CN219498083U - Lithium battery diaphragm and lithium battery - Google Patents
Lithium battery diaphragm and lithium battery Download PDFInfo
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- CN219498083U CN219498083U CN202222022869.9U CN202222022869U CN219498083U CN 219498083 U CN219498083 U CN 219498083U CN 202222022869 U CN202222022869 U CN 202222022869U CN 219498083 U CN219498083 U CN 219498083U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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Abstract
The utility model provides a lithium battery diaphragm, which comprises a base film and a coating arranged on the surface of the base film, wherein the coating comprises a first coating, the first coating is positioned on one side of the base film, and the first coating can perform lithium intercalation reaction with lithium. According to the lithium battery diaphragm provided by the utility model, the first coating with the lithium intercalation function is arranged on the surface of the diaphragm, so that lithium metal precipitated on the surface of the negative electrode can be effectively contained by the first coating, the growth of lithium dendrites is inhibited, and the short circuit caused by the fact that the lithium dendrites pass through the diaphragm to contact the positive electrode is avoided, thereby effectively improving the safety performance of the lithium battery. The utility model also provides a lithium battery.
Description
Technical Field
The utility model relates to the technical field of batteries, in particular to a lithium battery diaphragm and a lithium battery.
Background
With the rapid development of the new energy automobile industry, a power battery serving as an electric automobile heart becomes a research hot spot. The lithium ion battery is widely applied to the field of electric automobiles due to the advantages of high voltage, high specific energy, good cycle performance, cleanliness, no pollution and the like. High energy density, high safety and long service life become three basic elements of lithium ion batteries.
The cell of a lithium ion battery generally includes a positive electrode, a negative electrode, and a separator between the positive and negative electrodes for insulating the positive and negative electrodes. In order to improve the energy density of the lithium battery, the battery core is designed to use a cathode material with higher energy density, such as a silicon-carbon cathode or a lithium metal cathode, and the cathode material with high energy density is easy to separate lithium and generate lithium dendrite in the charge and discharge process, particularly in the high-current charge and discharge process.
The existence of lithium dendrite is a huge potential safety hazard to the battery cell, and when lithium dendrite grows to pass through the diaphragm and contact with the positive electrode, the internal short circuit of the battery cell is easily led to cause thermal runaway of the battery cell, and the electric vehicle fires and explodes.
Disclosure of Invention
The utility model aims to provide a lithium battery diaphragm, wherein a first coating with a lithium intercalation function is arranged on the surface of the diaphragm, and can effectively contain lithium metal precipitated on the surface of a negative electrode, inhibit growth of lithium dendrite and avoid short circuit caused by the fact that the lithium dendrite passes through the diaphragm to contact with a positive electrode, so that the safety performance of the lithium battery is effectively improved.
The utility model provides a lithium battery diaphragm, which comprises a base film and a coating arranged on the surface of the base film, wherein the coating comprises a first coating, the first coating is positioned on one side of the base film, and the first coating can perform lithium intercalation reaction with lithium.
In one implementation, the first coating includes a lithium-intercalatable species that is one or more of graphite, mesophase carbon microspheres, hard carbon, soft carbon, silicon carbon composites, lithium titanate.
In one implementation, the first coating further includes a first inorganic material bonded to the first binder, the first inorganic material being SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 One or more of the following.
In one possible implementation, the thickness of the first coating is 1 μm to 10 μm.
In one achievable manner, the porosity of the first coating is greater than or equal to 45%.
In one implementation, the coating further includes a second coating, the second coating being an insulating coating, the second coating being located between the base film and the first coating, the second coating being for improving the insulating properties of the lithium battery separator.
In one implementation, the second coating includes a second inorganic material that is SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 One or more of the following.
In one possible implementation, the thickness of the second coating is 1 μm to 10 μm.
In one implementation, the coating further includes a third coating, the third coating is an insulating coating, the third coating is located on a side of the base film away from the first coating, and the third coating is used for improving the insulating performance of the lithium battery separator.
In one implementation, the third coating layer includes an insulating material, the insulating material includes a third inorganic material and/or functional polymer nano-microspheres, and the third inorganic material is SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 The functional polymer nano-microsphere is PVDF-HFP copolymer and/or PMM.
In one implementation, at least one of the first, second, and third coatings further comprises a binder that is one or more of polyvinylidene fluoride, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, and styrene-butadiene latex.
In one possible implementation, the thickness of the third coating is 1 μm to 10 μm.
In one implementation, the base film is at least one of a polypropylene-based dry base film, a polypropylene/polyethylene/polypropylene three-layer dry base film, a polyethylene-based wet base film, a meta-aramid base film, a para-aramid base film, a PET base film, and a polyimide-based base film.
The utility model also provides a lithium battery, which comprises a battery cell, wherein the battery cell comprises the lithium battery diaphragm and a negative electrode, the negative electrode is positioned on one side of the lithium battery diaphragm, and the first coating is positioned on one side of the base film facing the negative electrode.
In one implementation, the battery cell further includes a positive electrode located on a side of the lithium battery separator away from the negative electrode; the coating further comprises a third coating, the third coating is an insulating coating and is used for improving the insulating property of the lithium battery diaphragm, and the third coating is positioned on one side of the base film facing the positive electrode.
According to the lithium battery diaphragm provided by the utility model, the first coating is arranged on the surface of the base film, so that the first coating can perform lithium intercalation reaction with lithium, namely, the first coating has a lithium intercalation function, the first coating can effectively contain lithium metal precipitated on the surface of the negative electrode, inhibit the growth of lithium dendrites, and avoid short circuit caused by the fact that the lithium dendrites pass through the diaphragm to contact the positive electrode, so that the safety performance of the lithium battery is effectively improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a lithium battery separator according to an embodiment of the present utility model.
Fig. 2 is a schematic cross-sectional view of a lithium battery separator according to another embodiment of the present utility model.
Fig. 3 is a schematic cross-sectional view of a lithium battery separator according to another embodiment of the present utility model.
Fig. 4 is a schematic cross-sectional view of a lithium battery separator according to another embodiment of the present utility model.
Fig. 5 is a schematic cross-sectional view of a cell according to an embodiment of the utility model.
Detailed Description
The following describes in further detail the embodiments of the present utility model with reference to the drawings and examples. The following examples are illustrative of the utility model and are not intended to limit the scope of the utility model.
The terms "first," "second," "third," "fourth" and the like in the description and in the claims, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.
The terms upper, lower, left, right, front, rear, top, bottom and the like (if any) in the description and in the claims are used for descriptive purposes and not necessarily for describing relative positions of structures in the figures and in describing relative positions of structures. It should be understood that the use of directional terms should not be construed to limit the scope of the application as claimed.
As shown in fig. 1 and 5, an embodiment of the present utility model provides a lithium battery separator 1 for being disposed between a positive electrode 2 and a negative electrode 3 of a lithium battery. The lithium battery separator 1 comprises a base film 11 and a coating layer arranged on the surface of the base film 11, wherein the coating layer comprises a first coating layer 12, the first coating layer 12 is positioned on one side of the base film 11, and the first coating layer 12 can perform lithium intercalation reaction with lithium.
Specifically, the first coating layer 12 is located on the side of the base film 11 facing the anode 3. According to the lithium battery diaphragm 1 provided by the embodiment, the first coating 12 is arranged on the surface of the base film 11, the first coating 12 can perform lithium intercalation reaction with lithium, namely, the first coating 12 has a lithium intercalation function, the first coating 12 can effectively contain lithium metal precipitated on the surface of the negative electrode 3, inhibit the growth of lithium dendrites, and avoid short circuit caused by the fact that the lithium dendrites pass through the diaphragm to contact the positive electrode 2, so that the safety performance of the lithium battery is effectively improved.
As shown in fig. 1, as an embodiment, the first coating layer 12 includes a lithium-intercalatable substance 121, and the lithium-intercalatable substance 121 is one or more of graphite, mesocarbon microbeads (MCMB), hard carbon, soft carbon, silicon-carbon composite, and lithium titanate, and the lithium-intercalatable substance 121 is capable of undergoing a lithium intercalation reaction with lithium.
Specifically, when the lithium battery uses the silicon-carbon material as the negative electrode 3, during the high-current charging process, particularly in the case of overcharging, the lithium metal precipitated on the surface of the negative electrode 3 is activated when contacting the first coating layer 12 on the surface of the lithium battery separator 1, so as to participate in the lithium intercalation reaction; equivalent to increasing the capacity of the negative electrode 3, the conditions for stopping lithium precipitation and continuing growth of lithium dendrites are stopped without contacting the positive electrode 2 through the separator. When the lithium battery uses metal lithium as the negative electrode 3, the phenomenon of lithium deintercalation exists under the condition that the first coating 12 on the surface of the lithium battery diaphragm 1 is in direct contact with the lithium metal pole piece, and in the charging process, a part of lithium is intercalated into the lithium-intercalated substance 121 of the diaphragm, and a large amount of lithium is still deposited on the negative electrode pole piece, so that the possibility that lithium dendrites penetrate through the diaphragm to reach the positive electrode 2 is eliminated, the risk of short circuit is avoided, and the safety performance of the battery core is improved.
As shown in fig. 1, as an embodiment, the first coating 12 further includes a first binder 122, and the first binder 122 is bonded to the lithium intercalation material 121. The first binder 122 is one or more of polyvinylidene fluoride, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, and styrene-butadiene latex.
As shown in fig. 1, as one embodiment, the lithium-intercalatable substance 121 is mixed with the first binder 122, i.e., the first binder 122 serves as a carrier for the lithium-intercalatable substance 121 to adhere the lithium-intercalatable substance 121 to the surface of the base film 11.
As shown in fig. 3, as another embodiment, the lithium-intercalatable substance 121 may be formed into a single-layer or multi-layer film structure by spraying, sputtering, or the like, and the first binder 122 is also a film structure, and the lithium-intercalatable substance 121 of the film structure is adhered to the surface of the base film 11 by the first binder 122. Of course, in other embodiments, the first binder 122 may also have a void structure formed therein, and the lithium-intercalatable substance 121 is intercalated into the void structure of the first binder 122.
As shown in fig. 2, as another embodiment, the first coating layer 12 further includes a first inorganic material 123, where the first inorganic material 123 is bonded to the first binder 122, and the first inorganic material 123 is used to improve the insulation performance of the first coating layer 12, and further improve the insulation performance of the lithium battery separator 1. The first inorganic material 123 is SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 One or more of the following.
As shown in fig. 2, as one embodiment, the lithium-intercalatable substance 121, the first inorganic material 123, and the first binder 122 are mixed together to form the first coating layer 12, and then applied to the surface of the base film 11.
As one embodiment, the thickness of the first coating layer 12 is 1 μm to 10 μm, or 4 μm to 5 μm, or 2 μm to 4 μm.
As an embodiment, the first coating layer 12 does not contain a conductive agent therein to improve the insulating property of the first coating layer 12 and thus the insulating property of the lithium battery separator 1.
As an embodiment, the first coating 12 is relatively loose in structure without being subjected to a rolling compacting process during manufacturing, and the porosity of the first coating 12 is greater than or equal to 45% (if compacted, the porosity is about 35%), so that lithium ion migration is not hindered, and the high-current charge and discharge of the lithium battery are facilitated.
As shown in fig. 1, as an embodiment, the first coating layer 12 has a single-layer structure. As another embodiment, as shown in fig. 4, the first coating layer 12 is a multilayer structure (for example, two or more layers), and the multilayer first coating layers 12 are sequentially stacked in the thickness direction of the lithium battery separator 1.
As shown in fig. 1, as an embodiment, the coating layer further includes a second coating layer 13, the second coating layer 13 is an insulating coating layer, the second coating layer 13 is located between the base film 11 and the first coating layer 12, and the second coating layer 13 is used to improve the insulating performance of the lithium battery separator 1.
As shown in fig. 1, as an embodiment, the second coating layer 13 includes a second inorganic material 131, and the second inorganic material 131 is used to improve the insulation performance of the second coating layer 13, thereby improving the insulation performance of the lithium battery separator 1. The second inorganic material 131 is SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 One or more of the following.
As shown in fig. 1, as an embodiment, the second coating layer 13 further includes a second binder 132, and the second binder 132 is bonded to the second inorganic material 131 (the bonding mode of the second inorganic material 131 and the second binder 132 may refer to the bonding mode of the lithium intercalation material 121 and the first binder 122). The second binder 132 is one or more of polyvinylidene fluoride, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, and styrene-butadiene latex.
As shown in fig. 1, as an embodiment, the thickness of the second coating layer 13 is 1 μm to 10 μm, or 2 μm to 6 μm, or 1 μm to 2 μm.
As shown in fig. 1, as an embodiment, the coating layer further includes a third coating layer 14, the third coating layer 14 is an insulating coating layer, the third coating layer 14 is located on a side of the base film 11 away from the first coating layer 12 (the third coating layer 14 is located on a side of the base film 11 facing the positive electrode 2), and the third coating layer 14 is used to improve the insulating performance of the lithium battery separator 1.
As shown in fig. 1, as an embodiment, the third coating layer 14 includes an insulating material 141, the insulating material 141 includes a third inorganic material and/or functional polymer nano-microspheres, and the insulating material 141 is used to improve the insulating performance of the third coating layer 14, thereby improving the insulating performance of the lithium battery separator 1. The third inorganic material is SiO 2 、Al 2 O 3 、AlO(OH)、ZrO 2 、B 2 O 3 、ZnO 2 、Li 3 PO 4 、SiS 2 、P 2 S 5 、Li 4 SiO 4 -B 2 O 3 、Li 2 S-SiS 2 -Li 4 SiO 4 And LiO 2 -P 2 O 5 -B 2 O 3 The functional polymer nano-microsphere is PVDF-HFP copolymer and/or PMM.
As shown in fig. 1, as an embodiment, the third coating layer 14 further includes a third binder 142, where the third binder 142 is bonded to the insulating material 141 (the bonding manner of the insulating material 141 and the third binder 142 may refer to the bonding manner of the lithium intercalation material 121 and the first binder 122). The third binder 142 is one or more of polyvinylidene fluoride, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, and styrene-butadiene latex.
As shown in FIG. 1, as an embodiment, the thickness of the third coating layer 14 is 1 μm to 10 μm, or 2 μm to 6 μm, or 1 μm to 2 μm.
As an embodiment, the base film 11 is one of a polypropylene-based dry base film, a polypropylene/polyethylene/polypropylene three-layer dry base film, a polyethylene-based wet base film, a meta-aramid base film, a para-aramid base film, a PET base film, and a polyimide-based base film.
As an embodiment, the method for preparing the lithium battery separator 1 may be:
40kg of mesophase carbon microspheres (MCMB, namely, lithium intercalation substance 121), 400g of dispersing agent polypyrrolidone, 1.6kg of polyacrylate (namely, first binder 122) are weighed, added into 158kg of distilled water, stirred and dispersed at a high speed to prepare MCMB slurry with the solid content of 20%; the surface of the aramid base film was coated using a micro gravure coater and dried at 80 ℃ for 15 minutes to obtain a lithium-intercalation functional separator having a first coating layer 12, wherein the thickness of the first coating layer 12 was 8 μm.
As shown in fig. 5, the embodiment of the utility model further provides a lithium battery, which includes a battery core, wherein the battery core includes the lithium battery separator 1 and the negative electrode 3 (the negative electrode 3 may be, for example, a negative electrode sheet). The negative electrode 3 is located on the side of the lithium battery separator 1, and the first coating layer 12 is located on the side of the base film 11 facing the negative electrode 3.
As shown in fig. 5, as an embodiment, the battery cell further includes a positive electrode 2 (the positive electrode 2 may be, for example, a positive electrode sheet), where the positive electrode 2 is located on a side of the lithium battery separator 1 away from the negative electrode 3, that is, the positive electrode 2 and the negative electrode 3 are located on opposite sides of the lithium battery separator 1, respectively. The coating further comprises a third coating layer 14, wherein the third coating layer 14 is an insulating coating layer, the third coating layer 14 is used for improving the insulating property of the lithium battery separator 1, and the third coating layer 14 is positioned on one side of the base film 11 facing the positive electrode 2.
According to the lithium battery diaphragm 1 provided by the embodiment, the first coating 12 is arranged on the surface of the base film 11, the first coating 12 can perform lithium intercalation reaction with lithium, namely, the first coating 12 has a lithium intercalation function, the first coating 12 can effectively contain lithium metal precipitated on the surface of the negative electrode 3, inhibit the growth of lithium dendrites, and avoid short circuit caused by the fact that the lithium dendrites pass through the diaphragm to contact the positive electrode 2, so that the safety performance of the lithium battery is effectively improved.
The foregoing is merely illustrative of the present utility model, and the present utility model is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present utility model. Therefore, the protection scope of the present utility model shall be subject to the protection scope of the claims.
Claims (9)
1. The lithium battery diaphragm is characterized by comprising a base film and a coating layer arranged on the surface of the base film, wherein the coating layer comprises a first coating layer, the first coating layer is positioned on one side of the base film, and the first coating layer can perform lithium intercalation reaction with lithium; the coating further comprises a third coating, wherein the third coating is an insulating coating, and the third coating is positioned on one side of the base film far away from the first coating.
2. The lithium battery separator of claim 1, wherein the first coating comprises a lithium-intercalatable substance that is graphite, mesophase carbon microspheres, hard carbon, soft carbon, silicon carbon composite, or lithium titanate, and a first binder that is bonded to the lithium-intercalatable substance; the lithium intercalation material and the first binder are both in a film layer structure, and the lithium intercalation material is adhered to the surface of the base film through the first binder; alternatively, the first binder has a hole structure formed therein, and the lithium-intercalatable substance is intercalated in the hole structure of the first binder, and the lithium-intercalatable substance is adhered to the surface of the base film through the first binder.
3. The lithium battery separator of claim 1, wherein the first coating has a thickness of 1 μιη to 10 μιη.
4. The lithium battery separator of claim 1, wherein the first coating has a porosity of greater than or equal to 45%.
5. The lithium battery separator of any one of claims 1-4, wherein the coating further comprises a second coating, the second coating being an insulating coating, the second coating being located between the base film and the first coating.
6. The lithium battery separator according to claim 5, wherein the thickness of the second coating layer is 1 μm to 10 μm.
7. The lithium battery separator according to claim 1, wherein the thickness of the third coating layer is 1 μm to 10 μm.
8. The lithium battery separator according to claim 1, wherein the base film is a polypropylene-based dry base film, a polypropylene/polyethylene/polypropylene three-layer dry base film, a polyethylene-based wet base film, a meta-aramid base film, a para-aramid base film, a PET base film, or a polyimide-based base film.
9. A lithium battery comprising a cell, wherein the cell comprises the lithium battery separator of any one of claims 1-8 and a negative electrode on one side of the lithium battery separator, the first coating on the side of the base film facing the negative electrode; the battery cell also comprises a positive electrode, the positive electrode is positioned on one side, far away from the negative electrode, of the lithium battery diaphragm, and the third coating is positioned on one side, facing the positive electrode, of the base film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202222022869.9U CN219498083U (en) | 2022-07-27 | 2022-07-27 | Lithium battery diaphragm and lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202222022869.9U CN219498083U (en) | 2022-07-27 | 2022-07-27 | Lithium battery diaphragm and lithium battery |
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| CN219498083U true CN219498083U (en) | 2023-08-08 |
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| CN202222022869.9U Active CN219498083U (en) | 2022-07-27 | 2022-07-27 | Lithium battery diaphragm and lithium battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117954791A (en) * | 2024-03-26 | 2024-04-30 | 宁德新能源科技有限公司 | Separator, electrochemical device, and electronic apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117954791A (en) * | 2024-03-26 | 2024-04-30 | 宁德新能源科技有限公司 | Separator, electrochemical device, and electronic apparatus |
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