CN117832407A - Battery pole piece coating process and application - Google Patents
Battery pole piece coating process and application Download PDFInfo
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- CN117832407A CN117832407A CN202410020608.4A CN202410020608A CN117832407A CN 117832407 A CN117832407 A CN 117832407A CN 202410020608 A CN202410020608 A CN 202410020608A CN 117832407 A CN117832407 A CN 117832407A
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- pole piece
- current collector
- battery
- coating
- slurry
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- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000002270 dispersing agent Substances 0.000 claims abstract description 53
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000011267 electrode slurry Substances 0.000 claims abstract description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 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 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 abstract description 6
- 230000002159 abnormal effect Effects 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000011888 foil Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 3
- 230000000153 supplemental effect Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a battery pole piece coating process and application, comprising the following steps: uniformly coating positive/negative electrode slurry containing a dispersing agent on the surface of a current collector, then supplementing the dispersing agent on the edge area of the current collector, and then drying to obtain a corresponding positive/negative electrode plate of the battery; before the drying step, the solid content of the slurry in the edge area of the current collector is 0.9-1.5% lower than that of the positive/negative slurry, and the dispersing agent is added to the current collector after the slurry is coated and before the drying process, so that the dispersing agent is moved and reduced in the pole piece drying process, the thickness of the edge area of the pole piece is kept consistent with that of the middle area, and the problem of abnormal belt breakage of the edge of the pole piece in the coating process is solved; meanwhile, the uniformity of the surface density of the pole piece slurry is ensured, the safety performance of the battery cell is enhanced, and the capacity of the pole piece battery cell is not adversely affected.
Description
Technical Field
The invention relates to the technical field of battery pole pieces, in particular to a battery pole piece coating process and application.
Background
The battery pole piece is usually obtained by baking after active material slurry is coated on a positive/negative electrode current collector, the obtained positive pole piece roll and negative pole piece roll are provided for the next procedure to process, the manufacturing quality of the pole piece basically has been determined for certain performances of the battery, and the battery pole piece coating process is very important in the whole battery manufacturing process.
In the existing battery anode and cathode plate coating process, the thickness of powder at the edge of a current collector is higher than that of the middle part after drying, and a drum edge is generated at a tail-in position, so that belt breakage is caused, and normal production is affected. In order to solve the problem of belt breakage of the drum edge, the common solution is to artificially thin the slurry at the edge of the current collector when the slurry is coated, so that the coating thickness of the edge area of the current collector is smaller than that of the middle area, and the slurry accumulation effect in the drying process is relieved, so that the thickness difference between the edge area and the middle area of the current collector after drying is not too high.
Although the method can reduce the situation of broken belt of the pole piece at the edge of the drum without influencing the production process, the slurry thickness of the edge area is low, the amount of powder (solid matters in the slurry) is small, and the capacity of the battery core is reduced; meanwhile, the thinning degree of the electrode plates is difficult to control, and thinning operation is carried out on the positive and negative electrode plates in the production process, so that abnormal lithium precipitation is caused due to the fact that the thinning degree is inconsistent and the negative electrode at the edge of the positive and negative electrode plates is excessive and insufficient, and the safety performance of the battery cell is affected.
Therefore, a scheme capable of solving the problem of broken belt of the edge of the battery pole piece and guaranteeing the electrochemical performance of the battery pole piece is needed.
Disclosure of Invention
In view of this, the application provides a battery pole piece coating process and application, which are used for solving the problem of how to prevent the edge of the battery pole piece from being broken and the electrochemical performance of the battery pole piece.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a battery pole piece coating process, comprising the steps of: uniformly coating positive/negative electrode slurry containing a dispersing agent on the surface of a current collector, then supplementing the dispersing agent on the edge area of the current collector, and then drying to obtain a corresponding positive/negative electrode plate of the battery; before the drying step, the slurry solid content of the edge region of the current collector is 0.9-1.5% lower than that of the positive/negative electrode slurry.
Preferably, the current collector includes a central region and an edge region, the edge region being a region formed by extending vertically 15-20nm from the end of the current collector toward the middle, and the remaining region being the central region.
Preferably, the solid content of the positive electrode slurry is 55-58%, the dispersing agent is N-methyl pyrrolidone, and the coating weight of the positive electrode slurry is 180-190g/m 2 The amount of the dispersant for the supplementary coating is 2.99-4.01g/m 2 And (5) finishing the coating process of the battery pole piece to obtain the battery positive pole piece.
Preferably, the thickness of the middle region of the current collector is 109-110 μm after the positive electrode slurry is uniformly coated on the surface of the current collector.
Preferably, the temperature of the drying is 95-110 ℃.
Preferably, the solid content of the anode slurry is 48-50%, the dispersing agent is N-methyl pyrrolidone and/or water, and the coating weight of the anode slurry is 90-100g/m 2 The amount of the dispersant for the supplementary coating is 2.21-2.78g/m 2 And (5) finishing the coating process of the battery electrode plate to obtain the battery negative electrode plate.
Preferably, the thickness of the central region of the current collector is 75-80 μm after the negative electrode slurry is uniformly coated on the surface of the current collector.
Preferably, the temperature of the drying is 80-100 ℃.
In a second aspect, the application provides a battery pole piece obtained by a battery pole piece coating process, wherein the difference value between the thickness and the area density of the middle area and the edge area of the battery pole piece is-1%.
In a third aspect, the present application provides the use of a battery pole piece coating process in the preparation of lithium and/or sodium batteries.
The beneficial effects of this application are as follows: according to the method, after the slurry is coated and before the drying process, the dispersing agent is supplemented to the current collector, so that the solid content of the edge area of the current collector is lower than that of the middle area of the current collector, the movement reduction of the dispersing agent in the pole piece drying process is realized, the accumulation effect of powder (solid content) of the raw slurry to the edge area is reduced, the thickness of the edge area of the pole piece after drying is consistent with that of the middle area, and the problem of abnormal belt breakage of the edge of the pole piece in the coating process is solved; meanwhile, the uniformity of the surface density of the pole piece slurry is ensured, the safety performance of the battery cell is enhanced, and the capacity of the pole piece battery cell is not adversely affected.
Drawings
Fig. 1 is a schematic cross-sectional view of a battery pole piece.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The application provides a battery pole piece coating process, which comprises the following steps: uniformly coating positive/negative electrode slurry containing a dispersing agent on the surface of a current collector, then supplementing the dispersing agent on the edge area of the current collector, and then drying to obtain a corresponding positive/negative electrode plate of the battery; before the drying step, the slurry solid content of the edge region of the current collector is 0.9-1.5% lower than that of the positive/negative electrode slurry.
The inventor surprisingly found that the reason why the powder thickness of the edge area of the battery pole piece is higher than that of the middle area is that the dispersing agent volatilizes in the process of coating and baking the battery pole piece, and the volatilization speed of the dispersing agent in the edge area of the battery pole piece is faster than that of the dispersing agent in the middle area of the battery pole piece due to the difference of the volatilization surface areas of the solvent in the middle area and the edge area of the pole piece, so that the edge is eventually bulged; according to the method, after the slurry is coated and before the drying process, when the dispersing agent is not volatilized, the dispersing agent is supplemented to the current collector, the solid content difference of the slurry in the middle area and the slurry in the edge area is adjusted, the dispersing agent in the edge area volatilizes fast but has high content, the dispersing agent in the middle area is low in content and volatilizes slowly, the movement of the dispersing agent in the drying process is reduced, the stacking effect of powder to the edge area is reduced, the dual effects that the surface density difference of the slurry in the two areas after drying is small and the thickness difference is small are achieved under the condition that the volatilization speed of the dispersing agent in the edge area of the battery pole piece is faster than that of the dispersing agent in the middle area of the battery pole piece, the problem that the pole piece is broken by edge of the pole piece is finally solved, and adverse effects on the capacity and safety of an electric core of the pole piece are avoided.
In this scheme, as shown in fig. 1, the current collector includes a middle region and an edge region, the edge region is a region formed by extending 15-20nm vertically from the end of the current collector to the middle, and the remaining region is a middle region.
The scheme is not only suitable for the positive pole piece but also suitable for the negative pole piece.
The coating process of the battery positive plate is realized by the following scheme:
the current collector of the positive electrode plate is an Al foil, and the positive electrode slurry comprises a positive electrode active material, a solvent and a dispersing agent, wherein the positive electrode active material comprises, but is not limited to, lithium iron phosphate, ternary materials, polyanion lamellar oxides and the like.
The solid content of the positive electrode slurry is 55-58%, the dispersing agent is N-methyl pyrrolidone, and the coating weight of the positive electrode slurry is 180-190g/m 2 The amount of the dispersant for the supplementary coating is 2.99-4.01g/m 2 The solid content of the slurry in the edge area of the current collector is 0.9-1.2% lower than that of the positive electrode slurry, and after the positive electrode slurry is uniformly coated on the surface of the current collector, the thickness of the middle area of the current collector is 109-110 mu m, and the coating process of the battery electrode plate is finished, so that the battery positive electrode plate is obtained.
When the positive electrode plate is prepared, the drying temperature is 95-110 ℃, the stacking condition is more obvious when the temperature is too high, the thickness difference between the middle area and the edge area is larger, cracks are easy to occur, the electrode plate cannot be dried when the temperature is too low, and the follow-up operation is influenced.
The coating process of the battery negative electrode plate is realized by the following scheme:
the current collector of the negative electrode plate is a Cu foil, and the negative electrode slurry comprises a negative electrode active material, a solvent and a dispersing agent, wherein the negative electrode active material comprises, but is not limited to, graphite and the like.
The solid content of the cathode slurry is 48-50%, the dispersing agent is N-methyl pyrrolidone and/or water, and the coating weight of the cathode slurry is 90-100g/m 2 The amount of the dispersant for the supplementary coating is 2.21-2.78g/m 2 The solid content of the slurry in the edge area of the current collector is 1.2-1.5% lower than that of the cathode slurry, after the cathode slurry is uniformly coated on the surface of the current collector, the thickness of the middle area of the current collector is 75-80 mu m, and the coating process of the battery electrode plate is finished, so that the battery cathode plate is obtained.
When the negative electrode plate is prepared, the drying temperature is 80-100 ℃, the stacking condition is more obvious when the temperature is too high, the thickness difference between the middle area and the edge area is larger, cracks are easy to occur, the electrode plate cannot be dried when the temperature is too low, and the follow-up operation is influenced.
The application provides a battery pole piece obtained by a battery pole piece coating process, wherein the difference value of the thickness and the area density of the middle area and the edge area of the battery pole piece is-1%.
The application provides an application of a battery pole piece coating process in preparing a lithium and/or sodium battery.
The present invention is further illustrated by the following specific examples.
Example 1
A battery pole piece coating process comprises the following steps: uniformly coating the positive electrode slurry containing N-methyl pyrrolidone dispersing agent with solid content of 55% on the middle area and the edge area of the Al foil, wherein the coating amount is 180g/m 2 The coating speed was 4m/min, the thickness of the slurry to the middle and edge regions of the Al foil was 109. Mu.m, and then 2.99g/m was applied 2 The supplementary amount of the aluminum foil is coated with N-methyl pyrrolidone until the solid content of the slurry in the edge area of the aluminum foil is 54.1 percent, and then the slurry is dried at 110 ℃ to remove the solvent, so as to obtain the positive plate of the battery.
Example 2
A battery pole piece coating process comprises the following steps: uniformly coating the anode slurry containing N-methyl pyrrolidone dispersing agent with solid content of 50% on the middle area and the edge area of the Cu foil, wherein the coating amount is 90g/m 2 The coating speed was 8m/min, the thickness of the paste to the middle and edge regions of the Cu foil was 75 μm, and then 2.21g/m was applied 2 And (3) coating N-methyl pyrrolidone on the edge area of the Cu foil until the solid content of the slurry in the edge area of the Al foil is 48.8%, and drying at 80 ℃ to remove the solvent to obtain the battery negative plate.
Example 3
A battery pole piece coating process, other contents are the same as those of the example 1, and the supplementing amount of the dispersing agent is 4.01g/m 2 。
Example 4
A battery pole piece coating process, otherwise the same as in example 2, with a dispersant make-up of 2.78g/m 2 。
Comparative examples 1 to 5
The procedure of example 1 was repeated except that the amount of dispersant (N-methylpyrrolidone) to be added and the solid content of the slurry in the rear edge region of the dispersant (N-methylpyrrolidone) to be added were adjusted as shown in Table 1.
Comparative examples 6 to 10
The procedure of example 2 was repeated except that the amount of the dispersant (N-methylpyrrolidone) to be added and the solid content of the slurry in the rear edge region of the dispersant (N-methylpyrrolidone) to be added were adjusted as shown in Table 1.
Comparative examples 11 to 17
A battery pole piece coating process was performed in the same manner as in example 1, except that the N-methylpyrrolidone used for the additional coating was replaced with ethylene glycol, and the additional amount and the additional dispersant (ethylene glycol) post-edge area slurry solids content were adjusted as shown in table 2.
Comparative examples 18 to 24
A battery pole piece coating process was performed in the same manner as in example 2, except that the supplemental coated N-methylpyrrolidone was replaced with ethylene glycol, and the supplemental amount and supplemental dispersant (ethylene glycol) rear edge area slurry solids content were adjusted as per table 2.
Evaluation test
The edge thicknesses of the battery pole pieces obtained in the examples and the comparative examples were tested and compared with the thickness of the middle part of the pole piece, and the thickness difference was calculated, and the results are shown in tables 1 and 2.
In examples 1 and 3, the surface densities of the middle region and the edge region of the pole piece were maintained at 180g/m before and after drying 2 The battery is unchanged, has no influence on the capacity of the battery core, and has high safety.
In examples 2 and 4, the surface densities of the middle region and the edge region of the pole piece were maintained at 90g/m before and after drying 2 The battery is unchanged, has no influence on the capacity of the battery core, and has high safety.
Table 1 pole piece test results supplemented with different amounts of N-methylpyrrolidone
According to the result, the N-methyl pyrrolidone which is the same as the dispersant component in the slurry is supplemented according to the supplementing amount of the application, after the slurry is dried, the thickness of the edge area and the thickness of the middle area of the pole piece are basically consistent, and the thickness difference between the edge area and the middle area of the pole piece is larger than or lower than the limiting range of the application, so that the thickness of the edge area and the thickness of the middle area of the pole piece are kept consistent according to the scheme of the application, and the problem of abnormal broken belt of the edge of the pole piece in the coating process is solved; meanwhile, the uniformity of the surface density of the pole piece slurry is ensured, the safety performance of the battery cell is enhanced, and the capacity of the pole piece battery cell is not adversely affected.
Table 2 pole piece test results supplemented with different amounts of ethylene glycol
From the above results, it is known that the situation that the thickness difference between the edge area and the middle area after the pole piece is dried still exists under the conditions that the other dispersing agents of ethylene glycol with different proportions are added, the adding proportion is different, and the solid content of the edge area is controlled to be the same as that of the N-methyl pyrrolidone, and the thickness difference between the edge area and the middle area after the pole piece is dried cannot be reduced by adding the other dispersing agents and changing the proportion, so that the problem of broken belt of the drum edge cannot be solved. The possible reason is that the mixed use of different dispersing agents can cause the failure of the adhesive, so that the slurry is totally failed, has no fluidity and is scrapped; the thickening of the edge area of the slurry is driven by the flow of the original dispersing agent in the slurry, and the supplementing amount of other dispersing agents is low, so that the whole flow belt movement condition of the original slurry dispersing agent is still difficult to resist.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. The battery pole piece coating process is characterized by comprising the following steps of: uniformly coating positive/negative electrode slurry containing a dispersing agent on the surface of a current collector, then, additionally coating the dispersing agent on the edge area of the current collector, and then, drying to obtain a corresponding positive/negative electrode plate of the battery; before the drying step, the slurry solid content of the edge region of the current collector is 0.9-1.5% lower than that of the positive/negative electrode slurry.
2. The process of claim 1, wherein the current collector comprises a central region and an edge region, the edge region being a region formed by extending vertically 15-20nm from the end of the current collector toward the central region, and the remaining region being the central region.
3. The process for coating a battery pole piece according to claim 2, wherein the solid content of the positive electrode slurry is 55-58%, the dispersing agent is N-methyl pyrrolidone, and the coating amount of the positive electrode slurry is 180-190g/m 2 The amount of the dispersant for the supplementary coating is 2.99-4.01g/m 2 And finishing the coating process of the battery pole piece to obtain the battery positive pole piece.
4. The process of claim 3, wherein the thickness of the middle region of the current collector is 109-110 μm after the positive electrode slurry is uniformly coated on the surface of the current collector.
5. A battery pole piece coating process according to claim 3, wherein the temperature of the drying is 95-110 ℃.
6. The process for coating a battery pole piece according to claim 2, wherein the solid content of the negative electrode slurry is 48-50%, the dispersing agent is N-methyl pyrrolidone and/or water, and the coating amount of the negative electrode slurry is 90-100g/m 2 The amount of the dispersant for the supplementary coating is 2.21-2.78g/m 2 And finishing the coating process of the battery pole piece to obtain the battery negative pole piece.
7. The process of claim 6, wherein the thickness of the central region of the current collector is 75-80 μm after the negative electrode slurry is uniformly coated on the surface of the current collector.
8. The battery pole piece coating process of claim 6, wherein the temperature of the drying is 80-100 ℃.
9. A battery pole piece obtained by the battery pole piece coating process according to any one of claims 1-8, wherein the difference in thickness and area density between the middle region and the edge region of the battery pole piece is-1%.
10. Use of a battery pole piece coating process according to any of claims 1-8 for the preparation of a lithium and/or sodium battery.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410020608.4A CN117832407A (en) | 2024-01-05 | 2024-01-05 | Battery pole piece coating process and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410020608.4A CN117832407A (en) | 2024-01-05 | 2024-01-05 | Battery pole piece coating process and application |
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