CN109817869B - Lithium ion battery diaphragm and preparation method thereof - Google Patents
Lithium ion battery diaphragm and preparation method thereof Download PDFInfo
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- CN109817869B CN109817869B CN201811619585.XA CN201811619585A CN109817869B CN 109817869 B CN109817869 B CN 109817869B CN 201811619585 A CN201811619585 A CN 201811619585A CN 109817869 B CN109817869 B CN 109817869B
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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
Abstract
The invention discloses a lithium ion battery diaphragm and a preparation method thereof, wherein the diaphragm is composed of a base layer and coating layers coated on two sides of the base layer, the coating layer on one side of the base layer close to a battery anode is a lithium polyacrylate coating layer, and the coating layer on the other side is a ceramic coating layer. According to the invention, lithium-like polyacrylate is adopted as a coating material and coated on one side of the base film to prepare the lithium ion diaphragm, the coating layer can be well fused with the positive pole piece to form a passivation layer, the occurrence of side reactions is reduced, the lithium ion diaphragm is well attached to the positive pole piece, the flatness of the battery core is improved, the electrical property and the safety performance of the battery core are effectively improved, and meanwhile, the liquid retention capacity of the battery is improved; meanwhile, the ceramic diaphragm coating layer on the other side of the base film can improve the safety performance of the battery cell and prevent the occurrence of large-area short circuit of the positive electrode and the negative electrode.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery diaphragm and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, high voltage, low self-discharge, no memory effect, long cycle life, environmental protection and the like, and is an important technology for realizing sustainable development of energy. At present, the method is mainly applied to the fields of transportation, electronic consumption, energy storage and the like.
The lithium ion battery consists of an anode, a cathode, a diaphragm, electrolyte and a shell, wherein the diaphragm is used for separating the anode and the cathode of the battery, so that the anode and the cathode are prevented from contacting and short-circuiting, and the migration process of the electrolyte between the anode and the cathode is not influenced. The performances of the diaphragm mainly comprise the performances of the diaphragm such as thickness, porosity, air permeability, aperture, uniformity, thermal shrinkage, puncture strength, tensile strength and the like. The performance of the diaphragm determines the interface structure, internal resistance and self-discharge of the battery, and directly influences the capacity, circulation, safety and other performances of the battery, so that the performance of the diaphragm has great influence on the performance of the lithium ion battery.
At present, the coating diaphragm has the advantages of improving the interface of a pole piece, improving the flatness of a battery cell, and improving the liquid retention capability and the safety performance, so the coating diaphragm becomes one of the development directions of the diaphragm in the future. The coated diaphragm is mainly formed by coating a material for improving performance on one side or two sides of a base film in a coating mode, for example, chinese patent CN106328869A discloses a ceramic diaphragm for a lithium ion battery, which comprises a ceramic base layer and a ceramic coating coated on the surface of at least one side of the base layer, wherein the ceramic coating comprises ceramic particles, a dispersing agent and a binder, and the binder is acrylate; acrylate or polyacrylate can fuse with positive pole piece, forms the passivation layer, reduces the emergence of side reaction, and is good with positive pole piece laminating, promotes electric core roughness, improves the electrical property, the security performance of electric core effectively, and coats ceramic particle and polyacrylate, acrylate mixture and be unfavorable for the formation of positive pole interface passivation layer in one side of base film, and then influences the battery performance.
Disclosure of Invention
The invention aims to provide a lithium ion battery diaphragm and a preparation method thereof, which solve the problems in the background technology.
The lithium ion battery diaphragm is composed of a base layer and coating layers coated on two sides of the base layer, wherein the coating layer on one side of the base layer, which is close to a battery anode, is a lithium polyacrylate coating layer, and the coating layer on the other side of the base layer is a ceramic coating layer.
Further, the thickness of the lithium polyacrylate-like coating layer is 0.1-4 μm.
Further, the thickness of the ceramic coating layer is 1 to 8 μm.
Further, the lithium polyacrylate is one or two of lithium polyacrylate and lithium polymethacrylate.
Furthermore, the ceramic particles adopted by the ceramic coating layer are one or more of alumina, magnesia, zirconia, zinc oxide, titanium dioxide, silicon oxide, aluminum hydroxide, calcium chloride and calcium carbonate nanoparticles, and the particle size of the ceramic particles is 50-100nm.
Furthermore, the thickness of the base layer is 6-40 μm, and the porosity of the base layer is 25% -70%.
Further, the base material is one of polyethylene, polypropylene/polyethylene/polypropylene, polyimide, polyvinylidene fluoride and non-woven fabrics.
The preparation method of the lithium ion battery separator is characterized by comprising the following steps:
s1: weighing a certain amount of lithium polyacrylate, pouring into deionized water, and preparing into 0.5-6% by mass of lithium polyacrylate solution;
s2: weighing a certain amount of ceramic particles, adding a solvent, a binder and a dispersant, scattering at a high speed to form ceramic slurry, and sieving;
s3: and respectively coating the lithium polyacrylate solution and the ceramic slurry on two sides of the base layer, and drying to obtain the lithium ion battery diaphragm.
Further, the viscosity of the ceramic slurry is 10-12 mPa.S, and the particle size of the slurry is less than 10 μm.
The invention discloses a lithium ion battery diaphragm, wherein a lithium polyacrylate-like coating layer is coated on the positive electrode side, the lithium polyacrylate-like coating layer is one of lithium polyacrylate and lithium polymethacrylate, the coating layer is aligned to the positive electrode surface, the lithium polyacrylate-like can be fused with a positive electrode pole piece to form a passivation layer, side reactions of an electrolyte and a pole piece interface can be effectively reduced, meanwhile, the coating layer is well attached to the positive electrode pole piece, the flatness of a battery cell is improved, the electrical property and the safety performance of the battery cell are effectively improved, and meanwhile, lithium in the lithium polyacrylate-like coating layer can serve as a small amount of lithium sources, so that the first effect of the battery is improved. The safety performance of electric core can be promoted in base film opposite side ceramic diaphragm coating, and at the charge-discharge in-process of battery, when the thermal runaway appeared, even the base film melts, the ceramic coating still remained intact, can prevent that large tracts of land positive negative pole short circuit from taking place, reduces the thermal runaway and takes place.
Has the beneficial effects that:
according to the invention, lithium-like polyacrylate is adopted as a coating material and coated on one side of the base film to prepare the lithium ion diaphragm, the coating layer can be well fused with the positive pole piece to form a passivation layer, the occurrence of side reactions is reduced, the lithium ion diaphragm is well attached to the positive pole piece, the flatness of the battery core is improved, the electrical property and the safety performance of the battery core are effectively improved, and meanwhile, the liquid retention capacity of the battery is improved; meanwhile, the ceramic diaphragm coating layer on the other side of the base film can improve the safety performance of the battery cell and prevent the occurrence of large-area short circuit of the positive electrode and the negative electrode.
Detailed Description
The present invention is further described in order to make the technical means, the creation features, the achievement purposes and the effects of the present invention easy to understand.
Example 1
A lithium ion battery diaphragm is of a lithium polyacrylate coating layer/polypropylene base film/ceramic coating layer composite structure, the lithium polyacrylate coating layer is located on one side, close to a battery anode, of a base film, the other side of the base film is a ceramic coating layer, the thickness of the polypropylene base film is 16 micrometers, the thickness of the lithium polyacrylate coating layer is 2 micrometers, the thickness of the ceramic coating layer is 2 micrometers, ceramic particles adopted by the ceramic coating layer are alumina particles, and the particle size is 50-100nm.
The preparation method of the lithium ion battery diaphragm comprises the following steps: the method comprises the following steps:
s1: weighing a certain amount of lithium polyacrylate, pouring into deionized water, and preparing into a lithium polymethacrylate solution with the mass percent of 4% -6%;
s2: weighing a certain amount of alumina ceramic particles, adding a solvent, a binder and a dispersant, scattering at a high speed to form ceramic slurry, and sieving, wherein the viscosity of the ceramic slurry is 10-12mPa & S, and the particle size of the slurry is less than 10 mu m;
s3: and respectively coating the lithium polyacrylate solution and the ceramic slurry on two sides of the base layer, and drying to obtain the lithium ion battery diaphragm.
The obtained lithium ion battery diaphragm is subjected to the working procedures of lamination, shell filling, liquid injection, formation, secondary sealing and capacity grading to prepare a 10164227-40Ah battery cell.
Example 2
A lithium ion battery diaphragm is of a composite structure of a lithium polymethacrylate coating layer/a polypropylene base film/a ceramic coating layer, wherein the lithium polymethacrylate coating layer is located on one side, close to a battery anode, of a base film, the other side of the base film is a ceramic coating layer, the thickness of the polypropylene base film is 20 micrometers, the thickness of the lithium polymethacrylate coating layer is 4 micrometers, the thickness of the ceramic coating layer is 2 micrometers, ceramic particles adopted by the ceramic coating layer are mixed particles of aluminum oxide, magnesium oxide and zirconium oxide, and the particle size is 50-100nm.
The preparation method of the lithium ion battery diaphragm comprises the following steps: the method comprises the following steps:
s1: weighing a certain amount of lithium polymethacrylate, pouring the lithium polymethacrylate into deionized water, and preparing a lithium polyacrylate solution with the mass percentage of 4% -6%;
s2: weighing a certain amount of mixed particles of aluminum oxide, magnesium oxide and zirconium oxide, adding a solvent, a binder and a dispersant, scattering at a high speed to form ceramic slurry, and sieving, wherein the viscosity of the ceramic slurry is 10-12mPa & S, and the particle size of the slurry is less than 10 mu m;
s3: and respectively coating the poly-lithium methacrylate solution and the ceramic slurry on two sides of the base layer, and drying to obtain the lithium ion battery diaphragm.
The obtained lithium ion battery diaphragm is subjected to the working procedures of lamination, shell filling, liquid injection, formation, secondary sealing and capacity grading to prepare a 10164227-40Ah battery cell.
Example 3
A lithium ion battery diaphragm is of a composite structure of a lithium polymethacrylate coating layer/a polypropylene base film/a ceramic coating layer, wherein the lithium polymethacrylate coating layer is located on one side, close to a battery anode, of the base film, the other side of the base film is a ceramic coating layer, the thickness of the polypropylene base film is 16 micrometers, the thickness of the lithium polymethacrylate coating layer is 2 micrometers, the thickness of the ceramic coating layer is 1 micrometer, ceramic particles adopted by the ceramic coating layer are mixed particles of aluminum oxide, magnesium oxide and zirconium oxide, and the particle size is 50-100nm.
The preparation method of the lithium ion battery diaphragm comprises the following steps: the method comprises the following steps:
s1: weighing a certain amount of lithium polymethacrylate, pouring the lithium polymethacrylate into deionized water, and preparing a lithium polyacrylate solution with the mass percentage of 4% -6%;
s2: weighing a certain amount of mixed particles of aluminum oxide, magnesium oxide and zirconium oxide, adding a solvent, a binder and a dispersant, scattering at a high speed to form ceramic slurry, and sieving, wherein the viscosity of the ceramic slurry is 10-12mPa & S, and the particle size of the slurry is less than 10 mu m;
s3: and respectively coating the poly-lithium methacrylate solution and the ceramic slurry on two sides of the base layer, and drying to obtain the lithium ion battery diaphragm.
The obtained lithium ion battery diaphragm is subjected to the working procedures of lamination, shell filling, liquid injection, formation, secondary sealing and capacity grading to prepare a 10164227-40Ah battery cell.
Comparative example 1: the difference from example 1 is that in this example, the separator is a polypropylene separator, the thickness of each separator is 20 μm, and 10164227-40Ah battery cells are manufactured through the procedures of lamination, shell filling, liquid injection, formation, secondary sealing and capacity grading.
Comparative example 2 is different from example 1 in that the example uses a composite structure of lithium polyacrylate coating layer/polypropylene base film/lithium polyacrylate coating layer as a diaphragm, the thickness of the polypropylene base film is 16 μm, the thickness of the two lithium polyacrylate coating layers is 2 μm, and 10164227-40Ah cell is manufactured through the procedures of lamination, shell entering, liquid injection, formation, secondary sealing and capacity grading.
Comparative example 3 is different from example 1 in that the example uses a composite structure of a diaphragm of ceramic coating layer/polypropylene-based film/ceramic coating layer, the thickness of the polypropylene-based film is 16 μm, the thickness of both ceramic coating layers is 2 μm, and 10164227-40Ah electric cores are manufactured through the procedures of lamination, shell entering, liquid injection, formation, secondary sealing and capacity grading.
Examples 1-3 and comparative examples 1-3 six 10164227-40Ah cells were tested for safety and electrical performance.
TABLE 1 safety test comparison
| Group of | Extrusion | Falling down | Short circuit | Acupuncture and moxibustion |
| Example 1 | By passing | By passing | By passing | By passing |
| Example 2 | By passing | By passing | By passing | By passing |
| Example 3 | By passing | By passing | By passing | By passing |
| Comparative example 1 | Do not pass through | Is not communicated withFor treating | Do not pass through | Do not pass through |
| Comparative example 2 | By passing | By passing | Do not pass through | Do not pass through |
| Comparative example 3 | By passing | By passing | By passing | By passing |
TABLE 2 comparison of Electrical Properties
Therefore, the lithium polyacrylate or the lithium polymethacrylate can be fused with the positive pole piece to form a passivation layer, so that the side reaction of the electrolyte and the interface of the pole piece can be effectively reduced, meanwhile, the lithium polyacrylate or the lithium polymethacrylate is well attached to the positive pole piece, the flatness of the battery cell is improved, and the electrical property and the safety performance of the battery cell are effectively improved; the ceramic diaphragm coating layer can improve the safety performance of the battery cell, prevent the short circuit of the anode and the cathode in a large area and reduce the thermal runaway.
While the foregoing shows and describes the fundamental principles and principal features of the invention and its advantages, the invention is not to be limited by the foregoing embodiments, which are presented for purposes of illustration only, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims and their equivalents.
Claims (2)
1. The lithium ion battery cell is characterized by comprising a lithium ion battery diaphragm, wherein the lithium ion battery diaphragm consists of a base layer and coating layers coated on two sides of the base layer, one side of the base layer, which is close to the positive electrode of the battery, is a polyacrylic acid lithium coating layer, the other side of the base layer is a ceramic coating layer, ceramic particles adopted by the ceramic coating layer are one or more of alumina, magnesia, zirconia, zinc oxide, titanium dioxide, silicon oxide, aluminum hydroxide, calcium chloride and calcium carbonate nanoparticles, and the particle size of the ceramic particles is 50-100nm; the thickness of the lithium polyacrylate coating layer is 0.1-4 mu m; the lithium polyacrylate is one or two of lithium polyacrylate and lithium polymethacrylate; the thickness of the ceramic coating layer is 1-8 mu m; the thickness of the base layer is 6-40 μm, and the porosity of the base layer is 25-70%; the lithium ion battery diaphragm is prepared by adopting a method comprising the following steps: s1: weighing a certain amount of lithium polyacrylate, pouring into deionized water, and preparing into 0.5-6% by mass of lithium polyacrylate solution; s2: weighing a certain amount of ceramic particles, adding a solvent, a binder and a dispersant, scattering at a high speed to form ceramic slurry, and sieving, wherein the viscosity of the ceramic slurry is 10-12mPa & S, and the particle size of the slurry is less than 10 mu m; s3: and respectively coating the lithium polyacrylate solution and the ceramic slurry on two sides of the base layer, and drying to obtain the lithium ion battery diaphragm.
2. The lithium ion battery cell of claim 1, wherein the base material is one of polyethylene, polypropylene/polyethylene/polypropylene, polyimide, polyvinylidene fluoride, and non-woven fabric.
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| CN112350026B (en) * | 2019-12-25 | 2023-03-17 | 万向一二三股份公司 | Diaphragm and lithium battery using same |
| CN112133874A (en) * | 2020-10-14 | 2020-12-25 | 昆山宝创新能源科技有限公司 | Lithium battery and application thereof |
| CN114171780A (en) * | 2021-11-30 | 2022-03-11 | 蜂巢能源科技有限公司 | Lithium ion battery cell, preparation method and application thereof |
| CN114696040B (en) * | 2022-06-01 | 2022-08-30 | 沧州明珠隔膜科技有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
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