CN117423801B - Negative electrode plate, preparation method thereof and battery - Google Patents
Negative electrode plate, preparation method thereof and battery Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 claims abstract description 121
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 121
- 239000011149 active material Substances 0.000 claims abstract description 106
- 239000011267 electrode slurry Substances 0.000 claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 28
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- 239000002270 dispersing agent Substances 0.000 claims description 24
- 239000006258 conductive agent Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
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- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
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- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
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- 238000003860 storage Methods 0.000 abstract description 18
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- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
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- 238000009830 intercalation Methods 0.000 description 6
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- 238000004146 energy storage Methods 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
The application provides a negative electrode plate, a preparation method thereof and a battery, wherein the negative electrode plate comprises a first active material layer, a second active material layer and a current collector layer which are sequentially laminated; the first active material layer is formed by manufacturing first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material; the second active material layer is formed by manufacturing second negative electrode slurry, and the second negative electrode slurry comprises a second hard carbon material; the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material. The negative electrode plate, the preparation method thereof and the battery are simple in structure and convenient to manufacture, side reactions of the negative electrode and electrolyte in the charge-discharge process and the high-temperature storage process can be effectively reduced, the cycle life and the high-temperature storage performance of the battery are improved, the capacity of the battery is high, and the service life of the battery is long.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a negative electrode plate, a preparation method thereof and a battery.
Background
With the increasing demand of energy, secondary batteries are the focus of attention, and at present, secondary batteries for power and energy storage are mainly lithium ion batteries, but with the gradual expansion of the scale of lithium ion batteries, lithium resources are increasingly scarce. The function of sodium ions is similar to that of lithium ions, the intercalation and deintercalation of sodium ions between the anode and the cathode can be utilized to realize the mutual conversion of electric energy and chemical energy, and the earth reserve of sodium resources is far more abundant than that of lithium, and the sodium resources are distributed more widely and at lower cost, so that the sodium ion battery has potential to replace the lithium ion battery to become a new generation electrochemical system.
The common positive pole piece materials of the sodium ion battery comprise transition metal layered oxides, polymeric anions and Prussian blue materials, and the negative pole piece material is generally a hard carbon material. The hard carbon material is an amorphous material, and the inside of the material is of a disordered and non-uniform structure composed of carbon atoms, and has a plurality of micropores and microcrystal defects and a large specific surface area, so that the influence on the battery capacity and the battery electrical property is large, but the capacity, the cycle performance, the high-temperature storage performance and the like of the sodium ion battery are difficult to be compatible, so that a cathode plate capable of improving the battery capacity and the battery electrical property simultaneously is needed.
Disclosure of Invention
In view of the above, the present application aims to provide a negative electrode tab, a preparation method thereof and a battery for solving the above technical problems.
In a first aspect of the present application, there is provided a negative electrode tab including a first active material layer, a second active material layer, and a current collector layer, which are sequentially stacked; the first active material layer is formed by manufacturing first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material; the second active material layer is formed by manufacturing second negative electrode slurry, and the second negative electrode slurry comprises a second hard carbon material; the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material.
Further, the specific surface area of the first hard carbon material is 2.6m 2 /g-4.6m 2 Per gram, the specific surface area of the second hard carbon material is 6.1m 2 /g-9.5m 2 /g。
Further, the first negative electrode slurry further comprises a first conductive agent, a first binder, a first dispersing agent and a first solvent, and the second negative electrode slurry further comprises a second conductive agent, a second binder, a second dispersing agent and a second solvent.
Further, the first hard carbon material and the second hard carbon material are independently one or more of a biomass-based hard carbon material, a resin-based hard carbon material, or a pitch-based hard carbon material; the first and second conductive agents are independently one or more of conductive carbon black (SP), conductive graphite (KS-6), or Carbon Nanotubes (CNT); the first binder and the second binder are independently one or more of styrene-butadiene rubber emulsion (SBR), polyacrylic acid (PAA), or Polyacrylonitrile (PAN); the first dispersant and the second dispersant are independently carboxymethylcellulose (CMC); the first solvent and the second solvent are water.
Further, the first negative electrode slurry includes 80 to 97 parts by weight of the first hard carbon material, 0.5 to 5 parts by weight of the first conductive agent, 1 to 5 parts by weight of the first binder, and 0.5 to 2 parts by weight of the first dispersant; the second negative electrode slurry comprises 80-97 parts by weight of the second hard carbon material, 0.5-5 parts by weight of the second conductive agent, 1-5 parts by weight of the second binder and 0.5-2 parts by weight of the second dispersant; the solid content of the first negative electrode slurry and the second negative electrode slurry is 50% -60%.
Further, the areal density of the first active material layer is greater than or equal to the areal density of the second active material layer.
Further, the areal density of the first active material layer and the second active material layer is 4mg/cm 2 -7mg/cm 2 。
Further, the current collector layer is aluminum foil and has a thickness of 10 μm to 15 μm.
In a second aspect of the present application, a method for preparing a negative electrode tab is provided, including: configuring a first negative electrode slurry and a second negative electrode slurry, wherein the first negative electrode slurry comprises a first hard carbon material, the second negative electrode slurry comprises a second hard carbon material, and the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material; coating the second negative electrode slurry on the current collector layer, and drying to form a second active material layer; and coating the first negative electrode slurry on one side of the second active material layer far away from the current collector layer, and drying to form a first active material layer.
In a third aspect of the present application, there is provided a battery comprising: the positive pole piece, the diaphragm, the negative pole piece and electrolyte, wherein the negative pole piece is the negative pole piece according to the first aspect.
From the above, the application provides a negative electrode plate, a preparation method thereof and a battery, wherein the negative electrode plate comprises a first active material layer, a second active material layer and a current collector layer which are sequentially stacked; the first active material layer is formed by manufacturing a first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material; the second active material layer is formed by manufacturing second negative electrode slurry, and the second negative electrode slurry comprises a second hard carbon material; wherein the specific surface area of the first hard carbon material is smaller than the specific surface area of the second hard carbon material; experiments prove that compared with a negative electrode plate with only one active material layer with low specific surface area, or only one active material layer with high specific surface area, or a first active material layer with high specific surface area and a negative electrode plate with a second active material layer with low specific surface area are arranged reversely, the negative electrode plate can enable a battery to have higher battery capacity and better battery electrical property, the battery energy density is above 130wh/kg, the cycle number of the capacity retention of 80% in a cycle experiment can reach 1200 times, and the recovery rate of the high-temperature storage capacity can reach 99%; the negative electrode plate, the preparation method thereof and the battery are simple in structure and convenient to manufacture, can effectively reduce side reactions of the negative electrode and electrolyte in the charge-discharge process and the high-temperature storage process, improve the cycle life and the high-temperature storage performance of the battery, and have high capacity and long service life.
Drawings
In order to more clearly illustrate the technical solutions of the present application or related art, the drawings that are required to be used in the description of the embodiments or related art will be briefly described below, and it is apparent that the drawings in the following description are only embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort to those of ordinary skill in the art.
Fig. 1 is a schematic structural diagram of a negative electrode sheet in an embodiment of the present application.
Fig. 2 is a schematic view showing the cycle performance test of the battery fabricated from the negative electrode sheet in examples and comparative examples of the present application.
Reference numerals: 1. a first active material layer; 2. a second active material layer; 3. and a current collector layer.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail below with reference to the accompanying drawings.
It should be noted that unless otherwise defined, technical or scientific terms used in the embodiments of the present application should be given the ordinary meaning as understood by one of ordinary skill in the art to which the present application belongs. The terms "first," "second," and the like, as used in embodiments of the present application, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed.
With the increasing demand of energy, secondary batteries are the focus of attention, and at present, secondary batteries for power and energy storage are mainly lithium ion batteries, but with the gradual expansion of the scale of lithium ion batteries, lithium resources are increasingly scarce. The function of sodium ions is similar to that of lithium ions, the intercalation and deintercalation of sodium ions between the anode and the cathode can be utilized to realize the mutual conversion of electric energy and chemical energy, and the earth reserve of sodium resources is far more abundant than that of lithium, and the sodium resources are distributed more widely and at lower cost, so that the sodium ion battery has potential to replace the lithium ion battery to become a new generation electrochemical system.
The common positive pole piece materials of the sodium ion battery comprise transition metal layered oxides, polymeric anions and Prussian blue materials, and the negative pole piece material is generally a hard carbon material. The hard carbon material is an amorphous material, and the inside of the material is of a disordered and non-uniform structure composed of carbon atoms, and has a plurality of micropores and microcrystal defects and a large specific surface area, so that the influence on the battery capacity and the battery electrical property is large, but the capacity, the cycle performance, the high-temperature storage performance and the like of the sodium ion battery are difficult to be compatible, so that a cathode plate capable of improving the battery capacity and the battery electrical property simultaneously is needed.
In the process of realizing the application, three sodium intercalation modes are generally found in the sodium ion battery charging process, namely, one is adsorption sodium intercalation corresponding to a charge-discharge curve slope area, the other is carbon layer intercalation corresponding to a platform area, and the other is pore filling sodium intercalation, so that the higher the capacity of the negative electrode is, the more pores are required to be formed in the hard carbon material, so that the larger specific surface area is provided, but the higher the specific surface area of the hard carbon material is, the higher the activity of the decomposition electrolyte for side reaction is, the charge-discharge cycle life and the high-temperature storage performance are both deteriorated, the negative electrode pole piece can be designed in a layered manner, the active material layers with different specific surface areas are arranged, and the battery capacity and the battery electrical property are balanced.
The following describes the technical solution of the present application in detail by means of specific embodiments in combination with fig. 1 to 2.
In some embodiments of the present application, there is provided a negative electrode tab, as shown in fig. 1, including a first active material layer 1, a second active material layer 2, and a current collector layer 3 that are sequentially stacked; the first active material layer 1 is formed by manufacturing a first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material; the second active material layer 2 is formed by manufacturing a second negative electrode slurry, and the second negative electrode slurry comprises a second hard carbon material; the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material.
The negative electrode plate comprises a first active material layer 1, a second active material layer 2 and a current collector layer 3 which are sequentially stacked, wherein the current collector layer 3 is used for collecting current generated by active materials so as to form larger current to be output outwards; the first active material layer 1 is formed by manufacturing a first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material, and can also comprise a first conductive agent, a first binder, a first dispersing agent and a first solvent; the second active material layer 2 is formed by manufacturing a second anode slurry including a second hard carbon material, and may further include a second conductive agent, a second binder, a second dispersant, and a second solvent.
The specific surface area of the first hard carbon material is smaller than that of the second hard carbon material, the first active material layer 1 is close to the battery diaphragm, has lower specific surface area, and can inhibit side reaction of the negative electrode and the electrolyte, so that the circularity and high-temperature storage performance of the sodium ion battery are improved; the second active material layer 2 has a higher specific surface area near the current collector layer 3, and can provide a higher battery capacity.
Experiments prove that compared with a cathode pole piece with only one active material layer with low specific surface area, or only one active material layer with high specific surface area, or a cathode pole piece with a first active material layer with high specific surface area and a cathode pole piece with a second active material layer with low specific surface area, the cathode pole piece of the embodiment can enable a battery to have higher battery capacity and better battery electrical property, the battery energy density is above 130wh/kg, the cycle number of the capacity retention of 80% in a cycle experiment can reach 1200 times, and the recovery rate of the high-temperature storage capacity can reach 99%.
The negative pole piece has the advantages of simple structure and convenient manufacture, can effectively reduce side reactions of the negative pole and electrolyte in the charge-discharge process and the high-temperature storage process, improves the cycle life and the high-temperature storage performance of the battery, and has high battery capacity and long service life.
In some embodiments, the first hard carbon material has a specific surface area of 2.6m 2 /g-4.6m 2 Per gram, the specific surface area of the second hard carbon material is 6.1m 2 /g-9.5m 2 /g。
The specific surface area of the first hard carbon material is, for example, 2.6m 2 /g、3m 2 /g、4m 2 /g or 4.6m 2 Per gram, etc., the specific surface area of the second hard carbon material is, for example, 6.1m 2 /g、7m 2 /g、8m 2 /g、9m 2 /g or 9.5m 2 According to the experimental test, the higher the specific surface area ratio of the second hard carbon material to the first hard carbon material is, the better the battery electrical property is, namely the specific surface area ratio of the second hard carbon material to the first hard carbon material and the battery electrical propertyThe sexuality is positively correlated.
In some embodiments, the first hard carbon material and the second hard carbon material are independently one or more of a biomass-based hard carbon material, a resin-based hard carbon material, or a pitch-based hard carbon material; the first and second conductive agents are independently one or more of conductive carbon black (SP), conductive graphite (KS-6), or Carbon Nanotubes (CNT); the first binder and the second binder are independently one or more of styrene-butadiene rubber emulsion (SBR), polyacrylic acid (PAA), or Polyacrylonitrile (PAN); the first dispersant and the second dispersant are independently carboxymethylcellulose (CMC); the first solvent and the second solvent are water.
The first hard carbon material and the second hard carbon material are, for example, a biomass-based hard carbon material and a resin-based hard carbon material, respectively; the first conductive agent and the second conductive agent are, for example, conductive carbon black and conductive graphite, respectively; the first binder and the second binder are, for example, polyacrylic acid and polyacrylonitrile, respectively; the first dispersant and the second dispersant are, for example, carboxymethyl cellulose, respectively, and the first solvent and the second solvent are both water.
In some embodiments, the first negative electrode slurry includes 80 to 97 parts by weight of the first hard carbon material, 0.5 to 5 parts by weight of the first conductive agent, 1 to 5 parts by weight of the first binder, and 0.5 to 2 parts by weight of the first dispersant.
The second negative electrode slurry includes 80-97 parts by weight of the second hard carbon material, 0.5-5 parts by weight of the second conductive agent, 1-5 parts by weight of the second binder, and 0.5-2 parts by weight of the second dispersant.
In the first negative electrode slurry, the first hard carbon material is, for example, 80, 85, 90, 95, 97, or the like, the first conductive agent is, for example, 0.5, 1, 2, 3, 4, or 5, the first binder is, for example, 1, 2, 3, 4, or 5, and the first dispersant is, for example, 0.2, 0.5, 1, or 2.
In the second negative electrode slurry, the weight part of the second hard carbon material is, for example, 80, 85, 90, 95, 97, or the like, the weight part of the second conductive agent is, for example, 0.5, 1, 2, 3, 4, or 5, the weight part of the second binder is, for example, 1, 2, 3, 4, or 5, and the weight part of the second dispersant is, for example, 0.2, 0.5, 1, or 2.
In some embodiments, the first negative electrode slurry and the second negative electrode slurry each have a solids content of 50% -60%.
The solid content of the first negative electrode slurry is, for example, 50%, 55%, 60%, or the like, and the solid content of the second negative electrode slurry is, for example, 50%, 55%, 60%, or the like.
In some embodiments, the areal density of the first active material layer 1 is greater than or equal to the areal density of the second active material layer 2.
The thicker the surface density is, the thicker the thickness of the active material layer is, the first active material layer 1 is close to the battery diaphragm, the lower specific surface area is provided, and by arranging the thicker first active material layer 1, the side reaction between the cathode and the electrolyte can be better inhibited, and the battery electrical property is improved.
In some embodiments, the areal density of the first active material layer 1 and the second active material layer 2 is 4mg/cm 2 -7mg/cm 2 。
The areal density of the first active material layer 1 is, for example, 4mg/cm 2 、5mg/cm 2 、6mg/cm 2 Or 7mg/cm 2 Etc., the areal density of the second active material layer 2 is, for example, 4mg/cm 2 、5mg/cm 2 、6mg/cm 2 Or 7mg/cm 2 Etc.
In some embodiments, the current collector layer 3 is aluminum foil having a thickness of 10 μm to 15 μm.
The thickness of the current collector layer 3 is, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, or the like.
In some embodiments of the present application, a method for preparing a negative electrode sheet is provided, including:
s1, configuring first negative electrode slurry and second negative electrode slurry, wherein the first negative electrode slurry comprises a first hard carbon material, the second negative electrode slurry comprises a second hard carbon material, and the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material.
The first negative electrode slurry comprises a first hard carbon material, a first conductive agent, a first binder, a first dispersing agent and a first solvent; the second negative electrode slurry includes a second hard carbon material, a second conductive agent, a second binder, a second dispersant, and a second solvent.
And S2, coating the second anode slurry on the current collector layer 3, and drying to form a second active material layer 2.
And S3, coating the first negative electrode slurry on one side, far away from the current collector layer 3, of the second active material layer 2, and drying to form a first active material layer 1.
The negative electrode plate obtained by the preparation method can balance the battery electrical property and the battery capacity.
In some embodiments of the present application, there is provided a battery including: the positive electrode plate, the diaphragm, the negative electrode plate and the electrolyte, wherein the negative electrode plate is the negative electrode plate in any embodiment.
The stacking type of the battery is, for example, a winding type battery or a lamination type battery, the structure type is, for example, a square shell battery, a soft package battery or a cylindrical battery, etc., and the battery is not particularly limited, and the battery has long cycle life, good high-temperature storage performance, high battery capacity and long service life.
Example 1
The negative electrode plate comprises a first active material layer 1, a second active material layer 2 and a current collector layer 3 which are sequentially laminated, wherein the surface density of the first active material layer 1 is 4mg/cm 2 The areal density of the second active material layer 2 was 7mg/cm 2 。
The first active material layer 1 is formed by manufacturing a first negative electrode slurry, the first negative electrode slurry comprises 97 parts by weight of a first hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the first negative electrode slurry is 50%.
The second active material layer 2 is formed by manufacturing a second negative electrode slurry, the second negative electrode slurry comprises 97 parts by weight of a second hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the second negative electrode slurry is 50%.
Wherein the first hard carbon material has a specific surface area of 2.6m 2 Resin-based hard carbon material per gram, the second hard carbon material having a specific surface area of 6.1m 2 Resin-based hard carbon material/g.
Example 2
The negative electrode plate comprises a first active material layer 1, a second active material layer 2 and a current collector layer 3 which are sequentially laminated, wherein the surface density of the first active material layer 1 is 7mg/cm 2 The areal density of the second active material layer 2 was 4mg/cm 2 。
The first active material layer 1 is formed by manufacturing a first negative electrode slurry, the first negative electrode slurry comprises 80 parts by weight of a first hard carbon material, 0.5 part by weight of conductive graphite, 1 part by weight of polyacrylic acid and 0.5 part by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the first negative electrode slurry is 60%.
The second active material layer 2 is formed by manufacturing a second negative electrode slurry, the second negative electrode slurry comprises 80 parts by weight of a second hard carbon material, 0.5 part by weight of conductive graphite, 1 part by weight of polyacrylic acid and 0.5 part by weight of carboxymethyl cellulose, the solvent is deionized water, and the solid content of the second negative electrode slurry is 60%.
Wherein the first hard carbon material has a specific surface area of 4.1m 2 Biomass-based hard carbon material per gram, the second hard carbon material having a specific surface area of 7.3m 2 Biomass-based hard carbon material per gram.
Example 3
The negative electrode plate comprises a first active material layer 1, a second active material layer 2 and a current collector layer 3 which are sequentially laminated, wherein the surface density of the first active material layer 1 is 5mg/cm 2 The areal density of the second active material layer 2 was 5mg/cm 2 。
The first active material layer 1 is formed by manufacturing a first negative electrode slurry, the first negative electrode slurry comprises 97 parts by weight of a first hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the first negative electrode slurry is 50%.
The second active material layer 2 is formed by manufacturing a second negative electrode slurry, the second negative electrode slurry comprises 97 parts by weight of a second hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the second negative electrode slurry is 50%.
Wherein the first hard carbon material has a specific surface area of 4.6m 2 Resin-based hard carbon material per gram, the second hard carbon material having a specific surface area of 9.5m 2 Resin-based hard carbon material/g.
Example 4
The negative electrode plate comprises a first active material layer 1, a second active material layer 2 and a current collector layer 3 which are sequentially laminated, wherein the surface density of the first active material layer 1 is 6mg/cm 2 The areal density of the second active material layer 2 was 4mg/cm 2 。
The first active material layer 1 is formed by manufacturing a first negative electrode slurry, the first negative electrode slurry comprises 97 parts by weight of a first hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the first negative electrode slurry is 50%.
The second active material layer 2 is formed by manufacturing a second negative electrode slurry, the second negative electrode slurry comprises 97 parts by weight of a second hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, a solvent is deionized water, and the solid content of the second negative electrode slurry is 50%.
Wherein the first hard carbon material has a specific surface area of 3.7m 2 Resin-based hard carbon material per gram, the second hard carbon material having a specific surface area of 8.4m 2 Resin-based hard carbon material/g.
Comparative example 1
The negative electrode plate comprises an active material layer and a current collector layer which are laminated, wherein the surface density of the active material layer is 10mg/cm 2 。
The active material layer is formed by manufacturing negative electrode slurry, the negative electrode slurry comprises 97 parts by weight of hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion and 2 parts by weight of carboxymethyl cellulose, the solvent is deionized water, and the solid content of the negative electrode slurry is 50%.
The hard carbon material has a specific surface area of 8.0m 2 Resin-based hard carbon material/g.
Comparative example 2
The negative electrode plate comprises a first active material layer, a second active material layer and a current collector layer which are sequentially laminated, wherein the surface density of the first active material layer is 4mg/cm 2 The areal density of the second active material layer was 7mg/cm 2 。
The first active material layer is formed by manufacturing first negative electrode slurry, the first negative electrode slurry comprises 97 parts by weight of first hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, the solvent is deionized water, and the solid content of the first negative electrode slurry is 50%.
The second active material layer is formed by manufacturing second anode slurry, the second anode slurry comprises 97 parts by weight of second hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion, 2 parts by weight of carboxymethyl cellulose, the solvent is deionized water, and the solid content of the second anode slurry is 50%.
Wherein the first hard carbon material has a specific surface area of 9.5m 2 Resin-based hard carbon material per gram, the second hard carbon material having a specific surface area of 4.6m 2 Resin-based hard carbon material/g.
Comparative example 3
The negative electrode plate comprises an active material layer and a current collector layer which are laminated, wherein the surface density of the active material layer is 10mg/cm 2 。
The active material layer is formed by manufacturing negative electrode slurry, the negative electrode slurry comprises 97 parts by weight of hard carbon material, 5 parts by weight of conductive carbon black, 5 parts by weight of styrene-butadiene rubber emulsion and 2 parts by weight of carboxymethyl cellulose, the solvent is deionized water, and the solid content of the negative electrode slurry is 50%.
The hard carbon material has a specific surface area of 4.6m 2 Resin-based hard carbon material/g.
Comparative example 1 is a negative electrode sheet provided with only one high specific surface area active material layer, comparative example 2 is a negative electrode sheet provided with a first active material layer of high specific surface area and a second active material layer of low specific surface area, comparative example 3 is a negative electrode sheet provided with only one low specific surface area active material layer, and examples 1 to 4 are negative electrode sheets provided with a first active material layer 1 of low specific surface area and a second active material layer 2 of high specific surface area.
The negative electrode sheets of the foregoing examples and comparative examples were fabricated into batteries, and the fabrication method of the batteries included mixing a sodium ion positive electrode material, an adhesive polyvinylidene fluoride (PVDF), conductive carbon black, and azomethyl pyrrolidone to form a positive electrode slurry, coating the slurry on an aluminum foil, and drying to fabricate a positive electrode sheet. And rolling and cutting the positive electrode plate and the negative electrode plate, isolating the positive electrode plate and the negative electrode plate by using a diaphragm, and stacking the positive electrode plate and the negative electrode plate layer by layer to form a pole group. The electrode group is fixed in a battery shell, baked at high temperature to remove water, then sodium ion electrolyte is injected, and the battery is manufactured by first charging and shell sealing.
The energy densities of the batteries of the previous examples and comparative examples were measured, the test methods were constant current charge and discharge methods, and the test results are shown in table 1, and the battery energy densities of the examples were all above 130wh/kg, with higher battery capacities.
The battery electrical properties of the foregoing examples and comparative examples were measured, and the battery electrical property test included a 45 ℃ cycle test and a storage test.
The method for 45 ℃ cycle testing comprises the following steps: and controlling the ambient temperature to 45+/-2 ℃, constant-current charging the battery 1C to 3.8V, constant-voltage charging the battery to 0.05C at 3.8V, constant-current discharging the battery 1C to 2.0V, recording the first discharge capacity C1, repeating the charging and discharging steps, recording the discharge capacity C2 after each cycle, calculating the capacity retention rate C2/C1 of each cycle by 100%, and finally recording the cycle times when the capacity retention rate is reduced to 80%.
The method for 60 ℃ storage test comprises the following steps: the environmental temperature is controlled to 60+/-2 ℃, after the battery is charged to 3.8V at a constant current of 0.33C and charged to 0.05C at a constant voltage of 3.8V, the battery is discharged to 2.0V at a constant current of 1C, the discharge capacity C3 before storage is recorded, then the battery is stored for 7 days after the battery is charged to 3.8V at a constant current of 0.33C and charged to 0.05C at a constant voltage of 3.8V, the battery 1C is discharged to 2.0V at a constant current, the discharge capacity C4 after storage is recorded, and the capacity recovery rate C4/C3 is calculated to be 100%.
The test results are shown in table 1 and fig. 2, and it can be seen that the battery electrical properties of the examples are better than those of the comparative examples, wherein the battery electrical properties of the example 1 are optimal, the cycle number of the capacity retention 80% in the cycle experiment can reach 1200 times, and the recovery rate of the high-temperature storage capacity can reach 99%.
Furthermore, as can be seen from the data of comparative examples 1 to 3, the specific surface area ratio of the second hard carbon material to the first hard carbon material is positively correlated with the battery electrical properties.
Table 1 battery electrical and capacity comparison table
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the application (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the present application, the steps may be implemented in any order, and there are many other variations of the different aspects of the embodiments of the present application as described above, which are not provided in detail for the sake of brevity.
In addition, where details are set forth to describe example embodiments of the present application, it will be apparent to one skilled in the art that embodiments of the present application may be practiced without, or with variation of, these details. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
Well-known power/ground connections to other components may or may not be shown in the drawings provided to simplify the illustration and discussion, and so as not to obscure the embodiments of the present application. Furthermore, the devices may be shown in block diagram form in order to avoid obscuring the embodiments of the present application, and this also takes into account the fact that specifics with respect to implementation of such block diagram devices are highly dependent upon the platform on which the embodiments of the present application are to be implemented (i.e., such specifics should be well within purview of one skilled in the art). Where specific details are set forth in order to describe example embodiments of the present application, it should be apparent to one skilled in the art that embodiments of the present application may be practiced without, or with variation of, these specific details. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
While the present application has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations of those embodiments will be apparent to those skilled in the art in light of the foregoing description. The present embodiments are intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Accordingly, any omissions, modifications, equivalents, improvements and/or the like which are within the spirit and principles of the embodiments are intended to be included within the scope of the present application.
Claims (9)
1. The negative electrode plate is applied to a sodium ion battery and is characterized by comprising a first active material layer, a second active material layer and a current collector layer which are sequentially stacked;
the first active material layer is formed by manufacturing first negative electrode slurry, and the first negative electrode slurry comprises a first hard carbon material; the second active material layer is formed by manufacturing second negative electrode slurry, and the second negative electrode slurry comprises a second hard carbon material; wherein the specific surface area of the first hard carbon material is smaller than the specific surface area of the second hard carbon material;
the specific surface area of the first hard carbon material is 2.6m 2 /g-4.6m 2 Per gram, the specific surface area of the second hard carbon material is 6.1m 2 /g-9.5m 2 And/g, wherein the first negative electrode slurry comprises 80-97 parts by weight of the first hard carbon material, the second negative electrode slurry comprises 80-97 parts by weight of the second hard carbon material, and the solid contents of the first negative electrode slurry and the second negative electrode slurry are 50-60%.
2. The negative electrode tab of claim 1, wherein the first negative electrode slurry further comprises a first conductive agent, a first binder, a first dispersant, and a first solvent, and the second negative electrode slurry further comprises a second conductive agent, a second binder, a second dispersant, and a second solvent.
3. The negative electrode tab of claim 2, wherein the first hard carbon material and the second hard carbon material are independently one or more of a biomass-based hard carbon material, a resin-based hard carbon material, or a pitch-based hard carbon material;
the first conductive agent and the second conductive agent are independently one or more of conductive carbon black, conductive graphite, or carbon nanotubes;
the first binder and the second binder are independently one or more of styrene-butadiene rubber emulsion, polyacrylic acid or polyacrylonitrile;
the first dispersant and the second dispersant are independently carboxymethyl cellulose;
the first solvent and the second solvent are water.
4. The negative electrode tab of claim 2, wherein the first negative electrode slurry comprises 0.5-5 parts by weight of the first conductive agent, 1-5 parts by weight of the first binder, and 0.5-2 parts by weight of the first dispersant; the second negative electrode slurry includes 0.5-5 parts by weight of the second conductive agent, 1-5 parts by weight of the second binder, and 0.5-2 parts by weight of the second dispersant.
5. The negative electrode tab of claim 1, wherein the areal density of the first active material layer is greater than or equal to the areal density of the second active material layer.
6. The negative electrode sheet according to claim 5, wherein the first active material layer and the second active material layer each have an areal density of 4mg/cm 2 -7mg/cm 2 。
7. The negative electrode tab of claim 1, wherein the current collector layer is aluminum foil having a thickness of 10 μm to 15 μm.
8. A method of producing the negative electrode sheet according to any one of claims 1 to 7, comprising:
configuring a first negative electrode slurry and a second negative electrode slurry, wherein the first negative electrode slurry comprises a first hard carbon material, the second negative electrode slurry comprises a second hard carbon material, and the specific surface area of the first hard carbon material is smaller than that of the second hard carbon material;
coating the second negative electrode slurry on the current collector layer, and drying to form a second active material layer;
and coating the first negative electrode slurry on one side of the second active material layer far away from the current collector layer, and drying to form a first active material layer.
9. A battery, comprising: a positive electrode sheet, a separator, a negative electrode sheet and an electrolyte, wherein the negative electrode sheet is the negative electrode sheet according to any one of claims 1 to 7.
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