the prior art. In some embodiments, the separator comprises a polymer or inorganic, etc., formed from a material that is stable to the electrolyte of the present application. In some embodiments, the separator film may be selected from the group consisting of polyethylene films, polypropylene films, polyvinylidene fluoride films, and multilayer composite films thereof.
For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer comprises at least one of polyethylene, polypropylene, polyethylene terephthalate or polyimide. Specifically, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
The surface treatment layer is provided on at least one surface of the base material layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or may be a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer includes inorganic particles including at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate, and a binder. The binder comprises at least one of polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylic polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene).
The lithium ion secondary battery consists of a negative electrode plate, a positive electrode plate, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode are immersed in the electrolyte, and lithium ions move between the positive electrode and the negative electrode by taking the electrolyte as a medium, so that the charge and discharge of the battery are realized. In order to avoid the short circuit of the positive electrode and the negative electrode through the electrolyte, the positive electrode and the negative electrode are required to be separated by a separation film. The lithium ion secondary battery may be in the form of a cylindrical shape (square cylindrical shape or cylindrical shape) having an aluminum case or a steel case as a case, or may be in the form of a soft-pack battery having an aluminum-plastic film as a case.
In some embodiments, the secondary battery is a lithium secondary battery or a sodium secondary battery. In some embodiments, lithium secondary batteries include, but are not limited to: lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
In some embodiments, the secondary battery may include an outer package, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The soft bag can be made of one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
In some embodiments, the shape of the secondary battery is not particularly limited, and may be cylindrical, square, or any other shape.
In some embodiments, the present application also provides a battery module. The battery module includes the secondary battery described above. The battery module of the present application employs the above-described secondary battery, and thus has at least the same advantages as the secondary battery. The number of secondary batteries contained in the battery module of the present application may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
In some embodiments, the present application also provides a battery pack including the above battery module. The number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
2. Device and method for controlling the same
The present application also provides an apparatus comprising at least one of the above secondary battery, battery module or battery pack.
In some embodiments, the apparatus includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric storage systems, and the like. In order to meet the high power and high energy density requirements of the device for the secondary battery, a battery pack or a battery module may be employed.
In other embodiments, the device may be a cell phone, tablet, notebook, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
The test methods for the primary particle graphite, the secondary particle graphite, the anode active material and the battery performance parameters in the following examples and comparative examples are as follows:
1. measurement of contact Angle
Adding primary particle graphite, secondary particle graphite or negative electrode active material (modified artificial graphite powder) into a pre-mold, and pressing to form, wherein the formed size can only hold liquid drops; water contact angle measurements were carried out at 25 c±5 ℃ using a contact angle tester (e.g., SDC-200S): the water drop is dripped on the surface of the formed artificial graphite powder, the quantity of the water drop is 10 mu L+/-1 mu L, the water contact angle is tested 3-5 seconds after the water drop is dripped, specifically, the average value of the angles of the left side and the right side of the water drop is adopted for measuring the water contact angle, and the specific value is automatically fit and read by an instrument.
2. Determination of oil absorption value
The oil absorption value L is the amount of linseed oil added dropwise when the torque generated by the viscosity characteristic change reaches 70% of the maximum torque, and is measured in mL/100g by using an ASAHI S-500 oil absorption value tester of ASAHISOUKEN.
Determination of Dv50
The particle size distribution was measured according to the particle size distribution laser diffraction method GB/T19077-2016 using a laser diffraction particle size distribution measuring instrument (Mastersizer 3000). For the volume distribution, the particle diameter at the cumulative frequency of 50% from the side where the particle diameter is small is D50.
4. Determination of tap Density
See methods specified in appendix F in GB/T24533-2019 lithium ion battery graphite-based negative electrode materials.
5. Determination of specific surface area
See GB/T19587-2017 for a method specified in the determination of specific surface area of solid substances by the gas adsorption BET method.
Determination of 6.300cls and 500cls Capacity Retention Rate
And (3) performing constant-current discharge on the lithium ion battery according to the current of 1C at the normal temperature of 25 ℃, and then performing constant-current charge according to the current of 1C, wherein the cutoff voltage is 2.3V, and the cutoff voltage is 3.8V, so that the operation is repeated. Recording the capacity of each charge and discharge, and calculating the capacity retention rate after 300 times of circulation according to the following formula after 300 times of charge and discharge:
after 500 cycles of charge and discharge, the capacity retention after 500 th cycle was calculated according to the following formula:
the values of capacity during the cycle were tested according to conventional test methods in the art.
7. Determination of Low temperature Performance
And (3) fully charging the lithium ion battery at the temperature of-10 ℃ for 20 times with the full charge of 0.4C and the full discharge of 0.5C, fully charging the lithium ion battery at the temperature of 0.4C, disassembling the negative electrode plate, and observing the lithium precipitation condition on the surface of the negative electrode plate.
And (3) fully charging the lithium ion battery at the temperature of-10 ℃ for 20 times with the full charge of 0.6C and the full discharge of 0.5C, fully charging the lithium ion battery at the temperature of 0.6C, then disassembling the negative electrode plate, and observing the lithium precipitation condition on the surface of the negative electrode plate.
The area of the lithium-separating area on the surface of the negative electrode plate is smaller than 10 percent and is regarded as slight lithium separation, the area of the lithium-separating area on the surface of the negative electrode plate is 10 to 50 percent and is regarded as moderate lithium separation, and the area of the lithium-separating area on the surface of the negative electrode plate is larger than 50 percent and is regarded as serious lithium separation.
The present application is further illustrated by the following examples, which are not intended to limit the scope of the present application. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The primary particulate graphite, the secondary particulate graphite and the negative electrode active material in the following examples and comparative examples were prepared by a method conventional in the art.
Examples and comparative examples
Example 1
Preparing a positive electrode plate: the positive electrode active material lithium iron phosphate, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 97:1.4:1.6, mixing, adding the mixture into a solvent N-methylpyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry, wherein the solid content in the positive electrode slurry is 60wt%; and uniformly coating the anode slurry on an anode current collector aluminum foil, drying at 85 ℃, cold pressing, trimming, cutting pieces and slitting, and finally continuously drying for 4 hours under the vacuum condition at 85 ℃ to obtain the anode sheet.
Preparing a negative electrode plate: artificial graphite, a conductive agent Super P, a thickener sodium carboxymethyl cellulose (CMC), a binder styrene-butadiene rubber emulsion (SBR) and 1, 3-butanediol according to the mass ratio of 96:1.4:1.1:1.5: and 0.4, mixing, adding the mixture into deionized water serving as a solvent, and uniformly stirring under the action of a vacuum stirrer to obtain negative electrode slurry. Wherein the solid content in the anode slurry was 54wt%. The negative electrode slurry is uniformly coated on a negative electrode current collector copper foil and dried at 85 ℃, then subjected to cold pressing, trimming, cutting and slitting, and finally dried for 12 hours under the vacuum condition of 120 ℃ to obtain a negative electrode plate.
Preparing an electrolyte: the organic solvent comprises a mixed solution of Ethylene Carbonate (EC) and Propylene Carbonate (PC), wherein EC: the volume ratio of PC is 50:50, which are 1% of the total mass of the electrolyte. In an argon atmosphere glove box with a water content of <10ppm, fully dried lithium salt (lithium hexafluorophosphate) is dissolved in the organic solvent, and then electrolyte additives LiSFI and LiPO2F2 are added, wherein LiFSI accounts for 1% of the total mass, liPO2F2 accounts for 1.5% of the total mass, and the electrolyte is obtained by uniform mixing. Wherein the concentration of the lithium salt is 1mol/L.
Preparation of a separation film: a polyethylene film (PE) having a thickness of 11 μm was used as a separator.
Preparation of a lithium ion battery: sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate to play a role of isolation, then stacking the positive electrode plate and the negative electrode plate to form a square bare cell, welding the electrode lugs, filling the bare cell into a packaging foil aluminum plastic film, baking at 80 ℃ to remove water, injecting electrolyte, sealing, standing, performing hot and cold pressing, forming (0.02C constant current charging to 3.3V, and then 0.1C constant current charging to 3.8V), shaping, testing the capacity and other working procedures to obtain the finished flexible package lithium ion battery, wherein the thickness is 4.0mm, the width is 60mm, and the length is 140mm.
Examples 2 to 5 and comparative examples 1 to 4 were carried out by adjusting the mass ratio of the primary particle graphite and the secondary particle graphite in the anode active material, the oil absorption value, the contact angle, and the like on the basis of example 1, and specific adjustment measures and detailed data are shown in table 1.
TABLE 1
Test results:
TABLE 2
As can be seen from table 2, the negative electrode active materials of the present application not only have better cycle performance, but also can overcome the low temperature problem, whereas the negative electrode active materials of comparative examples 1 to 4 have significantly reduced cycle performance or low temperature fast charge performance compared with examples 1 to 5.
While certain exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application, as described in the appended claims.

Claims (10)

1. A graphite anode active material comprising primary particle graphite and secondary particle graphite, wherein the primary particle graphite has an oil absorption value satisfying 30mL/100 g-51 mL/100g; and/or
The oil absorption value of the secondary particle graphite meets 40mL/100 g-65 mL/100g.
2. The graphite anode active material according to claim 1, wherein the graphite anode active material satisfies at least one of the following conditions:
the oil absorption value of the primary particle graphite meets 31mL/100 g-50 mL/100g;
the oil absorption value of the secondary particle graphite meets 44mL/100 g-63 mL/100g;
the contact angle of the primary particle graphite satisfies 16.0-20.0 degrees;
the contact angle of the secondary particle graphite satisfies 20.0 DEG to 41.0 deg.
3. The graphite anode active material according to claim 2, wherein the contact angle of the primary particle graphite satisfies 16.0 ° -19.0 °; and/or
The contact angle of the secondary particle graphite satisfies 22.0 DEG to 40.0 deg.
4. The graphite anode active material according to any one of claims 1 to 3, wherein the graphite anode active material satisfies at least one of the following conditions:
the Dv50 of the primary particle graphite satisfies 5.0-11.0 mu m;
the tap density of the primary particle graphite satisfies 0.8g/cm 3 ～1.3g/cm 3 ；
The specific surface area of the primary particle graphite satisfies 1.2m 2 /g～1.8m 2 /g；
The Dv50 of the secondary particle graphite satisfies 11.0-17.0 mu m;
the tap density of the secondary particle graphite meets 0.9g/cm 3 ～1.3g/cm 3 ；
The specific surface area of the secondary particle graphite satisfies 1.0m 2 /g～1.8m 2 /g；
The mass ratio of the primary particle graphite to the secondary particle graphite is (0.5-1.5): 1.
5. the graphite anode active material according to claim 4, wherein the graphite anode active material satisfies at least one of the following conditions:
the Dv50 of the primary particle graphite satisfies 7.0-9.0 mu m;
the tap density of the primary particle graphite satisfies 0.9g/cm 3 ～1.2g/cm 3 ；
The specific surface area of the primary particle graphite satisfies 1.3m 2 /g～1.6m 2 /g；
The Dv50 of the secondary particle graphite satisfies 12.0-16.0 mu m;
the tap density of the secondary particle graphite is 1.0g/cm 3 ～1.2g/cm 3 ；
The specific surface area of the secondary particle graphite is 1.1m 2 /g～1.4m 2 /g。
6. The graphite anode active material according to any one of claims 1 to 3, wherein the graphite anode active material satisfies at least one of the following conditions:
the Dv50 of the negative electrode active material is 11.0-14.0 μm;
the tap density of the negative electrode active material is 1.0g/cm 3 -1.3g/cm 3 ；
The specific surface area of the negative electrode active material was 1.2g/cm 2 -1.8g/cm 2 ；
The negative electrode active material further includes a silicon-based material.
7. The anode active material according to claim 6, wherein the silicon-based material includes at least one of silicon, a silicon alloy, a silicon carbon compound, and a silicon oxygen compound.
8. A negative electrode tab comprising a negative electrode current collector and a negative electrode material layer disposed on a surface of the negative electrode current collector, the negative electrode material layer comprising the negative electrode active material according to any one of claims 1-7.
9. A secondary battery comprising the negative electrode tab and the positive electrode tab of claim 8.
10. An apparatus comprising the secondary battery according to claim 9.
CN202311767284.2A 2023-12-20 2023-12-20 Graphite negative electrode active material, negative electrode sheet, secondary battery and device Pending CN117712376A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118263401A (en) * 2024-05-30 2024-06-28 宁德时代新能源科技股份有限公司 Battery, preparation method thereof and electricity utilization device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118263401A (en) * 2024-05-30 2024-06-28 宁德时代新能源科技股份有限公司 Battery, preparation method thereof and electricity utilization device

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